Pub Date : 2026-02-11DOI: 10.1016/S1872-2067(26)64954-6
Jun Yu , Yuzhuang Fu , Binju Wang , Zexing Cao
NvfI, a 2-oxoglutarate (2OG)-dependent non-heme Fe(II) dioxygenase, catalyzes the formation of endoperoxide-containing fumigatonoid A, a key step in the biosynthesis of novofumigatonin. However, the molecular mechanism underlying these processes remains elusive. To address this, extensive MD simulations and QM/MM calculations were performed. Our computational study suggests that the nascent Fe(IV)-oxo species is not able to conduct the H-abstraction from the target C13–H directly. Instead, the Fe(IV)-oxo species performs the H-abstraction from the proximal C7′–H, and the resulting C7′-centered radical can serve as the radical relay for the further oxidation of the distal C13–H bond. Such radical relay mechanism not only remarkably reduces the barrier for the activation of the distal C13–H bond, but also efficiently prevents the undesired OH-rebound pathway. Regarding the final OH-rebound at the C3′ site, our study suggests that the dynamic reorganization of the active site reduces the distance between the substrate radical and the Fe(III)-OH, facilitating the efficient OH-rebound at the C3′ site. These computational findings offer valuable insights for NvfI-catalyzed biosynthesis of endoperoxide.
{"title":"Enzymatic formation of endoperoxide by Fe(II)/α-KG-dependent dioxygenase NvfI: Insight into substrate-assisted activation of the distant C–H bond and incorporation of two oxygen molecules","authors":"Jun Yu , Yuzhuang Fu , Binju Wang , Zexing Cao","doi":"10.1016/S1872-2067(26)64954-6","DOIUrl":"10.1016/S1872-2067(26)64954-6","url":null,"abstract":"<div><div>NvfI, a 2-oxoglutarate (2OG)-dependent non-heme Fe(II) dioxygenase, catalyzes the formation of endoperoxide-containing fumigatonoid A, a key step in the biosynthesis of novofumigatonin. However, the molecular mechanism underlying these processes remains elusive. To address this, extensive MD simulations and QM/MM calculations were performed. Our computational study suggests that the nascent Fe(IV)-oxo species is not able to conduct the H-abstraction from the target C13–H directly. Instead, the Fe(IV)-oxo species performs the H-abstraction from the proximal C7′–H, and the resulting C7′-centered radical can serve as the radical relay for the further oxidation of the distal C13–H bond. Such radical relay mechanism not only remarkably reduces the barrier for the activation of the distal C13–H bond, but also efficiently prevents the undesired OH-rebound pathway. Regarding the final OH-rebound at the C3′ site, our study suggests that the dynamic reorganization of the active site reduces the distance between the substrate radical and the Fe(III)-OH, facilitating the efficient OH-rebound at the C3′ site. These computational findings offer valuable insights for NvfI-catalyzed biosynthesis of endoperoxide.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"82 ","pages":"Pages 363-377"},"PeriodicalIF":17.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146154255","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 : 2026-02-11DOI: 10.1016/S1872-2067(25)64877-7
Lan Jiang , Yang Zeng , Jianhua Chen , Songhai Xie , Yan Pei , Weiming Hua , Shirun Yan , Xueying Chen , Minghua Qiao , Baoning Zong
Crystal plane engineering is a powerful tool to optimize catalytic efficiency in heterogeneous catalysis. However, there is a surprising dearth in the exploration of the support plane effect on glycerol hydrogenolysis to 1,3-propanediol (1,3-PDO). In this work, we synthesized prism-shaped rutile TiO2 nanorods (RTNR-T) with tunable {110}/{111} exposure ratios by varying the hydrothermal temperature. The proportion of the {110} planes is identified to exhibit a volcano-like relationship with the hydrothermal temperature. The concentrations of oxygen vacancies and Ti3+ sites on both the RTNR-T nanorods and Pt-WOx/RTNR-T catalysts are positively correlated with the proportion of the {110} planes. Coherently, the Pt dispersion and surface acidity on the catalysts are parallel to the proportion of the {110} planes, attributable to the high defect density that facilitates the anchorage of Pt and promotes WOx-support interaction. In glycerol hydrogenolysis, the Pt-WOx/RTNR-453 catalyst with the highest proportion of the {110} planes displayed the best catalytic performance, with glycerol conversion and 1,3-PDO selectivity of 96.7% and 60.6%, respectively, affording an outstanding 1,3-PDO yield of 58.6% and excellent recyclability. Density functional theory calculations demonstrated that the presence of defects markedly reduced the dissociation and diffusion barriers, which greatly boosts hydrogen spillover to WOx for in-situ Brönsted acid site generation and oxocarbenium intermediate hydrogenation. This work offers a robust design principle based on the crystal plane-defect-activity correlation for high-performance glycerol hydrogenolysis catalysts.
