Metrics details Ask a synthetic chemist how to convert an alkyne to a cis-alkene and they will barely pause for thought before suggesting hydrogenation with a heterogeneous Lindlar catalyst This classic reaction is used on industrial scales requiring a substantial amount of precious metal palladium to produce alkene building blocks for polymers Mark Crimmin and co-workers from Imperial College London and Johnson Matthey have described the first example of a catalytic semi-hydrogenation of alkynes to cis-alkenes using a zinc complex Zinc catalysts are a promising replacement zinc is not considered a transition metal and is both relatively abundant and well distributed across the Earth the researchers developed a zinc–anilide complex (see the figure) possessing the remarkable ability to activate dihydrogen the two hydrogen atoms are split across the Zn–N bond This was determined to be a reversible reaction (favouring the zinc–anilide starting material); however the following loss of aniline gave the Zn–H complex which underwent non-reversible hydrozincation the Zn–H complex added across the alkene triple bond to generate a zinc vinyl complex This syn-addition of the Zn–H complex is responsible for the stereoselectivity in the final product protonation of the vinyl group with aniline generated the cis-alkene product and returned the zinc–anilide complex Prices may be subject to local taxes which are calculated during checkout Baker, G. J., White, A. J. P., Casely, I. J., Grainger, D. & Crimmin, M. R. Catalytic, Z-selective, semi-hydrogenation of alkynes with a zinc–anilide complex. J. Am. Chem. Soc. https://doi.org/10.1021/jacs.3c02301 (2023) Download references Nature Reviews Chemistry http://www.nature.com/natrevchem/ Reprints and permissions Download citation DOI: https://doi.org/10.1038/s41570-023-00497-8 Anyone you share the following link with will be able to read this content: a shareable link is not currently available for this article Sign up for the Nature Briefing newsletter — what matters in science Create your free account to receive personalised content alerts and Re:action our weekly newsletter of the top chemical science stories handpicked from a range of magazines journals and websites alongside insight and analysis from our expert editorial team Tell us what you think. Take part in our reader survey By Nour Tanbouza2022-09-14T13:01:00+01:00 Researchers have developed a lead- and palladium-free alternative for the Lindlar catalyst The cobalt-based heterogeneous catalyst proved to be efficient for catalysing the semi-hydrogenation of alkynes and exhibits high selectivity mitigating some of the problems encountered when using the traditional Lindlar catalyst ‘The Lindlar catalyst is a special catalyst which allows the selective hydrogenation of alkynes to alkenes. This is an important reaction step for the synthesis of vitamins, especially vitamin E,’ says Kathrin Junge from the Leibniz Institute for Catalysis in Germany the catalyst is far from perfect as it typically consists of 5wt% palladium supported on CaCO3 but the catalyst also suffers in terms of performance and can lead to over-hydrogenation and isomerisation Researchers have successfully addressed its performance issues by replacing lead with other precious metals alternatives using non-noble metals have had limited success a nitrogen doped carbon layer is created around the metal nanoparticles to regulate their behaviour and prevent over-hydrogenation Source: © Matthias Beller/Leibniz Institute for Catalysis Alkyne semi-hydrogenation is an important step in the production of vitamins and other fine chemicals Now, researchers in Leibniz, led by Junge and Matthias Beller have partnered with researchers at DSM Nutritional Products in Switzerland to develop a catalyst with improved activity and recyclability The new catalyst they have created is based on cobalt nanoparticles modified by nitrogen doped carbon and supported on silica ‘This new material can be applied as an alternative to the traditional Lindlar catalyst and promote the semi-hydrogenation of a range of vitamin precursors as well as other functionalised alkynes with good yields and selectivities,’ explains Junge Antonio Leyva-Pérez an expert in catalysis at UPV–CSIC in Spain says the work demonstrates ‘that catalysts based on cheap available materials provide a feasible pathway for the synthesis of these industrial intermediates’ ‘Although a plethora of alternatives for the Lindlar catalyst have been reported this new solid catalyst based on earth-abundant materials is of particular interest,’ he adds the catalyst exhibits high selectivity and can perform selective hydrogenations of C–C triple bond even in the presence of susceptible functional groups thus broadening its versatility in organic synthesis P McNeice et al, Green Chem., 2022, DOI: 10.1039/d2gc01400a Site powered by Webvision Cloud In this week’s newsletter: The Fresh Prince sidekick DJ Jazzy Jeff and more take a trip down memory lane and explore how 1988 revolutionised music forever • Don’t get Hear Here delivered to your inbox? 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Sign up here Picks of the weekTake That: This Life Global Player episodes weeklyAfter 30 years in the business Howard Donald and Mark Owen have a whole lot of stories – and the good news is they can remember most of them three-fifths of Take That get down to recalling their first impressions of each other this free-flowing chat about jacket potatoes giving up their day jobs and their multiple comebacks will be as lovable as Barlow’s songs View image in fullscreenClueless’s Cher Horowitz whose wardrobe features in Articles of Interest Photograph: Paramount Pictures/AllstarThis week Charlie Lindlar chooses five of the best spin-off podcasts from a miniseries investigating the unsolved killings of British birds to a podcast on the clothing decisions we make and why Today Explained, for Kids“Our world which demystifies the news agenda daily in tight 25-minute episodes for Kids – which has provided just what you’d expect in two short seasons in 2020 and 2022 While the earlier episodes focused on the coronavirus pandemic and the 2020 Black Lives Matter protests may have lost some relevancy latter episodes on evergreen subjects such as veganism and fossil fuels provide timely Killing the SkydancerReleased just this August this miniseries from the Guardian’s own Science Weekly podcast explores the unsolved and illegal killings of Britain’s birds of prey on hunting grounds – and how it became so hard to identify and prosecute those who carried out the attacks Guardian biodiversity reporter Phoebe Weston narrates the three gripping episodes whose three chicks were killed while being monitored by cameras The twisting tale sees Weston investigate failed police efforts meet those trying to protect birds in danger and encounter the “surprising silence” around this tragic trend LeadingThe Rest Is Politics has driven a career renaissance for former Labour spin doctor Alastair Campbell and exiled Tory minister Rory Stewart Their podcast and its brand of “disagreeing agreeably” has won over millions of listeners – and they hope to do the same with Leading a new spin-off in which the pair interview decision makers and seek to reach the heart of their lives Few podcasts have the pull to interview Tony Blair Gerry Adams and George Osborne in back-to-back weeks let alone interestingly – so try this show if you want important insights from influential figures this ingenious show will make you think again about the clothes you throw on daily it even delves into that eternal question: why are women so short-changed when it comes to pockets Head over to The Social Dose for daily roundups of all the best news insights and beefs from our favourite social media platforms From the host of Dutch podcast Dertig in een Dozijn, Thirty and a Bit focuses on tackling the issues women face during their third decade Home to edgy and honest conversations between actor Kelly Ripa and a celebrity guest, each episode is unfiltered and uncensored: Let’s Talk Off Camera with Kelly Ripa. If you want to read the complete version of the newsletter please subscribe to receive Hear Here in your inbox every Thursday by award-winning Vermont artist Floyd Scholz “Arctic Royalty Gyr Falcons” were at the peak of this auction for $8,850 Burnett; Images Courtesy Merrill’s Auctioneers and Appraisers — Merrill’s Auctioneers and Appraisers conducted its Sporting Adirondack and Fine Arts auction on July 21 presenting more than 600 lots of fine art from Vermont artists Native American art and many other related objects from nearby estates Works by known artists found the most favor with bidders Flying high to the top of the auction was a carved and painted group of two falcons on a cliff by Floyd Scholz (b 1958) and titled “Arctic Royalty Gyr Falcons.” Scholz’s career as an artist crediting much of his inspiration to raptors and birds of prey In 1996 he opened the Vermont Raptor Academy offering seminars at the Bennington Center for the Arts where there is a permanent installation of Scholz’s work Landscapes were especially popular with bidders Second in overall price was “The Rushing Torrent” by Johann Wilhelm Lindlar (1816-1896) at $7,080 Although not specifically of the Vermont wilderness trees and flowing river could easily pass for such a terrain who studied at the Dusseldorf Academy between 1846 and 1848 Johann Wilhelm Lindlar is mostly known for his landscapes although not much is known about the artist himself; his 42-by-34-inch oil on canvas “The Rushing Torrent” surged to $7,080 Two paintings by Vermont artist Charles Louis Heyde (1822-1892) followed in price The first was signed and inscribed on the reverse “Passage of the Black River/Ludlow/Vt.,” and was featured as Plate 132 in the Heyde catalogue raisonné by Nancy Price Graff and E The second Heyde in the auction was Plate 135 in that catalog and titled “Waterfall” therein including the collection of Monsignor John McSweeney The top gun of the auction was a Parker Brothers Grade 2 Damascus shotgun in overall excellent condition that was bid to $5,985 1875 and 1876 patent dates above a serial number and was decorated throughout with engravings of game birds Representing Native American art was an early Twentieth Century Navajo (Diné) handwoven rug which are mediating figures between the Great Spirit and humans in their culture The rug was in good condition and showed the original Fred Harvey dealer’s tag Correspondence archive of Civil War-era surgeon Dr Cornelius R Agnew multiplied its $250/500 estimate to $3,835 An unexpected top lot was an archive of correspondence once belonging to Dr Cornelius Agnew (1830-1888) a surgeon and founding member of the United States Sanitary Commission (USSC) the USSC was a private relief agency created with federal legislation to support wounded and sick Union soldiers during the Civil War The archive included business and personal correspondence Agnew’s 1859 certificate of appointment as surgeon general of the state of New York a letter from Gettysburg battlefield one year after the battle Agnew’s wife and education commissioner for the City of New York Prices quoted with buyer’s premium as reported by the auction house. 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Remember Ben with a gift to Thoroughbred aftercare Subscribe for FREE to the Daily PDF or the News Alerts Home » Archive » Top News » Trainer Howie Tesher Passes Away and a popular figure around the New York racetracks for decades Tesher passed away at the Majestic Memory Care Center in Hollywood and had been there for about five years dealing with dementia David said the cause of death was pneumonia “He was happy right up to the end,” David said “There was no patient there like him He was always grabbing the girls and giving them hugs there was a stream of employees coming by to kiss him goodbye.” Tesher was born in 1932 in Miami and was a journalism major in college at the University of Florida but soon discovered that he preferred to spend his time around horses Tesher ran his first horse at the old Tropical Park in 1961 and won his first race in 1962 with Weeper's Boy at Suffolk Downs He trained for such prominent owners as Joseph Allen “I got my assistant's license with Howie after I left Pat Byrne,” said trainer Steve Margolis I went through a divorce while I worked for him and that was hard on me because I was young He was always really helpful and was a really personable person eight years and it was a great job and I learned a lot from him He was a kind man and a friend to a lot of people.” “Howie was one of the nicest people I ever met on the track,” said former jockey agent turned lawyer Drew Mollica “He had a great sense of humor and was a guy who knew how to train a horse He was a great stand-up guy in a game with far too many not stand-up guys who made $1,039,702 and won the GII Cornhusker H He also won the 1986 GIII Illinois Derby in 1986 International with Lieutenant's Lark and the 1993 GI Florida Derby with Bull Inthe Heather He took over the training of 1982 GI Kentucky Derby winner Gato Del Sol after the horse was transferred from the Ed Gregson barn Tesher's Champagneforashley won the 1990 Tampa Bay Derby and then finished third as the favorite in the GI Wood Memorial Champagneforashley was being pointed for the GI Preakness S. but suffered a career-ending injury two days before the race Not a subscriber? 