Designing catalysts for the oxygen evolution reaction (OER) that are platinum group metal-free (PGM-free) is vital for making the production of hydrogen via water splitting more cost-effective. A trimetallic catalyst, NiFeW(OH)2, was synthesized and studied using electrochemical methods, exhibiting higher catalytic performance than bare nickel–iron, manifested by faster reaction kinetics, evidenced by a lower Tafel slope and reduced effective resistance. This catalyst served as a parent compound for heat-treated catalysts in various conditions, such as air and inert atmosphere, to study the effect of the mixed oxide/hydroxide phase on electrochemical performance. X-ray Diffraction (XRD) revealed that tungsten addition expanded the crystal lattice by ∼30% in the c direction, which had a significant impact on the electronic environment, resulting in lowered binding energies, as revealed by X-ray photoemission spectroscopy (XPS). The most active composition was later studied in an anion exchange membrane water electrolyzer (AEM-WE) and showed high performance, reaching current densities of 2.12 A cm–2 at ∼2.0 V. Density functional theory (DFT) calculations assisted in identifying iron as the active site. Electrochemical impedance spectroscopy (EIS), analyzed by distribution function of relaxation times (DFRT, a.k.a. DRT), revealed the contribution of tungsten toward reduced charge transfer resistance. The best performances were found with compositions close to the solubility limit of tungsten in the system.
设计无铂族金属（PGM-free）的析氧反应（OER）催化剂对于提高水裂解制氢的成本效益至关重要。采用电化学方法合成并研究了一种三金属催化剂NiFeW(OH)2，该催化剂比裸镍铁具有更高的催化性能，反应动力学更快，Tafel斜率更低，有效阻力更小。该催化剂作为热处理催化剂的母体化合物，在不同的条件下，如空气和惰性气氛，研究混合氧化物/氢氧化物相对电化学性能的影响。x射线衍射（XRD）显示，钨的加入使晶格在c方向扩展了约30%，这对电子环境产生了显著影响，导致结合能降低，x射线光电发射光谱（XPS）显示。最活跃的成分后来在阴离子交换膜水电解槽（aem -我们）中进行了研究，并表现出高性能，在~ 2.0 V下达到2.12 A cm-2的电流密度。密度泛函理论（DFT）计算有助于确定铁作为活性位点。通过弛豫时间分布函数（DFRT，又称DRT）分析电化学阻抗谱（EIS），揭示了钨对降低电荷转移电阻的贡献。当组分接近钨在体系中的溶解度极限时，其性能最好。
{"title":"Toward Efficient Hydrogen Production: Impact of Solid Solution of Tungsten on Nickel–Iron Hydroxide OER Catalysts","authors":"Lamea Abbas, Lakhanlal, Sourav Bhowmick, Rawnaq Batheesh, Lior Elbaz, Maytal Caspary Toroker, Yoed Tsur","doi":"10.1021/acscatal.5c07061","DOIUrl":"https://doi.org/10.1021/acscatal.5c07061","url":null,"abstract":"Designing catalysts for the oxygen evolution reaction (OER) that are platinum group metal-free (PGM-free) is vital for making the production of hydrogen via water splitting more cost-effective. A trimetallic catalyst, NiFeW(OH)<sub>2</sub>, was synthesized and studied using electrochemical methods, exhibiting higher catalytic performance than bare nickel–iron, manifested by faster reaction kinetics, evidenced by a lower Tafel slope and reduced effective resistance. This catalyst served as a parent compound for heat-treated catalysts in various conditions, such as air and inert atmosphere, to study the effect of the mixed oxide/hydroxide phase on electrochemical performance. X-ray Diffraction (XRD) revealed that tungsten addition expanded the crystal lattice by ∼30% in the c direction, which had a significant impact on the electronic environment, resulting in lowered binding energies, as revealed by X-ray photoemission spectroscopy (XPS). The most active composition was later studied in an anion exchange membrane water electrolyzer (AEM-WE) and showed high performance, reaching current densities of 2.12 A cm<sup>–2</sup> at ∼2.0 V. Density functional theory (DFT) calculations assisted in identifying iron as the active site. Electrochemical impedance spectroscopy (EIS), analyzed by distribution function of relaxation times (DFRT, a.k.a. DRT), revealed the contribution of tungsten toward reduced charge transfer resistance. The best performances were found with compositions close to the solubility limit of tungsten in the system.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"235 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122501","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}
Pub Date : 2026-02-05DOI: 10.1021/acscatal.5c08606
Shufen Ma, Yachao Wang, Guofeng Zhao, Weixin Huang, Cong Fu
