Electrochemical synthesis of amides from carbon- and nitrogen-containing small molecules is alluring from the view of carbon neutrality. Previous works were mainly focused on electro-reduction coupling of C–N bond to prepare amides coupled with the useless oxygen evolution reaction on the anode. But, the competing hydrogen evolution reaction is more favorable in dynamics on the cathode, severely retarding the Faradaic efficiency of the amides. Very recently, electro-oxidation construction of C–N bond via coupling the cheap C- and N-containing small molecules to achieve high energy efficiency emerges as a rising star, while the big challenge lies in preventing the sole oxidation of feedstocks. In this perspective, we highlight the recent progress in anodic electro-oxidation synthesis of amides and the potential reaction mechanism. We also discuss the application potential and the development opportunities of the electro-oxidation strategy for amides synthesis from carbon- and nitrogen-containing small molecules.
{"title":"Electro-oxidation synthesis of amides from carbon- and nitrogen-containing small molecules","authors":"Aijing Ma , Baian Shen , Minghao Guo , Chengying Guo , Yifu Yu","doi":"10.1016/S1872-2067(25)64855-8","DOIUrl":"10.1016/S1872-2067(25)64855-8","url":null,"abstract":"<div><div>Electrochemical synthesis of amides from carbon- and nitrogen-containing small molecules is alluring from the view of carbon neutrality. Previous works were mainly focused on electro-reduction coupling of C–N bond to prepare amides coupled with the useless oxygen evolution reaction on the anode. But, the competing hydrogen evolution reaction is more favorable in dynamics on the cathode, severely retarding the Faradaic efficiency of the amides. Very recently, electro-oxidation construction of C–N bond via coupling the cheap C- and N-containing small molecules to achieve high energy efficiency emerges as a rising star, while the big challenge lies in preventing the sole oxidation of feedstocks. In this perspective, we highlight the recent progress in anodic electro-oxidation synthesis of amides and the potential reaction mechanism. We also discuss the application potential and the development opportunities of the electro-oxidation strategy for amides synthesis from carbon- and nitrogen-containing small molecules.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 1-6"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915270","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 : 2026-01-01DOI: 10.1016/S1872-2067(25)64870-4
Yandong Xu, Zihui Jing, Wenhao Su, Jiale Xu, Mingliang Wang
The synergistic coupling of photocatalytic hydrogen peroxide (H2O2) production and green organic synthesis not only optimizes utilization of photogenerated electron-hole pairs but also circumvents kinetically sluggish water oxidation reaction. In this study, an efficient composite photocatalyst was developed through in-situ growth of irregular TpPa-Cl blocks on the surface of boron-doped TiO2, which boasts a large specific surface area. Boron doping enhances light absorption range and inhibits recombination of charge carriers. Additionally, deep integration of porous TiO2 with TpPa-Cl improves the contact between the reactants and the photocatalyst, extends the carrier lifetime, and provides more active sites. In the absence of a co-catalyst, the yield of H2O2 reached 2082.6 μmol g−1 h−1, with a furfuryl alcohol conversion rate of 94%. In-situ XPS and density functional theory calculations confirmed S-scheme charge transfer mechanism, which enhances carrier separation and transfer efficiency while retaining photogenerated electrons and holes with strong redox properties. Quenching experiments, electron paramagnetic resonance, and in-situ diffuse reflectance infrared Fourier transformed spectroscopy demonstrated that H2O2 was primarily generated via a 2-electron oxygen reduction reaction with ·O2− and OOH* as intermediates. Furthermore, furfuryl alcohol was oxidized to the radical ·C5H5O2 by h+ and subsequently converted to furfural or furoic acid through reactions with h+ or ·OH. This work presents a novel strategy for designing efficient composite photocatalysts for H2O2 production and green organic synthesis.
