ACS Catalysis 最新文献

{"title":"Gas–Liquid Interface Effects on a One-Pot Two-Enzyme Biocatalytic Oxidation Systems","authors":"Jingyu Wang, Elif Erdem, Luca Schmermund, Xiaodong Liang, Volker Sieber, John M. Woodley","doi":"10.1021/acscatal.5c00526","DOIUrl":"https://doi.org/10.1021/acscatal.5c00526","url":null,"abstract":"Biocatalytic oxidation provides a potentially efficient platform for chemical production, but the air–liquid interface formed in such reactions often affects the biocatalyst performance. Here, we report the kinetic stability of alcohol dehydrogenase (ADH), NADH oxidase (NOX), and associated cofactors upon exposure to various gas–liquid interfaces in a defined interface apparatus. Air and oxygen were bubbled individually to distinguish their effects. The observed loss of enzyme from the solution and the activity were mostly attributed to the enzyme removal via the gas–liquid interface, foaming, and aggregation. An engineered ADH with enhanced interactions between subunits showed a longer half-life and improved kinetic stability at interfaces. Meanwhile, four different NOX enzymes were also tested, resulting in different stability profiles. This study shows the importance of selecting the appropriate enzymes for oxygen-dependent biocatalytic processes and further highlights the importance of the relevant process equipment and conditions to test biocatalysts for subsequent scale-up.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"57 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066722","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A Minimal Mutation Trajectory Separates Inverting and Retaining Mechanisms on the Same Sialidase Structural Scaffold","authors":"Michael Jakob Pichler, Marina Corbella, Sebastian Meier, Maria Haugaard Bohl Andersen, Tine Sofie Nielsen, Sanchari Banerjee, Jens Preben Morth, Carme Rovira, Maher Abou Hachem","doi":"10.1021/acscatal.5c01023","DOIUrl":"https://doi.org/10.1021/acscatal.5c01023","url":null,"abstract":"The recently discovered sialidase <i>Am</i>GH181 from the human gut symbiont <i>Akkermansia muciniphila</i> is remarkably selective to the sialyl T-antigen, a glycan found on mucins and cancer cells. However, the molecular basis for specificity and catalytic mechanism remains unknown in this enzyme family. Combining mutagenesis, X-ray crystallography, and QM/MM metadynamics, we show that specificity is governed by a flexible tryptophan–histidine pair, forming a “sugar tang” that precisely positions the sialyl T-antigen for catalysis. Hydrolysis of the sialyl-T antigen proceeds via a single-step S_N2 reaction and a ^3,6<i>B</i>/³<i>S</i>_O → [^3,6<i>B</i>]^‡ → ^3,6<i>B</i>/³<i>S</i>_O → ²<i>C</i>₅ conformational itinerary of the sialyl unit at subsite <i>–1</i>, resulting in the inversion of anomeric configuration. Remarkably, we altered the reaction stereochemistry by a double mutation, introducing a tyrosine to perform nucleophilic attack on the C2 of the sialyl unit at subsite <i>–1</i>, assisted by acid catalysis to promote aglycone departure. This retaining mutant acquired trans-sialidase activity and performed synthesis of 3′-sialyllactose in remarkably high yields. These findings suggest that the evolutionary divergence of retaining and inverting sialidases hinges on minimal active site mutations. The successful conversion of an inverting hydrolase into a retaining one provides an innovative strategy for harnessing inverting glycosidases for oligosaccharide synthesis via transglycosylation reactions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"11 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066724","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Improved Activity and Durability of Carbon-Capped Pd and PdNi Catalysts─From Model Active Layers to Anion-Exchange Membrane Fuel Cell Electrodes","authors":"Ricardo Sgarbi, Huong Doan, Simon Amigues, Nicolas Bibent, Vincent Martin, Viktoriia Zemtsova, Frédéric Jaouen, Julien Thuilliez, Marian Chatenet","doi":"10.1021/acscatal.5c00704","DOIUrl":"https://doi.org/10.1021/acscatal.5c00704","url":null,"abstract":"Carbon-supported and carbon-capped Pd (Pd@C/C) and PdNi (PdNi@C/C) nanoparticles were synthesized and characterized physicochemically. The presence of the carbon cap minimizes surface metal oxides after synthesis, while the metal loading, size, and composition of the nanoparticles on the carbon support can be tuned. After mild electrochemical activation, these catalysts outperform commercial (non-carbon-capped) Pd/C and PdNi/C catalysts for the alkaline hydrogen oxidation reaction (HOR): the