{"title":"Crystal plane engineering of rutile TiO2 nanorods: Boosting Pt-WOx catalyzed glycerol hydrogenolysis to 1,3-propanediol via {110} plane-associated defects","authors":"Lan Jiang , Yang Zeng , Jianhua Chen , Songhai Xie , Yan Pei , Weiming Hua , Shirun Yan , Xueying Chen , Minghua Qiao , Baoning Zong","doi":"10.1016/S1872-2067(25)64877-7","DOIUrl":"10.1016/S1872-2067(25)64877-7","url":null,"abstract":"<div><div>Crystal plane engineering is a powerful tool to optimize catalytic efficiency in heterogeneous catalysis. However, there is a surprising dearth in the exploration of the support plane effect on glycerol hydrogenolysis to 1,3-propanediol (1,3-PDO). In this work, we synthesized prism-shaped rutile TiO<sub>2</sub> nanorods (RTNR-T) with tunable {110}/{111} exposure ratios by varying the hydrothermal temperature. The proportion of the {110} planes is identified to exhibit a volcano-like relationship with the hydrothermal temperature. The concentrations of oxygen vacancies and Ti<sup>3+</sup> sites on both the RTNR-T nanorods and Pt-WO<sub><em>x</em></sub>/RTNR-T catalysts are positively correlated with the proportion of the {110} planes. Coherently, the Pt dispersion and surface acidity on the catalysts are parallel to the proportion of the {110} planes, attributable to the high defect density that facilitates the anchorage of Pt and promotes WO<sub><em>x</em></sub>-support interaction. In glycerol hydrogenolysis, the Pt-WO<sub><em>x</em></sub>/RTNR-453 catalyst with the highest proportion of the {110} planes displayed the best catalytic performance, with glycerol conversion and 1,3-PDO selectivity of 96.7% and 60.6%, respectively, affording an outstanding 1,3-PDO yield of 58.6% and excellent recyclability. Density functional theory calculations demonstrated that the presence of defects markedly reduced the dissociation and diffusion barriers, which greatly boosts hydrogen spillover to WO<sub><em>x</em></sub> for <em>in-situ</em> Brönsted acid site generation and oxocarbenium intermediate hydrogenation. This work offers a robust design principle based on the crystal plane-defect-activity correlation for high-performance glycerol hydrogenolysis catalysts.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"82 ","pages":"Pages 312-326"},"PeriodicalIF":17.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146154285","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 : 2026-02-11DOI: 10.1016/S1872-2067(25)64888-1
Haoyu Zhang , Lujie Jin , Tanghong Zheng , Xinran Qiu , Yang Liu , Dongyun Chen , Qingfeng Xu , Youyong Li , Jianmei Lu
The electrocatalytic CO2 reduction reaction (CO2RR) offers a promising sustainable route for producing high-value C2+ chemicals and fuels by using renewable electricity. However, boosting C2+ product yields has been significantly hindered by insufficient *CO intermediate generation in confined spaces and limited activity of sites for subsequent hydrogenation and C-C coupling processes. Herein, we introduce an efficient strategy that involves carbene dual-function bridging of Ag-Cu sites to enable *CO pooling and facilitate *COCHO coupling. As a result, a remarkable C2+ Faradaic efficiency of 80.3% at 400 mA cm‒2 was achieved. In-situ surface-enhanced Raman spectroscopy, in-situ attenuated total reflection surface-enhanced infrared absorption spectroscopy, and density functional theory calculations collectively uncover the underlying mechanism. Carbene facilitates CO spillover from Ag to Cu sites, modulates the electronic structure of Cu, stabilizes CO intermediates, and reduces the energy barrier for CO hydrogenation. These effects synergistically enhance C-C coupling, thereby improving the Faradaic efficiency for C2+ product formation.
