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}
Pub Date : 2026-02-01DOI: 10.1016/S1872-2067(25)64908-4
Liting Huang , Yecheng Zhou , Yongfeng Lun, Qi Wang, Zhaobin Ding, Shuqin Song, Yi Wang
The application of thiolate-protected gold nanoclusters (NCs) for the electrochemical CO2 reduction reaction (CO2RR) has received widespread attentions. In this work, three types of atomically precise [Au25(SR)18]‒ NCs protected by 2-phenylethanethiol (PET), 1-hexanethiol (C6T), and 1-dodecanethiol (C12T), respectively, are employed as model catalysts for CO2RR, where the molecular configuration and length of thiolate ligands are varied. The electrochemical results demonstrate that the [Au25(C12T)18]‒ NC possesses lower activity and selectivity towards CO formation than [Au25(PET)18]‒ and [Au25(C6T)18]‒ NCs. Owing to their identical gold kernels, the differences in electrocatalytic CO2RR performance of these three Au25 NCs can be fully attributed to their distinctions in tail group structure. Density functional theory (DFT) calculations exclude the possible effects on the electronic structures of the active sites exerted by the distinctions in tail group structure, while molecular dynamics (MD) calculations reveal that different orientation modes of tail groups in aqueous solution affect the diffusion of the reactants to active sites. Overall, this work provides a unique perspective on the structure-property relationships for ligand-protected NCs in electrocatalytic CO2RR.
{"title":"Tail group structure effect of ligand-protected gold nanocluster catalysts on electrochemical CO2 reduction","authors":"Liting Huang , Yecheng Zhou , Yongfeng Lun, Qi Wang, Zhaobin Ding, Shuqin Song, Yi Wang","doi":"10.1016/S1872-2067(25)64908-4","DOIUrl":"10.1016/S1872-2067(25)64908-4","url":null,"abstract":"<div><div>The application of thiolate-protected gold nanoclusters (NCs) for the electrochemical CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) has received widespread attentions. In this work, three types of atomically precise [Au<sub>25</sub>(SR)<sub>18</sub>]<sup>‒</sup> NCs protected by 2-phenylethanethiol (PET), 1-hexanethiol (C6T), and 1-dodecanethiol (C12T), respectively, are employed as model catalysts for CO<sub>2</sub>RR, where the molecular configuration and length of thiolate ligands are varied. The electrochemical results demonstrate that the [Au<sub>25</sub>(C12T)<sub>18</sub>]<sup>‒</sup> NC possesses lower activity and selectivity towards CO formation than [Au<sub>25</sub>(PET)<sub>18</sub>]<sup>‒</sup> and [Au<sub>25</sub>(C6T)<sub>18</sub>]<sup>‒</sup> NCs. Owing to their identical gold kernels, the differences in electrocatalytic CO<sub>2</sub>RR performance of these three Au<sub>25</sub> NCs can be fully attributed to their distinctions in tail group structure. Density functional theory (DFT) calculations exclude the possible effects on the electronic structures of the active sites exerted by the distinctions in tail group structure, while molecular dynamics (MD) calculations reveal that different orientation modes of tail groups in aqueous solution affect the diffusion of the reactants to active sites. Overall, this work provides a unique perspective on the structure-property relationships for ligand-protected NCs in electrocatalytic CO<sub>2</sub>RR.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"81 ","pages":"Pages 195-205"},"PeriodicalIF":17.7,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098813","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)64886-8
Diankun Song , Yunyun Wu , Jiahui Hua , Chunfeng Shao , Zhaoyang Wei , Jianji Wang , Kai Dai
Imidazolium-based ionic liquids (ILs) exhibit great potential in promoting electrochemical CO2 reduction reaction (CO2RR) by reducing overpotential reduction and enhancing catalytic efficiency. However, the regulatory role of ILs structure in the local physicochemical region at the electrode/electrolyte interface and in reaction kinetics remain unclear. In this study, we designed imidazolium-based ILs with tunable cation alkyl chain length and systematically revealed the dynamic interfacial regulation mechanism controlled by cation structure, based on in-situ infrared spectroscopy and molecular dynamics simulations. The commercial Ag electrodes in electrolytes with critical chain length exhibit nearly 100% Faradaic efficiency for CO production while maintaining high current density. Imidazolium cations with critical chain length effectively regulate the electric double layer at the Ag electrode/electrolyte interface: they notably balance a range of positive and negative factors, including hydrophobicity, CO2 absorption, conductivity, viscosity, and hydrogen evolution reaction, etc. Collectively, these effects synergistically shape an optimized interfacial local physicochemical region, enhancing the rate of CO2 catalytic reactions. This work elucidates the mechanistic framework of interfacial regulation in CO2RR and delivers molecular design principles for engineering IL-based electrolytes toward enhanced catalytic selectivity.
