Pub Date : 2026-04-01Epub Date: 2026-02-09DOI: 10.1016/j.jcat.2026.116756
Changzhi Han , Tianci Chen , Shibo Lv , Jingwen Pan , Sihui Xiang , Jia-Xing Jiang
Anthraquinone (AQ) based organic conjugated polymers are promising photocatalysts for H2O2 photosynthesis from O2 and H2O, since the AQ unit with strong electron withdrawing ability can not only promote the charge separation but also act as redox active center to generate H2O2 via oxygen reduction reaction (ORR). Herein, three novel donor–acceptor type organic polymers are reported to elucidate the influence of simple donor functionalization on charge dynamics and ORR activity. Compared to biphenyl donor without functionalized group, acetylene functionalized diphenylacetylene donor and diacetylene functionalized 1,4-diphenylbutadiyne donor show reduced twisted angles between adjacent benzene rings and increased coplanarity of polymer chains, which promotes the charge transfer and separation along the polymer chains. Besides, the presence of diacetylene group in donor extends the π conjugation and broadens the light absorption range of DPB-AQ. Benefiting from the donor–acceptor structure, broad absorption range of visible light, upgraded charge transfer and separation ability, DPB-AQ exhibits a higher photocatalytic H2O2 yield of 7.8 mmol h−1 g−1 than BPH-AQ (1.0 mmol h−1 g−1) and DPA-AQ (3.8 mmol h−1 g−1) in pure water without additives. This work highlights the critical role of simple donor functionalization in polymers for H2O2 photosynthesis from H2O and O2.
{"title":"Simple donor functionalization in D-A type conjugated polymers for improved photocatalytic H2O2 production activity under visible light","authors":"Changzhi Han , Tianci Chen , Shibo Lv , Jingwen Pan , Sihui Xiang , Jia-Xing Jiang","doi":"10.1016/j.jcat.2026.116756","DOIUrl":"10.1016/j.jcat.2026.116756","url":null,"abstract":"<div><div>Anthraquinone (AQ) based organic conjugated polymers are promising photocatalysts for H<sub>2</sub>O<sub>2</sub> photosynthesis from O<sub>2</sub> and H<sub>2</sub>O, since the AQ unit with strong electron withdrawing ability can not only promote the charge separation but also act as redox active center to generate H<sub>2</sub>O<sub>2</sub> via oxygen reduction reaction (ORR). Herein, three novel donor–acceptor type organic polymers are reported to elucidate the influence of simple donor functionalization on charge dynamics and ORR activity. Compared to biphenyl donor without functionalized group, acetylene functionalized diphenylacetylene donor and diacetylene functionalized 1,4-diphenylbutadiyne donor show reduced twisted angles between adjacent benzene rings and increased coplanarity of polymer chains, which promotes the charge transfer and separation along the polymer chains. Besides, the presence of diacetylene group in donor extends the π conjugation and broadens the light absorption range of DPB-AQ. Benefiting from the donor–acceptor structure, broad absorption range of visible light, upgraded charge transfer and separation ability, DPB-AQ exhibits a higher photocatalytic H<sub>2</sub>O<sub>2</sub> yield of 7.8 mmol h<sup>−1</sup> g<sup>−1</sup> than BPH-AQ (1.0 mmol h<sup>−1</sup> g<sup>−1</sup>) and DPA-AQ (3.8 mmol h<sup>−1</sup> g<sup>−1</sup>) in pure water without additives. This work highlights the critical role of simple donor functionalization in polymers for H<sub>2</sub>O<sub>2</sub> photosynthesis from H<sub>2</sub>O and O<sub>2</sub>.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116756"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146013","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 : 2026-04-01Epub Date: 2026-02-04DOI: 10.1016/j.jcat.2026.116732
Ying Xu , Zihan Zhang , Yizhou Wang , Longfei Li , Ning Ma , Zheng Wang , Huiliang Li , Yanping Ma , Wen-Hua Sun
A family of new ligands (L1–L8) and non-pincer-type PN-Mn(I) complex Mn1 containing the imidazoline motif have been successfully employed for the transfer hydrogenation of N-unprotected indoles with H3NBH3 (AB) as the hydrogen source, giving high efficiencies (TON up to 7200) and good compatibility with functional groups, which surpasses the activity of most effective noble metal catalysts for this reaction. The reaction kinetics investigations, control experiments, and DFT computations highlighted that the central amido/amino-based bifunctional activation step employed a concerted N–H and B-H activation reaction pathway, and the hydride/proton-transfer process is the rate-determining step. More importantly, a proposed catalytic cycle involves an outer-sphere pathway for the reduction of the isomerized CN bond rather than the CC bond in the indole. Furthermore, this catalytic protocol provides a convenient and efficient method for the synthesis of a wide variety of indolines (26 examples) and saturated N-heterocycles such as tetrahydroberberine (2 examples).