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Copy Article Link Editor / News Stories:editor@thetdn.com Advertising:advertising@thetdn.com Customer Service:customerservice@thetdn.com Click Here to sign up for a free subscription Metrics details As a crucial industrial process for the production of bulk and fine chemicals semi-hydrogenation of alkynes faces the trade-off between activity and selectivity due to undesirable over-hydrogenation By breaking the energy linear scaling relationships we report an efficient additive-free WO3-based single-atom Pd catalytic system with a vertical size effect of hydrogen spillover Hydrogen spillover induced hydrophilic polar layer (HPL) with limited thickness on WO3-based support exhibits unconventional size effect to Pd site in which over-hydrogenation is greatly suppressed on Pd1 site due to the polar repulsive interaction between HPL and nonpolar C=C bonds whereas this is invalid for Pd nanoparticles with higher altitudes By further enhancing the HPL through Mo doping activated Pd1/MoWO3 achieves recorded performance of 98.4% selectivity and 10200 h−1 activity for semi-hydrogenation of 2-methyl-3-butyn-2-ol 26-fold increase in activity of Lindlar catalyst This observed vertical size effect of hydrogen spillover offers broad potential in catalytic performance regulation addresses these issues by poisoning Pd/CaCO3 with lead and quinoline its low activity and toxic additives limit its application in modern industry The key to resolving this paradox lies in breaking the LSRs which remains an underexplored area of research a Adsorption energy regulation to break the energy linear scale relationships b Vertical size effect of the hydrophilic polar layer the presence of spillover hydrogen at the metal-support interface enhances the reaction activity the thickness of the HPL ensured its repulsive effect on both non-polar C≡C and C=C bonds adsorbed on the single-atom Pd surface the addition of Mo facilitated hydrogen spillover and enhanced the HPL further improving the catalytic performance This vertical size effect of the HPL could be extended to other selective hydrogenation reactions such as p-chloronitrobenzene and nitrostyrene and represents a novel approach to address the trade-off between activity and selectivity using hydrogen spillover Comparison for the catalytic activity of the MBY hydrogenation with and without hydrogen pretreatment over reducible supports (a) and irreducible supports (b) c HRTEM of the fresh Pd/WO3 and activated Pd/WO3 d Evolution of in situ FT-IR spectra of H2 adsorbed on Pd/WO3 in a flow of H2 High-resolution XPS spectra of O 1 s specimens (e) and 400 MHz 1H MAS solid-state NMR spectra (f) for fresh Pd/WO3 and activated Pd/WO3 These results indicate that HPL gradually formed during the hydrogen pretreatment process which is closely related to the improved catalytic performance of Pd/WO3 a The catalytic performance over Pd/WO3 after pre-activation in H2 for different period (AT: activated time) b Reaction orders of MBY calculated over Pd/WO3 related to the pretreated time c Fourier transform (FT) EXAFS spectra of Pd1/WO3 the photoelectron wave number relative to the absorption edge energy; R d Reaction rate for the hydrogenation of MBY over fresh and activated Pd/WO3 loaded different size-controlled Pd NPs and single atoms e The conversion of MBY within 10 min over H2 pretreated Pd/WO3 of different loadings of Pd f Reaction rate normalized by Pd loading over H2 pretreated Pd/WO3 of different loadings of Pd g Schematic depiction of the contribution of overflowed H to hydrogenation through “hydrogen pool” Pd1/WO3-H demonstrated the highest performance with a 6-fold increase in activity Pd sites played a primary role in H2 dissociation and substrate hydrogenation while WO3 functioned as a medium to transport and store H atoms forming HxWO3 as a dynamic “hydrogen pool” to participate in the hydrogenation This dynamic process simultaneously avoided the competitive adsorption of substrates and H2 and accelerated the hydrogenation rate a The selectivity to MBE at full MBY conversion over fresh and activated Pd1/WO3 loaded different size-controlled Pd NPs and single atoms b Reaction rate and selectivity over Pd/WO3 with different pretreated time of hydrogen c Evolution of the water contact angle over Pd1/WO3 after hydrogen pretreatment Temperature-programmed desorption experiments of C2H2 and C2H4 over Pd1/WO3 (d) and Pd1/WO3-H (e) Configurations and the calculated Eads values of MBY and MBE adsorption on Pd1/WO3 and Pd1/WO3-H g Schematic depiction of influence of the HPL on the single atoms a series of verified experiments were further conducted which was weak enough to prevent the re-chemisorption and further hydrogenation of MBE the Eads of MBY decreased from −1.21 eV to −0.61 eV consistent with the weakened poisoning effect The Eads ratio of MBY to MBE on Pd1/WO3-H was enlarged When examining the adsorption configurations one can assumed the decrease of Eads for MBY and MBE resulted from the reduced free reaction space above Pd sites e Cycling stability test of the selective hydrogenation of MBY over Pd1/MoWO3 we have developed a WO3-based single-atom Pd catalyst featuring a unique hydrogen spillover size effect which demonstrates distinguished catalytic performance for additive-free semi-hydrogenation of alkynes a hydrophilic polar layer (HPL) forms on the catalyst surface serving as a hydrogen reservoir that provides an additional activity channel HPL imparts strong polarity to the micro-environment surrounding the Pd sites The polar incompatibility between HPL and reactants results in mutual repulsion weakening the adsorption of nonpolar C=C and C≡C bonds which finally suppresses the over-hydrogenation and reduces the poisoning effect of alkynes Due to the height limitation of hydroxyl group array a vertical size effect of hydrogen spillover is observed on Pd1/WO3 and further enhanced by Mo doping which exhibits exceptional performance in the selective hydrogenation of MBY and a variety of other substrates rendering selectivity regulation unavailable for Pd nanoparticle counterparts The vertical size effect of hydrogen spillover efficiently breaks the linear scaling relationships (LSRs) and is also applicable for other selective hydrogenation reactions offering more possibilities for selectivity control in challenging reactions and perhaps more importantly the expansion of the research field on hydrogen spillover and TiO2 were purchased from rom Aladdin Industrial Corporation and calcined at 500 °C for 1 h All chemicals were used as purchased without further purification and were commercially available: These chemicals include citric acid (AR) Lindlar catalyst (5% palladium on calcium carbonate poisoned by lead) was purchased from Aladdin The Pd1/WO3 catalysts were synthesized via the wetness impregnation method 300 mg of WO3 was dispersed in 15 ml of deionized water and stirred for 30 min 273 mg of NH4HCO3 was dissolved in 20 ml of deionized water The resulting solutions were then combined and stirred for an additional 30 min resulting in a flocculent blue precipitate 100 mg PdCl2 was first dissolved in 10 ml hydrochloric acid solution (0.6 M) to obtain PdCl2 solution 150 μL PdCl2 hydrochloric acid solution (containing 6 mg·ml−1 Pd) diluted with 8 ml deionized water was added in the WO3 dispersion and constantly stirred for 1 h The resulting product was separated via centrifugation and subsequently dried under vacuum at 70 °C the catalysts were reduced in H2 (flow rate = 50 ml·min−1 heating rate=2 °C·min−1) at 150 °C for 1 h The Pd/MoWO3 catalysts were prepared using the same protocol with MoWO3 was used as the support material The loading amount of Pd was regulated by the volume of the precursor solution Scanning electron microscopy (SEM) study was performed on a Hitachi SU8010 microscope An electron paramagnetic resonance (EPR) experiment was conducted on a Bruker A300-10/12 The high-resolution Transmission Electron Microscope (HRTEM) and EDS mapping was conducted on the JEOL JEM-2100F at an acceleration voltage of 200 kV Spherical aberration corrected Transmission Electron Microscope (HADDF-STEM) was performed on a FEI Titan G280-200 ChemiSTEM at an acceleration voltage of 200 kV Power X-ray diffraction (XRD) patterns were performed on a Rigaku Ultima IV operating at 40 kV and 20 mA with Cu Kα radiation The inductively coupled plasma-optical emission spectrometry (ICP-OES) was performed on a Perkin Elmer Optima OES 8000 Raman spectrum was collected on a LabRam HRUV The X-ray photoelectron spectra (XPS) was obtained on an ESCALAB MARK II spherical analyzer with an aluminum anode (1486.6 eV) X-ray source and the binding energy was calibrated by the C 1 s peak (284.6 eV) Contact angle measurements were carried on an optical tensiometer (OCA 20 Dataphysics) using the sessile drop method with DI water Solid state NMR measurements were performed on Bruker Avance III HD 400 MHz spectrometers using 3.2 mm magic-angle spinning probes The XAFS spectra were recorded at room temperature using a 4-channel Silicon Drift Detector (SDD) Bruker 5040 Pd K-edge extended X-ray absorption fine structure (EXAFS) spectra were recorded in fluorescence mode Temperature-programmed desorption (TPD) experiments were conducted with a TCD using 10 vol% C2H2 or C2H4 in Ar In situ FTIR spectra of H2 adsorbed on solid samples were collected on a Bruker Vector 70 The process of selective hydrogenation was carried out in a 50 ml three-necked round bottom flask 10 mg of catalyst and 1 mmol of substrate were dispersed in 10 ml of ethanol under constant stirring at 40 °C A balloon filled with H2 (1 bar) was then connected to the flask and purged for several times to remove any air before the reaction started Samples were collected at regular intervals using syringe to monitor the reaction progress and the product distribution was analyzed by a gas chromatography with a flame ionization detector (GC-FID) The product was further confirmed by gas chromatography-mass spectrometry (GC-MS) To ensure the reproducibility within ±0.5% conversion and selectivity values were repeatedly measured under the same reaction conditions hydrogen was introduced into the system for a certain period before adding the substrate with all other conditions remaining unchanged The reaction rate was calculated using Eq. (1) and the conversion was controlled to be less than 20% to eliminate the effect of reverse reaction where Etota is the total energy after a molecule adsorption on the catalyst Elsa is the energy of the clean catalyst alone and Emol is the energy of the molecule in the gas phase Transition states (TS) were obtained using the nudged elastic band (NEB) method with a force convergence criterion of 0.05 eV/Å The data that support the findings of this study can be found in the manuscript and Supplementary information or are available from the corresponding author upon request Fundamental aspects of alkyne semi-hydrogenation over heterogeneous catalysts Selective hydrogenation of ethyne in ethene‐rich streams on palladium catalysts Effect of changes to the catalyst during reaction Patterns of behavior in catalysis by metals Atomic overlayer of permeable microporous cuprous oxide on palladium promotes hydrogenation catalysis Dynamic modification of palladium catalysts with chain alkylamines for the selective hydrogenation of alkynes Atomic-layered Au clusters on α-MoC as catalysts for the low-temperature water-gas shift reaction Adsorption of unsaturated hydrocarbons on Pd(111) and Pt(111): A DFT study Achieving high selectivity for alkyne hydrogenation at high conversions with compositionally optimized PdAu nanoparticle catalysts in raspberry colloid-templated SiO2 Aminopolymer–silica composite-supported Pd catalysts for selective hydrogenation of alkynes Thiol treatment creates selective palladium catalysts for semihydrogenation of internal alkynes Engineering of surface environment of Pd nanoparticle catalysts on carbon support with pyrene–thiol ligands for semihydrogenation of alkynes Tuning the catalytic activity and selectivity of Pd nanoparticles using ligand-modified supports and surfaces BASF NanoSelect™ technology: Innovative supported Pd- and Pt-based catalysts for selective hydrogenation reactions Carrier-induced modification of palladium nanoparticles on porous boron nitride for alkyne semi-hydrogenation From the Lindlar catalyst to supported ligand-modified palladium nanoparticles: selectivity patterns and accessibility constraints in the continuous-flow three-phase hydrogenation of acetylenic compounds Tuning the catalytic performance for the semi-hydrogenation of alkynols by selectively poisoning the active sites of Pd catalysts Tailoring a dynamic metal–polymer interaction to improve catalyst selectivity and longevity in hydrogenation Dynamic metal-polymer interaction for the design of chemoselective and long-lived hydrogenation catalysts Highly selective acetylene semihydrogenation catalyst with an operation window exceeding 150°C Pd−Ga intermetallic compounds as highly selective semihydrogenation catalysts Isolated single-atom Pd sites in intermetallic nanostructures: High catalytic selectivity for semihydrogenation