Pub Date : 2026-03-01Epub Date: 2026-01-27DOI: 10.1016/j.jcat.2026.116726
Zhe Wang , Jie Huang , Min Zhou, Lin Ma, Min Zhang
A highly efficient one-pot synthesis of cyclobutenes is developed through a visible-light-driven [2 + 2] cycloaddition of 4-chlorocoumarin with benzofuran, followed by a basic alumina-mediated cascade sequence involving hydrolysis, decarboxylation, and elimination of HCl. This transition-metal-free protocol proceeds under mild conditions using readily available substrates, offering a green and practical approach to cyclobutene construction.
{"title":"A tandem visible-light/heterogeneous-alumina catalytic platform for sustainable transition-metal-free cyclobutene synthesis","authors":"Zhe Wang , Jie Huang , Min Zhou, Lin Ma, Min Zhang","doi":"10.1016/j.jcat.2026.116726","DOIUrl":"10.1016/j.jcat.2026.116726","url":null,"abstract":"<div><div>A highly efficient one-pot synthesis of cyclobutenes is developed through a visible-light-driven [2 + 2] cycloaddition of 4-chlorocoumarin with benzofuran, followed by a basic alumina-mediated cascade sequence involving hydrolysis, decarboxylation, and elimination of HCl. This transition-metal-free protocol proceeds under mild conditions using readily available substrates, offering a green and practical approach to cyclobutene construction.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116726"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146071915","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-07DOI: 10.1016/j.jcat.2025.116666
Juan Zhang , Mohamed Abbas , Weibin Fan , Jiangang Chen
{"title":"Corrigendum to “Robust rGO-supported α-FeOOH/Fe2O3 nanorods catalyst: Unveiling the role of χ-Fe5C2 phase and rGO for exceptional stability in Fischer–Tropsch synthesis”. [J. Catal. 453 (2026) 116584]","authors":"Juan Zhang , Mohamed Abbas , Weibin Fan , Jiangang Chen","doi":"10.1016/j.jcat.2025.116666","DOIUrl":"10.1016/j.jcat.2025.116666","url":null,"abstract":"","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116666"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145920100","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-16DOI: 10.1016/j.jcat.2026.116703
Haiyu Yao , Heng Zhang , Xuerong Shi, Shengming Zhang, Min Zhu, Haichao Xiong, Shusheng Xu
In the context of industrial-current density water electrolysis, material stability and catalytic activity remain critical challenges. Herein, a CoFeP/NF electrocatalyst enabled by pre-activation, hierarchical nanosheet architecture, bimetallic synergy, and carbon protection demonstrates good bifunctional OER/HER performance. The optimal CoFeP/NF requires overpotentials of 235 and 440 mV to achieve current densities of 10 and 2000 mA cm−2 for alkaline OER, respectively. In line with density-functional theory predictions, the CoFeP/NF also exhibits high alkaline HER activity, demanding an overpotential of 79 mV to reach 10 mA cm−2. The assembled CoFeP/NF||CoFeP/NF electrolyzer maintains stable operation for 1100 h at ∼200 mA cm−2. The comprehensive mechanism, encompassing the pre-activation mechanism, reaction kinetics, and origin of stability, has been meticulously investigated via the combination of theoretical calculations and in/ex-situ experimental characterizations. The findings offer a universal strategy for the rational design of efficient electrocatalysts for industrial-current–density water splitting.