Photocatalytic oxidative dehydrogenation of ethane (ODHE) is a promising route to ethylene under mild conditions, yet achieving a high yield and selectivity is challenging due to the inert C–H bonds and overoxidation to CO2. In this study, we present ZnO fine nanoparticles decorated with highly dispersed Pd species and featuring closely associated interfacial oxygen vacancies (Ov) for highly selective ODHE. The optimized catalyst achieves a C2H4 production rate of 8.5 mmol g–1 h–1 with a selectivity of up to 96.1%, surpassing most reported photo- and thermocatalysts and maintaining robust stability for over 10 h. Through a combination of operando DRIFTS, in situ XPS, and in situ EPR analyses, we demonstrate that the enhanced photocatalytic performance stems from a synergistic, spatially separated dual-site configuration involving Pd species and adjacent interfacial Ov. This configuration enhances spatial charge separation, promotes oxygen activation, and facilitates the selective conversion of C2H6 into key *C2H4 intermediates, thereby boosting ethylene formation. This work not only provides fundamental insights into the photocatalytic ODHE mechanism but also underscores the importance of interfacial engineering in the design of highly efficient photocatalysts for alkane conversion.
乙烷的光催化氧化脱氢（ODHE）是在温和条件下制备乙烯的一种很有前途的途径，但由于惰性的C-H键和过度氧化成二氧化碳，实现高收率和选择性是具有挑战性的。在这项研究中，我们提出了用高度分散的钯修饰的ZnO纳米粒子，并具有密切相关的界面氧空位（Ov），用于高选择性的ODHE。优化后的催化剂的C2H4产率为8.5 mmol g-1 h - 1，选择性高达96.1%，超过了大多数报道的光催化剂和热催化剂，并保持了超过10小时的稳定。通过operando DRIFTS、原位XPS和原位EPR分析的组合，我们证明了增强的光催化性能源于协同的、空间分离的双位点配置，涉及Pd物种和相邻的界面Ov。这种构型增强了空间电荷分离，促进氧活化，有利于C2H6选择性转化为关键的*C2H4中间体，从而促进乙烯的生成。这项工作不仅为光催化ODHE机理提供了基本的见解，而且强调了界面工程在设计高效烷烃转化光催化剂中的重要性。
{"title":"Synergistic Bifunctionality of Interfacial Pd–Ov Sites on ZnO for Highly Selective Photocatalytic Ethane Dehydrogenation","authors":"Shufen Ma, Yachao Wang, Guofeng Zhao, Weixin Huang, Cong Fu","doi":"10.1021/acscatal.5c08606","DOIUrl":"https://doi.org/10.1021/acscatal.5c08606","url":null,"abstract":"Photocatalytic oxidative dehydrogenation of ethane (ODHE) is a promising route to ethylene under mild conditions, yet achieving a high yield and selectivity is challenging due to the inert C–H bonds and overoxidation to CO<sub>2</sub>. In this study, we present ZnO fine nanoparticles decorated with highly dispersed Pd species and featuring closely associated interfacial oxygen vacancies (Ov) for highly selective ODHE. The optimized catalyst achieves a C<sub>2</sub>H<sub>4</sub> production rate of 8.5 mmol g<sup>–1</sup> h<sup>–1</sup> with a selectivity of up to 96.1%, surpassing most reported photo- and thermocatalysts and maintaining robust stability for over 10 h. Through a combination of <i>operando</i> DRIFTS, <i>in situ</i> XPS, and <i>in situ</i> EPR analyses, we demonstrate that the enhanced photocatalytic performance stems from a synergistic, spatially separated dual-site configuration involving Pd species and adjacent interfacial Ov. This configuration enhances spatial charge separation, promotes oxygen activation, and facilitates the selective conversion of C<sub>2</sub>H<sub>6</sub> into key *C<sub>2</sub>H<sub>4</sub> intermediates, thereby boosting ethylene formation. This work not only provides fundamental insights into the photocatalytic ODHE mechanism but also underscores the importance of interfacial engineering in the design of highly efficient photocatalysts for alkane conversion.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116055","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}
Pub Date : 2026-02-05DOI: 10.1021/acscatal.5c07197
Danial Farooq, Lucy Costley-Wood, Sebastian Stockenhuber, Antonis Vamvakeros, Stephen W. T. Price, Lisa J. Allen, Jakub Drnec, James Paterson, Mark Peacock, Daniel J. M. Irving, Philip A. Chater, Andrew M. Beale
The transition to net-zero emissions hinges on circular economy strategies that valorize waste and enhance resource efficiency. Among X-to-liquid (XTL) technologies, the Fischer-Tropsch (FT) process stands out for converting biomass, waste, and CO2 into hydrocarbons and chemicals, especially when powered by renewable hydrogen. Cobalt-based catalysts are preferred in FT synthesis due to their efficiency and CO2 tolerance, yet their catalytic performance is closely tied to their polymorphic structures─face-centered cubic (FCC), hexagonal close-packed (HCP), and stacking-faulted intergrowths thereof. HCP cobalt has been shown to exhibit high activity and selectivity for higher hydrocarbons and oxygenates, particularly when transformed into cobalt carbide (Co2C), which forms more readily at low H2/CO ratios. This study presents a quantitative analysis of cobalt polymorphs and stacking faults in Mn-promoted Co/TiO2 FT catalysts from in situ powder X-ray diffraction (XRD) data and X-ray Diffraction Computed Tomography (XRD-CT) data from spent catalysts in order to obtain a more complete correlation of structural features with catalytic performance. By modeling stacking fault probabilities using supercell simulations, the