of alkynes Intermetallic PdIn/Al2O3 catalysts with isolated single-atom Pd sites for one-pot hydrogenation of diphenylacetylene into trans-stilbene PdZn intermetallic on a CN@ZnO hybrid as an efficient catalyst for the semihydrogenation of alkynols PdZn intermetallic nanostructure with Pd–Zn–Pd ensembles for highly active and chemoselective semi-hydrogenation of acetylene Liquid-phase acetylene hydrogenation over Ag-modified Pd/Sibunit catalysts: Effect of Pd to Ag molar ratio Performance of Cu-alloyed Pd single-atom catalyst for semihydrogenation of acetylene under simulated front-end conditions AgPd and CuPd catalysts for selective hydrogenation of acetylene PdCx nanocrystals with tunable compositions for alkyne semihydrogenation Isolated metal atom geometries as a strategy for selective heterogeneous hydrogenations Facet engineering accelerates spillover hydrogenation on highly diluted metal nanocatalysts Unraveling 1-hexene hydrogenation over dilute Pd-in-Au alloys Breaking scaling relationships in alkynol semi-hydrogenation by manipulating interstitial atoms in Pd with d-electron gain On the role of surface modifications of Palladium catalysts in the selective hydrogenation of acetylene Identification of non-precious metal alloy catalysts for selective hydrogenation of acetylene Effects of d-band shape on the surface reactivity of transition-metal alloys Activation and spillover of hydrogen on sub-1 nm palladium nanoclusters confined within sodalite zeolite for the semi-hydrogenation of alkynes A magnetically separable Pd single-atom catalyst for efficient selective hydrogenation of phenylacetylene Heterogeneous hydrogenation with hydrogen Spillover enabled by nitrogen vacancies on boron nitride-supported Pd nanoparticles Spatial intimacy of binary active-sites for selective sequential hydrogenation-condensation of nitriles into secondary imines Hydrogen spillover and its relation to hydrogenation: Observations on structurally defined single-atom sites One-pot synthesis of single-crystal palladium nanoparticles with controllable sizes for applications in catalysis and biomedicine Catalyst support effects on hydrogen spillover Reversible hydrogen spillover in Ru-WO3-x enhances hydrogen evolution activity in neutral pH water splitting Comparative influence of surface tungstate species and bulk amorphous WO3 particles on the acidity and catalytic activity of tungsten oxide supported on silica Infrared and Raman study of WO3 tungsten trioxides and WO3 Solid-state 1H NMR studies of different tungsten blue oxides and related substances Acidity of mesoporous MoOx/ZrO2 and WOx/ZrO2 materials: A combined solid-state NMR and theoretical calculation study Direct electrochemical protonation of metal oxide particles Tailoring a local acid-like microenvironment for efficient neutral hydrogen evolution Effect of hydrogen spillover on the surface of tungsten oxide on hydrogenation of cyclohexene and N-propylcarbazole Impact of the local concentration of hydronium ions at tungstate surfaces for acid-catalyzed alcohol dehydration Controlling a spillover pathway with the molecular cork effect Molecular-level insight into how hydroxyl groups boost catalytic activity in CO2 hydrogenation into methanol Modifying interface of carbon support-stimulated hydrogen spillover for selective hydrogenation Nitrogen-doped bamboo-shaped carbon nanotube supported catalysts for heterogeneous hydrogenation Adsorption site regulation to guide atomic design of Ni-Ga catalysts for acetylene semi-hydrogenation Integration of bimetallic electronic synergy with oxide site isolation improves the selective hydrogenation of acetylene Thermochemistry of the hydrogen insertion compounds formed by the molybdic and tungstic acids HxMO3·nH2O (M = Mo Enhanced photocatalytic CO2 reduction to methane over WO3·0.33H2O via Mo doping Mo doping induced more active sites in urchin-like W18O49 nanostructure with remarkably enhanced performance for hydrogen evolution reaction Mechanism of hydrogen spillover on WO3 (001) and formation of HxWO3 (x = 0.125 Selectivity of the Lindlar catalyst in alkyne semi-hydrogenation: a direct liquid-phase adsorption study Download references Financial support from the National Key R&D Program of China (2021YFB3801600) the National Natural Science Foundation of China (22325204) and the “Pioneer” and “Leading Goose” R&D Program of Zhejiang (2023C01108 & 2022C01218 & 2022C01151) are greatly appreciated Center of Chemistry for Frontier Technologies State Key Laboratory of Clean Energy Utilization participated in the catalyst preparation and characterizations All authors discussed the results and commented on the manuscript The authors declare no competing interests Nature Communications thanks Antonio Leyva-Pérez reviewer(s) for their contribution to the peer review of this work Publisher’s note Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations Download citation DOI: https://doi.org/10.1038/s41467-024-45104-6 In this week’s newsletter: The seven-time grand slam winner and patron of the arts hosts a new series Plus: five of the best podcasts about the single life Harry and Paul are … DeviousWidely available episodes weeklyWhat this podcast from The Traitors’ Harry and Paul lacks in accurate facts They run down some of history’s biggest botched crimes laugh at each other’s jokes and lay out exactly how they’d have committed the crimes Week one is the Millennium Dome diamond heist View image in fullscreenMichael Sheen, the voice of the second season of climate show Buried. Photograph: Mario Anzuoni/ReutersBuriedWidely available episodes weeklyThe second season of this shocking eco pod is downright jaw-dropping Actor Michael Sheen claims that forever chemicals are leaking from ex-landfill sites – and he’s right horrifying investigation that finds seals so full of toxins they’re rotting alive supermarket fish riddled with poisons and more scandal than we can list Sonic FieldsWidely available episodes weeklyWhen Sam Tyler found a box of photos of his parents taken at festivals nailing the familiar experience of going overboard on the first night Alison Moyet – 40 Moyet MomentsWidely available episodes twice weekly“This good fortune should not have happened to Alf,” says the lovable and charismatic Alison Moyet as she looks back over her 40-year career She sounds like a woman who’s finally having her say with anecdotes about trauma at the hands of record companies as well as her huge success Silver doesn’t shy from talking about relationships or how to find one (if that’s what you’re after) and the hardships of dating – including an excellent episode with fellow journalist Nancy Jo Sales on the “corporate takeover” of dating and how a whole industry has conspired to make us feel inadequate alone Silver’s show went behind a paywall in 2022 but whether you subscribe or just check out her archive The Widow PodcastLosing a loved one is a unique form of singleness but nonetheless one that deserves its own space for stigma-free discussion “widow coach” Karen Sutton offers affirmations and advice to make the best of things after the worst happens She fearlessly confronts grief’s impact on the body how Covid brought a new form of loss to millions and so much more – never wavering from her belief that we must “lean into” our grief and accept it as a fact of life rather than denying its impact on our wellbeing and stridently laying out what they mean for parental rights SoloBehavioural economist Peter McGraw is on a mission to “destigmatise single living” in its many forms McGraw philosophises on almost anything one can do alone but expands to confront complex issues like family estrangement ethical non-monogamy and how to build families that exist outside the conventional nuclear structure More of a cerebral show about the meaning of our bonds with others than a practical advice podcast Solo has plenty of wisdom to offer those who commit to listening A Girl’s Guide to Travelling AloneOne of the more unspoken aspects of single life Gemma Thompson and guests tackle the joys and trials of solo globetrotting in this practical podcast Single life experts such as Alonement author Francesca Specter and photographer Suchitra Vijayan (who travelled alone for seven years capturing India’s borders) weigh in with motivating stories of going for it and living your dreams Standout episodes include chef Rachel Khoo on how to eat well alone and writer Nanjala Nyabola on the care she takes as a black woman travelling alone – it’s a revealing conversation about privilege A deep dive into the (surprisingly widespread) world of people faking Indigenous ancestry in Pretendians Crooked’s Killing Justice delves into shadowy goings-on in Indian politics From Sudan to Mexico, journalists tell their stories of risking everything for their reporting in Silenced Metrics details Ensemble control has been intensively pursued for decades to identify sustainable alternatives to the Lindlar catalyst (PdPb/CaCO3) applied for the partial hydrogenation of alkynes in industrial organic synthesis Although the geometric and electronic requirements are known a literature survey illustrates the difficulty of transferring this knowledge into an efficient and robust catalyst we report a simple treatment of palladium nanoparticles supported on graphitic carbon nitride with aqueous sodium sulfide which directs the formation of a nanostructured Pd3S phase with controlled crystallographic orientation exhibiting unparalleled performance in the semi-hydrogenation of alkynes in the liquid phase The exceptional behavior is linked to the multifunctional role of sulfur Apart from defining a structure integrating spatially-isolated palladium trimers the modifier imparts a bifunctional mechanism and weak binding of the organic intermediates Similar metal trimers are also identified in Pd4S evidencing the pervasiveness of these selective ensembles in supported palladium sulfides Six prominent catalyst families can be distinguished based on (i) supported metal nanoparticles and Lindlar-type formulations where Pd is poisoned by a second metal (iii) ligand-modified or hybrid materials featuring an organic surfactant that partially covers the surface of Pd nanoparticles The current industrially applied catalysts are indicated in bold Surface structures of representative examples of each catalyst family are illustrated it offers room to tailor the active phase with the most selective ensemble and amount of electronic poisoning at the atomic scale By introducing a facile and scalable procedure to prepare crystal phase and orientation controlled Pd3S nanoparticles supported on carbon nitride this article demonstrates that sulfur can play a multifunctional role enabling unparalleled hydrogenation performance in the continuous-flow three-phase semi-hydrogenation of linear This is linked to the presence of trimeric metal ensembles which are also shown to be present in palladium sulfides of different stoichiometry by the preparation and detailed interrogation of the supported Pd4S phase The superiority with respect to other major families of hydrogenation catalysts is established by determining the hierarchy of key descriptors for the performance Synthetic approach and microscopy images of the palladium sulfide catalysts. a Graphical depiction of the sulfidation of palladium nanoparticles supported on graphitic carbon nitride. The average particle size increased from 1.2 to 1.8 nm upon treatment with Na2S (see Supplementary Note 1) consistent with the distortion of the palladium lattice expected upon introduction of sulfur atoms b HAADF-STEM image with the particle size distribution (inset) of Pd3S/C3N4-423 fresh (left) and after 50 h on stream (right) excluding the occurrence of sintering c HRTEM image of Pd3S/C3N4-423 fresh (left) and after 50 h on stream (right) confirming the preserved crystalline structure d HAADF-STEM image (left) and the derived Pd particle size distribution (inset) down-shifts to –1.80 and –1.90 eV are evidenced for Pd3S(202) and Pd3S(001) compared to the reference value of –1.39 eV for Pd(111) Evaluation of the alkyne semi-hydrogenation performance of the catalysts a The contour plots map the effect of temperature and pressure on the rate (in 103 h–1) and b selectivity to 2-methyl-3-buten-2-ol (in %) of Pd3S/C3N4-423 compared to Pd4S/CNF The DFT results indicate that the adsorption of H atoms in subsurface positions is endothermic by 0.14 eV Since it was not possible to reach higher alkyne conversions in our continuous-flow set up additional batch tests were conducted to evaluate the selective performance under more challenging conditions An impressive 95% selectivity to 2-methyl-3-buten-2-ol was preserved even at 80% conversion over the Pd3S and Pd4S phases whereas much more significant losses were evidenced for the PdPb/CaCO3 (80%) and Pd-HHDMA (85%) catalysts Stability and substrate scope of the palladium sulfide catalysts a Both Pd3S/C3N4 (blue circles) and Pd4S/CNF (red triangles) display a stable performance on stream in the selective hydrogenation of 2-methyl-3-butyn-2-ol b The impact of the adsorption length (Lads) of functionalized alkynes of different sizes over Pd3S/C3N4-423 (blue circles) and Pd-HHDMA (green circles) we can conclude that the Pd3S/C3N4-423 catalyst matches and even exceeds the performance of Pd-HHDMA illustrating the