Efficient hydrogen activation and spillover remain critical challenges limiting the hydrogenation efficiency of heterogeneous catalytic systems. To address this limitation, we developed a TiO2 modification strategy involving the in-situ formation of reducible TiO2 on Al2O3, resulting in a Ni/TiO2-Al2O3 catalyst with enhanced hydrogen spillover efficiency. The modified catalyst exhibits significantly improved activity for the selective hydrogenation of quinoline under identical reaction conditions. Comprehensive characterization and experimental results demonstrate that TiO2 incorporation facilitates H2 activation and generates abundant hydrogen migration pathways, thereby increasing the concentration of active hydrogen species on the Al2O3 surface. DFT calculations further confirm that the hydrogen migration barrier at the TiO2-Al2O3 interface is lower than that of pure Al2O3, offering theoretical support for the enhanced spillover efficiency. Meanwhile, the spatial separation between quinoline adsorption sites, Lewis acid of Al2O3 and hydrogen activation sites, Ni nanoparticles, directly drive the enhanced hydrogenation performance. Furthermore, the use of an i-PrOH/ H2O mixed solvent significantly enhances catalysis, as water mediates the spillover of active hydrogen species from the catalyst into the aqueous phase, where they participate in the reaction via a Grotthuss proton-hopping mechanism, as evidenced by NMR. Delayed feeding experiments demonstrate that hydrogen stored in the aqueous phase can still drive quinoline hydrogenation even after H2 removal, highlighting the importance of both solid- and liquid-phase hydrogen transfer. This dual-phase spillover strategy offers a promising avenue for designing highly efficient heterogeneous catalytic hydrogenation systems.
{"title":"Selective hydrogenation of quinoline catalyzed by Ni/TiO2-Al2O3: role of TiO2 in promoting hydrogen spillover","authors":"Hong Zhao, Tongtong Fan, Chuang Liu, Huaguang Tong, Tong Li, Jiantai Ma, Zhengping Dong","doi":"10.1016/j.jcat.2026.116730","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116730","url":null,"abstract":"Efficient hydrogen activation and spillover remain critical challenges limiting the hydrogenation efficiency of heterogeneous catalytic systems. To address this limitation, we developed a TiO<sub>2</sub> modification strategy involving the in-situ formation of reducible TiO<sub>2</sub> on Al<sub>2</sub>O<sub>3</sub>, resulting in a Ni/TiO<sub>2</sub>-Al<sub>2</sub>O<sub>3</sub> catalyst with enhanced hydrogen spillover efficiency. The modified catalyst exhibits significantly improved activity for the selective hydrogenation of quinoline under identical reaction conditions. Comprehensive characterization and experimental results demonstrate that TiO<sub>2</sub> incorporation facilitates H<sub>2</sub> activation and generates abundant hydrogen migration pathways, thereby increasing the concentration of active hydrogen species on the Al<sub>2</sub>O<sub>3</sub> surface. DFT calculations further confirm that the hydrogen migration barrier at the TiO<sub>2</sub>-Al<sub>2</sub>O<sub>3</sub> interface is lower than that of pure Al<sub>2</sub>O<sub>3</sub>, offering theoretical support for the enhanced spillover efficiency. Meanwhile, the spatial separation between quinoline adsorption sites, Lewis acid of Al<sub>2</sub>O<sub>3</sub> and hydrogen activation sites, Ni nanoparticles, directly drive the enhanced hydrogenation performance. Furthermore, the use of an <em>i</em>-PrOH/ H<sub>2</sub>O mixed solvent significantly enhances catalysis, as water mediates the spillover of active hydrogen species from the catalyst into the aqueous phase, where they participate in the reaction via a Grotthuss proton-hopping mechanism, as evidenced by NMR. Delayed feeding experiments demonstrate that hydrogen stored in the aqueous phase can still drive quinoline hydrogenation even after H<sub>2</sub> removal, highlighting the importance of both solid- and liquid-phase hydrogen transfer. This dual-phase spillover strategy offers a promising avenue for designing highly efficient heterogeneous catalytic hydrogenation systems.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"91 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129540","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}
{"title":"Insight into the crucial role of carbon in LaFeO3@C composites for liquid-phase aerobic oxidation of benzyl alcohol to benzaldehyde","authors":"Wenwen Xiao, Joshua Gorimbo, Qingye Zhao, Zhiyan He, Shuai Lyu, Ping Xiao, Yali Yao, Junjiang Zhu","doi":"10.1016/j.jcat.2026.116747","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116747","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"9 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135420","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-02-05DOI: 10.1016/j.jcat.2026.116733
Arjun Neyyathala, Felix Jung, Claus Feldmann, Simon Barth, Jan-Dierk Grunwaldt, Ivana Jevtovik, 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 systems. 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 Jevtovik, Stephan A. Schunk, Paolo Dolcet, Silvia Gross, Schirin Hanf","doi":"10.1016/j.jcat.2026.116733","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116733","url":null,"abstract":"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 systems. 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.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"384 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-02-05","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 : 2026-02-04DOI: 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}
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