Pub Date : 2026-01-15DOI: 10.1016/j.checat.2025.101578
Huijun Lv, Rui Zhang, Rafikul Ali Saha, Abhisek Bandyopadhyay, Ruilin Wei, Gengfeng Zheng, Yongzheng Zhang, Weihua Ning, Yuhang Wang
Formic acid is the most economically viable CO2 electroreduction product, but its production faces challenges due to instability during long-term electrolysis and additional costs associated with acidifying the CO2-derived formate salt. Both issues arise from the use of electrolytes containing metal cations. Metal-cation-free acidic CO2 electrolysis can potentially clean the two hurdles, yet the absence of the cation effect overwhelmingly favors H2 evolution over formic acid formation. Here, we utilize a catalyst derived from Cs2AgBiBr6 perovskites, featuring highly dispersed Ag nanoparticles supported by hybridized Bi0/Bi2O2CO3 nanosheets, to synchronously increase local alkalinity and facilitate ∗OCHO intermediate formation. A metal-cation-free acidic CO2 electrolyzer equipped with this catalyst offers Faradaic efficiencies of more than 75% at industrially relevant current densities, with a CO2-to-HCOOH utilization efficiency of 50%. Under 90-h electrolysis at 200 mA cm−2 and 3.5 V, Faradaic efficiencies of ∼70% are achieved, representing a >65% improvement in formic acid productivity compared to the state of the art.
甲酸是最经济可行的CO2电还原产物，但由于长期电解过程中的不稳定性以及酸化CO2衍生的甲酸盐带来的额外成本，甲酸的生产面临挑战。这两个问题都源于使用含有金属阳离子的电解质。无金属阳离子的酸性CO2电解可以潜在地清除这两个障碍，但缺乏阳离子效应压倒性地有利于H2的演化而不是甲酸的形成。在这里，我们利用一种源自Cs2AgBiBr6钙钛矿的催化剂，具有高度分散的银纳米颗粒，由杂化的Bi0/Bi2O2CO3纳米片支撑，以同步增加局部碱度并促进∗OCHO中间体的形成。配备该催化剂的无金属阳离子酸性CO2电解槽在工业相关电流密度下的法拉第效率超过75%，CO2- hcooh利用率为50%。在200 mA cm - 2和3.5 V下电解90小时，法拉第效率达到了70%，与目前的技术水平相比，甲酸生产率提高了65%。
{"title":"Synchronized elementary step regulation and local environment control for metal-cation-free CO2 electroreduction to formic acid","authors":"Huijun Lv, Rui Zhang, Rafikul Ali Saha, Abhisek Bandyopadhyay, Ruilin Wei, Gengfeng Zheng, Yongzheng Zhang, Weihua Ning, Yuhang Wang","doi":"10.1016/j.checat.2025.101578","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101578","url":null,"abstract":"Formic acid is the most economically viable CO<sub>2</sub> electroreduction product, but its production faces challenges due to instability during long-term electrolysis and additional costs associated with acidifying the CO<sub>2</sub>-derived formate salt. Both issues arise from the use of electrolytes containing metal cations. Metal-cation-free acidic CO<sub>2</sub> electrolysis can potentially clean the two hurdles, yet the absence of the cation effect overwhelmingly favors H<sub>2</sub> evolution over formic acid formation. Here, we utilize a catalyst derived from Cs<sub>2</sub>AgBiBr<sub>6</sub> perovskites, featuring highly dispersed Ag nanoparticles supported by hybridized Bi<sup>0</sup>/Bi<sub>2</sub>O<sub>2</sub>CO<sub>3</sub> nanosheets, to synchronously increase local alkalinity and facilitate ∗OCHO intermediate formation. A metal-cation-free acidic CO<sub>2</sub> electrolyzer equipped with this catalyst offers Faradaic efficiencies of more than 75% at industrially relevant current densities, with a CO<sub>2</sub>-to-HCOOH utilization efficiency of 50%. Under 90-h electrolysis at 200 mA cm<sup>−2</sup> and 3.5 V, Faradaic efficiencies of ∼70% are achieved, representing a >65% improvement in formic acid productivity compared to the state of the art.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"141 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2026-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145968559","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
{"title":"Controllable co-generation of bulk and surface hydrogen species in a palladium membrane reactor via collaborative electrolysis","authors":"Kejian Kong, Xingjian Xu, Xiang Liu, An-Zhen Li, Mingfei Shao, Haohong Duan","doi":"10.1016/j.checat.2025.101602","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101602","url":null,"abstract":"","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"9 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2026-01-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145903492","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-01-02DOI: 10.1016/j.checat.2025.101625
Linsen Huang, Yao Zheng, Shi-Zhang Qiao
{"title":"Challenges and opportunities in the electrochemical production of ethylene glycol","authors":"Linsen Huang, Yao Zheng, Shi-Zhang Qiao","doi":"10.1016/j.checat.2025.101625","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101625","url":null,"abstract":"","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"130 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2026-01-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895311","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-29DOI: 10.1016/j.checat.2025.101601