{"title":"Synergistic coupling of H2O2 production and furoic acid synthesis over B-TiO2@COF S-scheme bifunctional photocatalyst","authors":"Yandong Xu, Zihui Jing, Wenhao Su, Jiale Xu, Mingliang Wang","doi":"10.1016/S1872-2067(25)64870-4","DOIUrl":"10.1016/S1872-2067(25)64870-4","url":null,"abstract":"<div><div>The synergistic coupling of photocatalytic hydrogen peroxide (H<sub>2</sub>O<sub>2</sub>) production and green organic synthesis not only optimizes utilization of photogenerated electron-hole pairs but also circumvents kinetically sluggish water oxidation reaction. In this study, an efficient composite photocatalyst was developed through in-situ growth of irregular TpPa-Cl blocks on the surface of boron-doped TiO<sub>2</sub>, which boasts a large specific surface area. Boron doping enhances light absorption range and inhibits recombination of charge carriers. Additionally, deep integration of porous TiO<sub>2</sub> with TpPa-Cl improves the contact between the reactants and the photocatalyst, extends the carrier lifetime, and provides more active sites. In the absence of a co-catalyst, the yield of H<sub>2</sub>O<sub>2</sub> reached 2082.6 μmol g<sup>−1</sup> h<sup>−1</sup>, with a furfuryl alcohol conversion rate of 94%. <em>In-situ</em> XPS and density functional theory calculations confirmed S-scheme charge transfer mechanism, which enhances carrier separation and transfer efficiency while retaining photogenerated electrons and holes with strong redox properties. Quenching experiments, electron paramagnetic resonance, and <em>in-situ</em> diffuse reflectance infrared Fourier transformed spectroscopy demonstrated that H<sub>2</sub>O<sub>2</sub> was primarily generated via a 2-electron oxygen reduction reaction with ·O<sub>2</sub><sup>−</sup> and OOH* as intermediates. Furthermore, furfuryl alcohol was oxidized to the radical ·C<sub>5</sub>H<sub>5</sub>O<sub>2</sub> by h<sup>+</sup> and subsequently converted to furfural or furoic acid through reactions with h<sup>+</sup> or ·OH. This work presents a novel strategy for designing efficient composite photocatalysts for H<sub>2</sub>O<sub>2</sub> production and green organic synthesis.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 135-145"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915315","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 : 2026-01-01DOI: 10.1016/S1872-2067(25)64859-5
Liyuan Xiao, Zhenlu Wang, Jingqi Guan
Metal-organic frameworks (MOFs) with mononuclear metal ion nodes have garnered significant attention in the electrocatalytic field owing to their high surface area and tunable structures, but their development is critically hindered by the limitation of active site availability. In contrast, multinuclear MOFs exhibit notable advantages by offering multi-metal active sites, constructing complex structures, enhancing structural and thermal stability, and coupling with in-depth studies on catalytic mechanisms, endowing them great application potential in complex multi-electron reactions. This work provides a comprehensive review on the precise construction, in-situ characterizations, reaction mechanisms, modulation strategies, and electrocatalytic applications of multinuclear MOFs, underlying their role in electrocatalytic processes with a focus on adsorption, active sites, and electron transfer. The effects of spin, polarization, orbital coupling, and pore confinement on catalytic performance are systematically elucidated. Furthermore, the unique tuning strategies of multinuclear MOFs are summarized to guide the precise construction, including adjusting the type and number of metal cores, optimizing electronic structures, and manipulating defects. Lastly, the future trends in the development of multinuclear MOFs for electrocatalysis are envisioned, laying a solid foundation for their practical applications.
{"title":"Advances in multinuclear metal-organic frameworks for electrocatalysis","authors":"Liyuan Xiao, Zhenlu Wang, Jingqi Guan","doi":"10.1016/S1872-2067(25)64859-5","DOIUrl":"10.1016/S1872-2067(25)64859-5","url":null,"abstract":"<div><div>Metal-organic frameworks (MOFs) with mononuclear metal ion nodes have garnered significant attention in the electrocatalytic field owing to their high surface area and tunable structures, but their development is critically hindered by the limitation of active site availability. In contrast, multinuclear MOFs exhibit notable advantages by offering multi-metal active sites, constructing complex structures, enhancing structural and thermal stability, and coupling with in-depth studies on catalytic mechanisms, endowing them great application potential in complex multi-electron reactions. This work provides a comprehensive review on the precise construction, <em>in-situ</em> characterizations, reaction mechanisms, modulation strategies, and electrocatalytic applications of multinuclear MOFs, underlying their role in electrocatalytic processes with a focus on adsorption, active sites, and electron transfer. The effects of spin, polarization, orbital coupling, and pore confinement on catalytic performance are systematically elucidated. Furthermore, the unique tuning strategies of multinuclear MOFs are summarized to guide the precise construction, including adjusting the type and number of metal cores, optimizing electronic structures, and manipulating defects. Lastly, the future trends in the development of multinuclear MOFs for electrocatalysis are envisioned, laying a solid foundation for their practical applications.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 59-91"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915311","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 : 2026-01-01DOI: 10.1016/S1872-2067(25)64860-1
