Pub Date : 2026-02-04DOI: 10.1016/j.jcat.2026.116725
Xin Huang, Jingyu Ren, Razium Ali Soomro, Shoujian Fu, Zixuan Li, Mengxi Fu, Li Guo, Chunming Yang, Danjun Wang
{"title":"Engineering electronic structure to modulate active site environment for enhanced photocatalytic nitrogen fixation","authors":"Xin Huang, Jingyu Ren, Razium Ali Soomro, Shoujian Fu, Zixuan Li, Mengxi Fu, Li Guo, Chunming Yang, Danjun Wang","doi":"10.1016/j.jcat.2026.116725","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116725","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"41 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-02-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146111029","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 development of efficient photocatalytic systems for hydrogen peroxide (H2O2) production from pure water remains a huge challenge due to rapid charge recombination and insufficient redox capability in single-component photocatalysts. Herein, we successfully constructed the S-scheme oxygen-vacancy-enriched MoO3 quantum dots (Ov-MoQDs)/sulfur-vacancy-rich Zn3In2S6 (Sv-ZIS) heterostructures by coupling Sv-ZIS nanosheets with Ov-MoQDs. The optimized 3Ov-MoQDs/Sv-ZIS sample achieves an outstanding H2O2 production rate of 85.8 ± 3.1 μM under visible light illumination for 1 h in the pure water, which is about 3.5 and 45.1 times higher than those of Sv-ZIS and Ov-MoQDs, respectively. Through comprehensive in situ and ex situ characterizations combined with theoretical calculations, we demonstrate that the enhanced activity stems from efficient charge separation and transfer across the heterogeneous interfaces via an S-scheme mechanism. Furthermore, the H2O2 photosynthesis over Ov-MoQDs/Sv-ZIS heterostructures is found to proceed through a two-step single-electron oxygen reduction reaction (ORR) pathway. This work provides valuable insights into the rational design of advanced heterostructured photocatalysts for sustainable chemical synthesis.
{"title":"Oxygen-vacancy-enriched MoO3 quantum dots anchored on sulfur-vacancy-rich Zn3In2S6 heterostructures for boosted hydrogen peroxide photosynthesis from pure water","authors":"Cheng-Jie Zheng, Ting Wang, Ren-Chang Zhang, Ke Xu, Zhi-Cai He, Jian Zhang, Guo-Bo Huang, Mingyuan Wang, Guiwu Liu, Wei Chen","doi":"10.1016/j.jcat.2026.116724","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116724","url":null,"abstract":"The development of efficient photocatalytic systems for hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) production from pure water remains a huge challenge due to rapid charge recombination and insufficient redox capability in single-component photocatalysts. Herein, we successfully constructed the S-scheme oxygen-vacancy-enriched MoO<sub>3</sub> quantum dots (Ov-MoQDs)/sulfur-vacancy-rich Zn<sub>3</sub>In<sub>2</sub>S<sub>6</sub> (Sv-ZIS) heterostructures by coupling Sv-ZIS nanosheets with Ov-MoQDs. The optimized 3Ov-MoQDs/Sv-ZIS sample achieves an outstanding H<sub>2</sub>O<sub>2</sub> production rate of 85.8 ± 3.1 μM under visible light illumination for 1 h in the pure water, which is about 3.5 and 45.1 times higher than those of Sv-ZIS and Ov-MoQDs, respectively. Through comprehensive in situ and ex situ characterizations combined with theoretical calculations, we demonstrate that the enhanced activity stems from efficient charge separation and transfer across the heterogeneous interfaces via an S-scheme mechanism. Furthermore, the H<sub>2</sub>O<sub>2</sub> photosynthesis over Ov-MoQDs/Sv-ZIS heterostructures is found to proceed through a two-step single-electron oxygen reduction reaction (ORR) pathway. This work provides valuable insights into the rational design of advanced heterostructured photocatalysts for sustainable chemical synthesis.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"17 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-02-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146110688","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}
In this study, we present a comprehensive investigation of the methane C–H activation catalyzed by an iron-containing hemicryptophane molecular cage FeO-TPA@Hm, combined with an in-depth exploration of the reaction mechanisms via electronic structure analysis, revealing distinctive features in both the reactivity and mechanism of this catalytic system. It was found that the modulation of the electronic states at the active center is achieved by the Hm molecular cage structure, breaking the conventional “inert framework + active center” paradigm and endowing the system with unprecedented activity and mechanisms. Furthermore, the hydrophobic microenvironment of the Hm cage further enhances the catalytic performance, providing a theoretical explanation for the exceptional catalytic behaviors observed experimentally. This study proposes a balanced catalyst design strategy that synergistically integrates moderate electronic effects with efficient hydrophobic enhancement, aiming to maximize both catalytic efficiency and selectivity in methane conversion processes. Overall, the findings offer significant theoretical insights and practical guidance for the development of methane activation catalysts, opening new avenues for research in catalytic chemistry and related fields.
