Xianhong Chen, Yang Wang, Jiaxiong Zhu, Chunyi Zhi, Wai-Yeung Wong
Green electrochemical energy storage is essential for carbon neutrality, and alkaline zinc batteries offer a compelling solution due to their inherent safety, low cost, and high energy density. However, their performance is limited by parasitic reactions, including corrosion, gas evolution, and slow Zn/ZnO conversion kinetics stemming from inefficient dissociation of the tetrahydroxozincate [Zn(OH)42−] intermediate. We address this by designing a series of cobalt porphyrins (Co-4N, Co-3N-O, Co-3N-S) that modulate the metal center's charge density for accelerating Zn(OH)42− decomposition, and control Zn2+ transport through the carboxyl-functionalized peripheries. The Co-3N-O-modified electrolyte achieves exceptional stability, maintaining stable cycle for over 80,000 s at 5 mA cm−2, which is more than four times longer than the <20,000 s achieved by the conventional KOH + ZnO electrolyte. In Zn||Ni batteries, this molecularly engineered electrolyte enables 110 stable cycles at 1 mA cm−2, significantly outperforming the unmodified system, which sustained only 20 cycles. These findings elucidate a structure-kinetics relationship for zincate regulation and demonstrate how customized molecular asymmetry can overcome persistent challenges in aqueous battery chemistry, offering a pathway to high-performance, durable energy storage systems.
{"title":"Asymmetric Electrolytes Govern Tetrahydroxozincate Dynamics for Stable Alkaline Zinc Batteries","authors":"Xianhong Chen, Yang Wang, Jiaxiong Zhu, Chunyi Zhi, Wai-Yeung Wong","doi":"10.1002/anie.202524438","DOIUrl":"https://doi.org/10.1002/anie.202524438","url":null,"abstract":"Green electrochemical energy storage is essential for carbon neutrality, and alkaline zinc batteries offer a compelling solution due to their inherent safety, low cost, and high energy density. However, their performance is limited by parasitic reactions, including corrosion, gas evolution, and slow Zn/ZnO conversion kinetics stemming from inefficient dissociation of the tetrahydroxozincate [Zn(OH)<sub>4</sub><sup>2−</sup>] intermediate. We address this by designing a series of cobalt porphyrins (Co-4N, Co-3N-O, Co-3N-S) that modulate the metal center's charge density for accelerating Zn(OH)<sub>4</sub><sup>2</sup><sup>−</sup> decomposition, and control Zn<sup>2</sup><sup>+</sup> transport through the carboxyl-functionalized peripheries. The Co-3N-O-modified electrolyte achieves exceptional stability, maintaining stable cycle for over 80,000 s at 5 mA cm<sup>−</sup><sup>2</sup>, which is more than four times longer than the <20,000 s achieved by the conventional KOH + ZnO electrolyte. In Zn||Ni batteries, this molecularly engineered electrolyte enables 110 stable cycles at 1 mA cm<sup>−2</sup>, significantly outperforming the unmodified system, which sustained only 20 cycles. These findings elucidate a structure-kinetics relationship for zincate regulation and demonstrate how customized molecular asymmetry can overcome persistent challenges in aqueous battery chemistry, offering a pathway to high-performance, durable energy storage systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"35 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139024","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}
Meltable organic–inorganic hybrid semiconductors are attractive for their potential for melt-based processing. Although meltable semiconducting metal halide perovskites have been extensively studied, meltable semiconducting coordination polymers (CPs) remain scarce, despite their excellent structural designability and the tunability of their optoelectronic properties. We report a new family of meltable semiconductive Pb(II) benzenethiolate CPs bearing long alkyl chains, formulated as [Pb(SPhOC6)2]n (KGF-34(C6); HSPhOC6 = 4-hexyloxybenzenethiol). For comparison, we also synthesized the classical analogue [Pb(SC6)2]n (KGF-59(C6); HSC6 = 1-hexanethiol). Single-crystal X-ray diffraction analyses revealed that both KGF-34(C6) and KGF-59(C6) adopt 2D architectures, albeit with distinct inorganic (–Pb–S–)n networks. A comprehensive characterization of the semiconducting properties, combined with first-principles calculations, revealed that KGF-34(C6) exhibits significantly higher photoconductivity, a narrower band gap, and a larger band dispersion than KGF-59(C6), attributable to differences in their inorganic (–Pb–S–)n network structures. Furthermore, both KGF-34(C6) and KGF-59(C6) exhibit multiple phase transitions, including melting and liquid crystalline formation, enabling the fabrication of optoelectronic devices via melt processing. Notably, this is the first report of meltable semiconducting CPs comprising benzenethiol-derived ligands. These findings offer a rational design strategy for developing melt-processable semiconductive materials based on metal–benzenethiolate CPs.