{"title":"Insight into the role of imidazolium cations in regulating Ag electrode interface for enhancing electrochemical CO2 reduction","authors":"Diankun Song , Yunyun Wu , Jiahui Hua , Chunfeng Shao , Zhaoyang Wei , Jianji Wang , Kai Dai","doi":"10.1016/S1872-2067(25)64886-8","DOIUrl":"10.1016/S1872-2067(25)64886-8","url":null,"abstract":"<div><div>Imidazolium-based ionic liquids (ILs) exhibit great potential in promoting electrochemical CO<sub>2</sub> reduction reaction (CO<sub>2</sub>RR) by reducing overpotential reduction and enhancing catalytic efficiency. However, the regulatory role of ILs structure in the local physicochemical region at the electrode/electrolyte interface and in reaction kinetics remain unclear. In this study, we designed imidazolium-based ILs with tunable cation alkyl chain length and systematically revealed the dynamic interfacial regulation mechanism controlled by cation structure, based on <em>in-situ</em> infrared spectroscopy and molecular dynamics simulations. The commercial Ag electrodes in electrolytes with critical chain length exhibit nearly 100% Faradaic efficiency for CO production while maintaining high current density. Imidazolium cations with critical chain length effectively regulate the electric double layer at the Ag electrode/electrolyte interface: they notably balance a range of positive and negative factors, including hydrophobicity, CO<sub>2</sub> absorption, conductivity, viscosity, and hydrogen evolution reaction, <em>etc</em>. Collectively, these effects synergistically shape an optimized interfacial local physicochemical region, enhancing the rate of CO<sub>2</sub> catalytic reactions. This work elucidates the mechanistic framework of interfacial regulation in CO<sub>2</sub>RR and delivers molecular design principles for engineering IL-based electrolytes toward enhanced catalytic selectivity.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"81 ","pages":"Pages 206-215"},"PeriodicalIF":17.7,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098814","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)64861-3
Ganghua Zhou , Jie Liu , Longyun Zhang , Chuanzhou Bi , Hangmin Xu , Weiyi Jiang , Xingwang Zhu , Xin Ning , Hui Xu , Xiaozhi Wang
The photocatalytic carbon dioxide reduction represents a promising route for solar-to-chemical energy conversion, enabling the sustainable production of carbon-neutral fuels. Achieving high selectivity toward specific products remains a major challenge due to the complex multi-electron transfer pathways and competing reaction intermediates. Herein, the Mn-doped Co3O4 (MMC) photocatalysts are synthesized based on an “impregnation-pyrolysis” strategy using in situ synthesized Mn-doped ZIF-67 as a precursor. The MOF-templated approach enables uniform Mn incorporation into the Co3O4 lattice while preserving a hierarchical porous architecture, thereby enhancing active-site accessibility and modulating the electronic environment of catalyst. The introduction of guest Mn effectively suppresses the competing hydrogen evolution reaction. As a result, the optimized 2MMC catalyst shows a 12.8-fold increase in CO production over undoped Co3O4 and enables selective CO2 conversion in pure water with diluted CO2. Photoelectrochemical characterizations reveal that guest Mn doping accelerates charge separation dynamics. In-situ irradiated X-ray photoelectron spectroscopy, in-situ Fourier transformed infrared spectra, and theoretical calculations unveil a Mn-mediated pathway that selectively promotes the formation of *CO2 and *CO intermediates. This work provides new atomic-level insights into the selective photocatalytic conversion of CO2 under green and sustainable conditions.