beneficial effect of Ni alloying and of the carbon cap makes PdNi@C/C the best catalyst because it exhibits a metal–metal oxide surface compatible with fast HOR, both initially and during accelerated stress tests performed using rotating disk electrodes. The carbon cap prevents significant oxidation/passivation and leaching of the metals, thereby enhancing the materials’ stability and minimizing their passivation. The Pd@C/C and PdNi@C/C catalysts were upscaled and integrated in low-loaded anodes in Pt-free anion-exchange membrane fuel cells designed to be anode-limiting. The Pd@C/C and PdNi@C/C anodes surpassed Pd/C and PdNi/C anodes, in terms of both activity and stability, thereby confirming the results obtained in liquid alkaline electrolytes, with PdNi@C/C being the winner HOR catalyst. Carbon capping is, therefore, a successful strategy to obtain active and stable HOR catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"96 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144067093","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ruthenium-Based Nanoparticles-Loaded Layered Silica Nanosheets-Assembled Stacked-Structure Nanoreactors for Efficient Production of Biomass-Based Pyrrolidinones","authors":"Jingfei Wang, Xuebin Lu, Yuanyu Wang, Zekun Sun, Run Jing, Zhihao Yu","doi":"10.1021/acscatal.4c08089","DOIUrl":"https://doi.org/10.1021/acscatal.4c08089","url":null,"abstract":"Pyrrolidones are a kind of versatile high-end chemicals used as drug intermediates, bioactive molecules, and organic solvents. Reductive amination of biomass-derived levulinic acid and esters to pyrrolidones is one of the most important routes for the production of biomass-based N-containing chemicals. In this paper, Ru-based nanoparticle-loaded layered silica nanosheets (LSNs) were developed as new-type stacked-structure nanoreactors for the efficient reductive amination of biomass-derived levulinates (EL) into 5-methyl-2-pyrrolidones (5-MPs). Using ammonium formate as both a hydrogen and amine source, a complete EL conversion, near-quantitative yield of 5-MPs, and a high productivity of 997 h^–1 could be achieved over Ru₁Co₁@LSNs nanoreactors under optimized conditions. Mechanistic studies from liquid ¹H NMR, <i>in situ</i> difference Fourier transform infrared (FTIR), and density functional theory (DFT) calculations suggest that the synergistic Lewis acid sites and metal sites favor the rapid formation of imine intermediates and subsequent imine hydrogenation. Molecular dynamics simulations show that EL molecules tended to diffuse in an orderly manner and increase in concentration in the near-surface region due to the space-confinement effects of the stacked structure, thus improving the catalytic efficiency. The nanoreactors developed herein may contribute to the development of multifunctional nanoreactors for valorization of renewable carbon-based resources for production of N-containing chemicals.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"39 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066679","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Transforming Boron Carbon Nitride: A Carbon-to-Oxygen Switch to Boost Propane Oxidative Dehydrogenation","authors":"Xinping Zhang, Bohua Ren, Zhenzhen Yang, Hao Chen, Sheng Dai","doi":"10.1021/acscatal.5c01353","DOIUrl":"https://doi.org/10.1021/acscatal.5c01353","url":null,"abstract":"Hexagonal boron nitride (h-BN) catalysts exhibit high alkene selectivity in the oxidative dehydrogenation of propane (ODHP). Nevertheless, the conversion-selectivity trade-off persisted primarily due to the low density of oxygen-containing boron active species, while simple and controllable modification strategies for h-BN still face challenges. Herein, we developed an <i>in situ</i> carbon-to-oxygen switch strategy within a tailored boron carbon nitride (BCN) framework, in which uniformly embedded B–C₃ were transformed into B–O₃ via oxidative treatment (denoted as BNO_<i>x</i>). The structural evolution from B–C₃ to B–O₃ was well characterized by spectroscopy and soft X-ray absorption techniques. The resulting BNO_<i>x</i> catalysts, enriched with B–O₃ units, demonstrated performance in ODHP, achieving a propane conversion of 50.4% with 32.7% olefin yield at 500 °C. Density functional theory (DFT) calculations confirmed that B–O₃ species preferentially lower activation barriers, rendering the process thermodynamically more favorable. This work introduced an <i>in situ</i> reconstruction method for atomic-level heteroatom-engineered h-BN catalysts, opening an avenue for advanced catalyst design across energy conversion systems.