Pub Date : 2026-03-26DOI: 10.1021/acscatal.5c08824
Kazuyuki Iwase, Itaru Honma, Takaaki Tomai
High-entropy oxides (HEOs) have emerged as promising electrocatalysts for the oxygen evolution reaction (OER) owing to their tunable electronic structures and compositions. Herein, a quinary high-entropy spinel oxide (HE-SOs) composed of Mn, Fe, Co, Ni, and Zn was synthesized via a supercritical hydrothermal process, and its element-specific behavior under OER potentials in alkaline solution was systematically investigated using in situ X-ray absorption spectroscopy (XAS). Under applied anodic potentials, distinct responses among the constituent metals were observed. Mn, Co, and Ni exhibited redox changes at the same potential range, whereas Fe and Zn exhibited no redox changes, serving as redox-inactive framework elements. The high-entropy matrix effectively suppresses structural reconstruction, balancing redox activity with structural stability. This study elucidates that the synergistic effect of the constituent elements is the origin of the high OER activity and durability of HEOs, providing fundamental insight into the design of multicomponent oxide electrocatalysts.
{"title":"Unveiling Synergistic Elemental Roles in High-Entropy Spinel Oxides for Oxygen Evolution Electrocatalysis","authors":"Kazuyuki Iwase, Itaru Honma, Takaaki Tomai","doi":"10.1021/acscatal.5c08824","DOIUrl":"https://doi.org/10.1021/acscatal.5c08824","url":null,"abstract":"High-entropy oxides (HEOs) have emerged as promising electrocatalysts for the oxygen evolution reaction (OER) owing to their tunable electronic structures and compositions. Herein, a quinary high-entropy spinel oxide (HE-SOs) composed of Mn, Fe, Co, Ni, and Zn was synthesized via a supercritical hydrothermal process, and its element-specific behavior under OER potentials in alkaline solution was systematically investigated using <i>in situ</i> X-ray absorption spectroscopy (XAS). Under applied anodic potentials, distinct responses among the constituent metals were observed. Mn, Co, and Ni exhibited redox changes at the same potential range, whereas Fe and Zn exhibited no redox changes, serving as redox-inactive framework elements. The high-entropy matrix effectively suppresses structural reconstruction, balancing redox activity with structural stability. This study elucidates that the synergistic effect of the constituent elements is the origin of the high OER activity and durability of HEOs, providing fundamental insight into the design of multicomponent oxide electrocatalysts.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"2017 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507788","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 electrooxidation of methane (CH4) to directly produce high-value ethanol is an attractive strategy to utilize natural gas; however, the current density for CH4 electrooxidation remains low (<10 mA cm–2) due to the chemical inertness of CH4 and its poor adsorption capacity on catalyst surfaces. Herein, we develop a composite catalyst containing conductive zeolite (ZSM-5), CuO, and ZrO2 for CH4 electrooxidation to ethanol. The abundant pore structure and Lewis acid sites of conductive ZSM-5 significantly enhance the CH4 adsorption capacity of the composite catalyst, achieving a 32-fold improvement over oxide catalysts (CuO–ZrO2). Meanwhile, CuO–ZrO2 exhibits strong CH4 activation capability. Benefiting from the synergistic effect of both active components, the current density for CH4 oxidation to ethanol reaches 60 mA cm–2 in the Na2SO4 electrolyte, with the yield reaching 136.51 mmol gcat–1 h–1. Mechanistic studies indicate that CuO oxidizes water to generate a large quantity of hydroxyl radicals (·OH), which then oxidizes adsorbed CH4 to produce a series of intermediates (*CH3, *OCH2, and *OCH2CH3), while the SO42–-adsorbed ZrO2 effectively stabilizes key intermediates and promotes C–C coupling, creating an efficient electrolyte–catalyst reaction interface. This work presents a strategy for enhancing CH4 adsorption and activation capabilities through composite zeolites and metal oxides.