{"title":"Manganese-catalyzed transfer hydrogenation of indoles to indolines: reaction scope and mechanistic investigation","authors":"Ying Xu , Zihan Zhang , Yizhou Wang , Longfei Li , Ning Ma , Zheng Wang , Huiliang Li , Yanping Ma , Wen-Hua Sun","doi":"10.1016/j.jcat.2026.116732","DOIUrl":"10.1016/j.jcat.2026.116732","url":null,"abstract":"<div><div>A family of new ligands (<strong>L1</strong>–<strong>L8</strong>) and non-pincer-type PN-Mn(I) complex <strong>Mn1</strong> containing the imidazoline motif have been successfully employed for the transfer hydrogenation of N-unprotected indoles with H<sub>3</sub>NBH<sub>3</sub> (AB) as the hydrogen source, giving high efficiencies (TON up to 7200) and good compatibility with functional groups, which surpasses the activity of most effective noble metal catalysts for this reaction. The reaction kinetics investigations, control experiments, and DFT computations highlighted that the central amido/amino-based bifunctional activation step employed a concerted N–H and B-H activation reaction pathway, and the hydride/proton-transfer process is the rate-determining step. More importantly, a proposed catalytic cycle involves an outer-sphere pathway for the reduction of the isomerized C<img>N bond rather than the C<img>C bond in the indole. Furthermore, this catalytic protocol provides a convenient and efficient method for the synthesis of a wide variety of indolines (26 examples) and saturated N-heterocycles such as tetrahydroberberine (2 examples).</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116732"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135421","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 : 2026-04-01Epub Date: 2026-02-05DOI: 10.1016/j.jcat.2026.116733
Arjun Neyyathala , Felix Jung , Claus Feldmann , Simon Barth , Jan-Dierk Grunwaldt , Ivana Jevtovikj , Stephan A. Schunk , Paolo Dolcet , Silvia Gross , Schirin Hanf
Crystalline palladium phosphide nanoparticles supported on silica (Pd3P/SiO2, 5 wt% Pd) are explored as catalysts for the alkoxycarbonylation of lignin-derived aromatic synthons, using model aryl halides as representative substrates. The detailed characterization by PXRD, HAADF-STEM, HRTEM, EDX, ICP-AES, XPS, CO-DRIFTS, and CO chemisorption confirmed the formation of the Pd3P phase with uniform nanoparticle size distribution. The catalytic performance was evaluated in a three-phase reaction system comprising a CO gas atmosphere, a liquid phase containing the solvent and substrate and a solid catalyst. The incorporation of phosphorus into the palladium lattice resulted in a more than two-fold enhancement in catalytic activity compared to conventional Pd-based heterogeneous catalysts. The Pd3P/SiO2 catalyst also outperformed several reported heterogeneous and commonly used homogeneous catalysts. This enhanced reactivity is attributed to the electronic and geometric effects introduced by phosphorus, which generate highly active, spatially-isolated Pd sites. These findings demonstrate the potential of Pd–P phase engineering for the design of the next-generation of carbonylation catalysts.
