Strained carbocycles such as cyclopropanes and cyclobutanes are privileged motifs in modern medicinal chemistry, which have also been verified by the over 20 strained carbocycle-containing drugs approved by the FDA between 2015 and 2019. Moreover, owing to their high intrinsic strain and distinctive reactivity, these small-ring carbocycles have become indispensable building blocks in synthetic chemistry. Carbonylation reactions employing carbon monoxide (CO) as a versatile C1 synthon offer efficient access to structurally diverse and industrially relevant carbonyl-containing compounds. Recent advances have consequently unveiled a powerful synergy between ring strain and carbonylation. Under these backgrounds, this review provides a systematic overview of developments from 2000 to 2025, with a focus on carbonylative cyclopropanation with CO and strain-release carbonylative transformations of strained carbocycles. By summarizing representative transformations and mechanistic trends, we furthermore highlight emerging opportunities in catalyst design, selectivity control, and synthetic applications.
{"title":"Carbonylative Construction and Transformation of Strained Carbocycles","authors":"Peng Yang, Le-Cheng Wang, Zhi-Peng Bao, Xiao-Feng Wu","doi":"10.1021/acscatal.5c08450","DOIUrl":"https://doi.org/10.1021/acscatal.5c08450","url":null,"abstract":"Strained carbocycles such as cyclopropanes and cyclobutanes are privileged motifs in modern medicinal chemistry, which have also been verified by the over 20 strained carbocycle-containing drugs approved by the FDA between 2015 and 2019. Moreover, owing to their high intrinsic strain and distinctive reactivity, these small-ring carbocycles have become indispensable building blocks in synthetic chemistry. Carbonylation reactions employing carbon monoxide (CO) as a versatile C1 synthon offer efficient access to structurally diverse and industrially relevant carbonyl-containing compounds. Recent advances have consequently unveiled a powerful synergy between ring strain and carbonylation. Under these backgrounds, this review provides a systematic overview of developments from 2000 to 2025, with a focus on carbonylative cyclopropanation with CO and strain-release carbonylative transformations of strained carbocycles. By summarizing representative transformations and mechanistic trends, we furthermore highlight emerging opportunities in catalyst design, selectivity control, and synthetic applications.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"59 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101825","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 : 2026-02-03DOI: 10.1021/acscatal.5c06508
Andrea Braga, Marina Armengol-Profitós, Laia Pascua-Solé, Lluís Soler, Isabel Serrano, Ignacio J. Villar-Garcia, Virginia Pérez-Dieste, Enrico Tusini, Andrea De Giacinto, Anna Zimina, Jan-Dierk Grunwaldt, Jordi Llorca, Núria J. Divins
Bimetallic PtNi/CeO2 catalysts were successfully synthesized via a mechanochemical approach, specifically ball milling, and evaluated for methane steam reforming (MSR). A fractional factorial design of experiments was employed to systematically explore the effects of key milling parameters─milling frequency, milling time, and ball-to-powder ratio─on the catalysts’ structural properties and catalytic performance. The catalysts were characterized by X-ray diffraction, H2 temperature-programmed reduction, transmission electron microscopy, and Raman spectroscopy. Catalytic activity tests were performed in a plug flow reactor under a high gas hourly space velocity (200,000 mL gcat–1 h–1) at a steam-to-carbon ratio of 2 between 700 and 950 °C. The mechanochemically synthesized catalysts were benchmarked against those prepared via incipient wetness impregnation. The most active milled catalysts achieved a methane conversion rate of ca. 22 mol CH4 gNi–1 h–1 at 700 °C (83.5% methane conversion for a PtNi/CeO2 mechanochemically synthesized), outperforming the impregnated counterpart (64% methane conversion under the same reaction conditions). Notably, increasing the milling intensity resulted in enhanced catalytic activity, with milling frequency emerging as the most influential factor─correlating with the formation of smaller NiO particles. To elucidate the role of Pt addition, in situ X-ray absorption near-edge structure (XANES) and near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) measurements were conducted on the most active milled catalysts under MSR conditions. NAP-XPS revealed surface segregation of Pt during MSR, alongside an inhibitory effect on solid carbon deposition, suggesting the potential for a coke-resistant catalyst. These findings highlight the power of mechanochemical synthesis in tuning catalyst properties, offering a scalable and efficient route to high-performance catalysts for methane reforming and hydrogen production.