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066725","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Electro-Bendable Metal–Organic Framework Nanosheets Enable Durable Electrocatalytic Water Oxidation at 1 A/cm2","authors":"Yuanwu Liu, Lirong Wang, Congcong Liu, Johannes Kresse, Marielle Deconinck, René Hübner, Daria Mikhailova, Yana Vaynzof, Xiaoming Zhang, Alexander Eychmüller","doi":"10.1021/acscatal.5c02167","DOIUrl":"https://doi.org/10.1021/acscatal.5c02167","url":null,"abstract":"The oxygen evolution reaction (OER) is a pivotal process in electrochemical systems, including metal-air batteries and water-splitting technologies. Despite the promise of metal–organic frameworks (MOFs) as OER electrocatalysts, their stability at elevated current densities (&gt;500 mA cm^–2) remains a key challenge for industrial applications. Herein, we developed a bimetallic MOF electrocatalyst, Fe_8.47Ni_91.53-2-amino-1,4-benzendedicarboxylate (Fe_8.47Ni_91.53-BDC-NH₂), exhibiting good stability at 1 A cm^–2 for 100 h, with overpotentials of only 210 mV at 10 mA cm^–2 and 273 mV at 100 mA cm^–2. The enhanced activity of the catalyst originates from the bending of freestanding FeNi-BDC-NH₂ nanosheets toward the nickel foam substrate during the OER, facilitating the formation of enlarged Mott–Schottky regions and accelerating electron transfer. Additionally, the reversible structural transformation of Ni-2-amino-1,4-benzendedicarboxylate (Ni-BDC-NH₂) during the OER, coupled with the introduction of Fe ions, effectively prevents the overoxidation of the active β-NiOOH intermediate to γ-NiOOH, further boosting the OER performance. This work provides insights into structural and electronic modifications that enable MOFs to achieve both high performance and stability at industrial current densities.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"22 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066382","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"NHC-Catalyzed Kinetic Resolution for the Synthesis of Boron-Stereogenic BODIPYs","authors":"Yuan-Yuan Gao, Yu-Jing Liang, Gaowei Li, Lu Li, Zhi-Yuan Hu, Wen-Hao Lin, Xue-Hui Huang, Yu Chen, Xuzhao Du, Peiyuan Yu, Qiuling Song, Lantao Liu","doi":"10.1021/acscatal.5c01629","DOIUrl":"https://doi.org/10.1021/acscatal.5c01629","url":null,"abstract":"The enantioselective synthesis of boron-stereogenic compounds remains a formidable challenge in modern synthetic chemistry due to the limited availability of efficient catalytic strategies. Herein, we report an N-heterocyclic carbene (NHC)-catalyzed kinetic resolution of 3-formyl BODIPYs, which provides access to enantioenriched 3-formyl BODIPYs and aryl 3-carboxylate BODIPYs in good to high yields with high enantioselectivities (up to 96% ee). This method features a broad substrate scope, mild reaction conditions, and exceptional functional group tolerance. Furthermore, the resulting chiral BODIPYs exhibit promising circularly polarized luminescence properties. This work represents the successful application of NHC catalysis for constructing boron-stereogenic centers, expanding the toolbox for asymmetric organocatalysis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"30 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066726","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Selective Reverse Water–Gas Shift Reaction through MnOx Modification of Supported Pd Catalysts","authors":"Shimpei Naniwa, Shintaro Oka, Shoji Iguchi, Kentaro Teramura","doi":"10.1021/acscatal.4c07622","DOIUrl":"https://doi.org/10.1021/acscatal.4c07622","url":null,"abstract":"Controlling the selectivity for CO₂ hydrogenation is crucial in catalysis. While the reverse water–gas shift (<i>r</i>WGS) reaction offers a promising strategy for recycling atmospheric CO₂, achieving selective <i>r</i>WGS with conventional supported metal catalysts is challenging owing to the successive hydrogenation of CO to CH₄ (methanation). In this study, we show that selective <i>r</i>WGS can be achieved by modifying an Al₂O₃-supported Pd catalyst with an amorphous manganese oxide (MnO<i>_<i>x</i></i>). We fabricated MnO<i>_<i>x</i></i>-modified Pd catalysts supported on Al₂O₃ using a coimpregnation method. Electron microscopy coupled with energy-dispersive spectroscopy revealed that Pd was loaded as nanoparticles with an average size of 7.7 nm, while MnO<i>_<i>x</i></i> was distributed across the catalyst surface. An in-depth analysis using X-ray photoelectron spectroscopy indicated that the Pd particles were covered with MnO<i>_<i>x</i></i> overlayers. A