effectiveness of the sulfur modification for preparing superior catalysts with clear practical scope Catalytic descriptors for alkyne semi-hydrogenation a Rate of alkene formation at T = 303 K and P = 1 bar versus the differential adsorption energy of acetylene and ethene for all classes of catalysts b Radar plot charting the relation of the rate with key theoretical indicators for the activity: the adsorption energy of the alkyne (Eads(C2H2)) and the activation energy for H2 dissociation (Ea(H2)) selectivity: the alkene adsorption energy (Eads(C2H4)) and the stability: the segregation energy (Eseg) Values closest to the perimeter lead to enhanced properties The blue shaded area connects the optimal values to date found for the Pd3S system Selectivity depends on (i) the adsorption energy of the alkene (Eads(C2H4)) which shows an optimal value close to 0 or positive and (ii) the ensemble area whose improved value (ca Activity is driven by two criterion with different relative weight: the adsorption of the alkyne (described by the negative Eads(C2H2)) is favorable over all catalysts while most importantly the hydrogen activation energy (Ea(H2)) discriminates between materials able of readily split molecular hydrogen and catalysts requiring harsh reaction conditions Consideration of these factors clearly emphasizes the superiority of Pd-based systems exhibiting the lowest barriers for H2 dissociation and strong alkyne adsorption energies stability could be assessed by several potential phenomena and scenarios but for the sake of simplicity the segregation energy (Eseg) which is the differential energy between the ground state (i.e. an alloyed metallic surface) and the system after segregating one atom towards the surface is taken as a measure for the robustness of the catalyst This explains the higher activity of Pd3S/C3N4 than the reference Pd/Al2O3 the combination of crystal phase and orientation control observed in the sulfidation process to form the Pd3S/C3N4 catalyst ensures that the best values for the set of descriptors are achieved in an elegant yet efficient manner constituting a revolutionary step in catalyst design supported palladium sulfides have been shown to possess unique ensembles with face- and phase-dependent geometric and electronic characteristics and high stability demonstrating exciting potential as catalysts for the selective hydrogenation of alkynes A mild sulfidation treatment over supported metallic Pd nanoparticles led to the incorporation of sulfur into the palladium lattice which drives the formation of a nanostructured Pd3S phase preferentially exposing the (202) crystal facets This surface displays isolated Pd3 ensembles surrounded by sulfur atoms featuring the right ensemble and electronic poisoning to allow the selective hydrogenation of linear Ensembles of similar architecture and functionality were also evidenced in Pd4S/CNF The PdxS catalysts outperformed all state-of-the-art catalysts in terms of alkene formation rate per mole of Pd and evidenced high durability with no sign of segregation A detailed comparison to the existing hydrogenation catalysts illustrated the hierarchy of key performance descriptors demonstrating that the reported synthetic protocol produces a catalyst that synergistically combines the best characteristics of bond polarization while keeping a two-dimensional nature enabling the superior performance for a broad set of compounds The present approach illustrates how the concept of ensemble control in kinetically-trapped crystal orientations can be employed in the precise design of evolved catalysts The mesoporous graphitic carbon nitride carrier (C3N4) was prepared by controlled polymerization 99%) and an aqueous dispersion of colloidal silica (12 g Sigma-Aldrich) were mixed and stirred at 373 K for 6 h to completely evaporate the water The resultant solids were ground and calcined at 823 K (2.3 K min–1 ramp) for 4 h under a nitrogen flow (15 cm3 min–1) The silica was removed by treating the solid in a 4 M aqueous solution of NH4HF2 (200 cm3 The template free mesoporous carbon nitride was collected by filtration washed thoroughly with distilled water and ethanol The incorporation of palladium nanoparticles was approached by wet deposition The carrier was dispersed in deionized water (0.01 gcarrier cm–3) under sonication for 1 h prior to the introduction of an aqueous solution (4.72 cm3 gcarrier–1) containing PdCl2 (0.01 M The resulting suspension was stirred at room temperature for 2 h in the dark an aqueous solution (1.4 cm3 gcarrier–1) of NaBH4 (0.5 M 99%) was subsequently added dropwise and the mixture was stirred overnight the solids (Pd/C3N4) were collected by filtration washed thoroughly with distilled water and ethanol and subsequently dried at 333 K overnight The atomic dispersion of palladium on C3N4 (Pd@C3N4) was achieved by microwave-assisted-deposition An aqueous solution of Pd(NH3)4(NO3)2 (0.05 cm3 ABCR Chemicals) was added to a suspension (20 cm3) of the dispersed C3N4 (0.5 g) and stirred overnight in the dark The resulting suspension was treated in a microwave reactor (CEM Discover SP) applying a cyclic program of 15 s irradiation and 3 min cooling with 20 repetitions using a power of 100 W and dried as described for the nanoparticle-based system The catalyst was added to a Teflon-lined autoclave containing an aqueous solution of Na2S·9H2O (Sigma-Aldrich The autoclave was then heated to the desired temperatures (373 extensively washed with deionized water and ethanol a supported Pd4S catalyst was prepared by incipient wetness impregnation of PdSO4 (ABCR-Chemicals After drying the resulting material was treated under 10 vol.% H2/He at 523 K for 1 h No quinoline was added to the PdPb/CaCO3 catalyst during testing The Pd and Na contents in the catalyst were determined by inductively coupled plasma-optical emission spectrometry (ICP-OES) using a Horiba Ultra 2 instrument equipped with a photomultiplier tube detector The samples were dissolved in piranha solution under sonication until the absence of visible solids The S content was determined by infrared spectroscopy using a LECO CHN-900 combustion furnace Nitrogen isotherms were obtained at 77 K using a Micrometrics Tristar instrument after evacuation of the samples at 423 K for 3 h The Brunauer–Emmett–Teller (BET) method was applied to calculate the total surface area (SBET) High-resolution transmission electron microscopy (HRTEM) high-angle annular dark field STEM (HAADF-STEM) and elemental mapping with EDX spectroscopy were conducted on a FEI Talos microscope operated at 200 kV Samples were prepared by dusting respective powders onto lacey-carbon coated nickel grids The particle size distribution was assessed by counting more than 100 individual Pd nanoparticles CO chemisorption was performed using a Micromeritics Autochem II 2920 chemisorption analyzed coupled with a MKS Cirrus 2 quadrupole mass spectrometer The sample was pretreated in situ at 393 K under He flow (20 cm3 min–1) for 60 min and reduced at 348 K under flowing 5 vol.% H2/N2 (20 cm3 min–1) for 30 min 0.491 cm3 of 1 vol.% CO/He was pulsed over the catalyst bed at 308 K every 4 min The palladium dispersion was calculated from the amount of chemisorbed CO considering an atomic surface density of 1.26 × 1019 atoms m–2 and an adsorption stoichiometry Pd/CO = 2 Powder XRD was measured using a PANalytical X’Pert PRO-MPD diffractometer and Cu-Kα radiation (λ = 0.154 nm) The data was recorded in the 10–70° 2θ range with an angular step size of 0.017 and a counting time of 0.26 s per step XPS was conducted with a Physical Electronics Instruments Quantum 2000 spectrometer using monochromatic Al Kα radiation generated from an electron beam operated at 15 kV and 32.3 W The spectra were recorded under ultra-high vacuum conditions (residual pressure = 5 × 10−8 Pa) at a pass energy of 50 eV In order to compensate for charging effects all binding energies were referenced to the C 1 s at 288.2 eV 13C solid-state cross-polarization/magic angle spinning nuclear magnetic resonance (CP/MAS NMR) spectra were recorded on a Bruker AVANCE III HD NMR spectrometer at a magnetic field of 16.4 T corresponding to a 1H Larmor frequency of 700.13 MHz A 4 mm double resonance probe head at a spinning speed of 10 kHz was used for all experiments The 13C spectra were acquired using a cross polarization experiment with a contact time of 2 ms and a recycle delay of 1 s A total of 64 × 103 scans were added for each sample 13C experiments used high-power 1H decoupling during acquisition using a SPINAL-64 sequence The liquid feed contained 5 wt.% of substrate The reactions were conducted at various temperatures (303–363 K) and total pressures (1–8 bar) keeping constant liquid (1 cm3 min–1) and H2 (36 cm3 min−1) flow rates The reaction orders were obtained as a function of the gas-phase H2 pressure and the 2-methyl-3-butyn-2-ol concentration Blank alkyne semi-hydrogenation experiments over the range of conditions investigated excluded the competitive hydrogenation of benzene or toluene The stability test was carried out at T = 303 K and P = 1 bar The products were collected after 20 min of steady-state operation The batch hydrogenation was carried out in a CEM Discover SP microwave reactor with a pressure-controlled vessel under continuous stirring the liquid feed (1.5 cm3) was heated in the presence of the catalyst (0.01–0.02 g) at 323 K the products were analyzed offline using a gas chromatograph (HP-6890) equipped with a HP-5 capillary column and a flame ionization detector The conversion (X) of the substrate was determined as the amount of reacted substrate divided by the initial amount of substrate The reaction rate (r) was expressed as the number of moles of 2-methyl-3-buten-2-ol produced per hour and total moles of Pd The selectivity (S) to each product was quantified as the amount of the particular product divided by the amount of reacted substrate The carbon balance exceeded 98% in all cases negligible differences were observed between the thermogravimetric profiles of both the fresh and used catalyst The authors declare that the data supporting the findings of this study are available within the article and its Supplementary Information file All other relevant source data are available from the corresponding author upon reasonable request Action of hydrogen on acetylene in presence of nickel One hundred years of vitamins - a success story of the natural sciences Recent advances in selective acetylene hydrogenation using palladium containing catalysts Über katalytische Wirkungen kolloidaler Metalle der Platingruppe The hydrogenation of substituted acetylenes with Raney nickel Process for refining unsatuated hydrocarbon material with an alkali or alkaline earth metal Ein neuer Katalysator für selektive Hydrierungen Selective hydrogenation of acetylene in ethylene and catalyst therefor Process for the production of olefinic carbinols Hydrogenation of 1-butene and 1,3-butadiene mixtures over Pd/ZnO catalysts Pd nanoparticles in hydrotalcite: mild and highly selective catalysts for alkyne semihydrogenation Acetylene hydrogenation on Au-based catalysts Cooperative effects in ternary Cu-Ni-Fe catalysts lead to enhanced alkene selectivity in alkyne hydrogenation Palladium-gallium intermetallic compounds for the selective hydrogenation of acetylene Structured catalyst of Pd/ZnO on sintered metal fibers for 2-methyl-3-butyn-2-ol selective hydrogenation Selectivity enhancement in acetylene hydrogenation over diphenyl sulphide-modified Pd/TiO2 catalysts Al13Fe4 as a low-cost alternative for palladium in heterogeneous hydrogenation BASF NanoSelect™ technology: innovative supported Pd- and Pt-based catalysts for selective hydrogenation reactions Ceria in hydrogenation catalysis: high selectivity in the conversion of alkynes to olefins Stereo- and chemoselective character of supported CeO2 catalysts for continuous-flow three-phase alkyne hydrogenation Interstitial modification of palladium nanoparticles with boron atoms as a green catalyst for selective hydrogenation Selective hydrogenation of acetylene over Pd–boron catalysts: a density functional theory study Beyond the use of modifiers in selective alkyne hydrogenation: silver and gold nanocatalysts in flow mode for sustainable alkene production A stable single-site palladium catalyst for hydrogenations Merging single-atom-dispersed silver and carbon nitride to a joint electronic system via copolymerization with silver tricyanomethanide Palladium sulphide - a highly selective catalyst for the gas phase hydrogenation of alkynes to alkenes Synthesis of supported planar iron oxide nanoparticles and their chemo- and stereoselectivity for hydrogenation of alkynes Semihydrogenation of acetylene on indium oxide: proposed single-ensemble catalysis Molecular understanding of alkyne hydrogenation for the design of selective catalysts Modern trends in catalyst and process design for alkyne hydrogenations Advances in the design of nanostructured catalysts for selective hydrogenation (eds) in Fine Chemicals Manufacture 59–124 (Elsevier Science B.V. (ed.) in Fine Chemicals: The Industry and the Business A density functional theory study of the ‘mythic’ Lindlar hydrogenation catalyst (eds) in Fine Chemicals through Heterogeneous Catalysis 351–471 (Wiley-VCH Verlag GmbH Promoters in the hydrogenation of