Shiyi Che , Zhengjun Li , Zhiguo Su , Zhikao Li , Aibing Yu , Minsu Liu , Songping Zhang
The clinical efficacy of mRNA-based therapeutics is critically dependent on the structural integrity of the mRNA molecule, which in turn is governed by the efficiency and robustness of its manufacturing process. Unlike conventional small-molecule synthesis, mRNA manufacturing relies on complex enzymatic cascades involving biomacromolecules with dynamic conformations as templates, intermediates, and catalysts. Key enzymatic modules, including plasmid linearization for DNA template preparation (Module 1), in vitro transcription (IVT) synthesis (Module 2), capping modification (Module 3) of mRNA, and different nucleases-aided removal of impurities (Module 4), are highly interdependent, each with specific catalytic enzymes and auxiliary cofactors. These modules present major engineering challenges of low efficiency and lack of modular compatibility across the multi-step enzymatic processes. Moreover, traditional approaches such as multienzyme immobilization or compartmentalization often fail to meet the demands of high-throughput, continuous and scalable manufacturing. This review systematically summarizes recent advances in the engineering of enzymatic modules for mRNA manufacturing, emphasizing challenges in catalytic regulation, module integration and process intensification. The potential strategies for improving reaction compatibility and enabling process integration and intensification are discussed, providing insights into future directions for engineering mRNA synthesis at scale.
{"title":"Engineering of enzymatic modules for mRNA manufacturing: Advances in catalytic regulation and process integration","authors":"Shiyi Che , Zhengjun Li , Zhiguo Su , Zhikao Li , Aibing Yu , Minsu Liu , Songping Zhang","doi":"10.1016/S1872-2067(25)64860-1","DOIUrl":"10.1016/S1872-2067(25)64860-1","url":null,"abstract":"<div><div>The clinical efficacy of mRNA-based therapeutics is critically dependent on the structural integrity of the mRNA molecule, which in turn is governed by the efficiency and robustness of its manufacturing process. Unlike conventional small-molecule synthesis, mRNA manufacturing relies on complex enzymatic cascades involving biomacromolecules with dynamic conformations as templates, intermediates, and catalysts. Key enzymatic modules, including plasmid linearization for DNA template preparation (Module 1), in vitro transcription (IVT) synthesis (Module 2), capping modification (Module 3) of mRNA, and different nucleases-aided removal of impurities (Module 4), are highly interdependent, each with specific catalytic enzymes and auxiliary cofactors. These modules present major engineering challenges of low efficiency and lack of modular compatibility across the multi-step enzymatic processes. Moreover, traditional approaches such as multienzyme immobilization or compartmentalization often fail to meet the demands of high-throughput, continuous and scalable manufacturing. This review systematically summarizes recent advances in the engineering of enzymatic modules for mRNA manufacturing, emphasizing challenges in catalytic regulation, module integration and process intensification. The potential strategies for improving reaction compatibility and enabling process integration and intensification are discussed, providing insights into future directions for engineering mRNA synthesis at scale.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 92-112"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915312","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 : 2026-01-01DOI: 10.1016/S1872-2067(25)64826-1
Xuan Zhang , Lin Zhou , Teng Yan , Xiaohu Zhang, Hao Chen
Covalent organic frameworks (COFs) have garnered significant attention in photocatalysis owing to their exceptional light absorption capacities, tunable band structures, and high specific surface areas. However, the rapid recombination of photogenerated carriers in COFs remains a critical bottleneck limiting their practical application. In this study, a novel S-scheme heterojunction was constructed by integrating a Ni-doped zeolitic imidazolate framework-8 (Ni-ZIF-8) with Py-COF, effectively addressing this challenge. Through precisely controlled synthesis, the heterojunction achieves efficient and stable material combination, which not only significantly enhances photogenerated charge separation efficiency and markedly reduces recombination rates, but also demonstrates outstanding catalytic performance (162.77 mmol·h−1·g−1) and cycling stability in hydrogen evolution reaction. This study provides new insights into the design of efficient ZIF/COF-based heterojunction catalysts. This study provides an important theoretical foundation for the design of high-performance photocatalytic materials with broad application prospects.