proportion of faulted FCC and HCP domains was determined across varying Mn loadings (0–5%). Increased Mn loading was found to decrease stacking faults in the FCC phase while increasing them in HCP, promoting the formation of HCP domains and ultimately Co2C under reaction conditions. Notably, the 3% Mn-loaded sample showed a marked rise in HCP content and Co2C formation, correlating with the highest observed alcohol and olefin selectivity. These findings highlight a critical structure–function relationship: Mn facilitates a transformation from FCC to HCP and then to Co2C, this final transition driven by similar stacking sequences and metal–support interactions. The findings show that Mn promotion not only stabilizes smaller Co particles and enhances its dispersion, but also modulates the distribution of Co polymorphs and stacking faults, leading to altered catalytic behavior. This highlights the importance of stacking fault characterization for optimizing FT catalyst design and performance, and suggests pathways to more efficient and selective carbon-neutral fuel production through engineered polymorphic and interfacial structures.
{"title":"Mn-Promoted Co/TiO2 Catalysts: Quantitative Analysis of Cobalt Polymorphs and Stacking Faults and Its Effect on Fischer-Tropsch Synthesis Performance","authors":"Danial Farooq, Lucy Costley-Wood, Sebastian Stockenhuber, Antonis Vamvakeros, Stephen W. T. Price, Lisa J. Allen, Jakub Drnec, James Paterson, Mark Peacock, Daniel J. M. Irving, Philip A. Chater, Andrew M. Beale","doi":"10.1021/acscatal.5c07197","DOIUrl":"https://doi.org/10.1021/acscatal.5c07197","url":null,"abstract":"The transition to net-zero emissions hinges on circular economy strategies that valorize waste and enhance resource efficiency. Among X-to-liquid (XTL) technologies, the Fischer-Tropsch (FT) process stands out for converting biomass, waste, and CO<sub>2</sub> into hydrocarbons and chemicals, especially when powered by renewable hydrogen. Cobalt-based catalysts are preferred in FT synthesis due to their efficiency and CO<sub>2</sub> tolerance, yet their catalytic performance is closely tied to their polymorphic structures─face-centered cubic (FCC), hexagonal close-packed (HCP), and stacking-faulted intergrowths thereof. HCP cobalt has been shown to exhibit high activity and selectivity for higher hydrocarbons and oxygenates, particularly when transformed into cobalt carbide (Co<sub>2</sub>C), which forms more readily at low H<sub>2</sub>/CO ratios. This study presents a quantitative analysis of cobalt polymorphs and stacking faults in Mn-promoted Co/TiO<sub>2</sub> FT catalysts from in situ powder X-ray diffraction (XRD) data and X-ray Diffraction Computed Tomography (XRD-CT) data from spent catalysts in order to obtain a more complete correlation of structural features with catalytic performance. By modeling stacking fault probabilities using supercell simulations, the proportion of faulted FCC and HCP domains was determined across varying Mn loadings (0–5%). Increased Mn loading was found to decrease stacking faults in the FCC phase while increasing them in HCP, promoting the formation of HCP domains and ultimately Co<sub>2</sub>C under reaction conditions. Notably, the 3% Mn-loaded sample showed a marked rise in HCP content and Co<sub>2</sub>C formation, correlating with the highest observed alcohol and olefin selectivity. These findings highlight a critical structure–function relationship: Mn facilitates a transformation from FCC to HCP and then to Co<sub>2</sub>C, this final transition driven by similar stacking sequences and metal–support interactions. The findings show that Mn promotion not only stabilizes smaller Co particles and enhances its dispersion, but also modulates the distribution of Co polymorphs and stacking faults, leading to altered catalytic behavior. This highlights the importance of stacking fault characterization for optimizing FT catalyst design and performance, and suggests pathways to more efficient and selective carbon-neutral fuel production through engineered polymorphic and interfacial structures.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"11 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116052","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}
Pub Date : 2026-02-05DOI: 10.1021/acscatal.5c07788
Yong Tang, Yongqi Zeng, Chunyu Wang, Chuang Du, Fengxi Li, Lei Wang