电催化二氧化碳还原反应（CO2RR）为利用可再生电力生产高价值的C2+化学品和燃料提供了一条有前途的可持续途径。然而，由于在密闭空间中产生的*CO中间体不足，以及后续加氢和C-C偶联过程中位点的活性有限，C2+产物产量的提高受到了严重阻碍。在此，我们引入了一种有效的策略，该策略涉及Ag-Cu位点的碳双功能桥接，以实现CO池化和促进COCHO耦合。结果表明，在400 mA cm-2下，C2+法拉第效率达到了80.3%。原位表面增强拉曼光谱、原位衰减全反射表面增强红外吸收光谱和密度泛函理论计算共同揭示了潜在的机制。卡宾促进CO从Ag向Cu位点的溢出，调节Cu的电子结构，稳定CO中间体，降低CO加氢的能垒。这些效应协同增强了C-C耦合，从而提高了C2+产物形成的法拉第效率。
{"title":"Carbene dual-function bridging of Ag-Cu sites enables *CO pooling for *COCHO coupling with > 80% C2+ selectivity in CO2 electroreduction","authors":"Haoyu Zhang , Lujie Jin , Tanghong Zheng , Xinran Qiu , Yang Liu , Dongyun Chen , Qingfeng Xu , Youyong Li , Jianmei Lu","doi":"10.1016/S1872-2067(25)64888-1","DOIUrl":"10.1016/S1872-2067(25)64888-1","url":null,"abstract":"<div><div>The electrocatalytic CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) offers a promising sustainable route for producing high-value C<sub>2+</sub> chemicals and fuels by using renewable electricity. However, boosting C<sub>2+</sub> product yields has been significantly hindered by insufficient *CO intermediate generation in confined spaces and limited activity of sites for subsequent hydrogenation and C-C coupling processes. Herein, we introduce an efficient strategy that involves carbene dual-function bridging of Ag-Cu sites to enable *CO pooling and facilitate *COCHO coupling. As a result, a remarkable C<sub>2+</sub> Faradaic efficiency of 80.3% at 400 mA cm<sup>‒2</sup> was achieved. <em>In-situ</em> surface-enhanced Raman spectroscopy, <em>in-situ</em> attenuated total reflection surface-enhanced infrared absorption spectroscopy, and density functional theory calculations collectively uncover the underlying mechanism. Carbene facilitates CO spillover from Ag to Cu sites, modulates the electronic structure of Cu, stabilizes CO intermediates, and reduces the energy barrier for CO hydrogenation. These effects synergistically enhance C-C coupling, thereby improving the Faradaic efficiency for C<sub>2+</sub> product formation.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"82 ","pages":"Pages 105-114"},"PeriodicalIF":17.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146154352","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 : 2026-02-11DOI: 10.1016/S1872-2067(25)64917-5
Jianchao Yue , Yu Zhang , Qianqian Xiong, Wei Luo
The rational design of high-performance electrocatalysts for alkaline hydrogen oxidation reaction (HOR) is significant to the widespread commercialization of alkaline exchange membrane fuel cells. However, precise regulation of proton adsorption states and interfacial transfer kinetics at the catalytic interface remains a significant challenge in advancing HOR under alkaline conditions. Herein, we demonstrate that construction of phosphorus-doped carbon-coated nickel (Ni) catalyst (Ni@PC) featuring the bridging oxygen structures (Ni–O–C/P) enables rapid desorption of adsorbed hydrogen species and dynamic reconstruction of interfacial hydrogen–bond network. Density functional theory calculations reveal that the Ni–O–P configuration induces a downward shift in the d-band center of Ni, thereby weakening hydrogen binding energy (HBE). Furthermore, the bridging oxygen atoms facilitate the formation of hydrogen bonds with interfacial water molecules, optimizing the proton transfer pathway. In-situ surface-enhanced infrared absorption spectroscopy confirms that the Ni–O–P structure effectively converts weakly hydrogen-bonded water into strongly hydrogen-bonded water, enhancing the connectivity of hydrogen-bond network and facilitating efficient proton transfer. This work successfully achieves optimization of proton dynamics during the alkaline HOR progress, while also providing a strategic framework for the rational design of advanced carbon-coated electrocatalysts.