{"title":"Atomic-level Mn incorporation into Co3O4 for selective CO2 photoreduction in pure water under dilute CO2 atmosphere","authors":"Ganghua Zhou , Jie Liu , Longyun Zhang , Chuanzhou Bi , Hangmin Xu , Weiyi Jiang , Xingwang Zhu , Xin Ning , Hui Xu , Xiaozhi Wang","doi":"10.1016/S1872-2067(25)64861-3","DOIUrl":"10.1016/S1872-2067(25)64861-3","url":null,"abstract":"<div><div>The photocatalytic carbon dioxide reduction represents a promising route for solar-to-chemical energy conversion, enabling the sustainable production of carbon-neutral fuels. Achieving high selectivity toward specific products remains a major challenge due to the complex multi-electron transfer pathways and competing reaction intermediates. Herein, the Mn-doped Co<sub>3</sub>O<sub>4</sub> (MMC) photocatalysts are synthesized based on an “impregnation-pyrolysis” strategy using in situ synthesized Mn-doped ZIF-67 as a precursor. The MOF-templated approach enables uniform Mn incorporation into the Co<sub>3</sub>O<sub>4</sub> lattice while preserving a hierarchical porous architecture, thereby enhancing active-site accessibility and modulating the electronic environment of catalyst. The introduction of guest Mn effectively suppresses the competing hydrogen evolution reaction. As a result, the optimized 2MMC catalyst shows a 12.8-fold increase in CO production over undoped Co<sub>3</sub>O<sub>4</sub> and enables selective CO<sub>2</sub> conversion in pure water with diluted CO<sub>2</sub>. Photoelectrochemical characterizations reveal that guest Mn doping accelerates charge separation dynamics. <em>In-situ</em> irradiated X-ray photoelectron spectroscopy, <em>in-situ</em> Fourier transformed infrared spectra, and theoretical calculations unveil a Mn-mediated pathway that selectively promotes the formation of *CO<sub>2</sub> and *CO intermediates. This work provides new atomic-level insights into the selective photocatalytic conversion of CO<sub>2</sub> under green and sustainable conditions.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"81 ","pages":"Pages 216-226"},"PeriodicalIF":17.7,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098815","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)64899-6
Xiong Wang , Chao Peng , Yongkang Xiao , Ziye Zhang , Huiping Zheng , Wenjie Yue , Sheng Tian , Xingsheng Hu , Weifan Shao , Guanghui Chen , Binghao Wang , Huijuan Wang , Mingming Yin , Jinxin Li , Yang Li , Lang Chen , Shuangfeng Yin
Oxygen vacancies (Ov) play a pivotal role in enhancing photocatalytic C–H bond oxidation, yet their susceptibility to depletion under oxidative conditions significantly compromises catalyst stability. To address this challenge, we developed a surface engineering strategy through in-situ growth of a Bi-MOF layer on oxygen vacancy-rich Bi2WO6 (Bi2WO6–x@Bi-MOF). This interfacial Bi–O interaction not only constructed a built-in charge transfer channel to boost electron migration from Bi2WO6–x to Bi-MOF, but also shifted the Bi p-band center closer to the Fermi level (Ef) to facilitate the adsorption of oxygen molecules and toluene. This surface engineering strategy preferentially adsorbs O2 on Bi-MOF and prevents its direct interaction with the Bi2WO6–x host, thereby mitigating oxygen vacancy depletion and enhancing catalyst stability. The optimized photocatalyst achieves 96% toluene conversion and 80% benzaldehyde selectivity within 2 h of light irradiation and maintains excellent structural stability and catalytic performance over ten consecutive cycles. This study offers a new design strategy for constructing robust and efficient Ov-based photocatalytic systems and expands the potential application of MOF materials in complex interfacial reactions.