在工业电流密度电解的背景下，材料的稳定性和催化活性仍然是关键的挑战。通过预活化、分层纳米片结构、双金属协同作用和碳保护，CoFeP/NF电催化剂表现出良好的双功能OER/HER性能。对于碱性OER，最佳CoFeP/NF需要235和440 mV的过电位才能分别达到10和2000 mA cm−2的电流密度。与密度泛函理论预测一致，CoFeP/NF也表现出高碱性HER活性，需要79 mV的过电位才能达到10 mA cm−2。组装的CoFeP/NF||CoFeP/NF电解槽在~ 200 mA cm−2下保持1100 h的稳定运行。综合机理，包括预活化机制，反应动力学和稳定性的起源，已经通过理论计算和原位/非原位实验表征的结合进行了细致的研究。这些发现为合理设计工业电流密度水分解的高效电催化剂提供了一种通用策略。
{"title":"Stable and efficient bifunctional cobalt-based phosphides for industrial-current water splitting: From multi-strategy engineering to mechanistic insights","authors":"Haiyu Yao , Heng Zhang , Xuerong Shi, Shengming Zhang, Min Zhu, Haichao Xiong, Shusheng Xu","doi":"10.1016/j.jcat.2026.116703","DOIUrl":"10.1016/j.jcat.2026.116703","url":null,"abstract":"<div><div>In the context of industrial-current density water electrolysis, material stability and catalytic activity remain critical challenges. Herein, a CoFeP/NF electrocatalyst enabled by pre-activation, hierarchical nanosheet architecture, bimetallic synergy, and carbon protection demonstrates good bifunctional OER/HER performance. The optimal CoFeP/NF requires overpotentials of 235 and 440 mV to achieve current densities of 10 and 2000 mA cm<sup>−2</sup> for alkaline OER, respectively. In line with density-functional theory predictions, the CoFeP/NF also exhibits high alkaline HER activity, demanding an overpotential of 79 mV to reach 10 mA cm<sup>−2</sup>. The assembled CoFeP/NF||CoFeP/NF electrolyzer maintains stable operation for 1100 h at ∼200 mA cm<sup>−2</sup>. The comprehensive mechanism, encompassing the pre-activation mechanism, reaction kinetics, and origin of stability, has been meticulously investigated via the combination of theoretical calculations and in/ex-situ experimental characterizations. The findings offer a universal strategy for the rational design of efficient electrocatalysts for industrial-current–density water splitting.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116703"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145993300","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-16DOI: 10.1016/j.jcat.2026.116698
Zhenke Fan , Haiping Li , Kai Gao , Quanhua Deng , Yuguo Xia , Shu Liu , Yunbo Zang , Wanguo Hou
Oxygen vacancy (Ov)-containing semiconductors hold great promise for photocatalytic nitrogen fixation, as Ovs serve as efficient N2 activation centers. However, the low photocatalytic stability of Ovs has often been overlooked, and few strategies have been explored to enhance their stability. Moreover, methods to effectively create Ovs are still under investigation. Herein, crystalline structure transformation from BiOBr microplates to hierarchical Bi2MoO6 microplates consisting of sharp-end nanobelts was found to facilitate creation of Ovs in Bi2MoO6 during mannitol reduction. The Ov-containing Bi2MoO6 (Ov-BMO) exhibits improved photocatalytic nitrogen fixation activity but low stability in pure water. To enhance the stability and activity, the Ov-BMO/α-Co(OH)2 heterojunction was constructed to spatially separate Ovs and photogenerated holes and exhibits a solar-to-chemical conversion efficiency of 0.1% and an apparent quantum yield of 4.6% at 420 nm, which are among the top of the reported values. This work offers effective strategies for creating and stabilizing Ovs in Bi2MoO6 to boost photocatalytic nitrogen fixation.
{"title":"Structural transformation promoted oxygen vacancy creation and spatial separation of vacancies and holes in bismuth molybdate boost photocatalytic nitrogen fixation and stability","authors":"Zhenke Fan , Haiping Li , Kai Gao , Quanhua Deng , Yuguo Xia , Shu Liu , Yunbo Zang , Wanguo Hou","doi":"10.1016/j.jcat.2026.116698","DOIUrl":"10.1016/j.jcat.2026.116698","url":null,"abstract":"<div><div>Oxygen vacancy (Ov)-containing semiconductors hold great promise for photocatalytic nitrogen fixation, as Ovs serve as efficient N<sub>2</sub> activation centers. However, the low photocatalytic stability of Ovs has often been overlooked, and few strategies have been explored to enhance their stability. Moreover, methods to effectively create Ovs are still under investigation. Herein, crystalline structure transformation from BiOBr microplates to hierarchical Bi<sub>2</sub>MoO<sub>6</sub> microplates consisting of sharp-end nanobelts was found to facilitate creation of Ovs in Bi<sub>2</sub>MoO<sub>6</sub> during mannitol reduction. The Ov-containing Bi<sub>2</sub>MoO<sub>6</sub> (Ov-BMO) exhibits improved photocatalytic nitrogen fixation activity but low stability in pure water. To enhance the stability and activity, the Ov-BMO/α-Co(OH)<sub>2</sub> heterojunction was constructed to spatially separate Ovs and photogenerated holes and exhibits a solar-to-chemical conversion efficiency of 0.1% and an apparent quantum yield of 4.6% at 420 nm, which are among the top of the reported values. This work offers effective strategies for creating and stabilizing Ovs in Bi<sub>2</sub>MoO<sub>6</sub> to boost photocatalytic nitrogen fixation.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116698"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995785","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-06DOI: 10.1016/j.jcat.2026.116677