Fangyu Gao, Yunxuan Zhao, Tierui Zhang
{"title":"Challenges and opportunities for the large-scale solar-driven production of nitrogenous fertilizers","authors":"Fangyu Gao, Yunxuan Zhao, Tierui Zhang","doi":"10.1016/j.checat.2025.101601","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101601","url":null,"abstract":"","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"23 1","pages":"101601"},"PeriodicalIF":9.4,"publicationDate":"2025-12-29","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145895362","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-24DOI: 10.1016/j.checat.2025.101583
Jian-Qiang Zhao, Liang Wei Benjamin Yep, Bin-Miao Yang, Yu Zhao
{"title":"Advances in catalytic enantioconvergent construction of carbon-nitrogen bonds","authors":"Jian-Qiang Zhao, Liang Wei Benjamin Yep, Bin-Miao Yang, Yu Zhao","doi":"10.1016/j.checat.2025.101583","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101583","url":null,"abstract":"","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"46 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145823631","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Photo(thermal) catalytic dry reforming of methane (DRM) is a promising approach for mitigating greenhouse effects. It simultaneously converts CO2 and CH4 into syngas and uses solar energy instead of traditional thermal energy to curb CO2 re-emission, thus enabling carbon neutrality and green chemical production. Considering the vision for industrializing photo(thermal) catalytic DRM technology, group VIII metal-based catalysts have become some of the most important and mainstream catalysts because of their strong light-to-fuel conversion ability. Therefore, this review systematically clarifies their design principles and structure-performance relationships. The discussion highlights characteristics of group VIII metal-based photo(thermal) catalysts, such as localized surface plasmon resonance (LSPR) and metal-support interactions, to clarify their contribution to thermodynamic barriers, activation, or stability. The synergistic effect between interfacial electron transfer and active sites is further unraveled. This review offers theoretical insights to guide the development of high-quality and cost-effective catalysts, thereby contributing to further developments.
{"title":"Prominent group VIII metal-based catalysts for photo(thermal) catalytic dry reforming of methane reaction systems","authors":"Dezheng Li, Shaoyuan Sun, Manqi Zhao, Chao Wang, Huimin Liu, Changxu Wang, Nan Wang, Yiming Lei, Heting Hou, Qijian Zhang, Xiaohao Liu","doi":"10.1016/j.checat.2025.101576","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101576","url":null,"abstract":"Photo(thermal) catalytic dry reforming of methane (DRM) is a promising approach for mitigating greenhouse effects. It simultaneously converts CO<sub>2</sub> and CH<sub>4</sub> into syngas and uses solar energy instead of traditional thermal energy to curb CO<sub>2</sub> re-emission, thus enabling carbon neutrality and green chemical production. Considering the vision for industrializing photo(thermal) catalytic DRM technology, group VIII metal-based catalysts have become some of the most important and mainstream catalysts because of their strong light-to-fuel conversion ability. Therefore, this review systematically clarifies their design principles and structure-performance relationships. The discussion highlights characteristics of group VIII metal-based photo(thermal) catalysts, such as localized surface plasmon resonance (LSPR) and metal-support interactions, to clarify their contribution to thermodynamic barriers, activation, or stability. The synergistic effect between interfacial electron transfer and active sites is further unraveled. This review offers theoretical insights to guide the development of high-quality and cost-effective catalysts, thereby contributing to further developments.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"28 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145813660","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-18DOI: 10.1016/j.checat.2025.101579
Jesse L. Peltier
In a recent Journal of the American Chemical Society publication, Sarazen and colleagues investigate a series of Fe metal-organic framework catalysts in the oxidation of styrene to elucidate design principles that govern rate and selectivity. They reveal a detailed mechanistic picture that decouples the active site and the microenvironment.