{"title":"Fabrication of S-scheme heterojunction between covalent organic frameworks and Ni-ZIF-8 and its photocatalytic hydrogen production performance","authors":"Xuan Zhang , Lin Zhou , Teng Yan , Xiaohu Zhang, Hao Chen","doi":"10.1016/S1872-2067(25)64826-1","DOIUrl":"10.1016/S1872-2067(25)64826-1","url":null,"abstract":"<div><div>Covalent organic frameworks (COFs) have garnered significant attention in photocatalysis owing to their exceptional light absorption capacities, tunable band structures, and high specific surface areas. However, the rapid recombination of photogenerated carriers in COFs remains a critical bottleneck limiting their practical application. In this study, a novel S-scheme heterojunction was constructed by integrating a Ni-doped zeolitic imidazolate framework-8 (Ni-ZIF-8) with Py-COF, effectively addressing this challenge. Through precisely controlled synthesis, the heterojunction achieves efficient and stable material combination, which not only significantly enhances photogenerated charge separation efficiency and markedly reduces recombination rates, but also demonstrates outstanding catalytic performance (162.77 mmol·h<sup>−1</sup>·g<sup>−1</sup>) and cycling stability in hydrogen evolution reaction. This study provides new insights into the design of efficient ZIF/COF-based heterojunction catalysts. This study provides an important theoretical foundation for the design of high-performance photocatalytic materials with broad application prospects.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 200-212"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915327","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 : 2026-01-01DOI: 10.1016/S1872-2067(25)64833-9
Juxia Xiong , Hao Ma , Yingjun Dong , Benjamin Liu , Xiangji Zhou , Linbo Li , Yuanmiao Sun , Xiaolong Zhang , Hui-Ming Cheng
Bi-based catalysts are known to promote the electrochemical reduction of CO2 to formic acid (HCOOH) or formate (HCOO−). However, their implementation presents challenges: the first H+/e− pair transfer to form the key *OCHO intermediate on a Bi surface is a slow, kinetically sluggish endergonic process, resulting in a large overpotential and narrow potential window for high HCOOH/HCOO− selectivity. Altering the localized p-orbital electron states of Bi to change intermediate binding behaviors is difficult. We addressed this problem by using an in-situ polymerization method to obtain a polyaniline-Bi hybrid (PANI-Bi) with Bi surrounded by PANI chains. Combined experimental and computational studies indicate that the polyaniline acted as an “electron pump” that facilitated charge transfer from the PANI backbone to the Bi surface and changed the p-orbital electrons of the Bi active sites. This lowered the energy barrier for the adsorption of intermediates and facilitated *OCHO formation. Consequently, a significant increase in formate production was observed, achieving a single-pass carbon efficiency exceeding 48.7% at 800 mA cm−2. This organic functionalization strategy, aimed at modifying the electronic structure of heterogeneous catalysts, offers a promising approach for achieving highly selective electroreduction of CO2 at a high current density.
已知铋基催化剂可以促进CO2电化学还原为甲酸（HCOOH）或甲酸（HCOO−）。然而，它们的实现面临着挑战：在Bi表面上形成键*OCHO中间体的第一次H+/e−对转移是一个缓慢的，动力学缓慢的自吸过程，导致高HCOOH/HCOO−选择性的过电位大，电位窗口窄。改变Bi的定域p轨道电子态来改变中间结合行为是很困难的。为了解决这一问题，我们采用原位聚合的方法得到了聚苯胺-铋杂化物（PANI-Bi）， Bi被PANI链包围。实验和计算相结合的研究表明，聚苯胺作为一个“电子泵”，促进电荷从聚苯胺骨架转移到Bi表面，改变了Bi活性位点的p轨道电子。这降低了中间体吸附的能垒，促进了*OCHO的形成。因此，甲酸产量显著增加，在800 mA cm−2下，单次碳效率超过48.7%。这种有机功能化策略旨在改变非均相催化剂的电子结构，为实现高电流密度下CO2的高选择性电还原提供了一种有前途的方法。
{"title":"Improving the electrocatalytic CO2 to formate conversion on bismuth using polyaniline as an electron pump","authors":"Juxia Xiong , Hao Ma , Yingjun Dong , Benjamin Liu , Xiangji Zhou , Linbo Li , Yuanmiao Sun , Xiaolong Zhang , Hui-Ming Cheng","doi":"10.1016/S1872-2067(25)64833-9","DOIUrl":"10.1016/S1872-2067(25)64833-9","url":null,"abstract":"<div><div>Bi-based catalysts are known to promote the electrochemical reduction of CO<sub>2</sub> to formic acid (HCOOH) or formate (HCOO<sup>−</sup>). However, their implementation presents challenges: the first H<sup>+</sup>/e<sup>−</sup> pair transfer to form the key *OCHO intermediate on a Bi surface is a slow, kinetically sluggish endergonic process, resulting in a large overpotential and narrow potential window for high HCOOH/HCOO<sup>−</sup> selectivity. Altering the localized <em>p</em>-orbital electron states of Bi to change intermediate binding behaviors is difficult. We addressed this problem by using an <em>in-situ</em> polymerization method to obtain a polyaniline-Bi hybrid (PANI-Bi) with Bi surrounded by PANI chains. Combined experimental and computational studies indicate that the polyaniline acted as an “electron pump” that facilitated charge transfer from the PANI backbone to the Bi surface and changed the <em>p</em>-orbital electrons of the Bi active sites. This lowered the energy barrier for the adsorption of intermediates and facilitated *OCHO formation. Consequently, a significant increase in formate production was observed, achieving a single-pass carbon efficiency exceeding 48.7% at 800 mA cm<sup>−2</sup>. This organic functionalization strategy, aimed at modifying the electronic structure of heterogeneous catalysts, offers a promising approach for achieving highly selective electroreduction of CO<sub>2</sub> at a high current density.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 237-247"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915429","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}