甲烷（CH4）电氧化直接生产高价值乙醇是一种有吸引力的天然气利用策略；然而，由于CH4的化学惰性及其在催化剂表面上的较差吸附能力，CH4电氧化的电流密度仍然很低（<10 mA cm-2）。在此，我们开发了一种含有导电沸石（ZSM-5）、CuO和ZrO2的复合催化剂，用于CH4电氧化制乙醇。导电ZSM-5丰富的孔隙结构和Lewis酸位点显著提高了复合催化剂对CH4的吸附能力，比氧化物催化剂（CuO-ZrO2）提高了32倍。同时，CuO-ZrO2表现出较强的CH4活化能力。得益于两种活性组分的协同作用，在Na2SO4电解液中，CH4氧化为乙醇的电流密度达到60 mA cm-2，产率达到136.51 mmol gcat-1 h-1。机理研究表明，CuO氧化水生成大量羟基自由基（·OH），氧化吸附的CH4生成一系列中间体（*CH3、*OCH2和*OCH2CH3），而SO42吸附的ZrO2有效稳定了关键中间体，促进了C-C偶联，形成了高效的电解质-催化剂反应界面。本文提出了一种通过复合沸石和金属氧化物增强CH4吸附和活化能力的策略。
{"title":"Electrooxidation of Methane to Ethanol at Large Current Densities on Conductive Zeolite–CuO–ZrO2 Composite Catalysts","authors":"Yu Bai, Hao Tian, Zhi-Feng Gao, Jia-Yi Chen, Wei Xi, Zhong-Li Wang","doi":"10.1021/acscatal.5c07632","DOIUrl":"https://doi.org/10.1021/acscatal.5c07632","url":null,"abstract":"The electrooxidation of methane (CH<sub>4</sub>) to directly produce high-value ethanol is an attractive strategy to utilize natural gas; however, the current density for CH<sub>4</sub> electrooxidation remains low (<10 mA cm<sup>–2</sup>) due to the chemical inertness of CH<sub>4</sub> and its poor adsorption capacity on catalyst surfaces. Herein, we develop a composite catalyst containing conductive zeolite (ZSM-5), CuO, and ZrO<sub>2</sub> for CH<sub>4</sub> electrooxidation to ethanol. The abundant pore structure and Lewis acid sites of conductive ZSM-5 significantly enhance the CH<sub>4</sub> adsorption capacity of the composite catalyst, achieving a 32-fold improvement over oxide catalysts (CuO–ZrO<sub>2</sub>). Meanwhile, CuO–ZrO<sub>2</sub> exhibits strong CH<sub>4</sub> activation capability. Benefiting from the synergistic effect of both active components, the current density for CH<sub>4</sub> oxidation to ethanol reaches 60 mA cm<sup>–2</sup> in the Na<sub>2</sub>SO<sub>4</sub> electrolyte, with the yield reaching 136.51 mmol g<sub>cat</sub><sup>–1</sup> h<sup>–1</sup>. Mechanistic studies indicate that CuO oxidizes water to generate a large quantity of hydroxyl radicals (·OH), which then oxidizes adsorbed CH<sub>4</sub> to produce a series of intermediates (*CH<sub>3</sub>, *OCH<sub>2</sub>, and *OCH<sub>2</sub>CH<sub>3</sub>), while the SO<sub>4</sub><sup>2–</sup>-adsorbed ZrO<sub>2</sub> effectively stabilizes key intermediates and promotes C–C coupling, creating an efficient electrolyte–catalyst reaction interface. This work presents a strategy for enhancing CH<sub>4</sub> adsorption and activation capabilities through composite zeolites and metal oxides.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"10 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507518","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 : 2026-03-26DOI: 10.1021/acscatal.6c00460
Mei Yang, Fanwei Kong, Yanmei Ma, Shujia Wang, Tiantian Su, Junli Guo, Yan-Yan Song, Zhida Gao, Junjian Zhao
Operando tracking of nanoscale catalytic dynamics is essential for elucidating transient interfacial events that dictate reaction efficiency. Here, we report a confined TiO2 nanopipette reactor integrated with Au and Pt nanozymes that enables single-entity, bubble-resolved tracking of plasmon–photocatalytic-coupled cascade catalysis. Within the nanoconfined channel, glucose oxidation on Au generates H2O2, which is subsequently decomposed on Pt to produce periodic O2 nanobubbles that transduce catalytic activity into well-defined ionic current oscillations. Quantitative kinetic descriptors, including the oscillation frequency, dwell time (τoff), and event interval time (τon), are extracted with high reproducibility. Under 532 nm excitation, the localized surface plasmon resonance (LSPR) of Au induces hot-electron injection into TiO2, promoting charge separation and accelerating Pt-catalyzed H2O2 decomposition. This coupling system enhances the O2 generation rate while reducing both τoff and τon. The nanoconfined environment enables robust catalytic detection down to 10 μM glucose, far below the macroscopic limit. Macro–micro correlated measurements further reveal synergistic regulation of the cascade kinetics by illumination and substrate concentration. This work establishes a versatile operando platform for quantifying nanoscale bubble dynamics and light-regulated cascade catalysis, offering opportunities for engineering responsive catalytic systems and next-generation microreactors.