alkynes in mixtures: insights from density functional theory Designing bimetallic catalysts for a green and sustainable future In situ XPS study of methanol reforming on PdGa near-surface intermetallic phases Unique reaction path in heterogeneous catalysis: the concerted semi-hydrogenation of propyne to propene on CeO2 Consecutive hydrogenation of benzaldehyde over Pd catalysts: influence of supports and sulfur poisoning Catalytic properties of single layers of transition metal sulfide catalytic materials Sulfur as a catalyst promoter or selectivity modifier in heterogeneous catalysis Biomimetic hydrogen evolution: MoS2 nanoparticles as catalyst for hydrogen evolution Detecting the genesis of a high-performance carbon-supported Pd sulfide nanophase and its evolution in the hydrogenation of butadiene Selective hydrogenation of mixed alkyne/alkene streams at elevated pressure over a palladium sulfide catalyst Enthalpies of formation of the palladium sulphides Tailoring supported palladium sulfide catalysts through H2-assisted sulfidation with H2S The influence of sulfidation on the crystalline structure of palladium rhodium and ruthenium catalysts supported on silica Shape dependent catalytic activity of nanoflowers and nanospheres of Pd4S generated via one pot synthesis and grafted on graphene oxide for Suzuki coupling and carbides in selective alkyne hydrogenation on palladium Exchange reactions of hydrogen on metallic catalysts Homolytic products from heterolytic paths in H2 dissociation on metal oxides: the example of CeO2 Evaluating the risk of C–C bond formation during selective hydrogenation of acetylene on palladium Bimetallic palladium catalysts: influence of the co-metal on the catalyst performance Surface dynamics of the intermetallic catalyst Pd2Ga Part II - Reactivity and stability in liquid-phase hydrogenation of phenylacetylene Origin of the increase of activity and selectivity of nickel doped by Au Periodic boundary conditions in ab initio calculations Semiempirical GGA-type density functional constructed with a long-range dispersion correction Improved description of the structure of molecular and layered crystals: ab initio DFT calculations with van der Waals corrections Costless derivation of dispersion coefficients for metal surfaces A climbing image nudged elastic band method for finding saddle points and minimum energy paths Improved tangent estimate in the nudged elastic band method for finding minimum energy paths and saddle points Managing the computational chemistry big data problem: the ioChem-BD platform Download references the Swiss National Science Foundation (Grant No The Barcelona Supercomputing Centre (BSC-RES) and ScopeM of ETH Zurich are thanked for access to their facilities Dr René Verel is thanked for help with the MAS NMR measurements thanks the COFUND program and MINECO for support through Severo Ochoa Excellence Accreditation 2014-2018 (SEV-2013-0319) These authors contributed equally: Davide Albani Department of Chemistry and Applied Biosciences Sharon Mitchell & Javier Pérez-Ramírez Institute of Chemical Research of Catalonia (ICIQ) and The Barcelona Institute of Technology Av. Swiss Federal Laboratories for Materials Science and Technology conceived and coordinated all stages of this research All authors contributed to writing the manuscript Publisher's note: Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations Download citation DOI: https://doi.org/10.1038/s41467-018-05052-4 In this week’s newsletter: A new series produced by the world’s most famous party girl delves into the origins of iconic clubs from London to Lagos you may dismiss the dramatic potential of a series by a charity that takes care of stately homes and gardens But – far from monotonous histories of damp old mansions – this podcast exposes the untold often completely unexpected truths about the hundreds of locations the National Trust looks after in England you can hear how the Trust helped foster the Black hiking movement why Surrey’s Box Hill is a cycling mecca and what the childhood homes of the Beatles reveal about them The Travel DiariesIn short it’s Desert Island Discs but with places rather than records each weekly episode sees journalist Holly Rubenstein meet celebrity guests from Lorraine Kelly to Stanley Tucci to hear about the holiday spots that mean the most to them – and their bucket list locations they’ve yet to hit BBC newsreader Clive Myrie’s account of the many war zones and natural disaster sites he’s reported from also provide a slightly different take on what it means to travel and experience the world Pack Your BagsTaking a step further down the celebrity travel rabbit hole Russell Kane hosts this much more ephemeral but no less addictive podcast series in which famous faces reveal the three things they can’t board a plane without it can grate to hear about the air miles the rich and famous rack up in relative luxury – butthere’s also the opportunity to rifle through the carry-ons of the rich and famous Author Candace Brathwaite’s tales of volunteering in India and Sue Perkins’s guide to working around her twin fears of flying and sea sickness are excellent starting points Anthony Bourdain: Parts UnknownAlready a revered travel and food journalist Anthony Bourdain (above) became perhaps best-known for his documentaries which went beyond the tourist traps and explored the truth of local life His CNN television series Parts Unknown is also available in podcast fashion – and can take you anywhere from Texas to Senegal or Myanmar with the click of a button Bourdain’s masterful narration and his genuine willingness to eat anything put in front of him means the audio version will leave you as hungry and full of wanderlust as his TV shows once did RamblingsFor a more lo-fi and local travel experience try this BBC Radio 4 series in which Clare Balding hikes with both everyday heroes and famous guests to better understand nature and find overlooked holiday locations on home turf Whether it’s trudging through Hackney Marshes with Anita Rani roaming the beaches of Sheppey or discovering the hidden beauty of the Hebrides,its immersive production and Balding’s wholesome commentary will transport you and have you itching to see more of our country with your own eyes (although at least this way you don’t have to endure the exhaustion and blisters) Big Sugar reveals the truth about a clandestine Head back to the 90s with Blur, Oasis and a host of other chart-botherers in the BBC’s The Rise and Fall of Britpop Celebrity therapist Esther Perel sensitively solves more relationship woes in the latest series of Where Should We Begin? Metrics details Pd catalysts are widely used in alkynol semi-hydrogenation due to the existence of scaling relationships of adsorption energies between the key adsorbed species the increase in conversion is frequently accompanied by side reactions thereby reducing the selectivity to alkenols We report that the simultaneous increase in alkenol selectivity and alkynol conversion is achieved by manipulating interstitial atoms including B A negative linear relationship is observed between the activation entropies of 2-methyl-3-butyn-2-ol and 2-methyl-3-buten-2-ol which is highly related to the filling of d-orbital of Pd catalysts by the modification of p-block elements A catalyst co-modified by B and C atoms has the maximum d charge of Pd that achieves a 17-fold increase in the turn-over frequency values compared to the Lindlar catalysts in the semi-hydrogenation of 2-methyl-3-butyn-2-ol The lack of vertically adsorbed bonds to the surface prevents effective dissociation and excellent selectivity and conversion can be achieved simultaneously General optimization of the metal nanocatalysts remains a significant challenge partially because of the lack of understanding of the properties of complex electronic structure materials The easy recycling of Pd nanocatalysts in the industry by combustion of carbon support has stimulated our study of the carbon-supported interstitial Pd catalysts that contain easily removal of light element atoms A versatile synthesis approach for industrially usable Pd nanocatalysts a quantitative correlation of surface electronic structure to conversion and selectivity for transition metal interstitial catalysts by a simple and experimentally measurable descriptor are greatly needed to break the linear relationships we explore a reverse atom diffusion approach to synthesize Pd interstitial nanocatalysts with a series of p-block atoms including B and N as sustainable alternatives to Lindlar catalysts for selective hydrogenation The well-defined structure allows for a direct determination of the structure-property relationship on the basis of the d-electron gain of Pd catalysts by the modification of p-block elements An increase in the d charge of Pd induces the rearrangement of MBE from an adsorption configuration through C=C bonds to one using the hydroxyl group (-OH) terminations which reduces the activation entropy together with the enhanced adsorption entropy of MBY and favors a simultaneous improvement of both the conversion and selectivity of MBY semi-hydrogenation The finding is a very important advance in rational catalyst design based on electronic descriptors e high-resolution SE-STEM image in STEM mode for Pd(B,C)/OMC f TPHD curves for Pd interstitial nanocatalysts with different interstitial atoms and Pd/OMC reference catalyst without interstitial atoms the EELS spectrum for adjacent carbonaceous pore wall is also provided Inset in g is the line scanning for a selected Pd nanoparticle h EELS spectra for interstitial Pd nanocatalysts containing P/C the EELS spectra for pure Pd/OMC are also provided i 11B solid-state NMR spectra of Pd(B,C)/OMC (red line) and B-OMC without Pd (navy line) Inset is the schematic of Pd nanoparticles modified with p-block atoms a XANES spectra of the Pd L3-edge of Pd interstitial nanocatalysts b XPS spectra of the 3d level of Pd with Pd binding energies fitting by peak fitting programs Pd(B,C)/OMC-R8 is the Pd(B,C)/OMC catalyst after eight catalytic runs c CO-DRIFTS spectra with schemes identifying the distinct adsorption modes for Pd interstitial nanocatalysts and the reference Pd/OMC catalyst This is possibly originated from the concentrations of B The synthesis of B-doped Pd with controllable subsurface B concentrations in Pd and ensemble structures to optimize the d charge is deserved further investigation a MBY conversion (Conv.) as a function of time b compile of the selectivity (Sel.) to MBE as a function of MBY conversion and c relationship between the TOF values and selectivity of MBE on the studied Pd nanocatalysts d Semi-hydrogenation of various alkynols on Pd(B,C)/OMC The reaction conditions were: 0.045 mol% Pd; 1.25 mmol of the substrate; 5 mL of ethanol; 25 °C; 800 rpm; and in the presence of hydrogen by an H2 balloon under atmospheric pressure indicating the stability of the Pd nanoparticles with no leaching the heterogenous reaction occurring on the Pd surface is the best model for semi-hydrogenation The increase in the binding energy of MBY for a modified Pd surface with the order of Pd(B,C) > Pd(P,C) > Pd(C) > Pd(S,C) > Pd(N,C) is reflected by the increase of ΔS0* value which leads to a greater restriction of the freedom of the C≡C bond in MBY the binding of the C=C bond in MBE for further hydrogenation follows the reverse order The general scope for the selective hydrogenation of various functionalized alkynols was then extended. It was interesting to find that Pd(B,C)/OMC served as a high-efficiency catalyst with high selectivity to alkenols production (Fig. 3d) a The most favorite adsorption configuration and C=C bond length in MBE on the pure Pd(111) b Reaction pathway for the semi-hydrogenation of MBY on the pure Pd(111) and B-Pd(111) surfaces The geometry structure of involved intermediates and transition states (TS) are illustrated To provide insight into the hydrogenation pathway, the energy profiles for the hydrogenation of MBY are given (Fig. 4b) Two-step hydrogenation is suggested with an intermediate of MBE over the pure Pd(111) The activation barrier for the first hydrogenation from MBY to MBE is calculated to be 0.91 eV B-modified Pd(111) shows a similar barrier indicating that these two surfaces have similar hydrogenation activities The difference occurs at the next hydrogenation step in the presence of B The hydrogenation of MBE can proceed over Pd(111) due to the lack of an obvious difference in the desorption and hydrogenation barriers (0.37 vs MBE prefers desorption rather than to be hydrogenated (0.27 vs 0.63 eV) over B-Pd(111) which is possibly related to the adsorption configuration with an unactivated C=C bond It should be noted that diffusion of dissociated H into the subsurface to form β-PdHX is observed in TS-2 on Pd(111) H cannot diffuse into the subsurface due to the presence of interstitial B the activation barrier for further hydrogenation is increased in the latter The interstitial atoms occupy the surface hcp sites and subsurface octahedral sites It is challenging to experimentally determine the relative amounts of dopant incorporated for each element We assume that this value may not greatly differ from each other due to the similar adsorption energies of different atoms on the Pd surface the high-temperature carbothermal reduction