Catalytic coupling of abundant CO2 or renewable CH3OH with nitrogenous small molecules, such as N2, NH3, and NO3−, has emerged as a promising strategy for synthesizing high-value organonitrogen compounds. However, conventional thermal catalysis for C–N bond formation often relies on external chemical reagents and energy-intensive conditions, raising concerns about process sustainability. Photocatalysis offers a sustainable alternative by utilizing sunlight to generate high-energy electron-hole pairs in semiconductors, which can activate inert chemical bonds (e.g., C=O and N≡N) for programmed coupling under ambient conditions. In this review, we dissect the fundamental activation mechanisms underlying photon-mediated C‒N coupling reactions, highlight key recent breakthroughs in the synthesis of urea, formamide, and amino acids, and analyze persistent challenges alongside emerging opportunities. This work aims to deepen the understanding of photocatalytic C–N coupling reactions and inspire research interest in sustainable nitrogen fixation and carbon utilization.
{"title":"Photocatalyzed C–N coupling reactions of small molecules","authors":"Lin-Xing Zhang , Chang-Long Tan , Ming-Yu Qi , Zi-Rong Tang , Yi-Jun Xu","doi":"10.1016/S1872-2067(25)64838-8","DOIUrl":"10.1016/S1872-2067(25)64838-8","url":null,"abstract":"<div><div>Catalytic coupling of abundant CO<sub>2</sub> or renewable CH<sub>3</sub>OH with nitrogenous small molecules, such as N<sub>2</sub>, NH<sub>3</sub>, and NO<sub>3</sub><sup>−</sup>, has emerged as a promising strategy for synthesizing high-value organonitrogen compounds. However, conventional thermal catalysis for C–N bond formation often relies on external chemical reagents and energy-intensive conditions, raising concerns about process sustainability. Photocatalysis offers a sustainable alternative by utilizing sunlight to generate high-energy electron-hole pairs in semiconductors, which can activate inert chemical bonds (e.g., C=O and N≡N) for programmed coupling under ambient conditions. In this review, we dissect the fundamental activation mechanisms underlying photon-mediated C‒N coupling reactions, highlight key recent breakthroughs in the synthesis of urea, formamide, and amino acids, and analyze persistent challenges alongside emerging opportunities. This work aims to deepen the understanding of photocatalytic C–N coupling reactions and inspire research interest in sustainable nitrogen fixation and carbon utilization.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 7-19"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915432","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
In recent decades, the unabated consumption of fossil fuels has resulted in a sustained increase in carbon dioxide emissions, exacerbating environmental challenges typified by the greenhouse effect, which has underscored the urgent imperative to develop highly efficient carbon dioxide capture and utilization technologies. The electrocatalytic carbon dioxide reduction reaction (eCO2RR) has emerged as a promising strategy for the conversion of CO2 into high-value-added chemical commodities. Recent investigations have demonstrated that alkali cations played a pivotal role in eCO2RR, encompassing enhancements in catalytic activity and modulations of product selectivity. Despite these advancements, how exactly the alkali cations affect the electrocatalytic reaction process and the key determinants of alkali cation effects remain subjects of ongoing debate. We analyzed current research on the effects of alkali cations, in which the concentration and type of alkali cations were generally correlated with eCO2RR performance. However, the distribution of alkali cations at the electrode interface is often overlooked. In this study, we first conclude recent advancements in electric double layer theory and elucidate three distinct modes of alkali cation distribution at the electrode-electrolyte interface. Subsequently, we systematically summarize the specific mechanisms through which these cations operate in different electrolyte systems. Furthermore, we propose fundamental perspectives for future investigations into alkali cation effects, aiming to provide guiding principles for the rational design of next-generation advanced eCO2RR electrolysis systems.