通过机械化学方法（特别是球磨）成功合成了双金属PtNi/CeO2催化剂，并对其甲烷蒸汽重整（MSR）进行了评价。采用分数析因试验设计，系统探讨了磨粉频率、磨粉时间和球粉比等关键磨粉参数对催化剂结构性能和催化性能的影响。通过x射线衍射、H2程序升温还原、透射电镜和拉曼光谱对催化剂进行了表征。催化活性测试在塞流反应器中进行，在700至950°C之间的高气体小时空速（200,000 mL gcat-1 h-1）下，蒸汽与碳比为2。将机械化学合成的催化剂与初湿浸渍法制备的催化剂进行了对比。在700℃条件下，磨粒催化剂的甲烷转化率为22 mol CH4 gNi-1 h-1（机械化学合成的PtNi/CeO2甲烷转化率为83.5%），优于浸渍催化剂（相同反应条件下甲烷转化率为64%）。值得注意的是，铣削强度的增加导致催化活性的增强，铣削频率成为最重要的影响因素，与较小的NiO颗粒的形成相关。为了阐明Pt添加的作用，在MSR条件下对活性最高的磨矿催化剂进行了原位x射线吸收近边结构（XANES）和近环境压力x射线光电子能谱（napp - xps）测量。NAP-XPS揭示了铂在MSR过程中的表面偏析，以及对固体碳沉积的抑制作用，这表明了抗焦催化剂的潜力。这些发现突出了机械化学合成在调整催化剂性能方面的力量，为甲烷重整和制氢的高性能催化剂提供了一条可扩展和有效的途径。
{"title":"Mechanochemically Engineered Bimetallic PtNi/CeO2 Catalysts for Enhanced Methane Steam Reforming","authors":"Andrea Braga, Marina Armengol-Profitós, Laia Pascua-Solé, Lluís Soler, Isabel Serrano, Ignacio J. Villar-Garcia, Virginia Pérez-Dieste, Enrico Tusini, Andrea De Giacinto, Anna Zimina, Jan-Dierk Grunwaldt, Jordi Llorca, Núria J. Divins","doi":"10.1021/acscatal.5c06508","DOIUrl":"https://doi.org/10.1021/acscatal.5c06508","url":null,"abstract":"Bimetallic PtNi/CeO<sub>2</sub> catalysts were successfully synthesized via a mechanochemical approach, specifically ball milling, and evaluated for methane steam reforming (MSR). A fractional factorial design of experiments was employed to systematically explore the effects of key milling parameters─milling frequency, milling time, and ball-to-powder ratio─on the catalysts’ structural properties and catalytic performance. The catalysts were characterized by X-ray diffraction, H<sub>2</sub> temperature-programmed reduction, transmission electron microscopy, and Raman spectroscopy. Catalytic activity tests were performed in a plug flow reactor under a high gas hourly space velocity (200,000 mL g<sub>cat</sub><sup>–1</sup> h<sup>–1</sup>) at a steam-to-carbon ratio of 2 between 700 and 950 °C. The mechanochemically synthesized catalysts were benchmarked against those prepared via incipient wetness impregnation. The most active milled catalysts achieved a methane conversion rate of ca. 22 mol CH<sub>4</sub> g<sub>Ni</sub><sup>–1</sup> h<sup>–1</sup> at 700 °C (83.5% methane conversion for a PtNi/CeO<sub>2</sub> mechanochemically synthesized), outperforming the impregnated counterpart (64% methane conversion under the same reaction conditions). Notably, increasing the milling intensity resulted in enhanced catalytic activity, with milling frequency emerging as the most influential factor─correlating with the formation of smaller NiO particles. To elucidate the role of Pt addition, <i>in situ</i> X-ray absorption near-edge structure (XANES) and near-ambient pressure X-ray photoelectron spectroscopy (NAP-XPS) measurements were conducted on the most active milled catalysts under MSR conditions. NAP-XPS revealed surface segregation of Pt during MSR, alongside an inhibitory effect on solid carbon deposition, suggesting the potential for a coke-resistant catalyst. These findings highlight the power of mechanochemical synthesis in tuning catalyst properties, offering a scalable and efficient route to high-performance catalysts for methane reforming and hydrogen production.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"41 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146110658","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 : 2026-02-03DOI: 10.1021/acscatal.5c08795
Rong-De He, Qi Cao, Yixin Lu
Ring-opening functionalization of gem-difluorinated cyclopropanes (gem-F2CPs) has become a powerful strategy for constructing 2-fluorinated allylic frameworks. However, most prior studies mainly form racemic monofluoroalkenes with linear selectivity. In this study, we report a rhodium-catalyzed highly enantioselective and regioselective sulfonylation of gem-F2CPs with readily available sodium sulfinates. This method represents a general catalytic approach to access enantiomerically enriched 2-fluorinated allylic sulfones, which are valuable structural motifs found in many biologically active molecules. The reported method operates under mild conditions, and the use of bulky Josiphos ligands is crucial, accounting for the delivery of sulfonylated products with good chemo-, regio-, and enantioselectivities.