合理设计高性能碱性氢氧化反应电催化剂对碱性交换膜燃料电池的广泛商业化具有重要意义。然而，在碱性条件下，质子吸附状态和催化界面转移动力学的精确调节仍然是推进HOR的重大挑战。在此，我们证明了具有桥接氧结构（Ni - o -c /P）的磷掺杂碳包覆镍（Ni）催化剂（Ni@PC）的构建能够快速解吸吸附的氢，并动态重建界面氢键网络。密度泛函理论计算表明，Ni - o - p结构导致Ni的d带中心向下移动，从而减弱氢结合能（HBE）。此外，桥接氧原子促进了与界面水分子形成氢键，优化了质子转移途径。原位表面增强红外吸收光谱证实，Ni-O-P结构有效地将弱氢键水转化为强氢键水，增强了氢键网络的连通性，促进了质子的高效转移。这项工作成功地实现了碱性HOR过程中质子动力学的优化，同时也为合理设计先进的碳包覆电催化剂提供了战略框架。
{"title":"Bridging oxygen-induced hydrogen-bond network reconstruction in phosphorus-doped carbon-coated Ni catalyst enhances alkaline hydrogen oxidation electrocatalysis","authors":"Jianchao Yue , Yu Zhang , Qianqian Xiong, Wei Luo","doi":"10.1016/S1872-2067(25)64917-5","DOIUrl":"10.1016/S1872-2067(25)64917-5","url":null,"abstract":"<div><div>The rational design of high-performance electrocatalysts for alkaline hydrogen oxidation reaction (HOR) is significant to the widespread commercialization of alkaline exchange membrane fuel cells. However, precise regulation of proton adsorption states and interfacial transfer kinetics at the catalytic interface remains a significant challenge in advancing HOR under alkaline conditions. Herein, we demonstrate that construction of phosphorus-doped carbon-coated nickel (Ni) catalyst (Ni@PC) featuring the bridging oxygen structures (Ni–O–C/P) enables rapid desorption of adsorbed hydrogen species and dynamic reconstruction of interfacial hydrogen–bond network. Density functional theory calculations reveal that the Ni–O–P configuration induces a downward shift in the <em>d</em>-band center of Ni, thereby weakening hydrogen binding energy (HBE). Furthermore, the bridging oxygen atoms facilitate the formation of hydrogen bonds with interfacial water molecules, optimizing the proton transfer pathway. <em>In-situ</em> surface-enhanced infrared absorption spectroscopy confirms that the Ni–O–P structure effectively converts weakly hydrogen-bonded water into strongly hydrogen-bonded water, enhancing the connectivity of hydrogen-bond network and facilitating efficient proton transfer. This work successfully achieves optimization of proton dynamics during the alkaline HOR progress, while also providing a strategic framework for the rational design of advanced carbon-coated electrocatalysts.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"82 ","pages":"Pages 144-152"},"PeriodicalIF":17.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146154354","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 : 2026-02-11DOI: 10.1016/S1872-2067(26)64955-8
Wanggang Zhang , Haochen Xie , Hongliang Wang , Rufeng Tian , Lei Liu , Jian Wang , Yiming Liu
This study developed a lattice-matching engineering strategy to construct atomic-level coherent interfaces in hexagonal WO3/TiO2 S-scheme heterojunctions to boost photoelectrocatalytic glycerol (Gly) valorization. Through precise annealing control, hexagonal WO3/TiO2 achieved an ultra-low lattice mismatch (m) of 0.027%, significantly lower than the 2.30% mismatch of its monoclinic counterparts, thus inducing a strong built-in electric field (3.71 eV) and optimized S-scheme charge transfer. These features resulted in 90% suppressed carrier recombination, 2.64-fold extended carrier lifetime, and enhanced secondary hydroxyl adsorption affinity (1.854 eV), collectively steering Gly oxidation toward high-value dihydroxyacetone with 35% selectivity (1.9-fold higher than that of monoclinic systems). The heterojunction also delivered a 21% Gly conversion rate (40% higher than its monoclinic counterparts), while maintaining > 85% total C3-product selectivity and stability over 40 h. This study identified the atomic-scale interface coherence as a critical factor for synchronizing charge dynamics and surface reactions in biomass upgrading.