{"title":"Surface engineering enhancing activity and stability of Bi2WO6–x for selective C–H bond photooxidation","authors":"Xiong Wang , Chao Peng , Yongkang Xiao , Ziye Zhang , Huiping Zheng , Wenjie Yue , Sheng Tian , Xingsheng Hu , Weifan Shao , Guanghui Chen , Binghao Wang , Huijuan Wang , Mingming Yin , Jinxin Li , Yang Li , Lang Chen , Shuangfeng Yin","doi":"10.1016/S1872-2067(25)64899-6","DOIUrl":"10.1016/S1872-2067(25)64899-6","url":null,"abstract":"<div><div>Oxygen vacancies (Ov) play a pivotal role in enhancing photocatalytic C–H bond oxidation, yet their susceptibility to depletion under oxidative conditions significantly compromises catalyst stability. To address this challenge, we developed a surface engineering strategy through <em>in-situ</em> growth of a Bi-MOF layer on oxygen vacancy-rich Bi<sub>2</sub>WO<sub>6</sub> (Bi<sub>2</sub>WO<sub>6–<em>x</em></sub>@Bi-MOF). This interfacial Bi–O interaction not only constructed a built-in charge transfer channel to boost electron migration from Bi<sub>2</sub>WO<sub>6–<em>x</em></sub> to Bi-MOF, but also shifted the Bi <em>p</em>-band center closer to the Fermi level (<em>E</em><sub>f</sub>) to facilitate the adsorption of oxygen molecules and toluene. This surface engineering strategy preferentially adsorbs O<sub>2</sub> on Bi-MOF and prevents its direct interaction with the Bi<sub>2</sub>WO<sub>6–<em>x</em></sub> host, thereby mitigating oxygen vacancy depletion and enhancing catalyst stability. The optimized photocatalyst achieves 96% toluene conversion and 80% benzaldehyde selectivity within 2 h of light irradiation and maintains excellent structural stability and catalytic performance over ten consecutive cycles. This study offers a new design strategy for constructing robust and efficient Ov-based photocatalytic systems and expands the potential application of MOF materials in complex interfacial reactions.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"81 ","pages":"Pages 246-258"},"PeriodicalIF":17.7,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098863","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)64827-3
Yufei Cao , Shuang Chen , Hui Liang , Junrong Yang , Wenyong Lou , Jun Ge
Enzymatic catalysis within surface- and volume-confined environments is common in biological cells or industrial applications. Despite their prevalence both in vivo and in vitro, a comprehensive mechanistic understanding of how these confinements tune the intrinsic activity of enzymes has remained elusive. Herein, we explore the role of confinement in shaping the activity of enzymes. Experiments show that the confinements induced by macromolecular crowding enhance lipase activity. To uncover the origin of the activity enhancement, thermodynamic activation parameters of lipase catalysis were calculated through extensive molecular dynamics (MD) and empirical valence bond (EVB) simulations. The EVB approach has proven to be an efficient method, enabling extensive sampling via MD and the evaluation of thermodynamic activation parameters for enzyme catalysis. Our findings reveal that confinement applied at the loop regions of lipase leads to higher intrinsic activities, and this effect depends on the degree of confinement. The lower free energy of activation originates from the gain of both enthalpy and entropy. Better preorganization of the active site and greater conformational space overlap between initial and transition states enhance lipase catalysis. We observe that the catalytic enhancement due to surface confinement is not exclusive to lipase but extends to PETase, highlighting its potential universality as a principle for enzyme design and engineering.