The stereoselective cross-dehydrogenative coupling (CDC) reaction represents a highly promising approach for the direct synthesis of high-value non-natural amino acids. The photoenzyme cascade strategy synergistically integrates the reactivity of photocatalysts with the selectivity of enzymes, demonstrating attractive potential for eco-friendly asymmetric synthesis. In this study, we report a photoartificial CDCase cascade method for the asymmetric CDC reaction between N-aryl glycine esters and cycloketones. The optimal artificial CDCase was constructed by anchoring the biotinylated Cu-phenanthroline cofactor (5-NH2Phen-biotin*Cu(OAc)2) within the double mutant (S112H–K121M) of streptavidin obtained through genetic engineering optimization. In a mild aqueous medium, the resulting artificial CDCase cooperates with photocatalysis, efficiently catalyzing the asymmetric CDC reaction at a low enzyme loading (0.5 mol %), yielding a series of α-cycloketone-substituted N-aryl glycine esters with good yields and stereoselectivities. Comprehensive molecular docking and molecular dynamics (MD) simulations provided insights into the critical complex intermediates involved in the proposed reaction mechanism and clarified the interactions between the artificial CDCase and its substrates. Furthermore, through analysis of interatomic distances between pivotal reactive carbon centers and probable nucleophilic attack directions, we have deciphered the structural foundation underlying the formation of the predominant conformation, concurrently rationalizing the enhanced reactivity and stereoselectivity observed for the S112H–K121 M mutant.
{"title":"Photoenzymatic Cascade Catalysis with an Artificial CDCase for Stereoselective Cross-Dehydrogenative Coupling","authors":"Yong Tang, Yongqi Zeng, Chunyu Wang, Chuang Du, Fengxi Li, Lei Wang","doi":"10.1021/acscatal.5c07788","DOIUrl":"https://doi.org/10.1021/acscatal.5c07788","url":null,"abstract":"The stereoselective cross-dehydrogenative coupling (CDC) reaction represents a highly promising approach for the direct synthesis of high-value non-natural amino acids. The photoenzyme cascade strategy synergistically integrates the reactivity of photocatalysts with the selectivity of enzymes, demonstrating attractive potential for eco-friendly asymmetric synthesis. In this study, we report a photoartificial CDCase cascade method for the asymmetric CDC reaction between <i>N</i>-aryl glycine esters and cycloketones. The optimal artificial CDCase was constructed by anchoring the biotinylated Cu-phenanthroline cofactor (5-NH<sub>2</sub>Phen-biotin*Cu(OAc)<sub>2</sub>) within the double mutant (S112H–K121M) of streptavidin obtained through genetic engineering optimization. In a mild aqueous medium, the resulting artificial CDCase cooperates with photocatalysis, efficiently catalyzing the asymmetric CDC reaction at a low enzyme loading (0.5 mol %), yielding a series of α-cycloketone-substituted <i>N</i>-aryl glycine esters with good yields and stereoselectivities. Comprehensive molecular docking and molecular dynamics (MD) simulations provided insights into the critical complex intermediates involved in the proposed reaction mechanism and clarified the interactions between the artificial CDCase and its substrates. Furthermore, through analysis of interatomic distances between pivotal reactive carbon centers and probable nucleophilic attack directions, we have deciphered the structural foundation underlying the formation of the predominant conformation, concurrently rationalizing the enhanced reactivity and stereoselectivity observed for the S112H–K121 M mutant.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"1 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146116054","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}
Pub Date : 2026-02-05DOI: 10.1021/acscatal.5c07232
Julia Fernández-Vidal, Marc T.M. Koper
Surface science has long provided the foundation for mechanistic understanding in electrocatalysis. In this perspective, we revisit its relevance through the lens of *H/*OH adsorption in the HUPD region of Pt and its role in CO electrooxidation, examples that illustrate principles that reach far beyond these systems. Electrochemical interfaces are complex and dynamic arenas where adsorbates, surface structure, and local electrolyte composition govern electrocatalytic performance. Untangling this complexity requires the atomic resolution of surface science, coupled with the reach of computational models. However, true predictive power comes only when theory and experiment act as partners, not substitutes. Rigorous mechanistic studies, often undervalued compared to the excitement of emerging materials, remain essential for achieving truly rational catalyst and electrolyte design.