for atom diffusion and the same occupation of the surface/subsurface sites in the Pd lattice a Relationship between the d charge of Pd sites and TOF (red line)/MBE selectivity (blue line) of the Pd interstitial nanocatalysts and the relationship between the d charge of Pd sites and the ΔS0* for the semi-hydrogenation of MBY to MBE (light cyan column) or MBE to MBA (light blue column) b Relationship between the ΔS0* for the semi-hydrogenation of MBY to MBE and MBE to MBA c In situ FT-IR spectra for MBE on Pd(B,C)/OMC and Pd/OMC and DFT calculations for MBE interaction with neutral and negatively charged Pd atoms (set 4/7 extra electron per Pd) the conjugated π orbitals of C=C bonds keep away from negatively charged Pd These results are in good consistency with the IR spectra In addition, the interstitial atoms inhibit the diffusion of H to the subsurface and the formation of a highly active β-PdHX phase, as verified by TPHD and DFT calculations. The electrochemical H adsorption experiment in the HClO4 solution also confirms this (Supplementary Fig. 20) from which the adsorption strength of H on Pd is qualitatively determined by the oxidation charge of the adsorbed hydrogen on the Pd surface Pd/OMC shows obvious hydrogen adsorption-desorption peaks in the CV curve while this peak disappears for Pd(B,C)/OMC The absence of a β-PdHX phase may be attributed to the inhibition of further hydrogenation of MBE over the B-modified Pd catalyst on which the desorption barrier of MBE is relatively low We report that the simultaneous increase in alkenol selectivity and alkynol conversion is achieved by manipulating interstitial atoms in Pd catalysts to gain d electron the understanding of p-block dopants in Pd catalysts are still limited Future works are expected to develop a feasible synthesis approach for metal nanocatalysts containing p-block elements with controllable compositions and ensemble structure by clarifying the atom diffusion and experimentally identifying the compositions and atomic structure of active ensembles in nanocatalysts and their effects on the geometric and electronic structure of Pd ordered mesoporous carbon-supported interstitial Pd catalysts have been synthesized and provide ways to circumvent the linear scaling relationship in the semi-hydrogenation of MBY to MBE The excellent activity (TOF value of 2.84 s−1) and stability of interstitial Pd(B,C)/OMC catalysts has been shown the pure Pd catalyst shows a high TOF value but a very low selectivity to MBE; and the Lindlar catalyst shows a high selectivity but the TOF value is pretty low (17 times lower than Pd(B,C)/OMC) The breaking of LSR is attributed to the rearrangement of MBE from an adsorption configuration using C=C bonds to one using the -OH terminations induced by the increase in the d charge of Pd A linear relationship was established for the activation entropy between MBY and MBE according to the filling of the d-orbital of interstitial Pd catalysts Our work not only provides a green and industrially available synthesis route for interstitial Pd nanocatalysts but also guides the rational design of industrial Pd catalysts with unique chemoselectivity in organic reactions Pd nanocatalysts with interstitial atoms encapsulated in ordered mesoporous carbonaceous carriers were synthesized using coordination-assisted and evaporation-induced self-assembly The synthesis involves carbon precursors of low-molecular-weight phenolic resins (PF) a phosphorus coordinating reagent (C18H15O3P a structure-directing agent (poly(ethylene oxide)-b-poly(propylene oxide)-b-poly(ethylene oxide) triblock copolymer F127 1.0 g of F127 was first mixed in the presence of 20.0 g of ethanol for 10 min 1.1 mL of PdCl2 solution (palladium concentration in ethanol: 56.4 mmol L−1) was added to the first solution 5.0 g of low-molecular-weight phenolic resins (PF) and coordinating reagent (0.5 g triphenyl borate or 0.2 g urea.) were mixed together to obtain a clear solution a solution containing 5.0 g of phenolic resins and a coordinating reagent was added dropwise to the first solution The solution was stirred for 10 min at 40 °C and then the mixture was transferred into evaporating dishes The solvent evaporation was carried out in a hood at ambient temperature for 8 h and the resins were polymerized in an oven at 100 °C for 24 h The as-made films were scratched from the dishes and ground into fine powders Calcination was carried out in a tubular furnace under nitrogen flow to obtain ordered mesoporous carbonaceous carriers supported Pd nanocatalysts with interstitial atoms including B The temperature program was from room temperature to 350 °C with a ramp of 1 °C min−1 The resulting catalysts were denoted as Pd (X,C)/OMC Customized commercial Pd catalysts including Pd/C and Lindlar catalysts poisoned with lead were purchased from Aladdin The XRD measurements were taken using a Rigaku Dmax-3C diffractometer using Cu Kα radiation (40 kV The metallic Pd sizes were calculated according to the Scherrer formula on the basis of the (111) diffraction peak in the wide-angle XRD patterns TEM images were recorded on a JEM 2100 microscope operating at 200 kV The AC-STEM images were performed on a Hitachi HF5000 Environmental STEM operated at 200 kV equipped with a HAADF-STEM detector The elemental analyses of the lines selected in the AC-HAADF-STEM images were performed using a Gatan 965 GIF Quantum instrument The EELS were obtained in STEM mode with a focused electron beam in the sub-nanometer range 11B solid-state NMR spectra was acquired at a static magnetic field strength of 14.1 T on a Bruker Advance III spectrometer operating at a 11B Larmor frequency of 192.50 MHz with a commercial triple-resonance 1.9 mm MAS probe Spectra were referenced to NaBH4 at −42.06 ppm The TPHD experiments were conducted with a Micromeritics Auto Chem II 2920 instrument 100 mg of catalyst was first reduced in a quartz reactor under a 10 vol.% H2/Ar with a flow rate of 30 cm3 min−1 at a temperature of 100 °C for 2 h Then the reactor was cooled to 30 °C under the same H2/Ar flow to avoid thermal decomposition of the Pd-H phase and it was further flushed with Ar flow (30 cm3 min−1) for 30 min to remove weakly adsorbed hydrogen it was heated to 150 °C at a temperature ramp of 5 °C min−1 under 10 vol.% H2/Ar with the same flow rate of 30 cm3 min−1 The spilled hydrogen in this process is monitored by a thermal conductivity detector (TCD) CO-DRIFTS was measured on a Thermo Scientific Nicolet iS50 spectrometer equipped with an in situ cell (PIKE DiffusIR KBr windows) and a liquid-N2-cooled mercury cadmium telluride (MCT) detector with CO as a probe molecule the catalysts were firstly dried in a vacuum at 100 °C for 1 h followed by a reduction in 10 vol.% H2/Ar (30 cm3 min−1) for 60 min at the same temperature After the sample was allowed to cool down to room temperature in argon (30 cm3 min−1) background spectra were acquired and the material was subsequently exposed to diluted CO (5 vol.% CO/Ar Spectra were acquired in the range of 4000–650 cm−1 with a resolution of 4 cm−1 after flushing with Ar (20 cm3 min−1) until no signal for gas-phase CO was detected the catalysts were firstly dried in a vacuum and reduced to 10 vol.% H2/Ar (30 cm3 min−1) for 1 h at 100 °C the liquid adsorbate (removed water by MgSO4) was introduced by bubbling with an Ar flow (50 cm3 min−1) to the in situ cell the Ar flow was also used to fully purge the gas-phase adsorbate the spectra were also collected in the range 4000–650 cm−1 with a resolution of 4 cm−1 The XPS information was performed on a Perkin-Elmer PHI 5000 CESCA instrument with a base pressure of 10−9 Torr The samples were evacuated in a loading locked chamber and then transferred to the analysis chamber (10−9 mbar) The measured XPS data was calibrated with a C 1 s binding energy of 284.6 eV The XANES measurement for the Pd L3-edge (3173 eV) were performed in fluorescence mode on beamline 9-BM-B with electron energy of 7 GeV and an average current of 100 mA which is located in the Advanced Photon Source at Argonne National Laboratory The radiation was monochromatized by a Si(111) double-crystal monochromator The data processing were performed using the Athena program The surface sites referred to the hcp sites of Pd(111) while the subsurface sites referred to the octahedron sites of Pd(111) The adsorption energies of non-metal atoms on the Pd(111) surface were calculated as follows: The transition states were confirmed by two rules: (1) all forces on atoms have been optimized to be less than 0.03 eV Å−1; (2) the total energy is a maximum along the reaction coordinate but a minimum with respect to all other degrees of freedom Vibrational frequency analyses were performed to confirm the integrity of the initial states Hydrogenation reactions of MBY or MBE were performed in a 10 mL round-bottom flask filled with a balloon containing 100% H2 125 μL of MBY or 131 μL of MBE and 5 mL of ethanol 8 mg of powdered Pd(B,C)/OMC catalyst were placed in the round-bottom flask Then the air in the round-bottom flask was replaced by 100% H2 three times and the flask was then sealed by an atmospheric balloon full of 100% H2 the stirring speed was fixed at 800 rpm and the temperature was kept at 25 °C the catalyst was separated by filtration and rinsed with 5 mL of ethanol The filtrate was identified and analyzed to determine the conversion and yield by gas chromatography spectrometry (GC) (Agilent 7890B) using an HP-INNOWax capillary column The MBY or MBE hydrogenation was repeated at least three times with ±5% experimental errors (standard deviation) The carbon balance for all tests was above 97% The reaction with deuterium gas was the same as above with the hydrogen replaced by D2 The catalytic results are shown in terms of the conversion of MBY the initial reaction rate (molecules of reactants converted per mole of Pd per second) molecules of reactants converted per surface atom of Pd per second) The TOF value was calculated at a conversion below 20% The exposed surface area of the dispersed Pd nanoparticles was estimated by pulsing CO chemisorption and ΔS0* for the hydrogenation reactions of MBY and MBE overall studied Pd catalysts were obtained and are described in the Supplementary Information The external mass transfer limitations were studied by ranging stirring speeds from 700 to 1000 rpm The internal diffusion effect on the reaction rate was studied by controlling the surface concentrations of palladium but with similar particle size the hot filtration test during the reaction was performed after achieving 50–60% MBY conversion and then removing the solid catalyst under hot conditions The liquid phase was analyzed by GC to determine the change of MBY conversion the MBY was hydrogenated under the same conditions as previously described the catalyst was recovered by washing thoroughly with large amounts of ethanol and water The recovered catalyst was further dried at 60 °C under vacuum overnight To ensure that the same catalyst amount was used in each cycle several parallel reactions were also carried out at the same time The reused catalyst was designated as Pd(B,C)/OMC-Ry Pd(B,C)/OMC-R8 was the Pd(B,C)/OMC catalyst after eight catalytic runs The solutions after each run were collected and combined to determine the metal leaching Thiol group modified mesoporous silica (SH-SBA-15) was used to trap the soluble palladium species that had leached into the solution 12 mg of SH-SBA-15 was placed in a reaction flask prior to the addition of the reaction solution to give a molar ratio of SH:Pd ≈30:1 The data that support the findings of this study are available from the corresponding author upon reasonable request In situ detection of hydrogen-induced phase transitions in individual palladium nanocrystals Catalysis in the industrial preparation of vitamins and nutraceuticals Kinetic study of selective hydrogenation of 2-methyl-3-butyn-2-ol over Pd-containing hypercrosslinked polystyrene Tailoring the framework composition of carbon nitride to improve the catalytic efficiency of the stabilised palladium atoms Semihydrogenation of a propargylic alcohol over highly active amorphous Pd81Si19 in “supercritical” carbon dioxide Optimizing alkyne hydrogenation performance of Pd on carbon in situ decorated with oxygen-deficient TiO2 by integrating the reaction and diffusion Discovery that quinoline and triphenylphosphine alter the electronic properties of hydrogenation catalysts On the role of surface modifications of palladium catalysts in the selective hydrogenation of acetylene Strategies to break linear scaling relationships Hybrid palladium nanoparticles for direct hydrogen peroxide synthesis: the key role of the ligand Selective ensembles in supported palladium sulfide nanoparticles for alkyne semi-hydrogenation Carrier-induced modification of palladium nanoparticles on porous boron nitride for alkyne semi-Hydrogenation The roles of subsurface carbon and hydrogen in palladium-catalyzed alkyne hydrogenation Highly selective semi-hydrogenation of alkynes with a Pd nanocatalyst modified with sulfide-based solid-phase ligands Contribution of interstitial boron in a boron-incorporated palladium catalyst toward formate oxidation in an alkaline direct formate fuel cell Performance of shape-controlled Pd nanoparticles in the selective hydrogenation of acetylene Poison