{"title":"Operando Electrochemical Tracking of Plasmon–Photocatalytic-Coupled Cascade Catalysis in a Confined TiO2 Nanopipette Reactor","authors":"Mei Yang, Fanwei Kong, Yanmei Ma, Shujia Wang, Tiantian Su, Junli Guo, Yan-Yan Song, Zhida Gao, Junjian Zhao","doi":"10.1021/acscatal.6c00460","DOIUrl":"https://doi.org/10.1021/acscatal.6c00460","url":null,"abstract":"Operando tracking of nanoscale catalytic dynamics is essential for elucidating transient interfacial events that dictate reaction efficiency. Here, we report a confined TiO<sub>2</sub> nanopipette reactor integrated with Au and Pt nanozymes that enables single-entity, bubble-resolved tracking of plasmon–photocatalytic-coupled cascade catalysis. Within the nanoconfined channel, glucose oxidation on Au generates H<sub>2</sub>O<sub>2</sub>, which is subsequently decomposed on Pt to produce periodic O<sub>2</sub> nanobubbles that transduce catalytic activity into well-defined ionic current oscillations. Quantitative kinetic descriptors, including the oscillation frequency, dwell time (τ<sub>off</sub>), and event interval time (τ<sub>on</sub>), are extracted with high reproducibility. Under 532 nm excitation, the localized surface plasmon resonance (LSPR) of Au induces hot-electron injection into TiO<sub>2</sub>, promoting charge separation and accelerating Pt-catalyzed H<sub>2</sub>O<sub>2</sub> decomposition. This coupling system enhances the O<sub>2</sub> generation rate while reducing both τ<sub>off</sub> and τ<sub>on</sub>. The nanoconfined environment enables robust catalytic detection down to 10 μM glucose, far below the macroscopic limit. Macro–micro correlated measurements further reveal synergistic regulation of the cascade kinetics by illumination and substrate concentration. This work establishes a versatile operando platform for quantifying nanoscale bubble dynamics and light-regulated cascade catalysis, offering opportunities for engineering responsive catalytic systems and next-generation microreactors.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"78 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507521","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 : 2026-03-26DOI: 10.1021/acscatal.6c00485
Hui Zhao, Xin-Pu Fu, Wei-Wei Wang, Chun-Jiang Jia
The Pt-GaOx combination is widely investigated for catalyzing propane dehydrogenation (PDH), as its efficient site synergy compensates for the low selectivity associated with single Pt sites. However, these catalysts suffer from rapid deactivation under harsh reaction conditions due to the thermal migration and sintering of active sites, alongside irreversible structural degradation. To address these challenges, we developed mesoporous silica-confined Sm2O3 to stabilize the Pt-Sm2O3 and GaOx-Sm2O3 interfaces. Based on comprehensive characterization, the as-formed small Sm2O3 species play a crucial role in boosting the catalytic performance. Specifically, the confined Sm2O3 clusters intensify interactions with both Pt and GaOx within the mesopores, which suppresses the excessive aggregation of Pt-Ga alloys and stabilizes the active Gaδ+–H species. As a result, the Pt-Ga/Sm@SiO2 catalyst exhibits a low deactivation constant (0.007 h–1) and a high specific activity of 2.28 s–1 after 100 h of continuous operation at 550 °C, significantly outperforming its conventional Pt-Ga counterparts. This work thus provides a robust strategy for enhancing the durability of Pt-GaOx catalysts and advances their practical implementation in industrial PDH processes.