{"title":"Mechanism of confinement enhancing enzyme intrinsic activity","authors":"Yufei Cao , Shuang Chen , Hui Liang , Junrong Yang , Wenyong Lou , Jun Ge","doi":"10.1016/S1872-2067(25)64827-3","DOIUrl":"10.1016/S1872-2067(25)64827-3","url":null,"abstract":"<div><div>Enzymatic catalysis within surface- and volume-confined environments is common in biological cells or industrial applications. Despite their prevalence both <em>in vivo</em> and <em>in vitro</em>, a comprehensive mechanistic understanding of how these confinements tune the intrinsic activity of enzymes has remained elusive. Herein, we explore the role of confinement in shaping the activity of enzymes. Experiments show that the confinements induced by macromolecular crowding enhance lipase activity. To uncover the origin of the activity enhancement, thermodynamic activation parameters of lipase catalysis were calculated through extensive molecular dynamics (MD) and empirical valence bond (EVB) simulations. The EVB approach has proven to be an efficient method, enabling extensive sampling <em>via</em> MD and the evaluation of thermodynamic activation parameters for enzyme catalysis. Our findings reveal that confinement applied at the loop regions of lipase leads to higher intrinsic activities, and this effect depends on the degree of confinement. The lower free energy of activation originates from the gain of both enthalpy and entropy. Better preorganization of the active site and greater conformational space overlap between initial and transition states enhance lipase catalysis. We observe that the catalytic enhancement due to surface confinement is not exclusive to lipase but extends to PETase, highlighting its potential universality as a principle for enzyme design and engineering.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"81 ","pages":"Pages 355-365"},"PeriodicalIF":17.7,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098855","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}
Reversible protonic ceramic cells (R-PCCs) represent a highly promising energy conversion and storage technology, offering high efficiency at intermediate temperatures (400–700 °C). However, their commercialization is significantly impeded by the sluggish oxygen reaction kinetics on air electrodes. This work reports a Mn-doped PrBa0.8Ca0.2Co2O5+δ air electrode with a nominal composition of PrBa0.8Ca0.2Co1.5Mn0.5O5+δ, which primarily segregates into a deficient double perovskite Pr1.25Ba0.5Ca0.25Co1.58Mn0.42O5+δ phase and a minor BaCo0.6Mn0.4O3–δ hexagonal perovskite phase, as suggested by the X-ray diffraction refinement. The formation of Mn-doped nanocomposites substantially enhances the activities of oxygen reduction/evolution reactions, attributed to elevated oxygen vacancy concentrations and improved oxygen surface exchange and bulk diffusion capabilities, relative to the undoped PrBa0.8Ca0.2Co2O5+δ. The synergistic effect between the two phases may enhance electrochemical performance. Single cells incorporating these nanocomposite air electrodes achieve exceptional electrochemical performance at 700 °C: peak power density of 2.05 W cm–2 in fuel cell (FC) mode and current density of –3.78 A cm–2 at 1.3 V in electrolysis (EL) mode. Furthermore, promising durability is demonstrated during a FC test (100 h), an EL test (100 h), and a FC-EL cycling test (120 h) at 600 °C. This Mn-doping approach establishes an effective strategy for developing advanced air electrode materials.
可逆质子陶瓷电池（R-PCCs）是一种非常有前途的能量转换和存储技术，在中等温度（400-700°C）下具有很高的效率。然而，空气电极上缓慢的氧反应动力学严重阻碍了它们的商业化。本文报道了一种mn掺杂的PrBa0.8Ca0.2Co2O5+δ空气电极，其标称成分为PrBa0.8Ca0.2Co1.5Mn0.5O5+δ， x射线衍射细化表明，该电极主要偏析为缺乏的双钙钛矿pr1.25 ba0.5 ca0.25 co1.58 mn0.2o5 +δ相和少量的BaCo0.6Mn0.4O3 -δ六方钙钛矿相。相对于未掺杂的PrBa0.8Ca0.2Co2O5+δ， mn掺杂纳米复合材料的形成大大增强了氧还原/析出反应的活性，这是由于氧空位浓度升高，氧表面交换和体扩散能力增强。两相之间的协同作用可以提高电化学性能。采用这些纳米复合空气电极的单个电池在700°C下具有优异的电化学性能：燃料电池（FC）模式下的峰值功率密度为2.05 W cm-2，电解（EL）模式下的电流密度为-3.78 A cm-2，电压为1.3 V。此外，在600°C的FC测试（100小时）、EL测试（100小时）和FC-EL循环测试（120小时）中，耐久性也得到了证明。这种掺杂锰的方法为开发先进的空气电极材料建立了有效的策略。