Pd catalyst afforded both CO and CH₄, whereas the MnO<i>_<i>x</i></i>-modified Pd catalyst, which was optimized with 2 mol % Pd and 22 mol % Mn, selectively afforded CO at 673 K with a 28.9% yield. This performance was 8.3 times higher than that of the Pd catalyst and 1.5–1.8 times than those of the reference catalysts (Cu/ZnO/Al₂O₃ and FeCrCuO<i>_<i>x</i></i>). <i>In situ</i> Fourier transform infrared spectroscopy and temperature-programmed desorption measurements proved that MnO<i>_<i>x</i></i> inhibited the adsorption of bridged CO species to suppress the successive hydrogenation of CO, while also providing adsorption sites for CO₂ to enhance the conversion of CO₂. Our findings demonstrate the effectiveness of MnO<i>_<i>x</i></i> modification in enhancing the performance of supported metal catalysts for the <i>r</i>WGS reaction, offering insights into efficient catalytic design for industrial CO₂ recycling.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"8 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066678","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"H-Bond-Assisted Cleavage of N–O Bond in the Electrochemical Reduction of N2O Catalyzed by Iron Tetraphenylporphyrin","authors":"Céline Naddour, Rana Deeba, Camille Chartier, Emmanuel Nicolas, Sylvie Chardon-Noblat, Cyrille Costentin","doi":"10.1021/acscatal.5c01965","DOIUrl":"https://doi.org/10.1021/acscatal.5c01965","url":null,"abstract":"Reductive deoxygenation reactions play a crucial role in electrocatalytic processes relevant to energy and environmental challenges, including the reduction of CO₂, O₂, and N₂O. In particular, N₂O reduction is essential for closing the nitrogen cycle and preventing its accumulation in the atmosphere. These reactions are also significant in chemical processes, such as the reduction of phosphine and sulfur oxides. In this context, we demonstrate that the molecular catalysis of N₂O to N₂ reduction by iron tetraphenylporphyrin occurs predominantly via an innersphere mechanism. We then reveal that acids of varying strengths, including water, ethanol, trifluoroethanol, phenol, and acetic acid, can accelerate N–O bond cleavage. Surprisingly, the effect of acid <i>pK</i>_<i>a</i> is minimal, suggesting that the acceleration arises from hydrogen-bond-assisted N–O bond cleavage rather than direct conventional protonation. The process begins with coordination of N₂O to the low-valent iron tetraphenylporphyrin, activating the bond. At high acid concentrations, this binding step becomes rate-determining. Density functional theory calculations support the proposed mechanism, highlighting the importance of a dual activation strategy: bond activation by a low-valent transition metal and hydrogen-bond assistance from an acid acting as an H-bond donor. These findings provide valuable insights for designing more effective catalysts for N–O bond activation and, more broadly, for advancing reductive deoxygenation reactions.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"30 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144067094","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Amorphous LiNxHy Boosts Low-Temperature Ammonia Decomposition over the Co/MgO Catalyst","authors":"Peijie Han, Yankun Du, Huiying Yang, Ning Yan","doi":"10.1021/acscatal.5c00078","DOIUrl":"https://doi.org/10.1021/acscatal.5c00078","url":null,"abstract":"Catalytic ammonia decomposition facilitated by lithium species such as LiNH₂ and Li₂NH has attracted increasing attention alongside growing interest in hydrogen energy. However, the active site requirements and reaction mechanisms of Li-assisted catalysts remain controversial. In this study, we demonstrate that the incorporation of lithium species significantly enhances the ammonia decomposition rate of a cobalt-based catalyst by up to 5-fold at 623 K and achieves almost the best low-temperature activity among reported Ru-free catalysts. Structural characterization and density functional theory (DFT) calculations suggest that Li sites with vacancies, located at the interface between the amorphous LiN_<i>x</i>H_<i>y</i> species and the Co surface, serve as the active sites for ammonia decomposition. For the N–H bond scission step during ammonia cracking, Li atoms located at this vacancy site exhibit a displacement of 1.7 Å per Li atom under a direct weak interaction with the Co surface to construct the energy-favorable geometry.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"29 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144066680","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}