{"title":"Carbonylation catalysis of aryl halides through active-site engineering","authors":"Arjun Neyyathala , Felix Jung , Claus Feldmann , Simon Barth , Jan-Dierk Grunwaldt , Ivana Jevtovikj , Stephan A. Schunk , Paolo Dolcet , Silvia Gross , Schirin Hanf","doi":"10.1016/j.jcat.2026.116733","DOIUrl":"10.1016/j.jcat.2026.116733","url":null,"abstract":"<div><div>Crystalline palladium phosphide nanoparticles supported on silica (Pd<sub>3</sub>P/SiO<sub>2</sub>, 5 wt% Pd) are explored as catalysts for the alkoxycarbonylation of lignin-derived aromatic synthons, using model aryl halides as representative substrates. The detailed characterization by PXRD, HAADF-STEM, HRTEM, EDX, ICP-AES, XPS, CO-DRIFTS, and CO chemisorption confirmed the formation of the Pd<sub>3</sub>P phase with uniform nanoparticle size distribution. The catalytic performance was evaluated in a three-phase reaction system comprising a CO gas atmosphere, a liquid phase containing the solvent and substrate and a solid catalyst. The incorporation of phosphorus into the palladium lattice resulted in a more than two-fold enhancement in catalytic activity compared to conventional Pd-based heterogeneous catalysts. The Pd<sub>3</sub>P/SiO<sub>2</sub> catalyst also outperformed several reported heterogeneous and commonly used homogeneous catalysts. This enhanced reactivity is attributed to the electronic and geometric effects introduced by phosphorus, which generate highly active, spatially-isolated Pd sites. These findings demonstrate the potential of Pd–P phase engineering for the design of the next-generation of carbonylation catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116733"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135422","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 : 2026-04-01Epub Date: 2026-02-09DOI: 10.1016/j.jcat.2026.116754
Zhihui Jia , Fengxiang Zhu , Xiao-Feng Wu
A copper-catalyzed, boron radical-mediated strategy for the 1,4-diboryldimerization of styrenes is described. This method enables the direct coupling of two olefin units with concomitant installation of two boryl groups, providing efficient access to 1,4-diboryl-1,4-diphenylbutane derivatives from simple starting materials. The reaction proceeds under mild conditions and exhibits broad functional group tolerance, accommodating various substituted styrenes with good efficiency and, in many cases, high diastereoselectivity. Mechanistic investigations, including radical-trapping and control experiments, support a pathway involving boryl and carbon-centered radical intermediates, distinguishing this process from classical two-electron migratory insertion mechanisms. This work offers a practical and step-economical route to extended diborylated frameworks and highlights the potential of merging copper catalysis with radical chemistry for olefin dimerofunctionalization.