{"title":"Mn-doping induced phase segregation of air electrodes enables high-performance and durable reversible protonic ceramic cells","authors":"Xiaofeng Chen, Yixuan Huang, Wanbin Lin, Jiaojiao Xia, Xirui Zhang, Wenjie Gong, Chuqian Jian, Hao Liu, Jiacheng Zeng, Jiang Liu, Yu Chen","doi":"10.1016/S1872-2067(25)64907-2","DOIUrl":"10.1016/S1872-2067(25)64907-2","url":null,"abstract":"<div><div>Reversible protonic ceramic cells (R-PCCs) represent a highly promising energy conversion and storage technology, offering high efficiency at intermediate temperatures (400–700 °C). However, their commercialization is significantly impeded by the sluggish oxygen reaction kinetics on air electrodes. This work reports a Mn-doped PrBa<sub>0.8</sub>Ca<sub>0.2</sub>Co<sub>2</sub>O<sub>5+<em>δ</em></sub> air electrode with a nominal composition of PrBa<sub>0.8</sub>Ca<sub>0.2</sub>Co<sub>1.5</sub>Mn<sub>0.5</sub>O<sub>5+<em>δ</em></sub>, which primarily segregates into a deficient double perovskite Pr<sub>1.25</sub>Ba<sub>0.5</sub>Ca<sub>0.25</sub>Co<sub>1.58</sub>Mn<sub>0.42</sub>O<sub>5+<em>δ</em></sub> phase and a minor BaCo<sub>0.6</sub>Mn<sub>0.4</sub>O<sub>3<em>–δ</em></sub> hexagonal perovskite phase, as suggested by the X-ray diffraction refinement. The formation of Mn-doped nanocomposites substantially enhances the activities of oxygen reduction/evolution reactions, attributed to elevated oxygen vacancy concentrations and improved oxygen surface exchange and bulk diffusion capabilities, relative to the undoped PrBa<sub>0.8</sub>Ca<sub>0.2</sub>Co<sub>2</sub>O<sub>5+<em>δ</em></sub>. The synergistic effect between the two phases may enhance electrochemical performance. Single cells incorporating these nanocomposite air electrodes achieve exceptional electrochemical performance at 700 °C: peak power density of 2.05 W cm<sup>–2</sup> in fuel cell (FC) mode and current density of –3.78 A cm<sup>–2</sup> at 1.3 V in electrolysis (EL) mode. Furthermore, promising durability is demonstrated during a FC test (100 h), an EL test (100 h), and a FC-EL cycling test (120 h) at 600 °C. This Mn-doping approach establishes an effective strategy for developing advanced air electrode materials.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"81 ","pages":"Pages 333-343"},"PeriodicalIF":17.7,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098854","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)64880-7
Haihong Zhong , Qianqian Xu , Weiting Yang , Nicolas Alonso-Vante , Yongjun Feng
Iron-group transition metal chalcogenides (IGTMCs) have emerged as promising electrocatalysts due to their tailorable electronic structures through composition engineering. This review summarizes the recent advancements in multi-component regulatory strategies employed in advanced IGTMC electrocatalysts, including anion substitution, cation doping, and the incorporation of zero-valent elements. Particular emphasis is placed on the roles of secondary and tertiary doping configurations, and chalcogen modulation in enhancing the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) of IGTMC electrocatalysts. Thus, regulating the electronic structure and optimizing the adsorption strengths on this family of materials are strategies to boost catalytic kinetics. Notably, dynamic surface reconstruction (e.g., oxidation) of IGTMC electrocatalysts during the OER has recently attracted significant attention. Advanced in-situ/operando characterization insights into reconstruction phenomenon of IGTMC electrocatalysts for OER process are critically analyzed. Finally, the challenges and prospects of IGTMC electrocatalysts for ORR/OER electrocatalysis are outlined.