Pt- gaox组合被广泛研究用于催化丙烷脱氢（PDH），因为其有效的位点协同作用弥补了单个Pt位点的低选择性。然而，由于活性位点的热迁移和烧结以及不可逆的结构降解，这些催化剂在恶劣的反应条件下会迅速失活。为了解决这些挑战，我们开发了介孔二氧化硅限制Sm2O3来稳定Pt-Sm2O3和GaOx-Sm2O3界面。综合表征表明，形成的Sm2O3小组分对提高催化性能起着至关重要的作用。具体来说，受限制的Sm2O3团簇加强了介孔内与Pt和GaOx的相互作用，从而抑制了Pt- ga合金的过度聚集并稳定了活性的Gaδ+ -H物质。结果表明，Pt-Ga/Sm@SiO2催化剂在550℃下连续运行100 h后，具有较低的失活常数（0.007 h - 1）和2.28 s-1的高比活度，显著优于传统的Pt-Ga催化剂。因此，这项工作为提高Pt-GaOx催化剂的耐久性提供了强有力的策略，并推进了它们在工业PDH工艺中的实际实施。
{"title":"Sm2O3-Induced Interactions Stabilized Pt-GaOx Catalysts Boosting Propane Dehydrogenation","authors":"Hui Zhao, Xin-Pu Fu, Wei-Wei Wang, Chun-Jiang Jia","doi":"10.1021/acscatal.6c00485","DOIUrl":"https://doi.org/10.1021/acscatal.6c00485","url":null,"abstract":"The Pt-GaO<sub><i>x</i></sub> combination is widely investigated for catalyzing propane dehydrogenation (PDH), as its efficient site synergy compensates for the low selectivity associated with single Pt sites. However, these catalysts suffer from rapid deactivation under harsh reaction conditions due to the thermal migration and sintering of active sites, alongside irreversible structural degradation. To address these challenges, we developed mesoporous silica-confined Sm<sub>2</sub>O<sub>3</sub> to stabilize the Pt-Sm<sub>2</sub>O<sub>3</sub> and GaO<sub><i>x</i></sub>-Sm<sub>2</sub>O<sub>3</sub> interfaces. Based on comprehensive characterization, the as-formed small Sm<sub>2</sub>O<sub>3</sub> species play a crucial role in boosting the catalytic performance. Specifically, the confined Sm<sub>2</sub>O<sub>3</sub> clusters intensify interactions with both Pt and GaO<sub><i>x</i></sub> within the mesopores, which suppresses the excessive aggregation of Pt-Ga alloys and stabilizes the active Ga<sup>δ+</sup>–H species. As a result, the Pt-Ga/Sm@SiO<sub>2</sub> catalyst exhibits a low deactivation constant (0.007 h<sup>–1</sup>) and a high specific activity of 2.28 s<sup>–1</sup> after 100 h of continuous operation at 550 °C, significantly outperforming its conventional Pt-Ga counterparts. This work thus provides a robust strategy for enhancing the durability of Pt-GaO<sub><i>x</i></sub> catalysts and advances their practical implementation in industrial PDH processes.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"14 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507522","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}
While conventional InNi alloy phases in supported Ni/In2O3 catalysts show limited performance for CO2-to-methanol hydrogenation, we demonstrate that carbon incorporation into the InNi3 gives rise to a distinct catalytic architecture. The saturated InNi3C0.5 exhibits better catalytic stability and 40-fold enhanced methanol productivity compared with noncarburized alloys. Although the in situ carburization of InNi3 in the CO2 hydrogenation reaction produced the unsaturated InNi3Cx, this catalyst had lower stability and activity compared to the saturated InNi3C0.5. Structural degradation mechanisms reveal atmosphere-dependent intermetallic carbon oxidation pathways in the InNi carbides. Furthermore, hierarchical engineering through an electrostatic assembly of the saturated InNi3C0.5 hexagonal nanosheets on In2O3 hollow nanotubes synergistically enhances both activity and durability. Density functional theory analysis unveils that carbon-induced electron redistribution creates Ni/C cooperation resembling uniform electron gas behavior, simultaneously optimizing hydrogenation capacity and oxygen vacancy dynamics on the oxide support. This work establishes intermetallic carbon saturation engineering as a general strategy for upgrading intermetallic catalysts in renewable fuel synthesis.