{"title":"Alkali cation effects in electrochemical carbon dioxide reduction","authors":"Jiaqi Xiang , Limiao Chen , Shanyong Chen , You-Nian Liu","doi":"10.1016/S1872-2067(25)64834-0","DOIUrl":"10.1016/S1872-2067(25)64834-0","url":null,"abstract":"<div><div>In recent decades, the unabated consumption of fossil fuels has resulted in a sustained increase in carbon dioxide emissions, exacerbating environmental challenges typified by the greenhouse effect, which has underscored the urgent imperative to develop highly efficient carbon dioxide capture and utilization technologies. The electrocatalytic carbon dioxide reduction reaction (eCO<sub>2</sub>RR) has emerged as a promising strategy for the conversion of CO<sub>2</sub> into high-value-added chemical commodities. Recent investigations have demonstrated that alkali cations played a pivotal role in eCO<sub>2</sub>RR, encompassing enhancements in catalytic activity and modulations of product selectivity. Despite these advancements, how exactly the alkali cations affect the electrocatalytic reaction process and the key determinants of alkali cation effects remain subjects of ongoing debate. We analyzed current research on the effects of alkali cations, in which the concentration and type of alkali cations were generally correlated with eCO<sub>2</sub>RR performance. However, the distribution of alkali cations at the electrode interface is often overlooked. In this study, we first conclude recent advancements in electric double layer theory and elucidate three distinct modes of alkali cation distribution at the electrode-electrolyte interface. Subsequently, we systematically summarize the specific mechanisms through which these cations operate in different electrolyte systems. Furthermore, we propose fundamental perspectives for future investigations into alkali cation effects, aiming to provide guiding principles for the rational design of next-generation advanced eCO<sub>2</sub>RR electrolysis systems.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 38-58"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915444","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 : 2026-01-01DOI: 10.1016/S1872-2067(25)64804-2
Wenbo Shi , Kai Zhu , Xiaogang Fu , Chenhong Liu , Yang Yuan , Jialiang Pan , Qing Zhang , Zhengyu Bai
Single atomic iron-nitrogen-carbon (Fe-N-C) have emerged as promising catalysts for the oxygen reduction reaction (ORR), however, the insufficient activity and stability hindered their application in proton exchange membrane fuel cells (PEMFCs). Simultaneously regulating the coordination environments and local carbon structures of atomic Fe-N sites is essential to boost Fe-N-C's ORR performance. In this study, a dual-site confinement strategy is proposed to precisely incorporate Mn single atoms at adjacent Fe sites to form active and stable FeMn-N catalytic structure within a graphitic carbon matrix, which is achieved via heat treatment of MnFe2O4 nanoparticles embedded ZIF-8. Experimental and theoretical calculations demonstrate that the incorporation of Mn atoms could effectively modulate the electronic structure of Fe atoms, enhance Fe–N bond stability and reduce Fe site dissolution. Moreover, in-situ Raman and in-situ attenuated total reflectance surface-enhanced infrared absorption spectroscopy spectra suggest that Mn doping could suppress Fenton reactions by optimizing the ORR pathway through facilitating *OH intermediate desorption and circumventing *OOH intermediate formation. The synthesized FeMn-N-C exhibits better catalytic activity than commercial Pt/C catalysts (E1/2 of 0.885 vs. 0.855 V) and maintains stable cycling operation over 20000 cycles with a small E1/2 gap of 95 mV. When applied in PEMFCs, FeMn-N-C achieves a high peak power density of 899.9 mW cm−2 and retains 66.4% of its initial performance after 20000 square-wave cycles, which is superior to Fe-N-C catalyst. This study provides an innovative design strategy for developing high-performance, long-lasting ORR catalysts for PEMFCs.