{"title":"Regio- and Enantioselective Rhodium-Catalyzed Sulfonylation of gem-Difluorinated Cyclopropanes","authors":"Rong-De He, Qi Cao, Yixin Lu","doi":"10.1021/acscatal.5c08795","DOIUrl":"https://doi.org/10.1021/acscatal.5c08795","url":null,"abstract":"Ring-opening functionalization of <i>gem</i>-difluorinated cyclopropanes (<i>gem</i>-F<sub>2</sub>CPs) has become a powerful strategy for constructing 2-fluorinated allylic frameworks. However, most prior studies mainly form racemic monofluoroalkenes with linear selectivity. In this study, we report a rhodium-catalyzed highly enantioselective and regioselective sulfonylation of <i>gem</i>-F<sub>2</sub>CPs with readily available sodium sulfinates. This method represents a general catalytic approach to access enantiomerically enriched 2-fluorinated allylic sulfones, which are valuable structural motifs found in many biologically active molecules. The reported method operates under mild conditions, and the use of bulky Josiphos ligands is crucial, accounting for the delivery of sulfonylated products with good chemo-, regio-, and enantioselectivities.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"8 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111028","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}
This work presents a synergistic dual-modification strategy to engineer distinct pathways for electrons and holes. Terbium (Tb) doping establishes a bulk ″electron highway″ within BiVO4, enhancing charge separation efficiency. Concurrently, a solution-processed high-entropy oxyhydroxide (CoFeMoCuOOH) overlayer acts as a multifunctional “hole-trapping net”, accelerating surface reaction kinetics. The modified photoanode after optimization exhibits a 6.8 mA/cm2 photocurrent density, with stable performance at 1.23 V vs RHE. The enhancement mechanism is unraveled through density functional theory (DFT) calculations and in situ Raman spectroscopy. In situ Raman spectroscopy confirms the accumulation of holes at the catalyst layer by detecting key metal-oxo (M═O) intermediates under operational conditions. DFT further verifies that Tb doping facilitates electron transport by reducing the effective electron mass, while the multimetal synergy in the high-entropy catalyst optimizes the adsorption of reaction intermediates and lowers the thermodynamic barrier of the oxygen evolution reaction. This work provides a design principle of directional charge management for advanced photoelectrodes.
这项工作提出了一种协同的双重修饰策略来设计电子和空穴的不同路径。铽（Tb）掺杂在BiVO4内建立了块状″电子高速公路″，提高了电荷分离效率。同时，溶液处理的高熵氢氧化氧（CoFeMoCuOOH）覆盖层作为多功能“空穴捕获网”，加速表面反应动力学。优化后的光阳极光电流密度为6.8 mA/cm2，在1.23 V vs RHE下性能稳定。通过密度泛函理论（DFT）计算和原位拉曼光谱分析揭示了增强机理。在操作条件下，原位拉曼光谱通过检测关键的金属-氧（M = O）中间体证实了催化剂层上空穴的积累。DFT进一步验证了Tb掺杂通过降低有效电子质量促进电子输运，而高熵催化剂中的多金属协同作用优化了反应中间体的吸附，降低了析氧反应的热力学势垒。本工作为先进光电极的定向电荷管理提供了一种设计原则。
{"title":"Dual-Channel Charge Manipulation for Enhancing Charge Separation and Transfer Kinetics in BiVO4 Photoanodes","authors":"Mingshi Shao, Shushi Hou, Xiang Li, Hao Yang, Yongchao Huang, Zhao-Qing Liu","doi":"10.1021/acscatal.5c09177","DOIUrl":"https://doi.org/10.1021/acscatal.5c09177","url":null,"abstract":"This work presents a synergistic dual-modification strategy to engineer distinct pathways for electrons and holes. Terbium (Tb) doping establishes a bulk ″electron highway″ within BiVO<sub>4</sub>, enhancing charge separation efficiency. Concurrently, a solution-processed high-entropy oxyhydroxide (CoFeMoCuOOH) overlayer acts as a multifunctional “hole-trapping net”, accelerating surface reaction kinetics. The modified photoanode after optimization exhibits a 6.8 mA/cm<sup>2</sup> photocurrent density, with stable performance at 1.23 V vs RHE. The enhancement mechanism is unraveled through density functional theory (DFT) calculations and <i>in situ</i> Raman spectroscopy. <i>In situ</i> Raman spectroscopy confirms the accumulation of holes at the catalyst layer by detecting key metal-oxo (M═O) intermediates under operational conditions. DFT further verifies that Tb doping facilitates electron transport by reducing the effective electron mass, while the multimetal synergy in the high-entropy catalyst optimizes the adsorption of reaction intermediates and lowers the thermodynamic barrier of the oxygen evolution reaction. This work provides a design principle of directional charge management for advanced photoelectrodes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"58 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101826","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}