{"title":"A roadmap for designing smarter metal-organic frameworks for catalytic oxidation","authors":"Jesse L. Peltier","doi":"10.1016/j.checat.2025.101579","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101579","url":null,"abstract":"In a recent <em>Journal of the American Chemical Society</em> publication, Sarazen and colleagues investigate a series of Fe metal-organic framework catalysts in the oxidation of styrene to elucidate design principles that govern rate and selectivity. They reveal a detailed mechanistic picture that decouples the active site and the microenvironment.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"93 1","pages":"101579"},"PeriodicalIF":9.4,"publicationDate":"2025-12-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145786311","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-04DOI: 10.1016/j.checat.2025.101581
Carlos Enrique Torres-Méndez, Haining Tian
Access to multiple redox states in electrocatalysts is vital to enhance the activity and stability of molecular catalysts toward the production of fuels. In this work, we have developed a catalyst based on two caffeine units covalently linked to a benzothiadiazole core. This catalyst can store three electrons in a fully reversible manner. Under reductive conditions and in the presence of strong acids, this molecule forms an organic hydride donor that is electroactive toward H2 evolution at mild potentials in DMSO. Faradaic efficiency up to 92% and a turnover number up to 23 were achieved after 4 h of controlled potential electrolysis with no decomposition of the catalyst. A reaction mechanism involving a hydride transfer step is proposed based on the chemical species found under electrocatalytic conditions and density functional theory (DFT) calculations. The development of this small organic molecule is a step forward in the quest to low-cost, active, and long-term stable electrocatalysts for H2 evolution.
{"title":"Hydrogen evolution via hydride transfer by a small organic benzothiadiazole-caffeine electrocatalyst","authors":"Carlos Enrique Torres-Méndez, Haining Tian","doi":"10.1016/j.checat.2025.101581","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101581","url":null,"abstract":"Access to multiple redox states in electrocatalysts is vital to enhance the activity and stability of molecular catalysts toward the production of fuels. In this work, we have developed a catalyst based on two caffeine units covalently linked to a benzothiadiazole core. This catalyst can store three electrons in a fully reversible manner. Under reductive conditions and in the presence of strong acids, this molecule forms an organic hydride donor that is electroactive toward H<sub>2</sub> evolution at mild potentials in DMSO. Faradaic efficiency up to 92% and a turnover number up to 23 were achieved after 4 h of controlled potential electrolysis with no decomposition of the catalyst. A reaction mechanism involving a hydride transfer step is proposed based on the chemical species found under electrocatalytic conditions and density functional theory (DFT) calculations. The development of this small organic molecule is a step forward in the quest to low-cost, active, and long-term stable electrocatalysts for H<sub>2</sub> evolution.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"28 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-12-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145689115","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-26DOI: 10.1016/j.checat.2025.101573
Yilin Zhao, Yu Zhang, Yi Wei, Jingyi Chen, Lei Fan, Junmei Chen, Shibo Xi, Mingchuan Luo, Lei Shen, Lei Wang
We develop an energy-efficient electrolytic system that integrates synchronized cathodic and anodic reactions for the electrochemical upcycling of waste polyethylene terephthalate (PET) plastics. This process is enabled by a palladium-nickel bimetallic anodic electrocatalyst exhibiting outstanding activity and selectivity toward the oxidation of ethylene glycol (EG), a key hydrolysis product of PET, into formate. Kinetic analysis and mechanistic studies reveal that nickel incorporation into palladium enhances EG dehydrogenation, thereby improving both the selectivity and activity for formate production. Furthermore, kilogram-scale commercial PET waste plastic upcycling is demonstrated in a 100 cm2 electrolyzer, achieving a high PET conversion yield of 89.3% after 100 h of continuous operation at a current of 20 A. Overall, this work represents a significant advancement in the development of energy-efficient electrocatalytic systems for PET plastic upgrading.