Yuyong Zhang , Yuanjun Zhao , Yuanyuan Zhu , Yudi Wu , Zhaozhan Wang , Jinglin Mu , Yong Yang
The integration of superior homogeneous catalytic activity with the practical advantages of facile separation and robust recyclability of heterogeneous systems remains a grand challenge. Here, we report a heterogenized bidentate phosphine ligand, constructed by integrating commercial Xantphos into a hypercrosslinked porous polymer, as a versatile platform for Pd-catalyzed alkoxycarbonylation. The tailored polymer, featuring a high surface area, hierarchical pores, and chemical robustness, provides privileged coordination microenvironments. It empowers highly efficient alkoxycarbonylation of diverse alkenes with various alcohols, including monoalcohols, diols, and polyols, to produce valuable esters with activity and selectivity comparable to its homogeneous molecular counterpart. Moreover, the catalytic system enables the in-situ formation of a robust Pd catalyst, wherein Pd nanoparticles are stabilized and uniformly dispersed via strong Pd-P coordination. This resulting catalyst demonstrates exceptional durability, being readily recycled over ten times without significant degradation in performance. This work pioneers a versatile platform for ligand immobilization that effectively bridges homogeneous efficiency with heterogeneous durability, unlocking efficient and sustainable pathways for carbonylation and other ligand-mediate transformations.
{"title":"Xantphos-derived porous polymer: a robust solid-state ligand for efficient Pd-catalyzed alkoxycarbonylation of alkenes from mono-alcohols to polyols","authors":"Yuyong Zhang , Yuanjun Zhao , Yuanyuan Zhu , Yudi Wu , Zhaozhan Wang , Jinglin Mu , Yong Yang","doi":"10.1016/j.jcat.2026.116677","DOIUrl":"10.1016/j.jcat.2026.116677","url":null,"abstract":"<div><div>The integration of superior homogeneous catalytic activity with the practical advantages of facile separation and robust recyclability of heterogeneous systems remains a grand challenge. Here, we report a heterogenized bidentate phosphine ligand, constructed by integrating commercial Xantphos into a hypercrosslinked porous polymer, as a versatile platform for Pd-catalyzed alkoxycarbonylation. The tailored polymer, featuring a high surface area, hierarchical pores, and chemical robustness, provides privileged coordination microenvironments. It empowers highly efficient alkoxycarbonylation of diverse alkenes with various alcohols, including monoalcohols, diols, and polyols, to produce valuable esters with activity and selectivity comparable to its homogeneous molecular counterpart. Moreover, the catalytic system enables the in-situ formation of a robust Pd catalyst, wherein Pd nanoparticles are stabilized and uniformly dispersed via strong Pd-P coordination. This resulting catalyst demonstrates exceptional durability, being readily recycled over ten times without significant degradation in performance. This work pioneers a versatile platform for ligand immobilization that effectively bridges homogeneous efficiency with heterogeneous durability, unlocking efficient and sustainable pathways for carbonylation and other ligand-mediate transformations.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116677"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145924007","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-23DOI: 10.1016/j.jcat.2026.116713
Meng Xu , Zhongliang Tang , Yue Wu , Menglin Xie , Biao Meng , Xiao Chi , Xiaojiang Yu , Xiaoling Liu , Shibo Xi , Yu Zhou , Jun Wang
Hydrogen borrowing amination provides a sustainable alcohol-based N-alkylation method for the amine synthesis and functionalization, yet the development of non-noble metal catalysts that are effective under additive- and solvent-free conditions remains a huge challenge. Herein, we report a Cobalt (Co)-containing zeolite, Co@Beta, prepared by directly encapsulating defect Co sites within BEA framework via an acid co-hydrolysis route. Co@Beta shows excellent catalytic performance in the N-alkylation of benzyl alcohol with aniline, achieving > 92% yield and a turnover frequency (TOF) of 466 h−1 without external solvent or additive. The catalyst is stable during the recycling amination and extendable to the amination between various aromatic alcohols and amines. In situ spectroscopic analysis, theoretical calculations, as well as step-by-step comparison with post-loaded analogues, reveal that defect Co sites within Co@Beta are active centers, thereby lowering the energy barrier for the rate-determining dehydrogenation step and underpinning the superior amination performance.
