Chem CatalysisPub Date : 2026-09-10DOI: 10.1016/j.checat.2026.101863
Dejing Xu,Tianyuan Pan,Ruozhou Huang,Chenjuan Yu,Zhicheng Deng,Yuping Wang
{"title":"Unimolecular synergistic precatalysts for visible-light-driven PINO catalysis","authors":"Dejing Xu,Tianyuan Pan,Ruozhou Huang,Chenjuan Yu,Zhicheng Deng,Yuping Wang","doi":"10.1016/j.checat.2026.101863","DOIUrl":"https://doi.org/10.1016/j.checat.2026.101863","url":null,"abstract":"Phthalimide-N-oxyl (PINO) radical is a powerful hydrogen atom transfer (HAT) catalyst, but its photochemical generation often relies on high-energy irradiation or exogenous photosensitizers, which introduce diffusion-dependent intermolecular activation. Here, we develop a photoactivatable unimolecular precatalyst by covalently integrating a PINO precursor with a fluorene unit. Upon visible light irradiation, the precatalyst undergoes intramolecular homolysis to generate PINO and a fluorenone precursor, enabling a synergistic dual HAT catalytic cycle without external photosensitizers. The optimized precatalyst achieves efficient aerobic oxidation of isochroman and outperforms physical mixtures of its components. Mechanistic studies reveal that photoexcited fluorenone regenerates PINO while serving as an independent HAT catalyst. This strategy further enables light-driven oxidative degradation of poly(methyl acrylate), polyurethane, and commercial polymer foam and establishes unimolecular synergistic precatalysts as a promising design strategy for integrated catalytic systems.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"144 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2026-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148915178","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}
Chem CatalysisPub Date : 2026-09-09DOI: 10.1016/j.checat.2026.101845
Manasa Rajeev,Fernanda Brito dos Santos,Shannon W. Boettcher,Paul A. Kempler
{"title":"Reverse polarization degradation of nickel iron oxyhydroxide anodes in alkaline water electrolysis","authors":"Manasa Rajeev,Fernanda Brito dos Santos,Shannon W. Boettcher,Paul A. Kempler","doi":"10.1016/j.checat.2026.101845","DOIUrl":"https://doi.org/10.1016/j.checat.2026.101845","url":null,"abstract":"We report the effect of reverse polarization on thin-film Ni(Fe)OOH anodes in conditions that mirror those seen in commercial alkaline water electrolyzer stacks. Regardless of the extent of the reverse polarization potential, the anodic charge capacity decreases over successive cycles, indicating loss of active Ni2+/Ni3+ sites. Electrodes held for a longer period in the reduced state exhibited an accelerated catalyst loss through dissolution and structural reorganization during reverse polarization. In situ Raman spectroscopy and X-ray photoelectron spectroscopy revealed a significant decrease in the Fe:Ni surface ratio after reverse polarization, which correlates with a measurable decline in activity toward the oxygen evolution reaction. These findings illustrate how nickel iron oxyhydroxide anodes degrade during reverse polarization conditions and how managing the dissolved ions in the recirculating KOH improves anode lifetimes.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"60 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2026-09-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148908876","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}
Chem CatalysisPub Date : 2026-09-02DOI: 10.1016/j.checat.2026.101839
Feifei Wang,Chunpeng Yang
{"title":"Designing molecular catalysts for zinc-iodine batteries","authors":"Feifei Wang,Chunpeng Yang","doi":"10.1016/j.checat.2026.101839","DOIUrl":"https://doi.org/10.1016/j.checat.2026.101839","url":null,"abstract":"Feifei Wang is currently a postdoctoral researcher at the Max Planck Institute of Microstructure Physics. His research focuses on interfacial chemistry and molecular engineering for aqueous zinc batteries, especially zinc-iodine systems, with a focus on regulating polyiodide conversion, ion desolvation, and interfacial stability for safe and durable energy storage. Chunpeng Yang is a professor at the School of Chemical Engineering and Technology, Tianjin University. His research focuses on high-safety, high-energy electrochemical energy-storage technologies, including solid-state batteries, as well as advanced electrode materials and aqueous zinc battery materials and devices.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"73 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2026-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148877423","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}
Chem CatalysisPub Date : 2026-09-02DOI: 10.1016/j.checat.2026.101843
Yuhan Cao,Wenrui Zheng,Fen Mi,Yi Han,Chunyan Chi,Yixin Lu
