Pub Date : 2026-02-08DOI: 10.1016/j.jcat.2026.116751
Natav Yatom, Prince Gollapalli, Daniel A Grave, Avner Rothschild, Maytal Caspary Toroker
{"title":"Understanding surface charging limitations of hematite photoanodes through combining cathodic discharge measurements and computational modeling","authors":"Natav Yatom, Prince Gollapalli, Daniel A Grave, Avner Rothschild, Maytal Caspary Toroker","doi":"10.1016/j.jcat.2026.116751","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116751","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"3 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146138525","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 : 2026-02-07DOI: 10.1016/j.jcat.2026.116744
Yi Qin, Wenhao Yang, Hao Liu, Jingjie Luo, Changhai Liang
Synthesis of hexamethylenediamine (HMDA), the crucial monomer for polyamides, is a significant catalyst process and can be proceeded by selectively hydrogenating the adiponitrile (ADN). Fine Co particles decorated by ReOx clusters were designed to configure rich Co-ReOx interfaces under optimized bimetallic synergy. The anchorage of Co particles on support is benefited in the presence of ReOx cluster with the Re atoms migrating onto the surface and into the lattices of cobalt. Modulation on the electronic environment occurs by electrons delivering from Reδ+ to Co to forge the Co0-Reδ+ cooperative pairs and stabilizes the sensitive electron-rich Co sites. The reaction process can be greatly promoted at the interfacial Co0-Reδ+ sites that both the H2 dissociation energy and the adsorption energy for reactant and intermediate are greatly tuned to cater to the high selectivity towards HMDA. The HMDA yield of 87.5% with a rate of 3.60 molHMDA·molCo−1·h−1 in the absence of alkali can be achieved by the Co3Re1/ZnO with stable re-usability and easy regeneration.
{"title":"Configuring Co0-Reδ+ cooperative sites for alkali-free hydrogenation of adiponitrile to hexamethylenediamine","authors":"Yi Qin, Wenhao Yang, Hao Liu, Jingjie Luo, Changhai Liang","doi":"10.1016/j.jcat.2026.116744","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116744","url":null,"abstract":"Synthesis of hexamethylenediamine (HMDA), the crucial monomer for polyamides, is a significant catalyst process and can be proceeded by selectively hydrogenating the adiponitrile (ADN). Fine Co particles decorated by ReO<sub>x</sub> clusters were designed to configure rich Co-ReO<sub>x</sub> interfaces under optimized bimetallic synergy. The anchorage of Co particles on support is benefited in the presence of ReO<sub>x</sub> cluster with the Re atoms migrating onto the surface and into the lattices of cobalt. Modulation on the electronic environment occurs by electrons delivering from Re<sup>δ+</sup> to Co to forge the Co<sup>0</sup>-Re<sup>δ+</sup> cooperative pairs and stabilizes the sensitive electron-rich Co sites. The reaction process can be greatly promoted at the interfacial Co<sup>0</sup>-Re<sup>δ+</sup> sites that both the H<sub>2</sub> dissociation energy and the adsorption energy for reactant and intermediate are greatly tuned to cater to the high selectivity towards HMDA. The HMDA yield of 87.5% with a rate of 3.60 mol<sub>HMDA</sub>·mol<sub>Co</sub><sup>−1</sup>·h<sup>−1</sup> in the absence of alkali can be achieved by the Co<sub>3</sub>Re<sub>1</sub>/ZnO with stable re-usability and easy regeneration.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"132 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-02-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146135418","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 oxidative esterification of alcohols is a key transformation in fine chemical synthesis and green chemistry. However, supported Au catalysts often suffer from nanoparticle agglomeration, leading to a significant loss of activity. Here, we report that Zn-doped hydroxyapatite (ZnHAP) can effectively stabilize ultra-small Au nanoclusters through Au-support interactions, even after high-temperature calcination at 400 ℃. The resulting Au/ZnHAP catalyst, with an ultralow Au loading of 0.25 wt%, exhibits outstanding performance in the base-free oxidative esterification of benzyl alcohol (Conv. 99%, Sele. 95%). Mechanistic investigations reveal that Zn incorporation into HAP modulates the surface basicity, thereby enhancing substrate adsorption and accelerating the key oxidative dehydrogenation step of the hemiacetal intermediate. Moreover, the increased Au0 fraction induced by higher calcination temperatures further promotes benzyl alcohol activation. Consequently, under base-free conditions, the ester formation rate is governed by both the number of exposed Au active sites and the balanced distribution of surface acid–base sites. This work provides new mechanistic insights and practical guidance for the rational design of efficient, base-free oxidative esterification catalysts based on supported Au systems.
{"title":"Ultra-small Au nanocluster supported on modified mesoporous hydroxyapatite for base-free oxidative esterification of alcohols","authors":"Tingting Ge, Zhili Miao, Xiaorui Liu, Ziyan Jia, Chao Liu, Jiahui Huang","doi":"10.1016/j.jcat.2026.116746","DOIUrl":"https://doi.org/10.1016/j.jcat.2026.116746","url":null,"abstract":"The oxidative esterification of alcohols is a key transformation in fine chemical synthesis and green chemistry. However, supported Au catalysts often suffer from nanoparticle agglomeration, leading to a significant loss of activity. Here, we report that Zn-doped hydroxyapatite (ZnHAP) can effectively stabilize ultra-small Au nanoclusters through Au-support interactions, even after high-temperature calcination at 400 ℃. The resulting Au/ZnHAP catalyst, with an ultralow Au loading of 0.25 wt%, exhibits outstanding performance in the base-free oxidative esterification of benzyl alcohol (Conv. 99%, Sele. 95%). Mechanistic investigations reveal that Zn incorporation into HAP modulates the surface basicity, thereby enhancing substrate adsorption and accelerating the key oxidative dehydrogenation step of the hemiacetal intermediate. Moreover, the increased Au<sup>0</sup> fraction induced by higher calcination temperatures further promotes benzyl alcohol activation. Consequently, under base-free conditions, the ester formation rate is governed by both the number of exposed Au active sites and the balanced distribution of surface acid–base sites. This work provides new mechanistic insights and practical guidance for the rational design of efficient, base-free oxidative esterification catalysts based on supported Au systems.","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"126 1","pages":""},"PeriodicalIF":7.3,"publicationDate":"2026-02-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146129468","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}
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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：