{"title":"BEA zeolite encapsulated defective Co sites for solvent- and additive-free N-alkylation of amines with aromatic alcohols","authors":"Meng Xu , Zhongliang Tang , Yue Wu , Menglin Xie , Biao Meng , Xiao Chi , Xiaojiang Yu , Xiaoling Liu , Shibo Xi , Yu Zhou , Jun Wang","doi":"10.1016/j.jcat.2026.116713","DOIUrl":"10.1016/j.jcat.2026.116713","url":null,"abstract":"<div><div>Hydrogen borrowing amination provides a sustainable alcohol-based N-alkylation method for the amine synthesis and functionalization, yet the development of non-noble metal catalysts that are effective under additive- and solvent-free conditions remains a huge challenge. Herein, we report a Cobalt (Co)-containing zeolite, Co@Beta, prepared by directly encapsulating defect Co sites within BEA framework <em>via</em> an acid co-hydrolysis route. Co@Beta shows excellent catalytic performance in the N-alkylation of benzyl alcohol with aniline, achieving > 92% yield and a turnover frequency (TOF) of 466 h<sup>−1</sup> without external solvent or additive. The catalyst is stable during the recycling amination and extendable to the amination between various aromatic alcohols and amines. <em>In situ</em> spectroscopic analysis, theoretical calculations, as well as step-by-step comparison with post-loaded analogues, reveal that defect Co sites within Co@Beta are active centers, thereby lowering the energy barrier for the rate-determining dehydrogenation step and underpinning the superior amination performance.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116713"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146033865","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-27DOI: 10.1016/j.jcat.2026.116722
Jiwoo Kim , Dong Hwan Kim , Seungki Hong , Tae Hoon Seo , Jaegeun Lee
As the demand for precisely tailored carbon nanotube (CNT) properties increases, catalyst design becomes increasingly important. In the field of catalysis, metal–support interaction (MSI) has been recognized as a key strategy for tuning catalyst performance. To better understand how MSI affects CNT synthesis, this study investigates cobalt-based catalysts supported on Al2O3 and MgO. CNTs synthesized using the Co/MgO exhibited higher crystallinity and broader diameter distribution than those synthesized using Co/Al2O3. Detailed characterization—including X-ray analyses, transmission electron microscopy, and temperature-programmed reduction—revealed that both catalysts exhibited MSI accompanied by compositional reconstruction, but through different mechanisms: Co/Al2O3 formed compounds, while Co/MgO developed solid solutions. Based on these findings, we proposed distinct mechanisms of metal nanoparticle formation to explain the different interphase formation behavior observed in the two catalyst systems. Utilizing this hypothesis, formation of solid solution in the Co/MgO catalyst was regulated by adjusting the calcination temperature, and enhanced solid solution formation promoted preferential growth of single-walled CNTs (SWCNTs) under specific conditions. Under these optimized Co/MgO conditions, the CNT product achieved ∼10% carbon yield, an IG/ID ratio of 4.5 ± 1.1, a TGA decomposition peak at 531.87 °C indicating high thermal stability, and facile purification leaving only 1.5% residual mass. Overall, this work highlights how different types of MSI—compound formation versus solid solution formation—can lead to fundamentally distinct CNT growth behaviors, providing new insights for the rational design of catalysts for SWCNT production.