{"title":"Atomic-level lattice matching in hexagonal WO3/TiO2 S-scheme heterojunctions for high-efficiency selective photoelectrocatalytic glycerol-to-dihydroxyacetone conversion","authors":"Wanggang Zhang , Haochen Xie , Hongliang Wang , Rufeng Tian , Lei Liu , Jian Wang , Yiming Liu","doi":"10.1016/S1872-2067(26)64955-8","DOIUrl":"10.1016/S1872-2067(26)64955-8","url":null,"abstract":"<div><div>This study developed a lattice-matching engineering strategy to construct atomic-level coherent interfaces in hexagonal WO<sub>3</sub>/TiO<sub>2</sub> S-scheme heterojunctions to boost photoelectrocatalytic glycerol (Gly) valorization. Through precise annealing control, hexagonal WO<sub>3</sub>/TiO<sub>2</sub> achieved an ultra-low lattice mismatch (<em>m</em>) of 0.027%, significantly lower than the 2.30% mismatch of its monoclinic counterparts, thus inducing a strong built-in electric field (3.71 eV) and optimized S-scheme charge transfer. These features resulted in 90% suppressed carrier recombination, 2.64-fold extended carrier lifetime, and enhanced secondary hydroxyl adsorption affinity (1.854 eV), collectively steering Gly oxidation toward high-value dihydroxyacetone with 35% selectivity (1.9-fold higher than that of monoclinic systems). The heterojunction also delivered a 21% Gly conversion rate (40% higher than its monoclinic counterparts), while maintaining > 85% total C3-product selectivity and stability over 40 h. This study identified the atomic-scale interface coherence as a critical factor for synchronizing charge dynamics and surface reactions in biomass upgrading.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"82 ","pages":"Pages 161-173"},"PeriodicalIF":17.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146154356","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 : 2026-02-11DOI: 10.1016/S1872-2067(25)64926-6
Run Pan , Abubakar Yusuf , Chengjun Wang , Jianrong Li , Zhiyu Xiao , Shuai Liu , Yidong Zhong , Yong Ren , Zheng Wang , Hainam Do , John L. Zhou , George Zheng Chen , Jun He
Natural gas vehicles (NGVs) offer significant environmental advantages by reducing pollutant emissions, but effective exhaust treatment remains a challenge due to high methane emissions and catalyst deactivation over time. This study introduces a core-shell Pd@CeO2/Al2O3 three-way catalyst (TWC) designed to enhance the efficiency and durability of NGV exhaust treatment. The core-shell structure significantly improves catalytic performance. The optimized Pd@Ce/Al (S-500) catalyst demonstrates excellent low-temperature activity, with T50 values of 336 °C for CH4 and 397 °C for NO. It also achieves remarkable reductions of 113 and 177 °C in the T90 for CH4 and NO conversion, respectively, compared to the non-core-shell counterpart, Pd-Ce/Al (S-500). Characterizations reveal enhanced metal-support interactions, increased oxygen vacancies, and optimized Pd-CeO2 interfaces as key active sites. Density functional theory calculations further demonstrate that the core-shell structure facilitates electron transfer at Pd-CeO2 interfaces and lowers energy barriers for three-way reactions, enhancing catalytic efficiency. Notably, the core-shell Pd@Ce/Al (S-500) catalyst maintains high conversion efficiency for CH4 and NO, with only slight losses (5.5% and 6.6%, respectively) over a 100-h time-on-stream stability test, following 16 h of harsh hydrothermal aging at 800 °C, showcasing its long-term stability. These findings provide a deeper understanding of the role of the core-shell Pd@CeO2 structure in Pd-based TWCs and offer valuable insights for designing durable and efficient catalysts to meet the stringent emission standards of NGVs.