{"title":"Composition regulation of iron-group transition metal chalcogenides for the oxygen electrocatalysis: Electronic structure and surface reconstruction","authors":"Haihong Zhong , Qianqian Xu , Weiting Yang , Nicolas Alonso-Vante , Yongjun Feng","doi":"10.1016/S1872-2067(25)64880-7","DOIUrl":"10.1016/S1872-2067(25)64880-7","url":null,"abstract":"<div><div>Iron-group transition metal chalcogenides (IGTMCs) have emerged as promising electrocatalysts due to their tailorable electronic structures through composition engineering. This review summarizes the recent advancements in multi-component regulatory strategies employed in advanced IGTMC electrocatalysts, including anion substitution, cation doping, and the incorporation of zero-valent elements. Particular emphasis is placed on the roles of secondary and tertiary doping configurations, and chalcogen modulation in enhancing the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) of IGTMC electrocatalysts. Thus, regulating the electronic structure and optimizing the adsorption strengths on this family of materials are strategies to boost catalytic kinetics. Notably, dynamic surface reconstruction (e.g., oxidation) of IGTMC electrocatalysts during the OER has recently attracted significant attention. Advanced <em>in</em>-<em>situ</em>/<em>operando</em> characterization insights into reconstruction phenomenon of IGTMC electrocatalysts for OER process are critically analyzed. Finally, the challenges and prospects of IGTMC electrocatalysts for ORR/OER electrocatalysis are outlined.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"81 ","pages":"Pages 37-68"},"PeriodicalIF":17.7,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098804","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)64887-X
Fang Li , Penghe Zhang , Yiran Wang , Yueming Liu , Mingyuan He
Precisely controlling acid center position in zeolites is still challenging. Pentene monomolecular cracking offers an ideal route to maximize ethylene and propylene yields simultaneously. To reveal the relationship between acid site distribution in FER-zeolite and pentene monomolecular cracking activity, this study proposes a novel strategy integrating pyridine pre-adsorption with K⁺ exchange modification to selectively shield acid sites within FER cages, while phosphorus modification is employed to selectively passivate acid sites in 10-MR channels and on the external surface. Adsorption infrared (IR) spectroscopy (CD3CN-IR, Py-IR, and 2,6-DMPy-IR), and OH-IR characterization verified the selectivity and efficiency of these modification process. FER zeolites with distinct acid site distributions exhibit typical monomolecular cracking characteristics in pentene cracking, where the pentene cracking activity is linearly related to the acid density in the 10-MR channel and independent of the FER cage acidity. This result identifies 10-MR channel as primary pentene monomolecular cracking reaction position for the first time, providing a theoretical basis for designing zeolite catalysts that maximize ethylene and propylene production. The synergistic application of the pre-adsorption-K⁺ exchange modification strategy using different size basic molecules and phosphorus modification will provide an effective approach for precise control of acid site locations in zeolites with diverse pore/cavities architectures.
精确控制沸石中酸中心位置仍然具有挑战性。戊烯单分子裂解提供了一个理想的途径，以最大限度地提高乙烯和丙烯的产量同时。为了揭示fe -沸石中酸位点分布与戊烯单分子裂解活性之间的关系，本研究提出了一种新的策略，将吡啶预吸附与K +交换修饰结合起来，选择性地屏蔽FER笼内的酸位点，同时采用磷修饰选择性地钝化10-MR通道和外表面的酸位点。吸附红外光谱（CD3CN-IR， Py-IR和2,6- dmpy -IR）和OH-IR表征验证了这些修饰过程的选择性和效率。具有不同酸位分布的铁分子筛在戊烯裂解中表现出典型的单分子裂解特征，其中戊烯裂解活性与10-MR通道中的酸密度线性相关，与铁分子筛笼酸度无关。该结果首次确定了10-MR通道为伯戊烯单分子裂化反应位置，为设计最大化乙烯和丙烯产量的沸石催化剂提供了理论依据。不同大小碱性分子的预吸附- k +交换修饰策略和磷修饰的协同应用，将为精确控制不同孔/腔结构沸石中酸位点的位置提供有效的方法。
{"title":"Precise regulation of acid centers in different cavities of FER-zeolite via selective passivation to identify pentene monomolecular cracking reaction position","authors":"Fang Li , Penghe Zhang , Yiran Wang , Yueming Liu , Mingyuan He","doi":"10.1016/S1872-2067(25)64887-X","DOIUrl":"10.1016/S1872-2067(25)64887-X","url":null,"abstract":"<div><div>Precisely controlling acid center position in zeolites is still challenging. Pentene monomolecular cracking offers an ideal route to maximize ethylene and propylene yields simultaneously. To reveal the relationship between acid site distribution in FER-zeolite and pentene monomolecular cracking activity, this study proposes a novel strategy integrating pyridine pre-adsorption with K⁺ exchange modification to selectively shield acid sites