Electrocatalytic reduction of CO2 to methane is one of the effective strategies for achieving carbon cycling and addressing environmental issues. Herein, we report the successful synthesis of an atomically precise Cu58 nanocluster. An optimized one-pot method involving sequential sodium borohydride reduction was developed. The crystal structure of the Cu58 nanocluster belongs to the space group Pca21 and features a central distorted face-centered cubic Cu14 kernel encapsulated within a Cu48S36P4 shell. This shell is composed of Cu7S2 and Cu10S8P2 units and is flanked by two peripheral Cu5S5P staple motifs. ESI-MS confirms the molecular formula, and XPS analyses establish that copper exists exclusively in the Cu+ oxidation state. The catalytic performance of Cu58 was evaluated for electrochemical CO2 reduction (CO2RR) upon dispersion on a C3N4 support. 15-Cu58/C3N4 achieves a CH4 Faradaic efficiency of 73% at 600 mA cm–2. The synergy between the topology structure of Cu58, the Cu+ sites of the nanocluster, and the pyridinic N sites of the C3N4 support is identified as the key factor for enhancing CO2 adsorption and suppressing the competing hydrogen evolution reaction, thereby steering the selectivity toward methane. This study underscores the potential of structurally defined copper nanoclusters as the premier electrocatalysts for fuel production.
电催化还原CO2制甲烷是实现碳循环和解决环境问题的有效策略之一。在此，我们报道了一个原子精确的Cu58纳米团簇的成功合成。提出了一种优化的硼氢化钠序贯还原一锅法。Cu58纳米团簇的晶体结构属于空间群Pca21，其核心是一个扭曲的面心立方Cu14内核，封装在Cu48S36P4外壳内。该外壳由Cu7S2和Cu10S8P2单元组成，两侧有两个外围cu555p短钉基序。ESI-MS证实了分子式，XPS分析证实了铜只存在于Cu+氧化态。研究了Cu58在C3N4载体上分散的电化学CO2还原（CO2RR）催化性能。15-Cu58/C3N4在600 mA cm-2下的CH4法拉第效率为73%。Cu58的拓扑结构、纳米簇的Cu+位点和C3N4载体的吡啶N位点之间的协同作用被认为是增强CO2吸附和抑制竞争性析氢反应的关键因素，从而引导对甲烷的选择性。这项研究强调了结构明确的铜纳米团簇作为燃料生产首要电催化剂的潜力。
{"title":"Steering CO2 Electroreduction to Methane with an Atomically Precise Copper Nanocluster","authors":"Tingting Ge, Runhua Chen, Xiaorui Liu, Ziyan Jia, Chao Liu, Jiahui Huang, Yongfu Sun","doi":"10.1021/acscatal.5c08305","DOIUrl":"https://doi.org/10.1021/acscatal.5c08305","url":null,"abstract":"Electrocatalytic reduction of CO<sub>2</sub> to methane is one of the effective strategies for achieving carbon cycling and addressing environmental issues. Herein, we report the successful synthesis of an atomically precise Cu<sub>58</sub> nanocluster. An optimized one-pot method involving sequential sodium borohydride reduction was developed. The crystal structure of the Cu<sub>58</sub> nanocluster belongs to the space group Pca21 and features a central distorted face-centered cubic Cu<sub>14</sub> kernel encapsulated within a Cu<sub>48</sub>S<sub>36</sub>P<sub>4</sub> shell. This shell is composed of Cu<sub>7</sub>S<sub>2</sub> and Cu<sub>10</sub>S<sub>8</sub>P<sub>2</sub> units and is flanked by two peripheral Cu<sub>5</sub>S<sub>5</sub>P staple motifs. ESI-MS confirms the molecular formula, and XPS analyses establish that copper exists exclusively in the Cu<sup>+</sup> oxidation state. The catalytic performance of Cu<sub>58</sub> was evaluated for electrochemical CO<sub>2</sub> reduction (CO<sub>2</sub>RR) upon dispersion on a C<sub>3</sub>N<sub>4</sub> support. 15-Cu<sub>58</sub>/C<sub>3</sub>N<sub>4</sub> achieves a CH<sub>4</sub> Faradaic efficiency of 73% at 600 mA cm<sup>–2</sup>. The synergy between the topology structure of Cu<sub>58</sub>, the Cu<sup>+</sup> sites of the nanocluster, and the pyridinic N sites of the C<sub>3</sub>N<sub>4</sub> support is identified as the key factor for enhancing CO<sub>2</sub> adsorption and suppressing the competing hydrogen evolution reaction, thereby steering the selectivity toward methane. This study underscores the potential of structurally defined copper nanoclusters as the premier electrocatalysts for fuel production.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"30 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111027","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 : 2026-02-03DOI: 10.1021/acscatal.5c08223