{"title":"The Role of Surface Science in Electrocatalysis","authors":"Julia Fernández-Vidal, Marc T.M. Koper","doi":"10.1021/acscatal.5c07232","DOIUrl":"https://doi.org/10.1021/acscatal.5c07232","url":null,"abstract":"Surface science has long provided the foundation for mechanistic understanding in electrocatalysis. In this perspective, we revisit its relevance through the lens of *H/*OH adsorption in the H<sub>UPD</sub> region of Pt and its role in CO electrooxidation, examples that illustrate principles that reach far beyond these systems. Electrochemical interfaces are complex and dynamic arenas where adsorbates, surface structure, and local electrolyte composition govern electrocatalytic performance. Untangling this complexity requires the atomic resolution of surface science, coupled with the reach of computational models. However, true predictive power comes only when theory and experiment act as partners, not substitutes. Rigorous mechanistic studies, often undervalued compared to the excitement of emerging materials, remain essential for achieving truly rational catalyst and electrolyte design.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"70 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122504","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}
Pub Date : 2026-02-05DOI: 10.1021/acscatal.5c08315
Abhijit Sen, Yuta Matsukawa, Atsuya Muranaka, Yu Hatakenaka, Abdullah J. Al Abdulghani, Nobutaka Maeda, Aya Ohno, Heeyoel Baek, Yoichi M. A. Yamada
A quadruple switchable catalysis was developed, enabling sp3 C–H arylation, aminomethylation, sp2 C–H arylation, and deiodination using aryl halides and formamides. The selectivity of this protocol was governed by the amine derivatives, wherein ammonium formate promoted sp3 C–H arylation, triethanolamine favored aminomethylation, and tripropanolamine facilitated sp2 C–H arylation. Additionally, temperature was found to play a crucial role, with aminomethylation occurring at 150 °C and deiodination at 110 °C. All reactions were performed using a reusable silicon nanowire array-supported Pd catalyst with an ultralow Pd loading of 65 mol ppm. The use of microwave irradiation was essential for promoting the catalytic reaction, with the magnetic field component proving more effective than the electric field.
{"title":"Quadruple Switchable Catalysis: sp3 C–H Arylation, Aminomethylation, sp2 C–H Arylation, and Deiodination","authors":"Abhijit Sen, Yuta Matsukawa, Atsuya Muranaka, Yu Hatakenaka, Abdullah J. Al Abdulghani, Nobutaka Maeda, Aya Ohno, Heeyoel Baek, Yoichi M. A. Yamada","doi":"10.1021/acscatal.5c08315","DOIUrl":"https://doi.org/10.1021/acscatal.5c08315","url":null,"abstract":"A quadruple switchable catalysis was developed, enabling sp<sup>3</sup> C–H arylation, aminomethylation, sp<sup>2</sup> C–H arylation, and deiodination using aryl halides and formamides. The selectivity of this protocol was governed by the amine derivatives, wherein ammonium formate promoted sp<sup>3</sup> C–H arylation, triethanolamine favored aminomethylation, and tripropanolamine facilitated sp<sup>2</sup> C–H arylation. Additionally, temperature was found to play a crucial role, with aminomethylation occurring at 150 °C and deiodination at 110 °C. All reactions were performed using a reusable silicon nanowire array-supported Pd catalyst with an ultralow Pd loading of 65 mol ppm. The use of microwave irradiation was essential for promoting the catalytic reaction, with the magnetic field component proving more effective than the electric field.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"58 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129539","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}
Pub Date : 2026-02-05DOI: 10.1021/acscatal.5c08014
Xin-Yu Da, Ming-Cheng Zuo, Tong-Qiu Lu, Yi Feng, Yang Zhao, Hui-Hui Wang, Yong-Zheng Chen, Nan-Wei Wan
The enantioselective desymmetrization of prochiral compounds provides a powerful strategy for accessing valuable chiral building blocks. Herein, we report a biocatalytic platform for the intermolecular enantioselective desymmetrization of prochiral oxetanes using an engineered halohydrin dehalogenase. Through comprehensive enzyme screening and directed evolution, we created an optimized biocatalyst that achieves highly enantioselective and efficient azidolysis of 3-substituted oxetanes on a preparative scale, affording a diverse range of chiral (R)-γ-azidoalcohols in good isolated yields (typically >80%) and high enantiopurity (all >99% ee). The synthetic scalability and utility of this biocatalytic system were further demonstrated through gram-scale reaction and downstream functionalizations, highlighting its practical utility in synthetic and pharmaceutical applications.