{"title":"Carbon Saturation Engineering of Intermetallic InNi Carbides for Enhanced CO2 Hydrogenation","authors":"Yanmei Cai, Zhirui Luo, Kok Bing Tan, Sajid Ali, Xiaoping Rao, Jian Cai, Dongren Cai, Gui-Lin Zhuang, Guowu Zhan","doi":"10.1021/acscatal.6c00175","DOIUrl":"https://doi.org/10.1021/acscatal.6c00175","url":null,"abstract":"While conventional InNi alloy phases in supported Ni/In<sub>2</sub>O<sub>3</sub> catalysts show limited performance for CO<sub>2</sub>-to-methanol hydrogenation, we demonstrate that carbon incorporation into the InNi<sub>3</sub> gives rise to a distinct catalytic architecture. The saturated InNi<sub>3</sub>C<sub>0.5</sub> exhibits better catalytic stability and 40-fold enhanced methanol productivity compared with noncarburized alloys. Although the <i>in situ</i> carburization of InNi<sub>3</sub> in the CO<sub>2</sub> hydrogenation reaction produced the unsaturated InNi<sub>3</sub>C<sub><i>x</i></sub>, this catalyst had lower stability and activity compared to the saturated InNi<sub>3</sub>C<sub>0.5</sub>. Structural degradation mechanisms reveal atmosphere-dependent intermetallic carbon oxidation pathways in the InNi carbides. Furthermore, hierarchical engineering through an electrostatic assembly of the saturated InNi<sub>3</sub>C<sub>0.5</sub> hexagonal nanosheets on In<sub>2</sub>O<sub>3</sub> hollow nanotubes synergistically enhances both activity and durability. Density functional theory analysis unveils that carbon-induced electron redistribution creates Ni/C cooperation resembling uniform electron gas behavior, simultaneously optimizing hydrogenation capacity and oxygen vacancy dynamics on the oxide support. This work establishes intermetallic carbon saturation engineering as a general strategy for upgrading intermetallic catalysts in renewable fuel synthesis.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"17 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507520","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 : 2026-03-26DOI: 10.1021/acscatal.5c08719
Connor P. Cox, Madeleine K. Wilsey, Kendra R. Watson, Teona Taseska, Yiwen Sun, Lydia R. Schultz, Samira Siahrostami, Astrid M. Müller
Electrocatalytic H2O2 synthesis enables decentralized production and reduces reliance on energy-intensive large-scale infrastructure. Practical application, however, requires catalyst materials that are affordable, scalable, and durable. Here, we show that oxygenated carbon fiber paper, hydrophilized through a rapid mild chemistry process developed in-house, serves as an efficient electrocatalyst for the oxygen reduction reaction (ORR) to H2O2. This catalyst achieves (95 ± 4)% faradaic efficiency and long-term stability for more than 31 h in a divided cell and 100 h in an undivided cell, significantly surpassing traditional particulate carbon catalysts while eliminating the need for supporting electrodes or binders. The analysis of onset potentials versus the reversible hydrogen electrode reveals pH dependence, indicating a nonproton-coupled electron transfer mechanism. When referenced to the standard hydrogen electrode, the onset potentials further suggest that the rate-determining step of the ORR is proton-dependent. Mechanistic studies highlight the coupled roles of oxygenated carbon sites, electrolyte pH, and spectator potassium ions in steering ORR pathways and show that binder-free catalysts are essential for probing the true reaction environment. Higher H2O2 production rates are obtained at elevated pH, attributed to the greater stability of oxygenated active sites, as confirmed experimentally and supported by density functional theory (DFT) calculations. Hydrophilic carbon fiber paper thus emerges as a robust and viable platform for H2O2 electrosynthesis. These results also provide mechanistic insight into how oxygen functional groups, electrolyte pH, and potassium cations govern activity and selectivity in ORR.