{"title":"Meltable Semiconductive Lead–Thiolate Coordination Polymers with Long Alkyl Chains","authors":"Ryohei Akiyoshi, Shunya Takamura, Chie Sawada, Naohiro Takahashi, Takashi Okubo, Akinori Saeki, Zi Lang Goo, Kunihisa Sugimoto, Yuki Mori, Shogo Kawaguchi, Yuiga Nakamura, Toshiaki Ina, Misaki Katayama, Hiroki Yamada, Seiya Shimono, Takuya Kurihara, Kazuyoshi Ogasawara, Daisuke Tanaka","doi":"10.1002/anie.202518379","DOIUrl":"https://doi.org/10.1002/anie.202518379","url":null,"abstract":"Meltable organic–inorganic hybrid semiconductors are attractive for their potential for melt-based processing. Although meltable semiconducting metal halide perovskites have been extensively studied, meltable semiconducting coordination polymers (CPs) remain scarce, despite their excellent structural designability and the tunability of their optoelectronic properties. We report a new family of meltable semiconductive Pb(II) benzenethiolate CPs bearing long alkyl chains, formulated as [Pb(SPhOC<sub>6</sub>)<sub>2</sub>]<i><sub>n</sub></i> (<b>KGF-34(C6)</b>; HSPhOC<sub>6</sub> = 4-hexyloxybenzenethiol). For comparison, we also synthesized the classical analogue [Pb(SC<sub>6</sub>)<sub>2</sub>]<i><sub>n</sub></i> (<b>KGF-59(C6)</b>; HSC<sub>6</sub> = 1-hexanethiol). Single-crystal X-ray diffraction analyses revealed that both <b>KGF-34(C6)</b> and <b>KGF-59(C6)</b> adopt 2D architectures, albeit with distinct inorganic (–Pb–S–)<i><sub>n</sub></i> networks. A comprehensive characterization of the semiconducting properties, combined with first-principles calculations, revealed that <b>KGF-34(C6)</b> exhibits significantly higher photoconductivity, a narrower band gap, and a larger band dispersion than <b>KGF-59(C6)</b>, attributable to differences in their inorganic (–Pb–S–)<i><sub>n</sub></i> network structures. Furthermore, both <b>KGF-34(C6)</b> and <b>KGF-59(C6)</b> exhibit multiple phase transitions, including melting and liquid crystalline formation, enabling the fabrication of optoelectronic devices via melt processing. Notably, this is the first report of meltable semiconducting CPs comprising benzenethiol-derived ligands. These findings offer a rational design strategy for developing melt-processable semiconductive materials based on metal–benzenethiolate CPs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"48 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-09","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139066","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}
The monomer conversion rate of thioctic acid (TA) and the cross-linking degree of polymer chains significantly influence the performance of materials, making them important research topics. Herein, by selecting a reduced polyoxometalate complex modified with 1-allylpyridinium cations, which exhibits strong near-infrared (NIR) light absorption capability, as both photothermal agent and cross-linking agent, the polymerization of TA is successfully achieved under NIR light irradiation. The incorporation of photothermal agents results in their multiple dispersion throughout the polymerization matrix, facilitating uniform internal heat generation and inside-out thermal diffusion. This mechanism significantly shortens the heat conduction pathway and effectively mitigates the inhomogeneous polymerization typically caused by temperature gradients inherent in conventional heating methods. Moreover, the C─S bonds formed via the reaction between the C═C groups and the disulfide linkages of TA not only suppress depolymerization but also serve as robust anchoring sites within the polymer network. By tuning the monomer composition, TA-based adhesives and elastomers are successfully fabricated, exhibiting excellent re-processability through NIR-triggered remelting or repair. The NIR-light-regulated polymerization approach offers distinct advantages, including operational simplicity, rapid response, and spatiotemporal control, thereby presenting a promising strategy for the synthesis of high-performance TA-based polymers.