{"title":"Biocatalytic Stereo-Perfect Desymmetrization of Oxetanes","authors":"Xin-Yu Da, Ming-Cheng Zuo, Tong-Qiu Lu, Yi Feng, Yang Zhao, Hui-Hui Wang, Yong-Zheng Chen, Nan-Wei Wan","doi":"10.1021/acscatal.5c08014","DOIUrl":"https://doi.org/10.1021/acscatal.5c08014","url":null,"abstract":"The enantioselective desymmetrization of prochiral compounds provides a powerful strategy for accessing valuable chiral building blocks. Herein, we report a biocatalytic platform for the intermolecular enantioselective desymmetrization of prochiral oxetanes using an engineered halohydrin dehalogenase. Through comprehensive enzyme screening and directed evolution, we created an optimized biocatalyst that achieves highly enantioselective and efficient azidolysis of 3-substituted oxetanes on a preparative scale, affording a diverse range of chiral (<i>R</i>)-γ-azidoalcohols in good isolated yields (typically >80%) and high enantiopurity (all >99% <i>ee</i>). The synthetic scalability and utility of this biocatalytic system were further demonstrated through gram-scale reaction and downstream functionalizations, highlighting its practical utility in synthetic and pharmaceutical applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"89 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146122505","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}
Pub Date : 2026-02-04DOI: 10.1021/acscatal.5c08299
Sergio Fernández, Klaudia Michaliszyn, Ekaterina S. Smirnova, Marc Robert, Josep M. Luis, Julio Lloret-Fillol
We report a Nickel CO2 reduction electrocatalyst based on a C3-symmetric tris(phosphino)alkyl ligand, CNPPh3, which displays a metalated axial carbon atom. Catalyst NiHBr selectively reduces CO2 to CO (FYCO = 94%) at −2.3 V vs Fc+/0 with a TO Fmax = 65 s–1 in DMF/[TBA]PF6 with 3.5 M of added H2O. Cyclic voltammetry (CV) and an exhaustive computational study of the reaction mechanism show that our NiII complex undergoes two one-electron reduction events before the CO2 binding step. Afterward, the catalytic CO2 reduction takes place through a reduction-first pathway. The formation of a Ni–CO intermediate along the CO2 reduction pathway was inferred by CV, and the corresponding [NiII–CO]+ complex was isolated. FTIR spectroelectrochemistry (SEC) allowed for the detection of three different Ni–CO species: [Ni–CO]+, [Ni–CO]0, and [Ni–CO]−. This work provides critical insights into the electrocatalytic CO2 reduction, laying the foundation for efficient CO2 conversion strategies.