{"title":"Copper-catalyzed boron radical-enabled 1,4-selective diboryldimerization of styrenes","authors":"Zhihui Jia , Fengxiang Zhu , Xiao-Feng Wu","doi":"10.1016/j.jcat.2026.116754","DOIUrl":"10.1016/j.jcat.2026.116754","url":null,"abstract":"<div><div>A copper-catalyzed, boron radical-mediated strategy for the 1,4-diboryldimerization of styrenes is described. This method enables the direct coupling of two olefin units with concomitant installation of two boryl groups, providing efficient access to 1,4-diboryl-1,4-diphenylbutane derivatives from simple starting materials. The reaction proceeds under mild conditions and exhibits broad functional group tolerance, accommodating various substituted styrenes with good efficiency and, in many cases, high diastereoselectivity. Mechanistic investigations, including radical-trapping and control experiments, support a pathway involving boryl and carbon-centered radical intermediates, distinguishing this process from classical two-electron migratory insertion mechanisms. This work offers a practical and step-economical route to extended diborylated frameworks and highlights the potential of merging copper catalysis with radical chemistry for olefin dimerofunctionalization.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116754"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146014","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 : 2026-04-01Epub Date: 2026-02-03DOI: 10.1016/j.jcat.2026.116727
Fei Ye , Xiao-Fang Wang , An-Jiu Wen , Chen-Li Jin, Wen-Hao Shi, Jian Cao, Zheng Xu, Li-Wen Xu
The development of mild and straightforward synthetic approaches that simultaneously construct the silacyclic scaffold and introduce of functional group in a single step remain largely elusive. Herein, we report a copper(I)-catalyzed borylative cyclization of silicon-tethered allenyl bromides with diboron reagents, enabling efficient access to novel boryl-functionalized silacyclohexenes. This robust method affords a diverse range of 4-silacyclohexenyl boronates in moderate to good yields with high regio- and chemoselectivity across a broad substrate scope. Further transformation of the alkenyl boronate moiety provides access to a series of novel functionalized six-membered silacycles. Mechanistic insights, supported by DFT calculations, reveal key factors governing the regioselectivity of the cyclization step.
{"title":"Cu-catalyzed regioselective borylative cyclization of silicon-bridged allenyl bromides: toward 4-silacyclohexenyl boronates","authors":"Fei Ye , Xiao-Fang Wang , An-Jiu Wen , Chen-Li Jin, Wen-Hao Shi, Jian Cao, Zheng Xu, Li-Wen Xu","doi":"10.1016/j.jcat.2026.116727","DOIUrl":"10.1016/j.jcat.2026.116727","url":null,"abstract":"<div><div>The development of mild and straightforward synthetic approaches that simultaneously construct the silacyclic scaffold and introduce of functional group in a single step remain largely elusive. Herein, we report a copper(I)-catalyzed borylative cyclization of silicon-tethered allenyl bromides with diboron reagents, enabling efficient access to novel boryl-functionalized silacyclohexenes. This robust method affords a diverse range of 4-silacyclohexenyl boronates in moderate to good yields with high regio- and chemoselectivity across a broad substrate scope. Further transformation of the alkenyl boronate moiety provides access to a series of novel functionalized six-membered silacycles. Mechanistic insights, supported by DFT calculations, reveal key factors governing the regioselectivity of the cyclization step.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116727"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146110696","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":"10.1016/j.jcat.2026.116731","url":null,"abstract":"<div><div>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.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116731"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","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 : 2026-04-01Epub Date: 2026-01-30DOI: 10.1016/j.jcat.2026.116723
Manish Maurya , Hannah Fejzić , Xavier C. Krull , Huy Nguyen , Matthew Neurock , Joseph T. Hupp , Chibueze V. Amanchukwu , Rachel B. Getman
Metal-organic frameworks (MOFs) present a compelling strategy for tuning electrochemical interfaces by reshaping interfacial solvent structure. In this study, we examine how MOF coatings influence the microenvironment at copper electrodes during the CO electroreduction reaction (CORR) using a combined approach of molecular dynamics (MD) simulations and electrochemical experiments. Two MOFs, NU-901 and ZIF-8, are selected to explore the impact of pore size and channel hydrophobicity on electrochemical activity and interfacial concentration in acetonitrile (ACN) and dimethyl sulfoxide (DMSO) electrolytes. Electrochemical measurements reveal that MOF@Cu electrodes exhibit lower Faradaic efficiencies for CO hydrogenation products (ethylene and methane) compared to bare copper but have dramatic impacts on the interfacial microenvironment. NU-901, with its larger pores and strong interactions with DMSO, traps DMSO molecules and enhances CO coordination in DMSO but suppresses CORR selectivity in favor of the hydrogen evolution reaction (HER). ZIF-8, with smaller pores and hydrophobic channels, limits the interfacial water concentration, and, in ACN, promotes CO coordination. The simulations provide insights into how MOFs can act as physical modulators of reactant delivery and interfacial structure to control electrochemical microenvironments. This work highlights the value of molecular dynamics in uncovering how structural features of MOFs influence interfacial phenomena, even when catalytic performance is not directly improved.