单原子铁-氮-碳（Fe-N-C）已成为氧还原反应（ORR）的催化剂，但其活性和稳定性不足阻碍了其在质子交换膜燃料电池（pemfc）中的应用。同时调节Fe-N原子位的配位环境和局部碳结构对提高Fe-N- c的ORR性能至关重要。在本研究中，提出了一种双位点约束策略，通过热处理嵌入ZIF-8的MnFe2O4纳米颗粒，将Mn单原子精确地结合在相邻的Fe位点上，在石墨碳基体内形成活性稳定的FeMn-N催化结构。实验和理论计算表明，Mn原子的掺入可以有效地调节Fe原子的电子结构，增强Fe - n键的稳定性，减少Fe位点的溶解。此外，原位拉曼光谱和原位衰减全反射表面增强红外吸收光谱表明，Mn掺杂可以通过促进*OH中间体解吸和规避*OOH中间体形成来优化ORR途径，从而抑制Fenton反应。合成的FeMn-N-C催化剂的催化活性优于商用Pt/C催化剂（E1/2为0.885 vs. 0.855 V），在20000次循环中保持稳定的循环运行，e2 /2间隙很小，为95 mV。当FeMn-N-C应用于pemfc时，经过20000次方波循环，FeMn-N-C的峰值功率密度达到899.9 mW cm - 2，保持了66.4%的初始性能，优于Fe-N-C催化剂。该研究为开发高性能、长效的pemfc ORR催化剂提供了一种创新的设计策略。
{"title":"Dual-site confinement strategy tuning Fe-N-C electronic structure to enhance oxygen reduction performance in PEM fuel cells","authors":"Wenbo Shi , Kai Zhu , Xiaogang Fu , Chenhong Liu , Yang Yuan , Jialiang Pan , Qing Zhang , Zhengyu Bai","doi":"10.1016/S1872-2067(25)64804-2","DOIUrl":"10.1016/S1872-2067(25)64804-2","url":null,"abstract":"<div><div>Single atomic iron-nitrogen-carbon (Fe-N-C) have emerged as promising catalysts for the oxygen reduction reaction (ORR), however, the insufficient activity and stability hindered their application in proton exchange membrane fuel cells (PEMFCs). Simultaneously regulating the coordination environments and local carbon structures of atomic Fe-N sites is essential to boost Fe-N-C's ORR performance. In this study, a dual-site confinement strategy is proposed to precisely incorporate Mn single atoms at adjacent Fe sites to form active and stable FeMn-N catalytic structure within a graphitic carbon matrix, which is achieved via heat treatment of MnFe<sub>2</sub>O<sub>4</sub> nanoparticles embedded ZIF-8. Experimental and theoretical calculations demonstrate that the incorporation of Mn atoms could effectively modulate the electronic structure of Fe atoms, enhance Fe–N bond stability and reduce Fe site dissolution. Moreover, <em>in-situ</em> Raman and <em>in-situ</em> attenuated total reflectance surface-enhanced infrared absorption spectroscopy spectra suggest that Mn doping could suppress Fenton reactions by optimizing the ORR pathway through facilitating *OH intermediate desorption and circumventing *OOH intermediate formation. The synthesized FeMn-N-C exhibits better catalytic activity than commercial Pt/C catalysts (<em>E</em><sub>1/2</sub> of 0.885 <em>vs</em>. 0.855 V) and maintains stable cycling operation over 20000 cycles with a small <em>E</em><sub>1/2</sub> gap of 95 mV. When applied in PEMFCs, FeMn-N-C achieves a high peak power density of 899.9 mW cm<sup>−2</sup> and retains 66.4% of its initial performance after 20000 square-wave cycles, which is superior to Fe-N-C catalyst. This study provides an innovative design strategy for developing high-performance, long-lasting ORR catalysts for PEMFCs.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 293-303"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915266","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 : 2026-01-01DOI: 10.1016/S1872-2067(25)64879-0
Shaodan Wang , Heng Yang , Lijun Xue , Jianjun Zhang , Shuxin Ouyang , Lili Wen
Cooperative coupling of photocatalytic hydrogen generation with oxidative organic synthesis is promising in simultaneously producing sustainable energy and value-added chemicals. However, the photocatalytic activity is constrained by restricted redox potentials and insufficient photocarrier separation and transfer. Herein, we construct S-scheme heterojunctions based on metal-doped ZnIn2S4 and covalent organic frameworks, denoted as M-ZIS/TpPa-1 (M = Ni or Mo). Theoretical calculations demonstrated that Mo-ZIS possess optimum H adsorption Gibbs free energies, deeper downshift of sulfur