within FER cages, while phosphorus modification is employed to selectively passivate acid sites in 10-MR channels and on the external surface. Adsorption infrared (IR) spectroscopy (CD<sub>3</sub>CN-IR, Py-IR, and 2,6-DMPy-IR), and OH-IR characterization verified the selectivity and efficiency of these modification process. FER zeolites with distinct acid site distributions exhibit typical monomolecular cracking characteristics in pentene cracking, where the pentene cracking activity is linearly related to the acid density in the 10-MR channel and independent of the FER cage acidity. This result identifies 10-MR channel as primary pentene monomolecular cracking reaction position for the first time, providing a theoretical basis for designing zeolite catalysts that maximize ethylene and propylene production. The synergistic application of the pre-adsorption-K⁺ exchange modification strategy using different size basic molecules and phosphorus modification will provide an effective approach for precise control of acid site locations in zeolites with diverse pore/cavities architectures.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"81 ","pages":"Pages 136-147"},"PeriodicalIF":17.7,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098808","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)64868-6
Qinghua Liu , Peiqing Cai , Hengshuai Li , Xue-Yang Ji , Dafeng Zhang , Xipeng Pu
S-scheme heterojunctions can offer an effective strategy for spatially separating photogenerated charge carriers, thereby sigFnificantly enhancing photocatalytic performance. In this study, cadmium sulfide (CdS)/copper tungstate (CFuWO4) (CdS/CW) S-scheme heterojunction photocatalysts with adjustable components were fabricated by decorating CdS nanorods with CuWO4 nanoparticles. The optimal hydrogen evolution rate (2725.91 μmol g–1 h–1) of CdS/CW-10% with excellent cycling stability under visible light is 10.1-fold higher than pure CdS. Density functional theory calculations and photoelectrochemical analyses confirmed that the S-scheme charge-transfer mechanism from CdS to CuWO4 is responsible for the enhanced photocatalytic performance by promoting charge separation. Additionally, the photothermal effect of CuWO4 increased the local temperature of the photocatalyst, further accelerating the reaction kinetics. This study highlights a dual-enhancement approach based on interfacial charge modulation by constructing an S-scheme heterojunction and photothermal activation, providing valuable insights into the design of high-efficiency S-scheme photocatalysts for solar-driven hydrogen production.
{"title":"Visible-light-driven hydrogen evolution over CdS/CuWO4 S-Scheme heterojunctions: Dual synergistic enhancement via interfacial charge transfer and photothermal activation","authors":"Qinghua Liu , Peiqing Cai , Hengshuai Li , Xue-Yang Ji , Dafeng Zhang , Xipeng Pu","doi":"10.1016/S1872-2067(25)64868-6","DOIUrl":"10.1016/S1872-2067(25)64868-6","url":null,"abstract":"<div><div>S-scheme heterojunctions can offer an effective strategy for spatially separating photogenerated charge carriers, thereby sig<del>F</del>nificantly enhancing photocatalytic performance. In this study, cadmium sulfide (CdS)/copper tungstate (C<del>F</del>uWO<sub>4</sub>) (CdS/CW) S-scheme heterojunction photocatalysts with adjustable components were fabricated by decorating CdS nanorods with CuWO<sub>4</sub> nanoparticles. The optimal hydrogen evolution rate (2725.91 μmol g<sup>–1</sup> h<sup>–1</sup>) of CdS/CW-10% with excellent cycling stability under visible light is 10.1-fold higher than pure CdS. Density functional theory calculations and photoelectrochemical analyses confirmed that the S-scheme charge-transfer mechanism from CdS to CuWO<sub>4</sub> is responsible for the enhanced photocatalytic performance by promoting charge separation. Additionally, the photothermal effect of CuWO<sub>4</sub> increased the local temperature of the photocatalyst, further accelerating the reaction kinetics. This study highlights a dual-enhancement approach based on interfacial charge modulation by constructing an S-scheme heterojunction and photothermal activation, providing valuable insights into the design of high-efficiency S-scheme photocatalysts for solar-driven hydrogen production.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"81 ","pages":"Pages 299-309"},"PeriodicalIF":17.7,"publicationDate":"2026-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146098803","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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