{"title":"Oxygen Reduction to Hydrogen Peroxide on Hydrophilic Carbon Fiber Paper: Dependence of the Mechanism and Active Site Stability on Electrolyte pH and Potassium Ion Concentration","authors":"Connor P. Cox, Madeleine K. Wilsey, Kendra R. Watson, Teona Taseska, Yiwen Sun, Lydia R. Schultz, Samira Siahrostami, Astrid M. Müller","doi":"10.1021/acscatal.5c08719","DOIUrl":"https://doi.org/10.1021/acscatal.5c08719","url":null,"abstract":"Electrocatalytic H<sub>2</sub>O<sub>2</sub> synthesis enables decentralized production and reduces reliance on energy-intensive large-scale infrastructure. Practical application, however, requires catalyst materials that are affordable, scalable, and durable. Here, we show that oxygenated carbon fiber paper, hydrophilized through a rapid mild chemistry process developed in-house, serves as an efficient electrocatalyst for the oxygen reduction reaction (ORR) to H<sub>2</sub>O<sub>2</sub>. This catalyst achieves (95 ± 4)% faradaic efficiency and long-term stability for more than 31 h in a divided cell and 100 h in an undivided cell, significantly surpassing traditional particulate carbon catalysts while eliminating the need for supporting electrodes or binders. The analysis of onset potentials versus the reversible hydrogen electrode reveals pH dependence, indicating a nonproton-coupled electron transfer mechanism. When referenced to the standard hydrogen electrode, the onset potentials further suggest that the rate-determining step of the ORR is proton-dependent. Mechanistic studies highlight the coupled roles of oxygenated carbon sites, electrolyte pH, and spectator potassium ions in steering ORR pathways and show that binder-free catalysts are essential for probing the true reaction environment. Higher H<sub>2</sub>O<sub>2</sub> production rates are obtained at elevated pH, attributed to the greater stability of oxygenated active sites, as confirmed experimentally and supported by density functional theory (DFT) calculations. Hydrophilic carbon fiber paper thus emerges as a robust and viable platform for H<sub>2</sub>O<sub>2</sub> electrosynthesis. These results also provide mechanistic insight into how oxygen functional groups, electrolyte pH, and potassium cations govern activity and selectivity in ORR.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"12 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147507519","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 : 2026-03-25DOI: 10.1021/acscatal.6c01852
Xiangyu Zhuang,Xiao Sun,Yirui Zou,Jun Liu,Gang Zhao,Hongyu Wang
Chiral sulfilimines are valuable sulfur-stereogenic motifs in medicinal chemistry and serve as versatile precursors to sulfoximines and sulfondiimines. Despite their importance, enantioselective S-alkylation of sulfenamides accessing to sulfilimines from abundant alkyl feedstocks remains largely unexplored, particularly via radical pathways. Herein, we report the enantioselective copper-photoredox-catalyzed S-alkylation of sulfenamides enabled by a family of amino-acid-derived N,N,N-tridentate ligands. This strategy allows the use of alkyl carboxylic acids via decarboxylative radical sulfilimination to afford enantioenriched sulfilimines in high yields and enantioselectivities. Importantly, the platform is further extended to alkyl iodides through an XAT-induced radical pathway, demonstrating the generality of this enantioselective S-alkylation manifold. A broad range of primary, secondary, and tertiary alkyl radicals, diverse sulfenamides, and complex bioactive substrates are well tolerated. Mechanistic studies support a radical process involving a stereoinvertive SH2-type substitution at a copper-sulfenamide intermediate. Gram-scale synthesis and downstream oxidation to pharmaceutically relevant sulfoximines underscore the synthetic utility of this method.
{"title":"Copper-Photocatalyzed Enantioselective S-Alkylation of Sulfenamides Enabled by Amino-Acid-Derived N,N,N-Tridentate Ligand","authors":"Xiangyu Zhuang,Xiao Sun,Yirui Zou,Jun Liu,Gang Zhao,Hongyu Wang","doi":"10.1021/acscatal.6c01852","DOIUrl":"https://doi.org/10.1021/acscatal.6c01852","url":null,"abstract":"Chiral sulfilimines are valuable sulfur-stereogenic motifs in medicinal chemistry and serve as versatile precursors to sulfoximines and sulfondiimines. Despite their importance, enantioselective S-alkylation of sulfenamides accessing to sulfilimines from abundant alkyl feedstocks remains largely unexplored, particularly via radical pathways. Herein, we report the enantioselective copper-photoredox-catalyzed S-alkylation of sulfenamides enabled by a family of amino-acid-derived N,N,N-tridentate ligands. This strategy allows the use of alkyl carboxylic acids via decarboxylative radical sulfilimination to afford enantioenriched sulfilimines in high yields and enantioselectivities. Importantly, the platform is further extended to alkyl iodides through an XAT-induced radical pathway, demonstrating the generality of this enantioselective S-alkylation manifold. A broad range of primary, secondary, and tertiary alkyl radicals, diverse sulfenamides, and complex bioactive substrates are well tolerated. Mechanistic studies support a radical process involving a stereoinvertive SH2-type substitution at a copper-sulfenamide intermediate. Gram-scale synthesis and downstream oxidation to pharmaceutically relevant sulfoximines underscore the synthetic utility of this method.