{"title":"Near-Infrared Photothermal Polymerization of Thioctic Acid Triggered by Polyoxometalate Crosslinker","authors":"Shuangyu Wu, Hongxue Wang, Bao Li, Lixin Wu","doi":"10.1002/anie.202523605","DOIUrl":"https://doi.org/10.1002/anie.202523605","url":null,"abstract":"The monomer conversion rate of thioctic acid (TA) and the cross-linking degree of polymer chains significantly influence the performance of materials, making them important research topics. Herein, by selecting a reduced polyoxometalate complex modified with 1-allylpyridinium cations, which exhibits strong near-infrared (NIR) light absorption capability, as both photothermal agent and cross-linking agent, the polymerization of TA is successfully achieved under NIR light irradiation. The incorporation of photothermal agents results in their multiple dispersion throughout the polymerization matrix, facilitating uniform internal heat generation and inside-out thermal diffusion. This mechanism significantly shortens the heat conduction pathway and effectively mitigates the inhomogeneous polymerization typically caused by temperature gradients inherent in conventional heating methods. Moreover, the C─S bonds formed via the reaction between the C═C groups and the disulfide linkages of TA not only suppress depolymerization but also serve as robust anchoring sites within the polymer network. By tuning the monomer composition, TA-based adhesives and elastomers are successfully fabricated, exhibiting excellent re-processability through NIR-triggered remelting or repair. The NIR-light-regulated polymerization approach offers distinct advantages, including operational simplicity, rapid response, and spatiotemporal control, thereby presenting a promising strategy for the synthesis of high-performance TA-based polymers.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"176 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139089","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}
The rapid proliferation of artificial intelligence (AI) and information technologies is driving a sharp increase in global electronic waste, creating an urgent demand for recovering precious metals like gold from secondary resources to achieve environmental and economic benefits. Herein, a polydopamine (PDA)-functionalized β-ketoenamine-linked covalent organic framework composite, denoted as TATP/PDA, is designed in combination with a light-assisted strategy for efficient gold recovery. Benefiting from the synergistic effects of hydrogen bonding and π-π interactions between PDA and the TATP COF, which enhance photoelectric activity and provide abundant adsorption sites, the TATP/PDA exhibits an exceptional adsorption capacity of 5220 mg·g−1, ultrafast adsorption kinetics (>99% removal efficiency within 30 s), and remarkable selectivity in complex matrices. Experimental characterizations disclose that the engineered abundant nitrogen and oxygen active sites, along with the inherent photocatalytic reduction capability, significantly enhance the gold adsorption performance. These key merits position TATP/PDA as one of the best-performing materials in terms of overall performance. In practical application, TATP/PDA exhibits exceptional performance in recovering gold from real e-waste leachate. Moreover, the recovered gold-loaded composite serves as a sustainable photocatalyst for hydrogen evolution. This dual-benefit strategy not only promotes resource recycling but also contributes to the goals of a green and circular economy.
{"title":"Light-Promoted Efficient Gold Recovery Enabled by a Polydopamine-Functionalized Covalent Organic Framework","authors":"Yanyin Wu, Yuyu Guo, Tianwei Xue, Zeyu Shao, Longzhao Xu, Junhua Kuang, Ruiqing Li, Guangkuo Xu, Peng Chen, Wenli Hao, Tongxin Qiao, Xiangcheng Cai, Shuliang Yang, Jun Li, Li Peng","doi":"10.1002/anie.202526042","DOIUrl":"https://doi.org/10.1002/anie.202526042","url":null,"abstract":"The rapid proliferation of artificial intelligence (AI) and information technologies is driving a sharp increase in global electronic waste, creating an urgent demand for recovering precious metals like gold from secondary resources to achieve environmental and economic benefits. Herein, a polydopamine (PDA)-functionalized β-ketoenamine-linked covalent organic framework composite, denoted as TATP/PDA, is designed in combination with a light-assisted strategy for efficient gold recovery. Benefiting from the synergistic effects of hydrogen bonding and π-π interactions between PDA and the TATP COF, which enhance photoelectric activity and provide abundant adsorption sites, the TATP/PDA exhibits an exceptional adsorption capacity of 5220 mg·g<sup>−1</sup>, ultrafast adsorption kinetics (>99% removal efficiency within 30 s), and remarkable selectivity in complex matrices. Experimental characterizations disclose that the engineered abundant nitrogen and oxygen active sites, along with the inherent photocatalytic reduction capability, significantly enhance the gold adsorption performance. These key merits position TATP/PDA as one of the best-performing materials in terms of overall performance. In practical application, TATP/PDA exhibits exceptional performance in recovering gold from real e-waste leachate. Moreover, the recovered gold-loaded composite serves as a sustainable photocatalyst for hydrogen evolution. This dual-benefit strategy not only promotes resource recycling but also contributes to the goals of a green and circular economy.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"3 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139088","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 carbohydrate-based drug discovery, fluorine-containing substituents are widely used to enhance pharmacodynamic and pharmacokinetic profiles. However, the precise incorporation of C(sp3)-perfluoroalkyl moieties at the C2 position of sugar scaffolds remains a significant synthetic challenge. In this study, we report a highly efficient and cost-effective protocol for the synthesis of 2-deoxy-2-perfluoroalkyl glycosides from readily available glycals. This protocol demonstrates exceptional substrate generality, encompassing glucal, galactal, rhamnal, sialic acid, and arabinofuranose derivatives. More importantly, this platform enables the efficient synthesis of diverse C-, N-, and O-glycosides (over 50 examples) under gold(I)-catalyzed conditions, including the synthesis of previously inaccessible 2-deoxy-2-CF3-substituted nucleoside analogues. Additionally, photocatalytically generated 2-deoxy-2-CF3 glycosyl anomeric radicals readily undergo Giese-type additions to alkenes, affording alkylated glycosides, or engage in cross-coupling with aryl bromides to deliver antidiabetic drug candidates. Preliminary biological evaluations indicate that 2-deoxy-2-CF3-modified glycosides exhibit enhanced pharmacological properties, underscoring the translational potential of this synthetic technique for advancing carbohydrate-based therapeutics.