{"title":"Unraveling the distinct catalytic features of methane activation in an iron-containing hemicryptophane cage FeO-TPA@Hm: insights from molecular cage architecture and electronic interactions","authors":"Xin-Rui Mao, Chao-Yu Zhao, Yi-Zhou Gong, Ke-Xin Xing, Guang-Shan Zhu, Cai-Yun Geng","doi":"10.1016/j.jcat.2026.116731","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116731","url":null,"abstract":"In this study, we present a comprehensive investigation of the methane C–H activation catalyzed by an iron-containing hemicryptophane molecular cage FeO-TPA@Hm, combined with an in-depth exploration of the reaction mechanisms via electronic structure analysis, revealing distinctive features in both the reactivity and mechanism of this catalytic system. It was found that the modulation of the electronic states at the active center is achieved by the Hm molecular cage structure, breaking the conventional “inert framework + active center” paradigm and endowing the system with unprecedented activity and mechanisms. Furthermore, the hydrophobic microenvironment of the Hm cage further enhances the catalytic performance, providing a theoretical explanation for the exceptional catalytic behaviors observed experimentally. This study proposes a balanced catalyst design strategy that synergistically integrates moderate electronic effects with efficient hydrophobic enhancement, aiming to maximize both catalytic efficiency and selectivity in methane conversion processes. Overall, the findings offer significant theoretical insights and practical guidance for the development of methane activation catalysts, opening new avenues for research in catalytic chemistry and related fields.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"57 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098233","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: 10.1016/j.jcat.2026.116729
Yongkun Zheng, Nacho Solá-Ferrer, Lluís Martínez-Belenguer, Belén Lerma-Berlanga, Antonio Leyva-Pérez
Ethyl methyl carbonate (EMC), as the simplest asymmetric carbonate, is considered a unique green liquid organic compound for lithium batteries (electrolyte) and gasoline blending (octane enhancer additive), with properties between dimethyl and diethyl carbonate. In accordance, its chemical production is expected to boost during the coming years, despite green chemical syntheses for EMC are still to be developed. Here we show the selective synthesis of EMC from DMC and ethanol with one of the cheapest commercially available solids, i.e. zeolites, as a heterogeneous catalyst for the reaction, surpassing most of the current soluble catalysts employed for this reaction. While a pristine commercial zeolite such as NaX already shows a significant catalytic activity (65% conversion, 91% selectivity to EMC) without any pre-activation treatment, is recoverable and reusable, and can be implemented in batch and in flow, the incorporation of alkaline oxide clusters inside the zeolitic framework, i.e. K2O, boosts the catalytic activity not only for the NaX zeolite but also for the parent H-USY and NaY zeolites, otherwise barely catalytically active for the reaction, to give yields up to >99% and ≈80% selectivity to EMC. These results bring a sustainable and cheap catalytic system for the production of EMC.