{"title":"Core-shell Pd@CeO2/γ‐Al2O3 catalysts: Boosting efficiency and durability in stoichiometric natural gas vehicle exhaust treatment","authors":"Run Pan , Abubakar Yusuf , Chengjun Wang , Jianrong Li , Zhiyu Xiao , Shuai Liu , Yidong Zhong , Yong Ren , Zheng Wang , Hainam Do , John L. Zhou , George Zheng Chen , Jun He","doi":"10.1016/S1872-2067(25)64926-6","DOIUrl":"10.1016/S1872-2067(25)64926-6","url":null,"abstract":"<div><div>Natural gas vehicles (NGVs) offer significant environmental advantages by reducing pollutant emissions, but effective exhaust treatment remains a challenge due to high methane emissions and catalyst deactivation over time. This study introduces a core-shell Pd@CeO<sub>2</sub>/Al<sub>2</sub>O<sub>3</sub> three-way catalyst (TWC) designed to enhance the efficiency and durability of NGV exhaust treatment. The core-shell structure significantly improves catalytic performance. The optimized Pd@Ce/Al (S-500) catalyst demonstrates excellent low-temperature activity, with <em>T</em><sub>50</sub> values of 336 °C for CH<sub>4</sub> and 397 °C for NO. It also achieves remarkable reductions of 113 and 177 °C in the <em>T</em><sub>90</sub> for CH<sub>4</sub> and NO conversion, respectively, compared to the non-core-shell counterpart, Pd-Ce/Al (S-500). Characterizations reveal enhanced metal-support interactions, increased oxygen vacancies, and optimized Pd-CeO<sub>2</sub> interfaces as key active sites. Density functional theory calculations further demonstrate that the core-shell structure facilitates electron transfer at Pd-CeO<sub>2</sub> interfaces and lowers energy barriers for three-way reactions, enhancing catalytic efficiency. Notably, the core-shell Pd@Ce/Al (S-500) catalyst maintains high conversion efficiency for CH<sub>4</sub> and NO, with only slight losses (5.5% and 6.6%, respectively) over a 100-h time-on-stream stability test, following 16 h of harsh hydrothermal aging at 800 °C, showcasing its long-term stability. These findings provide a deeper understanding of the role of the core-shell Pd@CeO<sub>2</sub> structure in Pd-based TWCs and offer valuable insights for designing durable and efficient catalysts to meet the stringent emission standards of NGVs.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"82 ","pages":"Pages 348-362"},"PeriodicalIF":17.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146154256","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 : 2026-02-11DOI: 10.1016/S1872-2067(25)64863-7
Wei Wang , Bin Chen , Ting Li , Zhengchu Chen , Lei Yuan , Qiang Fu , Siping Wei , Xiao-Feng Wu , Dong Yi
Cleavage and reassembly of C–C bonds is a fascinating and challenging strategy to forge complex high-value molecules in an atom- and step-efficient manner. Herein, we disclose a photoredox-catalyzed four-atom skeletal editing strategy, enabling highly selective reassembly of 1,3-diketones into architecturally distinct acylated 1,5-ketoalcohols with excellent atom, step, and redox economy. Notably, this propoxy insertion unit (i.e., three sp3-hybridized carbons and one oxygen atom) is derived from the other two simple and readily available starting materials (i.e., alkene and aldehyde). Experimental studies have elucidated the key intermediate (lactol) and reaction mechanism (radical-radical crossover cyclization/rearrangement), which are distinct from classical De Mayo reaction. More importantly, the rapid construction of high-value-added product γ,δ-unsaturated ketones and dihydropyrans is also achieved via photocatalytic synthesis of acylated 1,5-ketoalcohols/Lewis acid-promoted Wagner-Meerwein rearrangement cascade and photocatalytic formal [2, 2, 2] annulation/MsCl-promoted elimination cascade, respectively.
{"title":"Photoredox-catalyzed four-atom skeletal editing of 1,3-diketones with alkenes and aldehydes","authors":"Wei Wang , Bin Chen , Ting Li , Zhengchu Chen , Lei Yuan , Qiang Fu , Siping Wei , Xiao-Feng Wu , Dong Yi","doi":"10.1016/S1872-2067(25)64863-7","DOIUrl":"10.1016/S1872-2067(25)64863-7","url":null,"abstract":"<div><div>Cleavage and reassembly of C–C bonds is a fascinating and challenging strategy to forge complex high-value molecules in an atom- and step-efficient manner. Herein, we disclose a photoredox-catalyzed four-atom skeletal editing strategy, enabling highly selective reassembly of 1,3-diketones into architecturally distinct acylated 1,5-ketoalcohols with excellent atom, step, and redox economy. Notably, this propoxy insertion unit (<em>i.e</em>., three <em>sp</em><sup>3</sup>-hybridized carbons and one oxygen atom) is derived from the other two simple and readily available starting materials (<em>i.e</em>., alkene and aldehyde). Experimental studies have elucidated the key intermediate (lactol) and reaction mechanism (radical-radical crossover cyclization/rearrangement), which are distinct from classical De Mayo reaction. More importantly, the rapid construction of high-value-added product <em>γ,δ</em>-unsaturated ketones and dihydropyrans is also achieved via photocatalytic synthesis of acylated 1,5-ketoalcohols/Lewis acid-promoted Wagner-Meerwein rearrangement cascade and photocatalytic formal [<span><span>2</span></span>, <span><span>2</span></span>, <span><span>2</span></span>] annulation/MsCl-promoted elimination cascade, respectively.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"82 ","pages":"Pages 212-224"},"PeriodicalIF":17.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146154284","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 : 2026-02-11DOI: 10.1016/S1872-2067(25)64856-X