{"title":"Expeditious Synthesis of 2-Deoxy-2-perfluoroalkyl Glycosides","authors":"Shen Cao, Haobo Zhang, Niming Zhu, Peng Xu, Xiaoping Chen, Biao Yu, Xiaheng Zhang","doi":"10.1002/anie.1824435","DOIUrl":"https://doi.org/10.1002/anie.1824435","url":null,"abstract":"In carbohydrate-based drug discovery, fluorine-containing substituents are widely used to enhance pharmacodynamic and pharmacokinetic profiles. However, the precise incorporation of C(sp<sup>3</sup>)-perfluoroalkyl moieties at the C2 position of sugar scaffolds remains a significant synthetic challenge. In this study, we report a highly efficient and cost-effective protocol for the synthesis of 2-deoxy-2-perfluoroalkyl glycosides from readily available glycals. This protocol demonstrates exceptional substrate generality, encompassing glucal, galactal, rhamnal, sialic acid, and arabinofuranose derivatives. More importantly, this platform enables the efficient synthesis of diverse <i>C</i>-, <i>N</i>-, and <i>O</i>-glycosides (over 50 examples) under gold(I)-catalyzed conditions, including the synthesis of previously inaccessible 2-deoxy-2-CF<sub>3</sub>-substituted nucleoside analogues. Additionally, photocatalytically generated 2-deoxy-2-CF<sub>3</sub> glycosyl anomeric radicals readily undergo Giese-type additions to alkenes, affording alkylated glycosides, or engage in cross-coupling with aryl bromides to deliver antidiabetic drug candidates. Preliminary biological evaluations indicate that 2-deoxy-2-CF<sub>3</sub>-modified glycosides exhibit enhanced pharmacological properties, underscoring the translational potential of this synthetic technique for advancing carbohydrate-based therapeutics.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139087","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}
Ikuya Fujii, Rin Seki, Haruka Kido, Louis Jauffret, Kazuhiko Semba, Yoshiaki Nakao
Here we describe the generation of aryl Grignard reagents from phenol derivatives via C─O bond activation cooperatively catalyzed by Rh─Al heterobimetallic complexes. We discovered that the electron-rich arylmagnesium reagents could be efficiently prepared from the corresponding aryl carbamates, whereas the π-extended arylmagnesium reagents were obtained from the corresponding aryl ethers. This methodology enables the efficient conversion of a broad range of phenol derivatives into the corresponding Grignard reagents, which can subsequently react with various electrophiles to yield a diverse array of organic compounds.