我们报道了一种基于c3对称三（磷酸）烷基配体CNPPh3的镍CO2还原电催化剂，它显示了一个金属化的轴向碳原子。催化剂NiHBr在DMF/[TBA]PF6中，添加3.5 M的H2O，在−2.3 V vs Fc+/0条件下选择性地将CO2还原为CO (FYCO = 94%), to - Fmax = 65 s-1。循环伏安法（CV）和详尽的反应机理计算研究表明，我们的NiII配合物在CO2结合之前经历了两次单电子还原事件。之后，通过还原优先途径进行催化CO2还原。通过CV推测了Ni-CO中间体沿CO2还原途径的形成，并分离出相应的[NiII-CO]+配合物。FTIR光谱电化学（SEC）允许检测三种不同的Ni-CO物种：[Ni-CO]+， [Ni-CO]0和[Ni-CO]−。这项工作为电催化二氧化碳还原提供了重要的见解，为有效的二氧化碳转化策略奠定了基础。
{"title":"Selective CO2 Electroreduction to CO by an Organometallic Nickel Catalyst Featuring a C3–Symmetric Tris(Phosphino)Alkyl Ligand","authors":"Sergio Fernández, Klaudia Michaliszyn, Ekaterina S. Smirnova, Marc Robert, Josep M. Luis, Julio Lloret-Fillol","doi":"10.1021/acscatal.5c08299","DOIUrl":"https://doi.org/10.1021/acscatal.5c08299","url":null,"abstract":"We report a Nickel CO<sub>2</sub> reduction electrocatalyst based on a <i>C</i><sub>3</sub>-symmetric tris(phosphino)alkyl ligand, CNPPh<sub>3</sub>, which displays a metalated axial carbon atom. Catalyst <b>Ni</b><sup><b>H</b></sup><sub><b>Br</b></sub> selectively reduces CO<sub>2</sub> to CO (FY<sub>CO</sub> = 94%) at −2.3 V vs Fc<sup>+/0</sup> with a TO <i>F</i><sub>max</sub> = 65 s<sup>–1</sup> in DMF/[TBA]PF<sub>6</sub> with 3.5 M of added H<sub>2</sub>O. Cyclic voltammetry (CV) and an exhaustive computational study of the reaction mechanism show that our Ni<sup>II</sup> complex undergoes two one-electron reduction events before the CO<sub>2</sub> binding step. Afterward, the catalytic CO<sub>2</sub> reduction takes place through a reduction-first pathway. The formation of a Ni–CO intermediate along the CO<sub>2</sub> reduction pathway was inferred by CV, and the corresponding [Ni<sup>II</sup>–CO]<sup>+</sup> complex was isolated. FTIR spectroelectrochemistry (SEC) allowed for the detection of three different Ni–CO species: [Ni–CO]<sup>+</sup>, [Ni–CO]<sup>0</sup>, and [Ni–CO]<sup>−</sup>. This work provides critical insights into the electrocatalytic CO<sub>2</sub> reduction, laying the foundation for efficient CO<sub>2</sub> conversion strategies.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"294 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146110656","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}
The hydrodeoxygenation of furfural to 2-methylfuran represents a critical route for biomass valorization, although hindered by slow kinetics and undesired side reactions. Key challenges involve designing catalytic sites that enable enhanced H2 activation and vertically oriented furfural adsorption. Herein, we engineer a self-pillared silicalite-1 nanosheet-supported Cu–Zn bimetallic catalyst to overcome these limitations. The hierarchically porous silicalite-1 architecture serves dual functions: (1) stabilizing highly dispersed Cu–Zn alloy interfaces and (2) inducing electronic modulation that synergistically enhances dissociative H2 chemisorption and spillover. Crucially, this interface imposes a stable η1-(O)-aldehyde adsorption configuration for both furfural and its furfuryl alcohol intermediate, effectively suppressing ring-hydrogenation-inducing flat η2-(C,O) adsorption modes. At a moderate 180 °C, this integrated catalyst design achieves a 2-methylfuran turnover frequency (TOF) of 20.6 h–1 with near-quantitative selectivity (99.2% yield) after one hour of reaction.