Joseph Esposito, Aditya Parekh, Aditya Bhan
Selective propylene epoxidation on K-promoted Ag/CaCO3 in the presence of NO, CO2, and C3H5Cl occurs over a catalytic surface that is highly selective and stable for subsequent ethylene epoxidation (S ≈ 90%), indicating a generalized promotional effect of surface intermediates generated from NO, CO2, and C3H5Cl for light olefin epoxidation on supported K-promoted silver catalysts. Crucial to epoxidation selectivity is the NO-derived selectivity promoter proposed to be K–NOx surface moieties, whose removal reversibly reduces the epoxidation-to-combustion ratio for ethylene and propylene epoxidation by approximately an order of magnitude. K–NOx moieties are observed to be significantly less stable during propylene epoxidation than during ethylene epoxidation, attributed to orders of magnitude higher rates of O abstraction via combustion cascades during propylene epoxidation. Selective ethylene epoxidation is also shown to require Cl co-promotion, which significantly enhances selectivity (S ≈ 74 to 93%) and overall oxidation rates (∼2×)─effects similar to those previously reported on Cs/Re/Cl co-promoted Ag formulations. Co-epoxidation reactions reveal selective ethylene (S ≈ 85–90%) and propylene (S ≈ 55%) epoxidation compete for a shared oxidant on shared active sites. These studies demonstrate mechanistic similarities of oxidation and promotion within ethylene and propylene epoxidations on promoted silver catalysts.
{"title":"Common Active Sites and Oxidants within Ethylene and Propylene Epoxidation on Promoted Silver Catalysts","authors":"Joseph Esposito, Aditya Parekh, Aditya Bhan","doi":"10.1021/acscatal.5c08223","DOIUrl":"https://doi.org/10.1021/acscatal.5c08223","url":null,"abstract":"Selective propylene epoxidation on K-promoted Ag/CaCO<sub>3</sub> in the presence of NO, CO<sub>2</sub>, and C<sub>3</sub>H<sub>5</sub>Cl occurs over a catalytic surface that is highly selective and stable for subsequent ethylene epoxidation (<i>S</i> ≈ 90%), indicating a generalized promotional effect of surface intermediates generated from NO, CO<sub>2</sub>, and C<sub>3</sub>H<sub>5</sub>Cl for light olefin epoxidation on supported K-promoted silver catalysts. Crucial to epoxidation selectivity is the NO-derived selectivity promoter proposed to be K–NO<sub><i>x</i></sub> surface moieties, whose removal reversibly reduces the epoxidation-to-combustion ratio for ethylene and propylene epoxidation by approximately an order of magnitude. K–NO<sub><i>x</i></sub> moieties are observed to be significantly less stable during propylene epoxidation than during ethylene epoxidation, attributed to orders of magnitude higher rates of O abstraction via combustion cascades during propylene epoxidation. Selective ethylene epoxidation is also shown to require Cl co-promotion, which significantly enhances selectivity (<i>S</i> ≈ 74 to 93%) and overall oxidation rates (∼2×)─effects similar to those previously reported on Cs/Re/Cl co-promoted Ag formulations. Co-epoxidation reactions reveal selective ethylene (<i>S</i> ≈ 85–90%) and propylene (<i>S</i> ≈ 55%) epoxidation compete for a shared oxidant on shared active sites. These studies demonstrate mechanistic similarities of oxidation and promotion within ethylene and propylene epoxidations on promoted silver catalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"63 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101822","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 : 2026-02-02DOI: 10.1021/acscatal.5c08853
Santosh K. Singh, Kotaro Takeyasu