{"title":"PdNi bimetallic catalyst enables efficient electrochemical upcycling of waste plastics","authors":"Yilin Zhao, Yu Zhang, Yi Wei, Jingyi Chen, Lei Fan, Junmei Chen, Shibo Xi, Mingchuan Luo, Lei Shen, Lei Wang","doi":"10.1016/j.checat.2025.101573","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101573","url":null,"abstract":"We develop an energy-efficient electrolytic system that integrates synchronized cathodic and anodic reactions for the electrochemical upcycling of waste polyethylene terephthalate (PET) plastics. This process is enabled by a palladium-nickel bimetallic anodic electrocatalyst exhibiting outstanding activity and selectivity toward the oxidation of ethylene glycol (EG), a key hydrolysis product of PET, into formate. Kinetic analysis and mechanistic studies reveal that nickel incorporation into palladium enhances EG dehydrogenation, thereby improving both the selectivity and activity for formate production. Furthermore, kilogram-scale commercial PET waste plastic upcycling is demonstrated in a 100 cm<sup>2</sup> electrolyzer, achieving a high PET conversion yield of 89.3% after 100 h of continuous operation at a current of 20 A. Overall, this work represents a significant advancement in the development of energy-efficient electrocatalytic systems for PET plastic upgrading.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"47 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-11-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145600106","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-11-25DOI: 10.1016/j.checat.2025.101571
Christoph Kubis, Jiali Liu, Klaus Neymeyr, Robert Franke, Baoxin Zhang
Cobalt carbonyls are crucial for the 100% atom-economical hydroformylation of alkenes. While traditional industrial processes require harsh conditions (100–400 bar, 100°C–250°C), our work explores catalyst performance under significantly milder, energy-efficient parameters. Using in situ Fourier transform infrared (FTIR) spectroscopy complemented by density functional theory (DFT) calculations, we present a comprehensive investigation into the stability and interconversion of the active species, HCo(CO)4, and its precursors, Co2(CO)8 and Co4(CO)12. We establish that HCo(CO)4 is stable at pressures as low as 10 bar and 120°C. For the first time, we directly monitored the catalyst’s formation from various sources, including Co4(CO)12, Co(acac)2, and Co(OAc)2. The activation mechanism of a cationic bisphosphine Co(II) precursor is also elucidated. This research provides a critical foundation for analyzing and optimizing cobalt-based catalysts, paving the way for more sustainable industrial processes.
钴羰基对于100%原子经济型烯烃氢甲酰化至关重要。虽然传统的工业过程需要苛刻的条件（100 - 400 bar, 100°C - 250°C），但我们的工作探索了催化剂在更温和、更节能的参数下的性能。利用原位傅里叶变换红外（FTIR）光谱和密度泛函理论（DFT）计算，我们对活性物质HCo(CO)4及其前体Co2(CO)8和Co4(CO)12的稳定性和相互转化进行了全面的研究。我们确定HCo(CO)4在低至10 bar和120°C的压力下是稳定的。我们首次从不同的来源，包括Co4(CO)12, CO (acac)2和CO (OAc)2，直接监测催化剂的形成。本文还阐明了阳离子二膦前体Co（II）的活化机理。这项研究为分析和优化钴基催化剂提供了重要的基础，为更可持续的工业过程铺平了道路。
{"title":"Understanding the formation and stability of cobalt-based catalysts for homogeneous carbonylation reactions","authors":"Christoph Kubis, Jiali Liu, Klaus Neymeyr, Robert Franke, Baoxin Zhang","doi":"10.1016/j.checat.2025.101571","DOIUrl":"https://doi.org/10.1016/j.checat.2025.101571","url":null,"abstract":"Cobalt carbonyls are crucial for the 100% atom-economical hydroformylation of alkenes. While traditional industrial processes require harsh conditions (100–400 bar, 100°C–250°C), our work explores catalyst performance under significantly milder, energy-efficient parameters. Using <em>in situ</em> Fourier transform infrared (FTIR) spectroscopy complemented by density functional theory (DFT) calculations, we present a comprehensive investigation into the stability and interconversion of the active species, HCo(CO)<sub>4</sub>, and its precursors, Co<sub>2</sub>(CO)<sub>8</sub> and Co<sub>4</sub>(CO)<sub>12</sub>. We establish that HCo(CO)<sub>4</sub> is stable at pressures as low as 10 bar and 120°C. For the first time, we directly monitored the catalyst’s formation from various sources, including Co<sub>4</sub>(CO)<sub>12</sub>, Co(acac)<sub>2</sub>, and Co(OAc)<sub>2</sub>. The activation mechanism of a cationic bisphosphine Co(II) precursor is also elucidated. This research provides a critical foundation for analyzing and optimizing cobalt-based catalysts, paving the way for more sustainable industrial processes.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"47 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145594164","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
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