{"title":"Understanding metal-support interaction for single-walled carbon nanotube synthesis: a comparative study of Co on MgO and Al2O3","authors":"Jiwoo Kim , Dong Hwan Kim , Seungki Hong , Tae Hoon Seo , Jaegeun Lee","doi":"10.1016/j.jcat.2026.116722","DOIUrl":"10.1016/j.jcat.2026.116722","url":null,"abstract":"<div><div>As the demand for precisely tailored carbon nanotube (CNT) properties increases, catalyst design becomes increasingly important. In the field of catalysis, metal–support interaction (MSI) has been recognized as a key strategy for tuning catalyst performance. To better understand how MSI affects CNT synthesis, this study investigates cobalt-based catalysts supported on Al<sub>2</sub>O<sub>3</sub> and MgO. CNTs synthesized using the Co/MgO exhibited higher crystallinity and broader diameter distribution than those synthesized using Co/Al<sub>2</sub>O<sub>3</sub>. Detailed characterization—including X-ray analyses, transmission electron microscopy, and temperature-programmed reduction—revealed that both catalysts exhibited MSI accompanied by compositional reconstruction, but through different mechanisms: Co/Al<sub>2</sub>O<sub>3</sub> formed compounds, while Co/MgO developed solid solutions. Based on these findings, we proposed distinct mechanisms of metal nanoparticle formation to explain the different interphase formation behavior observed in the two catalyst systems. Utilizing this hypothesis, formation of solid solution in the Co/MgO catalyst was regulated by adjusting the calcination temperature, and enhanced solid solution formation promoted preferential growth of single-walled CNTs (SWCNTs) under specific conditions. Under these optimized Co/MgO conditions, the CNT product achieved ∼10% carbon yield, an <em>I</em><sub>G</sub>/<em>I</em><sub>D</sub> ratio of 4.5 ± 1.1, a TGA decomposition peak at 531.87 °C indicating high thermal stability, and facile purification leaving only 1.5% residual mass. Overall, this work highlights how different types of MSI—compound formation versus solid solution formation—can lead to fundamentally distinct CNT growth behaviors, providing new insights for the rational design of catalysts for SWCNT production.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116722"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146072539","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2025-12-31DOI: 10.1016/j.jcat.2025.116663
Ye Xu , Timm McNeese
Sulfonamides are a group of synthetic compounds widely used in human and veterinarian medicine (a.k.a. sulfa drugs) and can accumulate in the environment. We show theoretically that ceria can catalyze the hydrolysis of sulfonamides via S − N bond scission over a pair of Ce-O lattice sites, where Olatt attacks the S center and displaces the N center in a nucleophilic substitution, yielding a primary amine and a sulfonic acid as products. Our calculations shed light on how different substituents on the S and N centers affect S − N bond scission by comparing non-aromatic vs. aromatic groups, homo- vs. heterocyclic aromaticity, and further functionalization of the aromatic groups. Stabilizing the S and N centers is found to have the opposite effects on the facility of S -− N bond scission. The desorption of sulfonic acid is strongly endothermic in the gas phase but is calculated to be facilitated by solvation effects when sulfonic acid undergoes acid-base titration with the amine product to form an oxyanion and a pyridinium cation, or when it self-ionizes to a zwitterion.
{"title":"Theoretical investigation of decomposition and hydrolysis of sulfonamides on CeO2(111)","authors":"Ye Xu , Timm McNeese","doi":"10.1016/j.jcat.2025.116663","DOIUrl":"10.1016/j.jcat.2025.116663","url":null,"abstract":"<div><div>Sulfonamides are a group of synthetic compounds widely used in human and veterinarian medicine (a.k.a. sulfa drugs) and can accumulate in the environment. We show theoretically that ceria can catalyze the hydrolysis of sulfonamides via S − N bond scission over a pair of Ce-O lattice sites, where O<sub>latt</sub> attacks the S center and displaces the N center in a nucleophilic substitution, yielding a primary amine and a sulfonic acid as products. Our calculations shed light on how different substituents on the S and N centers affect S − N bond scission by comparing non-aromatic vs. aromatic groups, homo- vs. heterocyclic aromaticity, and further functionalization of the aromatic groups. Stabilizing the S and N centers is found to have the opposite effects on the facility of S -− N bond scission. The desorption of sulfonic acid is strongly endothermic in the gas phase but is calculated to be facilitated by solvation effects when sulfonic acid undergoes acid-base titration with the amine product to form an oxyanion and a pyridinium cation, or when it self-ionizes to a zwitterion.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116663"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895324","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-16DOI: 10.1016/j.jcat.2026.116702
Qianqian Shi , Keke He , Zhile Dang , Jing Zhang , Donghui Wei , Yu Lan
Discovering new radical generation mechanism and understanding origin of chemoselectivity of transformation reactions between the highly active radicals have been and continue to be the hot topics in radical chemistry. Different from the generally proposed single-electron transfer (SET) mechanism, the electron transfer along bond transformation (ETBT) mechanism has been suggested to be also possible and general for the radical reactions. To confirm this issue, the possible ETBT mechanisms and the theoretical method for chemoselectivity prediction of N-heterocyclic carbene (NHC)-catalyzed radical relay reactions have been systematically investigated by performing density functional theory (DFT) calculations. Herein, origin of chemoselectivity for these kinds of reactions has been explored by the distortion energy analysis, and a good linear relationship between the distortion energy (ΔEdist‡) and spin population change (Δe) of the radical species has been discovered for the first time. Furthermore, the Fukui function vector index has been successfully employed to predict chemical selectivity in radical relay reactions.