{"title":"Alkaline oxide clusters inside zeolites catalyze the selective synthesis of ethyl methyl carbonate","authors":"Yongkun Zheng, Nacho Solá-Ferrer, Lluís Martínez-Belenguer, Belén Lerma-Berlanga, Antonio Leyva-Pérez","doi":"10.1016/j.jcat.2026.116729","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116729","url":null,"abstract":"Ethyl methyl carbonate (EMC), as the simplest asymmetric carbonate, is considered a unique green liquid organic compound for lithium batteries (electrolyte) and gasoline blending (octane enhancer additive), with properties between dimethyl and diethyl carbonate. In accordance, its chemical production is expected to boost during the coming years, despite green chemical syntheses for EMC are still to be developed. Here we show the selective synthesis of EMC from DMC and ethanol with one of the cheapest commercially available solids, i.e. zeolites, as a heterogeneous catalyst for the reaction, surpassing most of the current soluble catalysts employed for this reaction. While a pristine commercial zeolite such as NaX already shows a significant catalytic activity (65% conversion, 91% selectivity to EMC) without any pre-activation treatment, is recoverable and reusable, and can be implemented in batch and in flow, the incorporation of alkaline oxide clusters inside the zeolitic framework, i.e. K<sub>2</sub>O, boosts the catalytic activity not only for the NaX zeolite but also for the parent H-USY and NaY zeolites, otherwise barely catalytically active for the reaction, to give yields up to >99% and ≈80% selectivity to EMC. These results bring a sustainable and cheap catalytic system for the production of EMC.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"58 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-02-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098234","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 : 2026-01-31DOI: 10.1016/j.jcat.2026.116720
Chuanmei Wang , Yihan Zhang , Ting Wang , Yanwei Cao , Zihang Yin , Houyu Tao , Zijun Huang , Dongyun Chen , Xianjie Fang , Jianmei Lu , Lin He
Piperidine derivatives serve as crucial synthetic building blocks for pharmaceuticals and agrochemicals. With breakthroughs in the production capacity of diamines (such as 2-methylpentanediamine and 1,5-pentanediamine), employing cyclization strategies to access piperidine frameworks has garnered increasing attention. Herein, we report an efficient strategy to rapidly access piperidines via a “hydrogen-borrowing” mechanism over Shvo Ru catalysis without any additives. Firstly, the interaction between the Shvo Ru complex and diamines was investigated by 1H NMR, FT-IR, mass spectrometry, and DFT calculations, revealing the role of diamines in dissociating the Shvo pre-catalyst and facilitating the formation of reactive intermediates. Based on this observation, Shvo-based catalysts with efficient activity for the solvent/promoter-free cyclization of diamines to piperidines were developed. This catalytic system is applicable not only to 100-gram scale-up synthesis with a record-high turnover number (TON) of 8645 and excellent selectivity (>99%), but also remains stable for over 4 cycles without significant loss of activity. Finally, the catalytic mechanism of the Shvo Ru-mediated, solvent/promoter-free cyclization of diamines to piperidines was proposed by DFT calculations and control experiments.
{"title":"Substrate-activated Shvo catalyst for the solvent/promoter-free cyclization of diamines to piperidines and analogues","authors":"Chuanmei Wang , Yihan Zhang , Ting Wang , Yanwei Cao , Zihang Yin , Houyu Tao , Zijun Huang , Dongyun Chen , Xianjie Fang , Jianmei Lu , Lin He","doi":"10.1016/j.jcat.2026.116720","DOIUrl":"10.1016/j.jcat.2026.116720","url":null,"abstract":"<div><div>Piperidine derivatives serve as crucial synthetic building blocks for pharmaceuticals and agrochemicals. With breakthroughs in the production capacity of diamines (such as 2-methylpentanediamine and 1,5-pentanediamine), employing cyclization strategies to access piperidine frameworks has garnered increasing attention. Herein, we report an efficient strategy to rapidly access piperidines via a “hydrogen-borrowing” mechanism over Shvo Ru catalysis without any additives. Firstly, the interaction between the Shvo Ru complex and diamines was investigated by <sup>1</sup>H NMR, FT-IR, mass spectrometry, and DFT calculations, revealing the role of diamines in dissociating the Shvo pre-catalyst and facilitating the formation of reactive intermediates. Based on this observation, Shvo-based catalysts with efficient activity for the solvent/promoter-free cyclization of diamines to piperidines were developed. This catalytic system is applicable not only to 100-gram scale-up synthesis with a record-high turnover number (TON) of 8645 and excellent selectivity (>99%), but also remains stable for over 4 cycles without significant loss of activity. Finally, the catalytic mechanism of the Shvo Ru-mediated, solvent/promoter-free cyclization of diamines to piperidines was proposed by DFT calculations and control experiments.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116720"},"PeriodicalIF":6.5,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095947","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 : 2026-01-31DOI: 10.1016/j.jcat.2026.116716