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"18 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506426","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 H2O2 photosynthesis efficiency by carbon nitride (CN) via a two-electron oxygen reduction reaction (ORR) is limited by insufficient charge separation, sluggish O2 supply in aqueous solution, and difficulty in O2 adsorption and activation. Here, we modulated CN with sulfonic acid and cyano groups, which impart multiple favorable electronic properties for H2O2 photogeneration, including broadened light absorption, enhanced charge separation due to the polarized electronic structure, and improved O2 adsorption and activation. H2O2 photogeneration experiments showed that it delivered a 41-fold enhancement in H2O2 yield, reaching a value of 44.5 mmol g–1 h–1 with a high AQY of 36.5% at 400 nm and a high selectivity of >94%. Experiments and density functional theory (DFT) calculations revealed the preferential two-step 1e ORR mechanism. Further fabrication of a triphase flow photoreactor by immobilizing the functionalized CN on a gas diffusion layer achieved fast O2 supply and continuous-flow H2O2 photogeneration with a 4 times higher yield of 171 mmol m–2 in 6 h than in a two-phase system. As a proof-of-concept, continuous-flow H2O2 photogeneration was further coupled with organic synthesis exemplified by furfuryl alcohol photooxidation conversion. This work solves multiple important issues of CN in H2O2 photogeneration by combining electronic polarity modulation with a triphase continuous-flow photoreactor design.
{"title":"Polarized Electronic Structure of Carbon Nitride Enhances Selective Triphase Continuous-Flow Photosynthesis of Hydrogen Peroxide","authors":"Mao He,Shuai Xiong,Zongxing Tu,Suqin Wu,Xiaoying Peng,Jianming Chen,Tianle Ding,Chen Lai,Dou Chen,Guiming Peng","doi":"10.1021/acscatal.6c00507","DOIUrl":"https://doi.org/10.1021/acscatal.6c00507","url":null,"abstract":"The H2O2 photosynthesis efficiency by carbon nitride (CN) via a two-electron oxygen reduction reaction (ORR) is limited by insufficient charge separation, sluggish O2 supply in aqueous solution, and difficulty in O2 adsorption and activation. Here, we modulated CN with sulfonic acid and cyano groups, which impart multiple favorable electronic properties for H2O2 photogeneration, including broadened light absorption, enhanced charge separation due to the polarized electronic structure, and improved O2 adsorption and activation. H2O2 photogeneration experiments showed that it delivered a 41-fold enhancement in H2O2 yield, reaching a value of 44.5 mmol g–1 h–1 with a high AQY of 36.5% at 400 nm and a high selectivity of >94%. Experiments and density functional theory (DFT) calculations revealed the preferential two-step 1e ORR mechanism. Further fabrication of a triphase flow photoreactor by immobilizing the functionalized CN on a gas diffusion layer achieved fast O2 supply and continuous-flow H2O2 photogeneration with a 4 times higher yield of 171 mmol m–2 in 6 h than in a two-phase system. As a proof-of-concept, continuous-flow H2O2 photogeneration was further coupled with organic synthesis exemplified by furfuryl alcohol photooxidation conversion. This work solves multiple important issues of CN in H2O2 photogeneration by combining electronic polarity modulation with a triphase continuous-flow photoreactor design.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"83 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506428","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 : 2026-03-25DOI: 10.1021/acscatal.6c00713
Matthew T. Zambri,Matthew H. L. Chow,Mark S. Taylor
Hemiaminals formed by the addition of azoles to aldehydes can be trapped via acylation. Previously, such O-acylated hemiaminals have been applied as prodrugs for bioactive NH-azoles. Here, we show that azole hemiaminal derivatives can be repurposed as versatile substrates for nickel-catalyzed reductive couplings by the incorporation of a redox-active mixed oxalate group. The method enables the modular and regioselective synthesis of azoles bearing branched alkyl substituents from readily available NH-azoles, aldehydes, and haloarenes, or carboxylic acid anhydrides. Density functional theory calculations provide insight into the scope and limitations of the transformation, including how the heterocycle structure influences the formation and reactivity of the putative azolylmethyl radicals.