{"title":"Modulating Cu electrode microenvironments with MOF coatings: insights from molecular dynamics and electrochemical experiments of CO reduction","authors":"Manish Maurya , Hannah Fejzić , Xavier C. Krull , Huy Nguyen , Matthew Neurock , Joseph T. Hupp , Chibueze V. Amanchukwu , Rachel B. Getman","doi":"10.1016/j.jcat.2026.116723","DOIUrl":"10.1016/j.jcat.2026.116723","url":null,"abstract":"<div><div>Metal-organic frameworks (MOFs) present a compelling strategy for tuning electrochemical interfaces by reshaping interfacial solvent structure. In this study, we examine how MOF coatings influence the microenvironment at copper electrodes during the CO electroreduction reaction (CORR) using a combined approach of molecular dynamics (MD) simulations and electrochemical experiments. Two MOFs, NU-901 and ZIF-8, are selected to explore the impact of pore size and channel hydrophobicity on electrochemical activity and interfacial concentration in acetonitrile (ACN) and dimethyl sulfoxide (DMSO) electrolytes. Electrochemical measurements reveal that MOF@Cu electrodes exhibit lower Faradaic efficiencies for CO hydrogenation products (ethylene and methane) compared to bare copper but have dramatic impacts on the interfacial microenvironment. NU-901, with its larger pores and strong interactions with DMSO, traps DMSO molecules and enhances CO coordination in DMSO but suppresses CORR selectivity in favor of the hydrogen evolution reaction (HER). ZIF-8, with smaller pores and hydrophobic channels, limits the interfacial water concentration, and, in ACN, promotes CO coordination. The simulations provide insights into how MOFs can act as physical modulators of reactant delivery and interfacial structure to control electrochemical microenvironments. This work highlights the value of molecular dynamics in uncovering how structural features of MOFs influence interfacial phenomena, even when catalytic performance is not directly improved.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116723"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146089693","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 : 2026-04-01Epub Date: 2026-02-03DOI: 10.1016/j.jcat.2026.116743
Salman Khan , Enxi Wu , Yi Dai , Kaijie Wang , Lixia Bao , Zhen Wang , Tong Wang , Qi Liu , Yaoyuan Zhang , Qin Wu , Daxin Shi , Kangcheng Chen , Guiyuan Jiang , Hansheng Li
Designing suitable catalysts for catalytic processes involving alkanes and efficiently activating C−H bond in light alkanes are both theoretically and practically significant. The present study shows that bare Ga2O3 without any supported species or dopants can effectively catalyze the PDH reaction. A clear structure–activity relationship based on crystallite size, acid density, and hydroxyl group density is established, the smaller the crystallite size, the higher the activity. Ga2O3 with a smaller crystallite size owns a higher concentration of hydroxyl species and oxygen vacancies. Comprehensive experimental investigations and DFT calculations indicate that the presence of oxygen vacancy in Ga2O3 decreases the apparent activation energy of PDH compared with the pristine Ga2O3 surface. Importantly, the existence of hydroxyl groups on the Ga2O3 surface can significantly improve the ability to activate C−H bond by altering the PDH reaction from a non-oxidative to the oxidative pathway at the initial stage. It is expected that these findings offer fundamental insights into regulating the physicochemical properties of metal oxides for efficient C−H bond activation and hydrogenation reactions.