We highlight hydration control and the degree of pz/π* orbital localization as dual keys for designing durable carbon electrocatalysts for the oxygen reduction reaction in acidic media. While N-doped carbon catalysts exhibit adequate activity in alkaline conditions, their decreased activity in acidic environments remains a major barrier to practical fuel cell applications. We first discuss how pyridinic nitrogen sites serve as prototypical active centers, where protonation-electron transfer coupling promotes oxygen adsorption but simultaneously enhances hydration and counteranion crowding that deactivate the catalytic active site. Introducing hydrophobic domains provides a strategy to control hydration and recover accessibility to reactants. Beyond hydration effects, recent studies reveal that defect motifs such as five-membered rings can localize nonbonding orbitals near the Fermi level, complementing the extended π* states of pyridinic nitrogen and thereby stabilizing oxygenated intermediates. These insights suggest that mesoscale hydration control and the degree of pz/π* orbital localization at the atomic scale are synergistic design principles. Importantly, the improved CO tolerance and durability of metal-free carbon catalysts make them particularly advantageous when fuel flexibility is required, such as in direct methanol and formic acid fuel cells. Together, these principles provide a blueprint for constructing efficient, fuel-flexible, and durable carbon catalysts for future hydrogen and beyond-hydrogen energy systems.
{"title":"Control of Hydration and Degree of pz/π* Orbital Localization as Dual Keys for Durable Carbon Electrocatalysts in Acidic ORR","authors":"Santosh K. Singh, Kotaro Takeyasu","doi":"10.1021/acscatal.5c08853","DOIUrl":"https://doi.org/10.1021/acscatal.5c08853","url":null,"abstract":"We highlight hydration control and the degree of p<sub>z</sub>/π* orbital localization as dual keys for designing durable carbon electrocatalysts for the oxygen reduction reaction in acidic media. While N-doped carbon catalysts exhibit adequate activity in alkaline conditions, their decreased activity in acidic environments remains a major barrier to practical fuel cell applications. We first discuss how pyridinic nitrogen sites serve as prototypical active centers, where protonation-electron transfer coupling promotes oxygen adsorption but simultaneously enhances hydration and counteranion crowding that deactivate the catalytic active site. Introducing hydrophobic domains provides a strategy to control hydration and recover accessibility to reactants. Beyond hydration effects, recent studies reveal that defect motifs such as five-membered rings can localize nonbonding orbitals near the Fermi level, complementing the extended π* states of pyridinic nitrogen and thereby stabilizing oxygenated intermediates. These insights suggest that mesoscale hydration control and the degree of p<sub>z</sub>/π* orbital localization at the atomic scale are synergistic design principles. Importantly, the improved CO tolerance and durability of metal-free carbon catalysts make them particularly advantageous when fuel flexibility is required, such as in direct methanol and formic acid fuel cells. Together, these principles provide a blueprint for constructing efficient, fuel-flexible, and durable carbon catalysts for future hydrogen and beyond-hydrogen energy systems.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"292 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146097897","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}
N-Fused 5/7/6 tricyclic scaffold is the core structure of tetrapetalone family alkaloids. Herein, we disclose a strategy for the atom- and step-economic synthesis of N-fused 5/7/6 tricyclic scaffolds via a bis-Lewis acid and chloride cooperatively catalyzed one-pot five-step cascade reaction of o-alkenylaryl isocyanides with α,β-unsaturated carbonyls. The reaction is initiated by a [4 + 1] cycloaddition to form a furan intermediate, which is followed by furan-based [4 + 2] cycloaddition, C–O scission, C–C cleavage, and finally C–N formation. Notably, instead of the conventional [4 + 2] cycloaddition of furan to form a benzene ring, in this domino process, the in situ generated six-membered ring is reopened to create a N-fused 5/7/6 tricyclic framework. Based on the results of control experiments and DFT calculations, both the bis-Lewis acid and the nucleophilic chloride participated in reactivity regulation. Furthermore, this efficient domino transformation could be applied to assemble N-fused 5/6/6 tricycles and the amino analog of (±)-tetrapetalone G.