tolerance to the selective hydrogenation of cinnamaldehyde in water over an ordered mesoporous carbonaceous composite supported Pd catalyst Interstitial boron atoms in the palladium lattice of an industrial type of nanocatalyst: properties and structural modifications Inherent size effects on XANES of nanometer metal clusters: size-selected platinum clusters on silica Influence of Sb on the structure and performance of Pd-based catalysts: an X-ray spectroscopic study Theoretical modelling and facile synthesis of a highly active boron-doped palladium catalyst for the oxygen reduction reaction Catalytically active highly metallic palladium on carbon support for oxidation of HCOO- In situ surface characterization of the intermetallic compound PdGa-a highly selective hydrogenation catalyst Hydrogen production from formic acid decomposition at room temperature using a Ag-Pd core-shell nanocatalyst Prominent electronic and geometric modifications of palladium nanoparticles by polymer stabilizers for hydrogen production under ambient conditions Mercaptopropyl-modified mesoporous silica: a remarkable support for the preparation of a reusable heterogeneous palladium catalyst for coupling reactions Strong evidence of solution-phase catalysis associated with palladium leaching from immobilized thiols during Heck and Suzuki coupling of aryl iodides Kinetic isotope effects in the study of organometallic reaction mechanisms Chemoselective hydrogenation of nitroaromatics at the nanoscale iron(III)-OH-platinum interface The role of heterogeneity in the kinetics of a surface reaction: III Distributions in activation enthalpy and entropy Enthalpy-entropy compensation (EEC) effect: decisive role of free energy Enthalpy-entropy compensation (EEC) effect: a revisit Activation entropy and electronic properties of metal catalysts Catalytic consequences of the thermodynamic activities at metal cluster surfaces and their periodic reactivity trend for methanol oxidation Selective hydrogenation of acetylene over Pd-boron catalysts: a density functional theory study and surface alloying on the activity and selectivity of acetylene hydrogenation on Pd surfaces: a density functional theory study Particle size effect of hydride formation and surface hydrogen adsorption of nanosized palladium catalysts: L3 edge vs K edge X-ray absorption spectroscopy Pressure and temperature effects on the formation of a Pd/C surface carbide: insights into the role of Pd/C as a selective catalytic state for the partial hydrogenation of acetylene Study on carbon deposition associated with catalytic CH4 reforming by using density functional theory CVD-Grown horizontally aligned single-walled carbon nanotubes: synthesis routes and growth mechanisms Amplified interfacial effect in an atomically dispersed RuOx-on-Pd 2D inverse nanocatalyst for high-performance oxygen reduction Tilt the molecule and change the chemistry: mechanism of S-promoted chemoselective catalytic hydrogenation of crotonaldehyde on Cu(111) strongly promotes chemoselective catalytic hydrogenation: stereochemistry and reactivity of crotonaldehyde on clean and S-modified Cu(111) Influence of Sn additives on the selectivity of hydrogenation of α-β-unsaturated aldehydes with Pt catalysts: a density functional study of molecular adsorption Optimising surface d charge of AuPd nanoalloy catalysts for enhanced catalytic activity Mechanistic and kinetic insights into the Pt-Ru synergy during hydrogen generation from ammonia borane over PtRu/CNT nanocatalysts Efficient iterative schemes for ab initio total-energy calculations using a plane-wave basis set Ab initio molecular-dynamics simulation of the liquid-metal-amorphous-semiconductor transition in germanium Generalized gradient approximation made simple Special points for Brillouin-zone integrations Edge sites as a gate for subsurface carbon in palladium nanoparticles Adsorption and decomposition of H2S on Pd(111) surface: a first-principles study An evaluation of harmonic vibrational frequency scale factors Download references This work was supported by the National Natural Science Foundation of China (22025204 the Innovation Program of the Shanghai Municipal Education Commission (2021-01-07-00-02-E00119) and the Shanghai Science & Technology (19070502700) These authors contributed equally: Yang Yang The Education Ministry Key Laboratory of Resource Chemistry Joint International Research Laboratory of Resource Chemistry of Ministry of Education Shanghai Key Laboratory of Rare Earth Functional Materials and Shanghai Frontiers Science Center of Biomimetic Catalysis School of Chemistry and Chemical Engineering Frontiers Science Center for Transformative Molecules Shanghai Key Laboratory of Molecular Catalysis and Innovative Materials iChEM and State Key Laboratory of Molecular Engineering of Polymers supervised STEM and EELS experiments and discussed the presence of interstitial atoms performed the electron-microscopy characterization All authors discussed the results and commented on the paper Nature Communications thanks Sharon Mitchell and the other reviewer for their contribution to the peer review of this work Download citation DOI: https://doi.org/10.1038/s41467-022-30540-z Metrics details An Erratum to this article was published on 23 February 2015 This article has been updated Lindlar catalysts comprising of palladium/calcium carbonate modified with lead acetate and quinoline are widely employed industrially for the partial hydrogenation of alkynes and the risk of its leaching from catalyst surface the catalysts also exhibit poor selectivities in a number of cases Here we report that a non-surface modification of palladium gives rise to the formation of an ultra-selective nanocatalyst Boron atoms are found to take residence in palladium interstitial lattice sites with good chemical and thermal stability This is favoured due to a strong host–guest electronic interaction when supported palladium nanoparticles are treated with a borane tetrahydrofuran solution The adsorptive properties of palladium are modified by the subsurface boron atoms and display ultra-selectivity in a number of challenging alkyne hydrogenation reactions which outclass the performance of Lindlar catalysts It is therefore interesting to develop new Pd nanocatalysts modified with interstitial atoms as a greener alternative to Lindlar catalysts for selective hydrogenation reactions this approach requires a complex procedure to remove the surface carbon for subsequent catalytic applications which can also reduce the interstitial carbon content The interstitial carbon atom in the Pd lattice is unstable which limits its potential applications in catalysis It is thus highly desirable to develop supported Pd catalysts modified with other interstitial atoms that are both formed under ambient conditions and are stable under mild catalytic testing conditions as well as the enthalpy (electronic stabilization) and entropy of surface adsorption versus lattice entrapment are all expected to be important factors none of the above have achieved a method that incorporates the criteria of low temperature synthesis high degree of doping with intB and also importantly use a low toxicity B source equivalent which are essential in modern catalysis synthesis There have been some computational simulations for intB on other metal lattices and related catalysis studies stability evaluation and more importantly the direct structure–activity relationship with important catalytic applications are still lacking It is demonstrated that the new supported and stable Pd-intB/C nanocatalyst displays ultra-selectivity for alkyne partial hydrogenations to cis-alkenes in both the liquid and gas phase without inducing hydrogenolysis for unnecessary bond cleavage isomerization and double bond shift that commonly occur on conventional Lindlar catalyst surfaces within delicate fine chemical or pharmaceutical applications The dramatic enhancement in selectivity for the chemical transformations over Pd is attributed to the presence of intB It is believed that this extra stabilization must come from a direct electronic interaction with the host lattice atoms the mixing of the B s-p orbitals with Pd d-orbitals (DFT calculations shown later) one should be cautious of examining this type of catalysts for reactions under different gas atmospheres at unsustainable high temperatures It is important to establish whether these new Pd-intB nanoparticles supported on activated carbon or calcium carbonate with electronically-modified Pd by the subsurface B atoms can be of any significance for selective hydrogenation transformations under mild conditions Selective partial hydrogenation of fine and speciality chemicals in the liquid phase was chosen as these present significant challenges for ultra-selectivity (delicate molecules may easily undergo side reactions that need to be eliminated) (a) H2 uptake curves for hydrogenation of o-CNB on: (i) commercial 5% Pd/C (red); (ii) non-modified 3% Pd/C (black); (iii) 3% Pd-intB/C (blue) (b) GC results in the hydrogenation of o-CNB Stop: sample collected before rate change in the H2 uptake (at 190 170 and 155 ml H2 uptake for commercial 5% Pd/C End: sample collected at the end of H2 uptake All samples were at 100% conversion of o-CNB; H2 uptake value of ~65 ml for 1 mol equiv (a) Hydrogen uptake curves in the hydrogenation of 3-hexyn-1-ol for: (i) non-modified 3% Pd/C (black); (ii) Pd-intB/C (blue); (iii) Lindlar’s 5% PdPb/CaCO3 (red) Conditions: 30 mmol 1,4-dioxane and 3-hexyn-1-ol H2 uptake value of ~650 ml for 1 mol equiv (b) GC results for the stereoselective hydrogenation of 3-hexyn-1-ol Stop: sample collected before the change in hydrogen uptake End: sample collected at the end of hydrogen uptake Yellow dot represents percent of conversion (a) Hydrogen uptake curves in the hydrogenation of (i) Diphenylacetylene (DPA) over Pd-intB/C catalyst (black); (ii) DPA over Lindlar’s catalyst (red); (iii) Phenylacetylene (PA) over Pd-intB/C catalyst (green); (iv) PA over Lindlar’s catalyst (blue) H2 uptake value of ~62 ml for 1 mole equiv (b) Structure of substrate molecule (top: DPA the hydrogenation of DPA molecule beyond 1 mol hydrogen equivalent was very slow giving higher stilbene selectivity and cis/trans ratio than that of the boron absent Pd sample even in excess of hydrogen atmosphere at prolonged time This clearly suggests that intB has a significant role on minimizing over-hydrogenation and isomerization processes respectively) superimposed on the adsorbate/surface structure (units=0.3 electron per angstrom cube) we demonstrate that a low temperature incorporation of boron atoms into the metal lattice of supported Pd nanoparticles is favourable due to the strong electronic interaction within the host–guest sites using BH3.THF as a modifying reagent This simple chemical modification can be applied directly to existing metal supported catalysts It is also shown for the first time that the Pd metal modified with subsurface boron atoms as a catalyst can give ultra-selectivity in selected partial hydrogenation reactions outperforming those of Lindlar catalysts and Pd-intC in the liquid phase owing to the stronger electronic perturbation to the parent metal atoms With regards to the growing demands for greener catalysts in partial hydrogenations and the limitations of Lindlar catalysts the subsurface modification of Pd with boron atoms may thus find new uses in catalytic applications for fine-tuning adsorptivity/reactivity over the conventional surface methods The average metal crystallite size was found to be 13±3 nm The preparation of Pd-intB/C nanocatalysts was performed in a three-neck round bottom flask equipped with hydrogen and nitrogen switch purged with nitrogen gas and then evacuated overnight for 20 h in vacuum at 80 °C to ensure that any residual oxygen or moisture do not prematurely oxidize the BH3.THF added at later time Catalyst was then pretreated in situ at 100 °C for 1 h then cooled down to room temperature in hydrogen 2 ml of tetrahydrofuran was added to pre-wet the catalyst followed by a dose of BH3.THF solution (1.8 ml The flask was warmed to 40 °C to aid solvent evaporation before measurement A correction has been published and is appended to both the HTML and PDF versions of this paper Handbook of Heterogeneous Catalytic Hydrogenation for Organic Synthesis Wiley (2001) Structure sensitivity of alkynol hydrogenation on shape- and size-controlled palladium nanocrystals: which sites are most active and selective Development of a palladium on boron nitride catalyst and its application to the semihydrogenation of alkynes A revisit to carbon monoxide oxidation on Pd(111) surfaces Kinetic evidence for the influence of subsurface oxygen on palladium surfaces towards CO oxidation at high temperatures Ethylene epoxidation on silver(110): the role of subsurface oxygen Palladium with interstitial carbon atoms as a catalyst for ultraselective hydrogenation in the liquid phase New environmentally friendly catalysts containing Pd-interstitial carbon made from Pd-glucose precursors for ultraselective hydrogenations in the liquid phase Zur Konstitution von Palladium-Bor-Legierungen 73 Powder diffraction data for borides Pd3B and Pd5B2 and the formation of an amorphous boride Pd2B The structure of the palladium-rich boride Pd5B (Pd16B3) Magnetic