Xin Xin , Peng Gao , Shenggang Li
Zeolites are important components of catalysts for aromatics synthesis from methanol and CO/CO2. Although generally attributed to their confinement effects, the key reaction steps and the role of methanol or other C1 intermediates remain unclear. Herein, extensive first principles calculations were performed to reveal the mechanism of aromatics formation from light olefins such as propene and methanol within H-ZSM-5 zeolites. Propene was found to undergo chain growth, ring formation, and ring methylation, resulting in various aromatics. Our calculations show that the above steps become increasingly more difficult, so aromatic ring methylation by methanol to form protonated polymethylbenzenes was the most challenging. This can largely be attributed to both the zeolite confinement effect due to the higher spatial demand for the methylation of the aromatic ring than that of the carbon chain by methanol, and the disruption of its aromaticity. Our prediction agrees with the experimentally observed delayed formation of aromatic species, and also explains the improved production of specific aromatics by co-feeding aromatic species to change the hydrocarbon pool composition and suppress the chain growth. Thus, theoretical insights can enable the rational design of better catalysts and processes for the valorization of C1 molecules.
{"title":"Selectivity control mechanism of aromatics formation in C1 catalysis within H-ZSM-5 zeolites","authors":"Xin Xin , Peng Gao , Shenggang Li","doi":"10.1016/S1872-2067(25)64856-X","DOIUrl":"10.1016/S1872-2067(25)64856-X","url":null,"abstract":"<div><div>Zeolites are important components of catalysts for aromatics synthesis from methanol and CO/CO<sub>2</sub>. Although generally attributed to their confinement effects, the key reaction steps and the role of methanol or other C1 intermediates remain unclear. Herein, extensive first principles calculations were performed to reveal the mechanism of aromatics formation from light olefins such as propene and methanol within H-ZSM-5 zeolites. Propene was found to undergo chain growth, ring formation, and ring methylation, resulting in various aromatics. Our calculations show that the above steps become increasingly more difficult, so aromatic ring methylation by methanol to form protonated polymethylbenzenes was the most challenging. This can largely be attributed to both the zeolite confinement effect due to the higher spatial demand for the methylation of the aromatic ring than that of the carbon chain by methanol, and the disruption of its aromaticity. Our prediction agrees with the experimentally observed delayed formation of aromatic species, and also explains the improved production of specific aromatics by co-feeding aromatic species to change the hydrocarbon pool composition and suppress the chain growth. Thus, theoretical insights can enable the rational design of better catalysts and processes for the valorization of C1 molecules.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"82 ","pages":"Pages 301-311"},"PeriodicalIF":17.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146154254","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 : 2026-02-11DOI: 10.1016/S1872-2067(25)64927-8
Syeda Maria Hashmi , Yilin Wang , Nida Rehman , Xinyi Tan , Javier García-Martínez , Ume Aiman , Muhammad Sajid , Zhenyu Sun
Organic electrosynthesis is particularly appealing for transformations that would otherwise be challenging because of its intrinsic ability to synthesize extremely reactive species under mild conditions via anodic oxidation or cathodic reduction. It has sparked much attention as an effective, environmentally friendly synthesis tool because it generates less waste, uses fewer chemicals, and often requires fewer reaction steps than previous procedures. The processes that underpin organic electrosynthesis include functional group interconversion and formation of C−C and C−heteroatom bonds (such as C−N, C−O, C−S, and C−H) through a controlled electrode potential. Some of the strategies mentioned as aiding the overall process optimization include the use of indirect electrosynthesis, paired electrochemical processes, and electrochemical microreactors. Furthermore, the use of electrochemical flow reactors has resulted in accurate reaction control and optimization. This review discusses strategic developments in organic electrosynthesis, focusing on fundamental concepts, novel approaches, and future directions for sustainable chemical manufacturing.