Fan Shao, Fengzhi Guo, Tianyu Bai, Rongrong Li, Shixuan Guo, Jinxiao Sun, Yasong Zhou, Wenbin Huang, Lu Gong, Gang Wang, Qiang Wei
{"title":"Influence of tailoring acidic sites and silicon distribution of SAPO-11 zeolite via in-situ Zn modification for superior hydroisomerization of Fischer-Tropsch wax","authors":"Fan Shao, Fengzhi Guo, Tianyu Bai, Rongrong Li, Shixuan Guo, Jinxiao Sun, Yasong Zhou, Wenbin Huang, Lu Gong, Gang Wang, Qiang Wei","doi":"10.1016/j.jcat.2026.116716","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116716","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"94 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095946","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 : 2026-01-31DOI: 10.1016/j.jcat.2026.116721
Isabel Poves-Ruiz, Beatriz Sánchez-Page, M.Victoria Jiménez, Miguel Gallegos, Julen Munarriz, Vincenzo Passarelli, Jesús J. Pérez-Torrente
In-depth studies on the residual hydrosilylation catalytic activity of samples of compound [Cp*RhI{(MeIm)2CH2}]+, bearing an unfunctionalized bis-NHC ligand, lead to the discovery of the excellent catalytic performance of the simple complex [Cp*RhI2(IMe)] (IMe = 1,3-dimethylimidozolin-2-ylidene). It This compound efficiently catalyzes the hydrosilylation of wide a range of terminal alkynes, with complete regio- and stereoselectivity toward the thermodynamically less stable β-(Z)-vinylsilane isomer. The reaction mechanism has been explored by DFT calculations. The reaction seems to proceed through an ionic outer-sphere mechanism, involving heterolytic activation of the hydrosilane assisted by the rhodium center and a solvent molecule (acetone). In the absence of acetone, a metal–ligand cooperation reaction pathway is proposed, in which the Cp* ligand acts as a proton-relay within the coordination sphere of the Rh(III) center. The cooperative activation of the hydrosilane by the metallocene moiety of the catalyst precursor generates a reactive Rh(I)–silyl intermediate bearing a pentamethylcyclopenta-1,3-diene ligand, [η4-Cp*H], formed through protonation of the Cp* moiety.
{"title":"Mechanistic Insights on the β-(Z) alkyne hydrosilylation by a NHC-based Cp*Rh(III) catalyst: from catalyst design to an alternative model for H-Si activation","authors":"Isabel Poves-Ruiz, Beatriz Sánchez-Page, M.Victoria Jiménez, Miguel Gallegos, Julen Munarriz, Vincenzo Passarelli, Jesús J. Pérez-Torrente","doi":"10.1016/j.jcat.2026.116721","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116721","url":null,"abstract":"In-depth studies on the residual hydrosilylation catalytic activity of samples of compound [Cp*RhI{(MeIm)<sub>2</sub>CH<sub>2</sub>}]<sup>+</sup>, bearing an unfunctionalized bis-NHC ligand, lead to the discovery of the excellent catalytic performance of the simple complex [Cp*RhI<sub>2</sub>(IMe)] (IMe = 1,3-dimethylimidozolin-2-ylidene). <del>It</del> This compound efficiently catalyzes the hydrosilylation of wide a range of terminal alkynes, with complete regio- and stereoselectivity toward the thermodynamically less stable β-(Z)-vinylsilane isomer. The reaction mechanism has been explored by DFT calculations. The reaction seems to proceed through an ionic outer-sphere mechanism, involving heterolytic activation of the hydrosilane assisted by the rhodium center and a solvent molecule (acetone). In the absence of acetone, a metal–ligand cooperation reaction pathway is proposed, in which the Cp* ligand acts as a proton-relay within the coordination sphere of the Rh(III) center. The cooperative activation of the hydrosilane by the metallocene moiety of the catalyst precursor generates a reactive Rh(I)–silyl intermediate bearing a pentamethylcyclopenta-1,3-diene ligand, [η<sup>4</sup>-Cp*H], formed through protonation of the Cp* moiety.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"140 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-01-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146095953","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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