p-band center and higher integrated crystal orbital Hamilton population (ICOHP) value than Ni-ZIS and ZIS to optimize H adsorption/desorption dynamics. Besides, metal-doping reasonably enhanced the interfacial charge transfer in heterostructures, identifying the enlarged internal electric field (IEF) in Mo-ZIS/TpPa-1 than Ni-ZIS/TpPa-1 and ZIS/TpPa-1. Moreover, experimental explorations of photoelectrochemical measurements, femtosecond transient absorption spectroscopy, in-situ irradiated X-ray photoelectron spectroscopy and electron paramagnetic resonance verified the facilitated photocarrier separation and migration in metal-doped S-scheme heterojunctions. Ultimately, Mo0.01-ZIS/TpPa-1 exhibited visible-light driven H2 evolution rate of 1648 μmol g−1 h−1 and N-benzylidenebenzylamine formation rate of 1812 μmol g−1 h−1, better than Ni0.048-ZIS/TpPa-1, and superior to parent ZIS/TpPa-1. This work might provide insights into the modulation of H adsorption/desorption behavior and IEF within S-scheme heterostructures via rational metal-doping strategy for efficient dual-functional photocatalysis.
{"title":"S-scheme heterojunctions of metal-doped ZnIn2S4/TpPa-1: Regulating H adsorption/desorption and internal electric field for boosted dual-functional photocatalysis","authors":"Shaodan Wang , Heng Yang , Lijun Xue , Jianjun Zhang , Shuxin Ouyang , Lili Wen","doi":"10.1016/S1872-2067(25)64879-0","DOIUrl":"10.1016/S1872-2067(25)64879-0","url":null,"abstract":"<div><div>Cooperative coupling of photocatalytic hydrogen generation with oxidative organic synthesis is promising in simultaneously producing sustainable energy and value-added chemicals. However, the photocatalytic activity is constrained by restricted redox potentials and insufficient photocarrier separation and transfer. Herein, we construct S-scheme heterojunctions based on metal-doped ZnIn<sub>2</sub>S<sub>4</sub> and covalent organic frameworks, denoted as <em>M</em>-ZIS/TpPa-1 (<em>M</em> = Ni or Mo). Theoretical calculations demonstrated that Mo-ZIS possess optimum H adsorption Gibbs free energies, deeper downshift of sulfur <em>p</em>-band center and higher integrated crystal orbital Hamilton population (ICOHP) value than Ni-ZIS and ZIS to optimize H adsorption/desorption dynamics. Besides, metal-doping reasonably enhanced the interfacial charge transfer in heterostructures, identifying the enlarged internal electric field (IEF) in Mo-ZIS/TpPa-1 than Ni-ZIS/TpPa-1 and ZIS/TpPa-1. Moreover, experimental explorations of photoelectrochemical measurements, femtosecond transient absorption spectroscopy, <em>in-situ</em> irradiated X-ray photoelectron spectroscopy and electron paramagnetic resonance verified the facilitated photocarrier separation and migration in metal-doped S-scheme heterojunctions. Ultimately, Mo<sub>0.01</sub>-ZIS/TpPa-1 exhibited visible-light driven H<sub>2</sub> evolution rate of 1648 μmol g<sup>−1</sup> h<sup>−1</sup> and N-benzylidenebenzylamine formation rate of 1812 μmol g<sup>−1</sup> h<sup>−1</sup>, better than Ni<sub>0.048</sub>-ZIS/TpPa-1, and superior to parent ZIS/TpPa-1. This work might provide insights into the modulation of H adsorption/desorption behavior and IEF within S-scheme heterostructures via rational metal-doping strategy for efficient dual-functional photocatalysis.</div></div>","PeriodicalId":9832,"journal":{"name":"Chinese Journal of Catalysis","volume":"80 ","pages":"Pages 159-173"},"PeriodicalIF":17.7,"publicationDate":"2026-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145915324","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}
扫码关注我们
求助内容：
应助结果提醒方式：
京公网安备 11010802042870号