{"title":"Copper-catalyzed enantioselective CO2-bridged hydrodimerization of 1,3-enynes to access C2-symmetric alkynylols","authors":"Yuhan Cao,Wenrui Zheng,Fen Mi,Yi Han,Chunyan Chi,Yixin Lu","doi":"10.1016/j.checat.2026.101843","DOIUrl":"https://doi.org/10.1016/j.checat.2026.101843","url":null,"abstract":"Converting CO2 into value-added products via catalysis is a promising strategy in sustainable chemistry. 1,3-Enynes, which contain both alkene and alkyne moieties and multiple latent reactive sites, are versatile substrates for synthesis. Leveraging alkene moiety in 1,3-enynes for 1,2-hydrofunctionalization and using CO2 as a molecular “bridge,” we document a copper-catalyzed enantioselective synthesis of C2-symmetric alkynylols bearing 1,6-diyne groups. The protocol is efficient, highly enantioselective, applicable to various substrates, and tolerant of a wide range of functional groups. The resulting C2-symmetric alkynylols serve as effective monomers for functional chiral polymers via either copolymerization or homopolymerization. Mechanistic studies indicate that a key aldehyde intermediate, formed via hydroformylation, is crucial for generating the CO2-linked homocoupling product.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"9 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2026-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148877426","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":"Electrofuel recipes for decoupled electro-biosystems in zero-carbon biomanufacturing","authors":"Tingting Zheng,Yuan Ji,Mingming Guo,Xiang Gao,Chuan Xia","doi":"10.1016/j.checat.2026.101840","DOIUrl":"https://doi.org/10.1016/j.checat.2026.101840","url":null,"abstract":"Renewable electricity can decarbonize energy supply, but sustainable carbon feedstocks remain a major challenge for manufacturing chemicals, materials, and food. Decoupled electro-biosystems address this challenge by combining electrochemical CO2 conversion with biological upgrading. In this perspective, we argue that the key design question is not which single intermediate to produce, but what combination of intermediates best meets biological demand. We introduce the concept of an electrofuel recipe, in which electrochemically generated products serve distinct roles as carbon sources and energy sources. This approach provides a framework for separating carbon and energy metabolism and may improve carbon utilization beyond that achievable with single-substrate fermentation. We discuss the opportunities and limitations of different intermediates, the importance of conditioning and flux matching, and future directions for catalyst, reactor, and process designs in electro-biosystems.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"17 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2026-09-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148877431","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}
Chem CatalysisPub Date : 2026-08-31DOI: 10.1016/j.checat.2026.101837
Xiaocheng Lan,Chuanyu Si,Dehuai Liu,Shusen Liu,Tiefeng Wang
{"title":"Bifunctional dual active center design for selective hydrogenation of unsaturated functional groups","authors":"Xiaocheng Lan,Chuanyu Si,Dehuai Liu,Shusen Liu,Tiefeng Wang","doi":"10.1016/j.checat.2026.101837","DOIUrl":"https://doi.org/10.1016/j.checat.2026.101837","url":null,"abstract":"The selective hydrogenation of unsaturated functional groups plays a critical role in fine chemical synthesis. Bifunctional dual active centers (bi-DACs) have emerged as an efficient catalytic strategy, significantly enhancing both activity and selectivity. Center A, typically a metallic site, dissociates H2, while center B, derived from metal oxides or metallic sites, adsorbs and activates the unsaturated functional group. Bi-DACs are classified as metal site-metal oxide (MA-MBOx) or metal site-metal site (MA-MB) systems. MA-MBOx catalysts utilize oxygen vacancies to provide electrophilic properties that facilitate the activation of the unsaturated functional group, whereas MA-MB catalysts leverage charge transfer between metals to modulate their electronic properties. This review summarizes advances in bi-DAC catalysts for the hydrogenation of the unsaturated functional group, focusing on their structural diversity, mechanisms of catalytic enhancement, and design strategies. Challenges are discussed alongside future perspectives to guide the development of bi-DAC catalysts.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"17 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2026-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148877424","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":"Nickel-catalyzed precision deuteration of pharmaceutical for deuterated drug development","authors":"Chloé Tatol,Anvi Laëtitia Nguyen,Florence Castelli,Edmond Gravel,Maxime Jay,Sophie Feuillastre,Grégory Pieters","doi":"10.1016/j.checat.2026.101827","DOIUrl":"https://doi.org/10.1016/j.checat.2026.101827","url":null,"abstract":"Facilitating the access to therapeutic agents with optimized pharmacological properties remains a priority to improve human health. For azine-based active pharmaceutical ingredients, deuteration at their metabolic soft spot showed promise in improving the safety and pharmacokinetic profile of related drug candidates. In this context, the development of straightforward and efficient methods enabling the precise deuteration at these specific positions is essential to foster drug discovery and development. Herein, we describe an easy-to-implement method achieving high isotopic enrichments and regioselectivities for the precise deuteration of various azines, including pharmaceuticals. This hydrogen isotope exchange reaction relied on the in situ generation of nickel nanoparticles using deuterium gas as the isotopic source. While the broad substrate scope, excellent functional group tolerance, and ease of implementation of this method demonstrate its potential to accelerate the development of deuterated drugs, we further established that precise deuterium incorporation can serve as a strategic tool in prodrug design.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"268 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2026-08-31","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148877425","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}