{"title":"Modular, Regioselective Synthesis of N-Alkylated Azoles by Nickel-Catalyzed Reductive Couplings of Hemiaminal Oxalates","authors":"Matthew T. Zambri,Matthew H. L. Chow,Mark S. Taylor","doi":"10.1021/acscatal.6c00713","DOIUrl":"https://doi.org/10.1021/acscatal.6c00713","url":null,"abstract":"Hemiaminals formed by the addition of azoles to aldehydes can be trapped via acylation. Previously, such O-acylated hemiaminals have been applied as prodrugs for bioactive NH-azoles. Here, we show that azole hemiaminal derivatives can be repurposed as versatile substrates for nickel-catalyzed reductive couplings by the incorporation of a redox-active mixed oxalate group. The method enables the modular and regioselective synthesis of azoles bearing branched alkyl substituents from readily available NH-azoles, aldehydes, and haloarenes, or carboxylic acid anhydrides. Density functional theory calculations provide insight into the scope and limitations of the transformation, including how the heterocycle structure influences the formation and reactivity of the putative azolylmethyl radicals.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"95 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506427","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}
Zinc oxide is a defect-tunable support that exhibits appreciable surface reducibility when promoted by metals. Previous studies have shown that tuning the metal–support interaction can improve desulfurization performance. However, in Cu/ZnO, the inherently weak Cu–ZnO metal-support interaction can limit ultradeep thiophene removal from coke oven gas. To address this limitation, the support morphology and surface-defect characteristics of ZnO were tuned to modify the Cu–Zn interfacial electronic environment in Cu/ZnO. At 200 °C, the plate-like Cu/ZnO achieved a breakthrough sulfur capacity of 34.1 mg/g which is approximately 26% higher than that of commercial ZnO, indicating improved performance for the removal of refractory organosulfur species during fine desulfurization. Combined structural characterization and structure-performance analysis indicate that ZnO morphology plays an important role in regulating the Cu–Zn interface. Controlling support morphology, defect-related surface properties, and synthesis conditions can strengthen the Cu–Zn electronic interaction and alter the local structure of Cu species. These changes are reflected in the Cu electronic state and coordination environment, and are closely linked to the desulfurization performance. These results show that coupling facet/morphology control with surface-defect regulation is an effective way to improve Cu–Zn interfacial properties for the removal of refractory organosulfur compounds from coal-derived gases.
{"title":"Breaking the Thiophene-Removal Limit via Facet-Engineered Electronic Metal-Support Interaction on Cu/ZnO","authors":"Xiaoxia Zhang,Yongjin Wang,Junjie Liao,Jiancheng Wang,Liping Chang,Weiren Bao,Kechang Xie","doi":"10.1021/acscatal.6c00801","DOIUrl":"https://doi.org/10.1021/acscatal.6c00801","url":null,"abstract":"Zinc oxide is a defect-tunable support that exhibits appreciable surface reducibility when promoted by metals. Previous studies have shown that tuning the metal–support interaction can improve desulfurization performance. However, in Cu/ZnO, the inherently weak Cu–ZnO metal-support interaction can limit ultradeep thiophene removal from coke oven gas. To address this limitation, the support morphology and surface-defect characteristics of ZnO were tuned to modify the Cu–Zn interfacial electronic environment in Cu/ZnO. At 200 °C, the plate-like Cu/ZnO achieved a breakthrough sulfur capacity of 34.1 mg/g which is approximately 26% higher than that of commercial ZnO, indicating improved performance for the removal of refractory organosulfur species during fine desulfurization. Combined structural characterization and structure-performance analysis indicate that ZnO morphology plays an important role in regulating the Cu–Zn interface. Controlling support morphology, defect-related surface properties, and synthesis conditions can strengthen the Cu–Zn electronic interaction and alter the local structure of Cu species. These changes are reflected in the Cu electronic state and coordination environment, and are closely linked to the desulfurization performance. These results show that coupling facet/morphology control with surface-defect regulation is an effective way to improve Cu–Zn interfacial properties for the removal of refractory organosulfur compounds from coal-derived gases.","PeriodicalId":9,"journal":{"name":"ACS Catalysis ","volume":"52 1","pages":""},"PeriodicalIF":12.9,"publicationDate":"2026-03-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147506444","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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