{"title":"Hydroxyl-facilitated efficient propane dehydrogenation over bare Ga2O3 via altering reaction pathway","authors":"Salman Khan , Enxi Wu , Yi Dai , Kaijie Wang , Lixia Bao , Zhen Wang , Tong Wang , Qi Liu , Yaoyuan Zhang , Qin Wu , Daxin Shi , Kangcheng Chen , Guiyuan Jiang , Hansheng Li","doi":"10.1016/j.jcat.2026.116743","DOIUrl":"10.1016/j.jcat.2026.116743","url":null,"abstract":"<div><div>Designing suitable catalysts for catalytic processes involving alkanes and efficiently activating C−H bond in light alkanes are both theoretically and practically significant. The present study shows that bare Ga<sub>2</sub>O<sub>3</sub> without any supported species or dopants can effectively catalyze the PDH reaction. A clear structure–activity relationship based on crystallite size, acid density, and hydroxyl group density is established, the smaller the crystallite size, the higher the activity. Ga<sub>2</sub>O<sub>3</sub> with a smaller crystallite size owns a higher concentration of hydroxyl species and oxygen vacancies. Comprehensive experimental investigations and DFT calculations indicate that the presence of oxygen vacancy in Ga<sub>2</sub>O<sub>3</sub> decreases the apparent activation energy of PDH compared with the pristine Ga<sub>2</sub>O<sub>3</sub> surface. Importantly, the existence of hydroxyl groups on the Ga<sub>2</sub>O<sub>3</sub> surface can significantly improve the ability to activate C−H bond by altering the PDH reaction from a non-oxidative to the oxidative pathway at the initial stage. It is expected that these findings offer fundamental insights into regulating the physicochemical properties of metal oxides for efficient C−H bond activation and hydrogenation reactions.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116743"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146110690","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 : 2026-04-01Epub Date: 2026-02-03DOI: 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
Exploring advanced photocatalysts for efficient photocatalytic nitrogen reduction reaction (pNRR) by regulating their active site chemical environment to facilitate nitrogen molecule (N2) activation is very promising. Nevertheless, elucidating the effect of electronic structures refining on modulate the local chemical environment to promote N2 activation remains challenging. Herein, a series of 3d transition metal cations (Mn, Fe, Co, Ni, Cu, Zn) were introduced into crystal lattice of Bi2WO6 to precisely tailor its electronic structure and surface physical properties (surface energy, polarity force and London force). Based on aerobic photocatalytic pNRR performance and physical properties, Cu-doped Bi2WO6 (Cu-BWO) was identified as the most promising candidate. Excited-state calculations indicate that Cu doping attenuates the Coulomb interaction between electrons and holes in Bi2WO6, triggering the exciton effect that enhance the separation efficiency of photogenerated carriers. Furthermore, the doped Cu2+ ions act as the active site: the lowest unoccupied molecular orbital (LUMO, ) of Cu2+ facilitates N2 adsorption, while electrons in its highest occupied molecular orbital (HOMO, dxz orbital) interact with the antibonding orbital (LUMO, 1πg) of N2, thereby boosting the aerobic pNRR process. This work reveals, for the first time, that Cu doping refines local chemical environment of Bi2WO6 through the electronic structure regulation, thus regulating its achieving efficient enhance aerobic pNRR.