susceptibility and hydrogen absorption of palladium-boron alloys Zeitschrift Fur Naturforschung Part a-Astrophysik Physik Und Physikalische Chemie A 23 Berichte Der Bunsen-Gesellschaft-Physical Chemistry Chemical Physics 80 The formation of interstitial solid solutions based on solvents showing the fcc structure: elastic versus chemical interaction Decomposition of diborane on Pd(111): thermal and chemical behaviour of surface boron Boron-Doped Palladium Nanoparticles on Carbon Black as a Superior Catalyst for Formic Acid Electro-oxidation 321-3 Materials Science Forumeds (eds Delhez R. Formation of interstitial palladium-carbon phase by interaction of ethylene A surface study on model Pd(111) catalyst modified with boron EXAFS study of the structure of boron in palladium An excellent Pd-based nanocomposite catalyst for the selective hydrogenation of para-chloronitrobenzene Excellent catalytic properties over nanocomposite catalysts for selective hydrogenation of halonitrobenzenes Selective hydrogenation of nitroarenes using gum acacia supported Pt colloid an effective reusable catalyst in aqueous medium Convenient and selective hydrogenation of nitro aromatics with a platinum nanocatalyst under ambient pressure A remarkable synergic effect of polymer-anchored bimetallic palladium-ruthenium catalysts in the selective hydrogenation of p-chloronitrobenzene Hydrogenation of o-chloronitrobenzene over polymer-stabilized palladium-platinum bimetallic colloidal clusters Modification effects of magnetic supports and bimetallic structures on palladium nanocluster catalysts Highly efficient catalysts for the hydrogenation of nitro-substituted aromatics Modification mechanism of Sn4+ for hydrogenation of p-chloronitrobenzene over PVP-Pd/[gamma]-Al2O3 First example of high loaded polymer-stabilized nanoclusters immobilized on hydrotalcite: effects in alkyne hydrogenation The composition of reduced palladium oxide and its behavior as a catalyst for liquid phase hydrogenation Surface chemistry and catalysis studies on the palladium-boron system in the semihydrogenation of alkynes Chemical Bonding at Surfaces and Interfaces 532Elsevier (2007) Absorption of hydrogen by palladium+boron and palladium+silver+boron alloys Download references UK and Johnson Matthey for funding this work and a DPhil studentship to ACWAC We also thank Miss Elisabeth Wolf (Oxford Chemistry) for the assistance in the experiments of acetylene hydrogenation thanks the European Commission for fellowship (PIIF-GA-2009-252242: NANOTUNE) EXAFS experiments were undertaken at the Diamond Light Source (experiment SM-6693-1) is indebted to the Royal Society for an Industrial Fellowship and a membership of the UK's HPC Materials Chemistry Consortium (EP/F067496) the UK's national high-performance computing service provided by UoE HPCx Ltd at the University of Edinburgh Molly Meng-Jung Li & Shik Chi Edman Tsang Christopher Michael Brown & Peter Trenton Bishop contributed to microscopic and EDX analysis contributed to synchrotron XRD characterization; G.J The authors declare no competing financial interests Supplementary Methods and Supplementary References Download citation You may not be able to find the page you were after because of: You might find one of the following links useful: Discover how ATLANT 3D's DALP technology revolutionizes thin-film deposition enabling rapid prototyping and advanced material applications in nanofabrication Precise Nano Corporation is transforming nanogold production with innovative methods that ensure purity Ramakrishna shares his insights into his ongoing electrospinning work and highlights nanofibers' transformative potential in addressing critical challenges InProcess' FIDES is the perfect tool for nanoparticle size characterization for turbid sample analysis The Leica EM VCT500 Vacuum Cryo Transfer System can transfer samples under cryogenic conditions or at room temperature The CT-2 is an ultra-thin vibration isolation platform with superior stability and easy setup you can trust me to find commercial scientific answers from AZoNetwork.com please log into your AZoProfile account first Registered members can chat with Azthena, request quotations, download pdf's, brochures and subscribe to our related newsletter content A few things you need to know before we start Read the full Terms & Conditions Connecting decision makers to a dynamic network of information Bloomberg quickly and accurately delivers business and financial information The T-Systems division will cut as many as 10,000 jobs The tech unit that’s struggling to compete with more agile cloud startups and multinational giants employs about 37,000 people Seven former Anglican clergy were ordained to the Catholic priesthood for the Personal Ordinariate of Our Lady of Walsingham by Archbishop Peter Smith in Saint George's Cathedral Southwark 4 June.In his homily Archbishop Peter promised them the support of the Archdiocese: "...you know you will have the companionship and support of the people to whom you have been pastors for many years religious and laity."He concluded: "I pray that your example and way of life as shepherds of the flock will bring those you serve closer to Christ and to a deeper holiness of life they will continue to grow in the love of God and of their neighbour and become more credible witnesses to the Gospel of Jesus Christ who is the Way the Truth and the Life."Monsignor Keith Newton Apart from the ordination of three former Anglican bishops in January this was the first priestly ordination of former Anglican clergy and begins a wave that will continue throughout the month with more than 50 ordinations expected around the country Source: Ordinariate of Our Lady of Walsingham/Archdiocese of Southwark Archbishop Peter Smith has died + funeral arrangements UPDATED Celebrations to mark Feast Day of St Oscar Romero St Mary's introduces MA in Catholic Social Teaching Filipino Bishop in UK calling banks to stop financing fossil fuels We offer publicity space for Catholic groups/organisations. See our advertising page if you would like more information ICN aims to provide speedy and accurate news coverage of all subjects of interest to Catholics and the wider Christian community As our audience increases - so do our costs You can support our journalism by advertising with us or donating to ICN. 2013Photo: (clockwise from top left) Cale Mason (3); Marko MacPherson | Stylist: Renate LindlarSave this storySaveSave this storySaveIf the setting sounds like something out of a movie—a tiny off-the-beaten-path enclave of Southern Bali sandwiched between the ocean and lush rainforest—that’s because it is “then you’re not far off.” When the Indonesian model turned designer moved to the island about ten years ago before setting up her sunglasses label in 2011 she was surprised to find a community of creatives working on fashion and interior design projects of their own Fellow Bali-based designer Nikki Penny is the latest to strike out with a new line of neoprene swimwear “Our stylist friends would pull from both of us and end up shooting our samples together,” says Empel With a shared love of geometric form and hot it only made sense that the duo collaborate on a capsule collection of sunglasses to match Penny’s eye-catching swimsuits And given that Bali gets a solid eight months of sunshine a year the shades-and-bikini combo ends up being a daily uniform for both of them but luckily you can get Wi-Fi on most parts of the island,” says Empel who lives in a idyllic treehouse sans Internet Needless to say they conceived of the collab while stretched out by the pool of Penny’s secluded villa just minutes from the island’s picture-perfect sandy shores A.T.G. Women swimwear, $50-$280atgishere.com the company is expanding its presence to five strategically important locations Zurich (Switzerland) and Barcelona (Spain) Lang will offer its proven product and service portfolio in Dubai which includes high brightness projection systems Lang ME will provide direct and efficient support to customers in the region in order to better customise technical products to local market requirements comments: “It is fantastic to be here so close to our customers in the Middle East Not only have we opened a new location some 7000km closer to one of the most exciting global hubs in the world we have reduced our delivery time for clients from days & weeks As the Middle East continues to grow as a global business and events hub we see endless opportunities to collaborate with our customers and partners not just in delivering equipment but also in fostering grass root skills creativity and driving innovation in the AV industry." Friday marked the culmination of six month's worth of sweat as the Kansas State 6A wrestling tournament kicked off in Wichita The Dodge City Red Demon wrestling program qualified seven of their 14 wrestlers for the competition as head coach Lars Lueders was looking for a fourth consecutive finish within the top-10 in the state the Demons had two wrestlers enter the semifinals in Alex Garcia and Dane Edwards while five of the seven won their first round match with six of them winning at least one match during the opening rounds      "It's tough to see any senior go out when they've put it all out there but it's also exciting when a senior goes out there and performs well on the first day," Lueders said "Overall I think it's a start and hopefully we can put together a good day two." who came into the tournament as the number one ranked wrestler in 6A dispatching of his opponents en route to a final matchup with Michael Lindlar of Wichita Northwest It has been a rollercoaster season for Garcia as he has hit his peak over the past month refusing to take his foot off the gas pedal His route to the finals included a pin over Emilio Amunatigui of Shawnee Mission Northwest an 11-5 decision over Armond McCray of Wichita Heights and a 7-4 decision over Garrett Girard of Lawrence      Today's final against Lindlar will be the ultimate test for Garcia who looks to add his name to the list of wrestlers that have won a state title for Dodge City he needs to stay that way and if he does that who was the other Demon to advance to the semifinals dropped a heartbreaking 3-1 decision to T.J but not before cruising during his first two matches of the day He picked up wins against Chuck McBride of Blue Valley Northwest A win tomorrow puts him in contention for third or fourth place      As for the rest of the Demon wrestlers it was a successful day as David Montoya earned a first round victory over Barrett Cooper of Shawnee Mission East Jacob Eggers picked up a win against Tilden Edwards of Leavenworth Freddy Hernandez won 11-1 over Deryk Hadl of Olathe North and Francisco Serna bounced back from an opening round defeat to pin Ryan Carter of Blue Valley North      Those six wrestlers will all be in the running for medals tomorrow the Demons sit in ninth place with 44 team points one point ahead of Leavenworth and one point behind Junction City Top-15 6A State wrestling day one team results Please enter your search criteria in the form below to find a team Full Listings: Boys' Commits & Girls' Commits We just rolled out our annual wedding guide detailing everything from stationery to bouquet Today we turn our attention to the groom (or grooms plural thanks to this week’s Supreme Court ruling) with five suits to suit any occasion See our slideshow of handmade wedding decor by PSimadethis. Take a look at Irreverent Brides: Unconventional Wedding Dressing. Read our article After the First Dance: DJ Cassidy on How to Keep the Wedding Party Going. See Jessica Sailer’s wedding inspiration Pinterest board. Cick here to see our Wedding Guide. Raishun Burch began competing in the Back To The Timing International Horse Jumping Event at Lindlar in Germany Burch finished 3rd riding Fiona H 3 after the pair had a clear round time of 61.61 finished 35th after they clocked a time of 70.20 #Equestrian Category: All, Sports Raishun Burch was back in action competing in the Back To The Timing International Horse Jumping Event at Lindlar in Germany Burch only competed in one class on the day Competing in the Point Jumping Competition L in 2 Phases Class Burch and Cutie 3 had a clear round first phase time of 65.00 they would then clock a clear round second phase time of 62.68 to finish 12th they had a clear round first phase time of 60.85 they would then clock a second phase time of 57.00 this after they clocked a clear round first phase time of 62.73 they would then have 6 penalty fault points in the second phase Raishun Burch concluded competing in the Back to the Timing International Horse Jumping Event at Lindlar in Germany The Bermudian equestrian competed in one class on the day and competed on two horses Competing in the Point Jumping Competition M in 2 Phases Class Burch finished 6th riding Fiona H 3; they clocked a Clear Round First Phase time of 65.84 and then a Clear Round Second Phase time of 65.00 finished 47th clocking a Clear First Phase time of 75.15 they were halted at 22.00 with ten Penalty Fault Points Raishun Burch was back in action competing in the Back to the Timing International Horse Jumping Event at Lindlar in Germany Burch only competed in one class on the day and competed on one horse Burch and Firefly 41 finished 15th competing in the Springprüfung Kl