{"title":"Towards sustainable chemistry: Advances, challenges and opportunities in organic electrosynthesis","authors":"Syeda Maria Hashmi , Yilin Wang , Nida Rehman , Xinyi Tan , Javier García-Martínez , Ume Aiman , Muhammad Sajid , Zhenyu Sun","doi":"10.1016/S1872-2067(25)64927-8","DOIUrl":"10.1016/S1872-2067(25)64927-8","url":null,"abstract":"<div><div>Organic electrosynthesis is particularly appealing for transformations that would otherwise be challenging because of its intrinsic ability to synthesize extremely reactive species under mild conditions via anodic oxidation or cathodic reduction. It has sparked much attention as an effective, environmentally friendly synthesis tool because it generates less waste, uses fewer chemicals, and often requires fewer reaction steps than previous procedures. The processes that underpin organic electrosynthesis include functional group interconversion and formation of C−C and C−heteroatom bonds (such as C−N, C−O, C−S, and C−H) through a controlled electrode potential. Some of the strategies mentioned as aiding the overall process optimization include the use of indirect electrosynthesis, paired electrochemical processes, and electrochemical microreactors. Furthermore, the use of electrochemical flow reactors has resulted in accurate reaction control and optimization. This review discusses strategic developments in organic electrosynthesis, focusing on fundamental concepts, novel approaches, and future directions for sustainable chemical manufacturing.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"82 ","pages":"Pages 1-41"},"PeriodicalIF":17.7,"publicationDate":"2026-02-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146154359","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 : 2026-02-01DOI: 10.1016/S1872-2067(25)64904-7
Bolin Yang , Fei Jin , Zhiliang Jin
Rational energy band engineering and the exposure of catalytically active sites critically enhance the efficiency of the hydrogen evolution reaction. In this study, TAPT-TFPT-COF/Mn0.2Cd0.8S composite photocatalysts were prepared by wet impregnation. The energy bands of non-precious-metal sulfide nanorods and a covalent organic framework (COF) were interleaved for effective heterojunction construction, enabling a three-fold enhancement in hydrogen evolution compared to that of the pure Mn0.2Cd0.8S catalyst. The enhanced catalyst performance is attributed to the construction of heterojunctions and the synergistic photothermal dynamics of the flexible monomers under illumination, which facilitates localized charge carrier migration. Furthermore, the hydrogen evolution mechanism in the Mn0.2Cd0.8S/COF composites was elucidated through photoelectrochemical experiments, in-situ irradiation X-ray photoelectron spectroscopy, surface photovoltage measurements, and density functional theory. The loaded organic semiconductor materials were combined with non-precious-metal semiconductors to construct S-scheme heterojunctions with increased hydrophilicity, and the tight combination of Mn0.2Cd0.8S and COF optimized the photogenerated electron utilization efficiency.
{"title":"Efficient photocatalytic hydrogen production by a heterojunction strategy with covalent organic frameworks loaded with non-precious-metal semiconductors","authors":"Bolin Yang , Fei Jin , Zhiliang Jin","doi":"10.1016/S1872-2067(25)64904-7","DOIUrl":"10.1016/S1872-2067(25)64904-7","url":null,"abstract":"<div><div>Rational energy band engineering and the exposure of catalytically active sites critically enhance the efficiency of the hydrogen evolution reaction. In this study, TAPT-TFPT-COF/Mn<sub>0.2</sub>Cd<sub>0.8</sub>S composite photocatalysts were prepared by wet impregnation. The energy bands of non-precious-metal sulfide nanorods and a covalent organic framework (COF) were interleaved for effective heterojunction construction, enabling a three-fold enhancement in hydrogen evolution compared to that of the pure Mn<sub>0.2</sub>Cd<sub>0.8</sub>S catalyst. The enhanced catalyst performance is attributed to the construction of heterojunctions and the synergistic photothermal dynamics of the flexible monomers under illumination, which facilitates localized charge carrier migration. Furthermore, the hydrogen evolution mechanism in the Mn<sub>0.2</sub>Cd<sub>0.8</sub>S/COF composites was elucidated through photoelectrochemical experiments, <em>in-situ</em> irradiation X-ray photoelectron spectroscopy, surface photovoltage measurements, and density functional theory. The loaded organic semiconductor materials were combined with non-precious-metal semiconductors to construct S-scheme heterojunctions with increased hydrophilicity, and the tight combination of Mn<sub>0.2</sub>Cd<sub>0.8</sub>S and COF optimized the photogenerated electron utilization efficiency.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"81 ","pages":"Pages 172-184"},"PeriodicalIF":17.7,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098811","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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