Chem CatalysisPub Date : 2026-08-28DOI: 10.1016/j.checat.2026.101838
Yuan Ji,Binbin Chen,Xun Yu,Yajie Wang
{"title":"Thermostable artificial nicotinamide cofactor with reduced redox potential for biocatalysis","authors":"Yuan Ji,Binbin Chen,Xun Yu,Yajie Wang","doi":"10.1016/j.checat.2026.101838","DOIUrl":"https://doi.org/10.1016/j.checat.2026.101838","url":null,"abstract":"Oxidoreductases are valuable biocatalysts, but their industrial use is limited by the cost and instability of natural nicotinamide cofactors under harsh conditions. Here, we report CNMN+, a thermostable carbocyclic nicotinamide mononucleotide with a more negative redox potential than NADP+ and NMN+. An engineered nicotinamide riboside kinase from Kluyveromyces marxianus enabled chemoenzymatic CNMN+ synthesis in 97% yield, approximately 5.7-fold higher than that achieved by chemical synthesis. We further engineered Zymomonas mobilis glucose-6-phosphate dehydrogenase to regenerate CNMNH. The best variant, M12, showed a 202-fold increase in catalytic efficiency and a 145-fold increase in specific activity toward CNMN+ relative to wild type. The CNMNH regeneration system was coupled with thermostable hydrogenase for H2 evolution and ene-reductase for levodione production, resulting in higher product yields at 60°C than the NMN⁺- or NADP⁺-based systems under the tested conditions.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"271 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2026-08-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148858192","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}
Chem CatalysisPub Date : 2026-08-25DOI: 10.1016/j.checat.2026.101835
Qiuhui Zhu,Xue Xiao,Aoxiang Song,Ximing Li,Yan Zhou,Haitao Ren,Jiapeng Hu,Chuanyi Wang
{"title":"Spin-state engineering of atomic iron-based frustrated Lewis pairs for enhanced photocatalytic nitrogen fixation to ammonia","authors":"Qiuhui Zhu,Xue Xiao,Aoxiang Song,Ximing Li,Yan Zhou,Haitao Ren,Jiapeng Hu,Chuanyi Wang","doi":"10.1016/j.checat.2026.101835","DOIUrl":"https://doi.org/10.1016/j.checat.2026.101835","url":null,"abstract":"Photocatalytic nitrogen fixation offers a sustainable alternative to the energy-intensive Haber-Bosch process but remains limited by inefficient N2 adsorption and activation. Here, we construct atomic iron (Fe)-based frustrated Lewis pairs (Fe···OHSA FLPs) on defective bismuth (Bi)/bismuth oxybromide (BiOBr), where isolated Fe sites and surface hydroxyl groups function as Lewis acid and Lewis base centers, respectively. Characterizations and theoretical calculations reveal that the Fe···OH FLPs synergistically strengthen N2 adsorption, facilitate N≡N activation, and promote proton-coupled electron transfer. Consequently, the optimized catalyst achieves an ammonia (NH3) production rate of 502.64 μmol g−1 h−1 under sacrificial-agent-free conditions, representing a 13.96-fold enhancement over BiOBr. Mechanistically, oxygen-vacancy-induced tetracoordinated Fe decreases the crystal-field splitting between the t2g and eg orbitals, forming a high-spin electronic configuration. The resulting enhanced Fe 3d-N2 2p orbital coupling promotes electron transfer into antibonding orbitals and accelerates N≡N bond cleavage. This work establishes spin-state engineering as an effective strategy for activating N2 on single-atom-based FLP photocatalysts.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"11 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2026-08-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148821601","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}
Chem CatalysisPub Date : 2026-08-24DOI: 10.1016/j.checat.2026.101834
Haifeng Chen,Chenxi Wu,Liang Yi,Magnus Rueping
{"title":"Electrochemical atom-transfer radical addition to [1.1.1]propellane for the synthesis of bench-stable BCP–Br linchpins","authors":"Haifeng Chen,Chenxi Wu,Liang Yi,Magnus Rueping","doi":"10.1016/j.checat.2026.101834","DOIUrl":"https://doi.org/10.1016/j.checat.2026.101834","url":null,"abstract":"Selective termination of carbon-centered radicals under electrochemical conditions remains challenging, particularly in strained systems where over-reduction and unselective quenching can compete with productive atom transfer. Herein, we report an electrochemically enabled atom-transfer radical bromoalkylation of [1.1.1]propellane that converts activated alkyl bromides into isolable, bench-stable 1-alkyl-3-bromobicyclo[1.1.1]pentanes. Constant-current electrolysis with a zinc anode, nickel-foam cathode, and tetrabutylammonium bromide electrolyte initiates alkyl radical formation while favoring bromine atom transfer to the bicyclopentyl radical intermediate. The reaction accommodates primary, secondary, and tertiary activated alkyl bromides, including complex drug-like substrates, and the resulting BCP–Br products undergo C-, B-, P-, Se-, O-, and N-functionalization. Mechanistic experiments, including radical-clock and radical-trapping studies, cyclic voltammetry, and charge analysis, are consistent with an electrochemically initiated ATRA chain. This method provides a modular entry to brominated BCP linchpins and illustrates how electrochemical initiation can guide radical reactivity in strained molecular scaffolds.","PeriodicalId":53121,"journal":{"name":"Chem Catalysis","volume":"53 1","pages":""},"PeriodicalIF":9.4,"publicationDate":"2026-08-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148806380","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}