{"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":"10.1016/j.jcat.2026.116725","url":null,"abstract":"<div><div>Exploring advanced photocatalysts for efficient photocatalytic nitrogen reduction reaction (pNRR) by regulating their active site chemical environment to facilitate nitrogen molecule (N<sub>2</sub>) activation is very promising. Nevertheless, elucidating the effect of electronic structures refining on modulate the local chemical environment to promote N<sub>2</sub> activation remains challenging. Herein, a series of 3d transition metal cations (Mn, Fe, Co, Ni, Cu, Zn) were introduced into crystal lattice of Bi<sub>2</sub>WO<sub>6</sub> to precisely tailor its electronic structure and surface physical properties (surface energy, polarity force and London force). Based on aerobic photocatalytic pNRR performance and physical properties, Cu-doped Bi<sub>2</sub>WO<sub>6</sub> (Cu-BWO) was identified as the most promising candidate. Excited-state calculations indicate that Cu doping attenuates the Coulomb interaction between electrons and holes in Bi<sub>2</sub>WO<sub>6</sub>, triggering the exciton effect that enhance the separation efficiency of photogenerated carriers. Furthermore, the doped Cu<sup>2+</sup> ions act as the active site: the lowest unoccupied molecular orbital (LUMO, <span><math><mrow><msub><mtext>d</mtext><msup><mrow><mtext>z</mtext></mrow><mtext>2</mtext></msup></msub><mspace></mspace><mi>o</mi><mi>r</mi><mi>b</mi><mi>i</mi><mi>t</mi><mi>a</mi><mi>l</mi></mrow></math></span>) of Cu<sup>2+</sup> facilitates N<sub>2</sub> adsorption, while electrons in its highest occupied molecular orbital (HOMO, d<sub>xz</sub> orbital) interact with the antibonding orbital (LUMO, 1π<sub>g</sub>) of N<sub>2</sub>, thereby boosting the aerobic pNRR process. This work reveals, for the first time, that Cu doping refines local chemical environment of Bi<sub>2</sub>WO<sub>6</sub> through the electronic structure regulation, thus regulating its achieving efficient enhance aerobic pNRR.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116725"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","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 structural reconstruction of Cu-based catalysts during the hydrodeoxygenation (HDO) process typically leads to the loss of active Cu+ species and catalyst sintering, resulting in catalyst deactivation. Herein, we found that Pr-doped CuOx catalyst undergoes in-situ reconstruction to generate stable Cu+ species during the HDO of vanillin (VAN) to 2-methoxy-4-methylphenol (MMP). This affords a high MMP yield of 85.5% using methanol as both the solvent and hydrogen donor, which is significant higher than that of pristine CuOx and previously reported catalysts for the HDO of VAN in MeOH. Electronic interactions between Pr dopants and the CuOx matrix strengthen the Cu–O bonds and stabilize Cu+ species, thereby increasing the density of acidic sites and oxygen vacancies in the catalyst. This not only promotes MeOH decomposition for H2 generation, but also facilitates VAN adsorption and activation, thereby boosting HDO activity. This work offers new insights for the in-situ construction of highly active and durable Cu+ sites in Cu-based catalysts.
{"title":"In-situ construction of durable Cu+ species for the catalytic hydrodeoxygenation of biomass-derived aldehydes","authors":"Yuting Luo, Qingyi Lv, Huai Liu, Rui Zhang, Wenlong Jia, Lincai Peng","doi":"10.1016/j.jcat.2026.116752","DOIUrl":"10.1016/j.jcat.2026.116752","url":null,"abstract":"<div><div>The structural reconstruction of Cu-based catalysts during the hydrodeoxygenation (HDO) process typically leads to the loss of active Cu<sup>+</sup> species and catalyst sintering, resulting in catalyst deactivation. Herein, we found that Pr-doped CuO<sub>x</sub> catalyst undergoes in-situ reconstruction to generate stable Cu<sup>+</sup> species during the HDO of vanillin (VAN) to 2-methoxy-4-methylphenol (MMP). This affords a high MMP yield of 85.5% using methanol as both the solvent and hydrogen donor, which is significant higher than that of pristine CuO<sub>x</sub> and previously reported catalysts for the HDO of VAN in MeOH. Electronic interactions between Pr dopants and the CuO<sub>x</sub> matrix strengthen the Cu–O bonds and stabilize Cu<sup>+</sup> species, thereby increasing the density of acidic sites and oxygen vacancies in the catalyst. This not only promotes MeOH decomposition for H<sub>2</sub> generation, but also facilitates VAN adsorption and activation, thereby boosting HDO activity. This work offers new insights for the in-situ construction of highly active and durable Cu<sup>+</sup> sites in Cu-based catalysts.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"456 ","pages":"Article 116752"},"PeriodicalIF":6.5,"publicationDate":"2026-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146146679","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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