{"title":"Bis-Lewis Acid and Chloride Anion Cooperatively Catalyzed One-Pot Five-Step Cascade toward N-Fused 5/7/6 and 5/6/6 Tricycles","authors":"Wenhui Yang, Wenwen Zhao, Jianbiao Liu, Shu Chen, Licai Ma, Mengying Jia, Xianxiu Xu","doi":"10.1021/acscatal.5c08631","DOIUrl":"https://doi.org/10.1021/acscatal.5c08631","url":null,"abstract":"<i>N</i>-Fused 5/7/6 tricyclic scaffold is the core structure of tetrapetalone family alkaloids. Herein, we disclose a strategy for the atom- and step-economic synthesis of <i>N</i>-fused 5/7/6 tricyclic scaffolds via a bis-Lewis acid and chloride cooperatively catalyzed one-pot five-step cascade reaction of <i>o</i>-alkenylaryl isocyanides with α,β-unsaturated carbonyls. The reaction is initiated by a [4 + 1] cycloaddition to form a furan intermediate, which is followed by furan-based [4 + 2] cycloaddition, C–O scission, C–C cleavage, and finally C–N formation. Notably, instead of the conventional [4 + 2] cycloaddition of furan to form a benzene ring, in this domino process, the <i>in situ</i> generated six-membered ring is reopened to create a <i>N</i>-fused 5/7/6 tricyclic framework. Based on the results of control experiments and DFT calculations, both the bis-Lewis acid and the nucleophilic chloride participated in reactivity regulation. Furthermore, this efficient domino transformation could be applied to assemble <i>N</i>-fused 5/6/6 tricycles and the amino analog of (±)-tetrapetalone G.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"8 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098120","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 : 2026-02-02DOI: 10.1021/acscatal.5c07146
Li-Nan Huang, Han Zhao, Lei Jiang, Jiahao Geng, Zhiqiang Li, Yuelun Li, Kongzhai Li
The activation of CH4 and CO2 as well as the formation of carbon deposit are crucial for dry reforming of methane (DRM), and mechanistic insights into the relationship between reactant activation and carbon evolution during the DRM process are expected to provide guidance for the design of high-performance catalysts. Herein, by utilizing carefully defined Ni/CeO2 model catalysts with different CeO2 crystal planes, we elucidate at the atomic scale the roles of crystal plane in determining the reactant activation and carbon deposit formation in DRM by a joint experimental–theoretical method. The crystal planes of CeO2 determine the active sites and activation ability for CH4 and CO2 by influencing Ni–CeO2 interactions and oxygen vacancy (OV) concentrations. Both the metal and interface active sites of Ni/CeO2(111) and Ni/CeO2(110) can activate CH4 and exhibit good DRM activity. In contrast, only the metal site on Ni/CeO2(100) can activate CH4, leading to a reduced DRM activity. The relatively balanced CH4 and CO2 activation pathways for Ni/CeO2(110) and Ni/CeO2(100) catalysts ensured the stability of the catalysts, whereas Ni/CeO2(111) was rapidly deactivated due to carbon deposits. This study provides insights into the roles of metal–support interactions and OV sites on catalysts for CH4 dissociation activity, CO2 activation, and carbon deposit elimination in the DRM process, which can provide valuable guidance for the design of efficient catalysts with high activity and stability in DRM.