{"title":"Construction of Synergistic Cu–Zn Alloy Interfaces within Hierarchical Zeolite Nanosheets for High-Efficiency Production of 2-Methylfuran from Furfural","authors":"Xiaozhou Chen,Xin Yu,Shuaishuai Zhou,Hao Yang,Qian Li,Qiang Deng,Zhenheng Diao,Zongjing Lu,Zongyuan Wang,Jianxing Gan,Yajie Tian","doi":"10.1021/acscatal.5c05480","DOIUrl":"https://doi.org/10.1021/acscatal.5c05480","url":null,"abstract":"The hydrodeoxygenation of furfural to 2-methylfuran represents a critical route for biomass valorization, although hindered by slow kinetics and undesired side reactions. Key challenges involve designing catalytic sites that enable enhanced H2 activation and vertically oriented furfural adsorption. Herein, we engineer a self-pillared silicalite-1 nanosheet-supported Cu–Zn bimetallic catalyst to overcome these limitations. The hierarchically porous silicalite-1 architecture serves dual functions: (1) stabilizing highly dispersed Cu–Zn alloy interfaces and (2) inducing electronic modulation that synergistically enhances dissociative H2 chemisorption and spillover. Crucially, this interface imposes a stable η1-(O)-aldehyde adsorption configuration for both furfural and its furfuryl alcohol intermediate, effectively suppressing ring-hydrogenation-inducing flat η2-(C,O) adsorption modes. At a moderate 180 °C, this integrated catalyst design achieves a 2-methylfuran turnover frequency (TOF) of 20.6 h–1 with near-quantitative selectivity (99.2% yield) after one hour of reaction.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"41 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111154","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}
Pub Date : 2026-02-04DOI: 10.1021/acscatal.5c07065
Ivan Surin,Evgenii V. Kondratenko,Javier Pérez-Ramírez
Ammonia (NH3) oxidation to nitrous oxide (N2O) is a promising route to obtain this selective oxidant, but controlling product distribution is inherently challenging because N2O occupies an intermediate nitrogen oxidation state between N2 and NO. Despite recent advances, leading CeO2-based catalytic systems have consistently encountered a selectivity limit in the range of 80–85%. Herein, CeO2-supported Mn single atoms are employed as a stable, selective benchmark to investigate the origins of the N2O selectivity losses. Thorough kinetic analysis revealed that direct oxidation of NH3 to N2 is the main reason for incomplete N2O selectivity. This reaction dominates in a thin upstream catalyst bed layer, driven by its strong dependence on the NH3 partial pressure that ensures dense surface coverage by N-containing intermediates and promotes their irreversible coupling to N2. However, due to the inhibiting effect of H2O, this reaction is increasingly hindered along the catalyst bed, with N2O becoming the dominant product. Based on these insights, N2O selectivity could be increased from 81% to 90% while N2 selectivity decreased to 6% by water cofeeding and adjusting reactant partial pressures to tune surface coverage by N-containing intermediates. Evaluation of side reactions revealed a negligible impact of N2O decomposition or N2O reduction on product distribution. Conversely, employing isotopic tracing, reduction of in situ-formed NO by NH3 was established as a significant route to secondary N2O, and to a lesser extent, N2. This was shown to be a general feature of CeO2-based catalysts, including Mn, Au, and Cr systems, providing a lever for selectivity control. This work demonstrates how kinetic analysis can disentangle complex reaction pathways and identify both catalyst- and process-level strategies to advance NH3 oxidation to N2O beyond current limits.
{"title":"Origins of N2O Selectivity Limits in Catalyzed Ammonia Oxidation","authors":"Ivan Surin,Evgenii V. Kondratenko,Javier Pérez-Ramírez","doi":"10.1021/acscatal.5c07065","DOIUrl":"https://doi.org/10.1021/acscatal.5c07065","url":null,"abstract":"Ammonia (NH3) oxidation to nitrous oxide (N2O) is a promising route to obtain this selective oxidant, but controlling product distribution is inherently challenging because N2O occupies an intermediate nitrogen oxidation state between N2 and NO. Despite recent advances, leading CeO2-based catalytic systems have consistently encountered a selectivity limit in the range of 80–85%. Herein, CeO2-supported Mn single atoms are employed as a stable, selective benchmark to investigate the origins of the N2O selectivity losses. Thorough kinetic analysis revealed that direct oxidation of NH3 to N2 is the main reason for incomplete N2O selectivity. This reaction dominates in a thin upstream catalyst bed layer, driven by its strong dependence on the NH3 partial pressure that ensures dense surface coverage by N-containing intermediates and promotes their irreversible coupling to N2. However, due to the inhibiting effect of H2O, this reaction is increasingly hindered along the catalyst bed, with N2O becoming the dominant product. Based on these insights, N2O selectivity could be increased from 81% to 90% while N2 selectivity decreased to 6% by water cofeeding and adjusting reactant partial pressures to tune surface coverage by N-containing intermediates. Evaluation of side reactions revealed a negligible impact of N2O decomposition or N2O reduction on product distribution. Conversely, employing isotopic tracing, reduction of in situ-formed NO by NH3 was established as a significant route to secondary N2O, and to a lesser extent, N2. This was shown to be a general feature of CeO2-based catalysts, including Mn, Au, and Cr systems, providing a lever for selectivity control. This work demonstrates how kinetic analysis can disentangle complex reaction pathways and identify both catalyst- and process-level strategies to advance NH3 oxidation to N2O beyond current limits.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"53 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111153","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}
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