{"title":"Prediction on origin of chemoselectivity for N-Heterocyclic carbene (NHC)-catalyzed radical relay reactions","authors":"Qianqian Shi , Keke He , Zhile Dang , Jing Zhang , Donghui Wei , Yu Lan","doi":"10.1016/j.jcat.2026.116702","DOIUrl":"10.1016/j.jcat.2026.116702","url":null,"abstract":"<div><div>Discovering new radical generation mechanism and understanding origin of chemoselectivity of transformation reactions between the highly active radicals have been and continue to be the hot topics in radical chemistry. Different from the generally proposed single-electron transfer (SET) mechanism, the electron transfer along bond transformation (ETBT) mechanism has been suggested to be also possible and general for the radical reactions. To confirm this issue, the possible ETBT mechanisms and the theoretical method for chemoselectivity prediction of N-heterocyclic carbene (NHC)-catalyzed radical relay reactions have been systematically investigated by performing density functional theory (DFT) calculations. Herein, origin of chemoselectivity for these kinds of reactions has been explored by the distortion energy analysis, and a good linear relationship between the distortion energy (Δ<em>E</em><sub>dist</sub><sup>‡</sup>) and spin population change (Δ<em>e</em>) of the radical species has been discovered for the first time. Furthermore, the Fukui function vector index has been successfully employed to predict chemical selectivity in radical relay reactions.</div></div>","PeriodicalId":346,"journal":{"name":"Journal of Catalysis","volume":"455 ","pages":"Article 116702"},"PeriodicalIF":6.5,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145995784","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-30DOI: 10.1016/j.jcat.2026.116718
Zhixian Bao , Huibin Liu , Yizhou Zhang , Zhiheng Wang , Hao Li , Haoquan Hu
Ammonia decomposition is considered an ideal carbon-free pathway to hydrogen production. However, the limited catalytic activity of non-noble metal catalysts for ammonia decomposition remains a major barrier to their industrial deployment. Here, we developed a modulation strategy that simultaneously tunes the structural and electronic properties of Ni-based catalysts to improve their catalytic performance. Yttrium (Y) was introduced as a dopant via a citrate sol–gel auto-combustion method into Ni/CeO2, enabling compositionally controlled Y incorporation over the electron–defect landscape. This method yields a well-defined Ni1Ce1-xYxOα structure, in which Y3+, with its different ionic radius from Ce4+, is homogeneously incorporated into the CeO2 lattice to form a solid solution, generating abundant and stable surface oxygen vacancies and modulating the electronic environment of Ni active sites. Among the Ni1Ce1-xYxOα catalysts prepared, Ni1Ce0.5Y0.5Oα exhibits the highest activity, achieving 84% NH3 conversion at 550 °C (GHSV = 30000 mL·gcat-1·h−1) and a H2 production rate of 1687 ± 14 mmol·gcat-1·h−1, along with robust thermal stability. The calculated results suggest that Y doping decreases the formation energy of oxygen vacancies and perturbs the local electronic environment, which enhances electron transfer to the Ni active sites, increasing Ni valence electron density. N associative desorption as the rate-determining step (RDS) was determined at Ni1Ce0.5Y0.5Oα, in which the electronic modulation, in synergy with surface oxygen vacancies, reduces the energy barrier for N association by 0.21 eV and renders this step thermodynamically favorable. This work demonstrates that the strategic use of Y as a dual-functional promoter enhances the catalytic activity in ammonia decomposition.
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