{"title":"Mechanistic Insights into the Role of CH4 and CO2 Activation in Dry Reforming of Methane over Ni/CeO2 Catalysts with Different Crystal Planes","authors":"Li-Nan Huang, Han Zhao, Lei Jiang, Jiahao Geng, Zhiqiang Li, Yuelun Li, Kongzhai Li","doi":"10.1021/acscatal.5c07146","DOIUrl":"https://doi.org/10.1021/acscatal.5c07146","url":null,"abstract":"The activation of CH<sub>4</sub> and CO<sub>2</sub> as well as the formation of carbon deposit are crucial for dry reforming of methane (DRM), and mechanistic insights into the relationship between reactant activation and carbon evolution during the DRM process are expected to provide guidance for the design of high-performance catalysts. Herein, by utilizing carefully defined Ni/CeO<sub>2</sub> model catalysts with different CeO<sub>2</sub> crystal planes, we elucidate at the atomic scale the roles of crystal plane in determining the reactant activation and carbon deposit formation in DRM by a joint experimental–theoretical method. The crystal planes of CeO<sub>2</sub> determine the active sites and activation ability for CH<sub>4</sub> and CO<sub>2</sub> by influencing Ni–CeO<sub>2</sub> interactions and oxygen vacancy (O<sub>V</sub>) concentrations. Both the metal and interface active sites of Ni/CeO<sub>2</sub>(111) and Ni/CeO<sub>2</sub>(110) can activate CH<sub>4</sub> and exhibit good DRM activity. In contrast, only the metal site on Ni/CeO<sub>2</sub>(100) can activate CH<sub>4</sub>, leading to a reduced DRM activity. The relatively balanced CH<sub>4</sub> and CO<sub>2</sub> activation pathways for Ni/CeO<sub>2</sub>(110) and Ni/CeO<sub>2</sub>(100) catalysts ensured the stability of the catalysts, whereas Ni/CeO<sub>2</sub>(111) was rapidly deactivated due to carbon deposits. This study provides insights into the roles of metal–support interactions and O<sub>V</sub> sites on catalysts for CH<sub>4</sub> dissociation activity, CO<sub>2</sub> activation, and carbon deposit elimination in the DRM process, which can provide valuable guidance for the design of efficient catalysts with high activity and stability in DRM.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"145 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098122","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 discovery of high-performance oxygen evolution reaction (OER) catalysts is often hindered by the vast compositional space of high-entropy materials, making conventional trial-and-error methods time-consuming and resource-intensive. In this work, we demonstrate a machine learning (ML)-guided strategy for the design of high-entropy FeCoCrMnCu layered double hydroxides (LDHs) as advanced OER catalysts in alkaline media. An experimental data set of only 70 compositions was used to train an Extreme Gradient Boosting (XGBoost) regression model, which achieved high predictive accuracy (R2 = 0.84, RMSE = 9.95 mV). The ML model identified an optimal composition (Fe0.15Co0.10Cr0.30Mn0.30Cu0.15) with a predicted overpotential of 261.3 mV, closely matching the experimentally obtained 270 mV (error ∼ 3%). This approach effectively reduced the need for exhaustive testing of more than 10,626 possible compositions, achieving a 99.3% reduction in time and effort. The ML-optimized catalyst exhibited favorable morphology, homogeneous elemental distribution, and strong intrinsic activity, with a Tafel slope of 74.2 mV dec–1, high turnover frequency (0.225 s–1), and stable operation for 72 h. This study highlights the power of integrating ML with entropy-driven materials design to accelerate the development of next-generation electrocatalysts.
{"title":"Machine Learning-Guided Design of High-Entropy FeCoCrMnCu Layered Double Hydroxides for Efficient Oxygen Evolution in Alkaline Media","authors":"Chandrasekaran Pitchai, Chao-Fang Huang, Ting-Yu Lo, Hung-Chung Li, Ming-Der Yang, Chih-Ming Chen","doi":"10.1021/acscatal.5c07303","DOIUrl":"https://doi.org/10.1021/acscatal.5c07303","url":null,"abstract":"The discovery of high-performance oxygen evolution reaction (OER) catalysts is often hindered by the vast compositional space of high-entropy materials, making conventional trial-and-error methods time-consuming and resource-intensive. In this work, we demonstrate a machine learning (ML)-guided strategy for the design of high-entropy FeCoCrMnCu layered double hydroxides (LDHs) as advanced OER catalysts in alkaline media. An experimental data set of only 70 compositions was used to train an Extreme Gradient Boosting (XGBoost) regression model, which achieved high predictive accuracy (<i>R</i><sup>2</sup> = 0.84, RMSE = 9.95 mV). The ML model identified an optimal composition (Fe<sub>0</sub>.<sub>15</sub>Co<sub>0</sub>.<sub>10</sub>Cr<sub>0</sub>.<sub>30</sub>Mn<sub>0</sub>.<sub>30</sub>Cu<sub>0</sub>.<sub>15</sub>) with a predicted overpotential of 261.3 mV, closely matching the experimentally obtained 270 mV (error ∼ 3%). This approach effectively reduced the need for exhaustive testing of more than 10,626 possible compositions, achieving a 99.3% reduction in time and effort. The ML-optimized catalyst exhibited favorable morphology, homogeneous elemental distribution, and strong intrinsic activity, with a Tafel slope of 74.2 mV dec<sup>–1</sup>, high turnover frequency (0.225 s<sup>–1</sup>), and stable operation for 72 h. This study highlights the power of integrating ML with entropy-driven materials design to accelerate the development of next-generation electrocatalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"30 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146101827","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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