{"title":"Magnesiation of Phenol Derivatives Catalyzed by a Rhodium─Aluminum Complex","authors":"Ikuya Fujii, Rin Seki, Haruka Kido, Louis Jauffret, Kazuhiko Semba, Yoshiaki Nakao","doi":"10.1002/anie.202518631","DOIUrl":"https://doi.org/10.1002/anie.202518631","url":null,"abstract":"Here we describe the generation of aryl Grignard reagents from phenol derivatives <i>via</i> C─O bond activation cooperatively catalyzed by Rh─Al heterobimetallic complexes. We discovered that the electron-rich arylmagnesium reagents could be efficiently prepared from the corresponding aryl carbamates, whereas the π-extended arylmagnesium reagents were obtained from the corresponding aryl ethers. This methodology enables the efficient conversion of a broad range of phenol derivatives into the corresponding Grignard reagents, which can subsequently react with various electrophiles to yield a diverse array of organic compounds.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"59 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139067","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}
Yongxin Yang, Kun Zeng, Yan Feng, Qi An, Lu Liu, Futong Ren, Xilin Liang, Genfu Zhao, Songsong Zhi, Hong Guo
The inherent factors influencing the growth of lithium (Li) dendrites and the kinetics of Li+ migration in polymer electrolytes lie in the electron cloud density distribution in the electrolyte. Localized electrons accumulation can trigger the uneven Li+ deposition, ultimately leading to battery failure. To address this critical challenge, the concept of p–π conjugation and B–O sp2 hybridization is innovatively incorporated into covalent organic frameworks (COFs) to mitigate local interfacial Li+ accumulation and improve Li+ migration kinetics in electrolytes by electron delocalization. Furthermore, perfluoroalkyl group with virtues of superior electron regulating capabilities and improved electrochemical-window, is strategically grafted to better match high-voltage cathodes. Under the synergistic role of electron regulation, the electrolyte with pπ–sp2-COF significantly improves overall electrochemical performance of solid-state batteries. Thus, regulating electron density via p-π conjugation and B-O sp2 hybridization promises to open new avenues for the development of COFs-modified polymer electrolytes in solid-state batteries.
{"title":"Modulating Electron Delocalization Structure in Covalent Organic Frameworks Through Conjugation and Hybridization to Boost Li-ion Migration Dynamics","authors":"Yongxin Yang, Kun Zeng, Yan Feng, Qi An, Lu Liu, Futong Ren, Xilin Liang, Genfu Zhao, Songsong Zhi, Hong Guo","doi":"10.1002/anie.202525864","DOIUrl":"https://doi.org/10.1002/anie.202525864","url":null,"abstract":"The inherent factors influencing the growth of lithium (Li) dendrites and the kinetics of Li<sup>+</sup> migration in polymer electrolytes lie in the electron cloud density distribution in the electrolyte. Localized electrons accumulation can trigger the uneven Li<sup>+</sup> deposition, ultimately leading to battery failure. To address this critical challenge, the concept of p–π conjugation and B–O sp<sup>2</sup> hybridization is innovatively incorporated into covalent organic frameworks (COFs) to mitigate local interfacial Li<sup>+</sup> accumulation and improve Li<sup>+</sup> migration kinetics in electrolytes by electron delocalization. Furthermore, perfluoroalkyl group with virtues of superior electron regulating capabilities and improved electrochemical-window, is strategically grafted to better match high-voltage cathodes. Under the synergistic role of electron regulation, the electrolyte with pπ–sp<sup>2</sup>-COF significantly improves overall electrochemical performance of solid-state batteries. Thus, regulating electron density via p-π conjugation and B-O sp<sup>2</sup> hybridization promises to open new avenues for the development of COFs-modified polymer electrolytes in solid-state batteries.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"57 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139070","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}
Dongxu Zhang, Deli Jiang, Yanhong Liu, Qitao Chen, Lei Xing, Hui Huang, Wei Zhang, Weidong Shi, Zhenhui Kang, Baodong Mao
Modern electrocatalysis typically involves multi-species cascade systems, imposing stringent requirements on catalysts to exhibit multi-component and multifunctional characteristics. Such complexity poses great challenges for identifying and understanding the structural and functional nature of the true active phase. Herein, we report the formation of Cu111 nanolaminates confined within the interface of Cu1.94S/In2S3 heterojunction via in situ electrochemical reconstruction. The synthesized Cu111 nanolaminates act as a single-phase co-activating nanoreactor to preferentially adsorb carbon dioxide (CO2) and cascade N-intermediates, enabling C─N coupling for urea synthesis within an ultra-low and distinct potential window. The optimized Cu1.94S/Cu111/In2S3 catalyst achieves a urea yield rate of 11823.65 µg h−1 mgCu111−1 and an exceptionally high Faradaic efficiency of 69.34% at -0.35 V versus the reversible hydrogen electrode in a flow cell, surpassing all previously reported transition metal electrocatalysts. In situ spectroscopic analyses and theoretical calculations reveal a favorable reaction pathway and nanoconfined synergy on the Cu111 nanolaminates, where CO2 is initially anchored and reduced to *CO and cascaded *NO2 undergoes C─N coupling to form the key *CONO2 intermediate toward urea. This study unveils the true active phase within a complex heterostructure electrocatalyst, which also provides new insights into the rational design of advanced electrocatalysts for other energy and environmental applications.
{"title":"Confined Cu111 Nanolaminates as a Single-Phase Nanoreactor for Efficient Urea Electrosynthesis","authors":"Dongxu Zhang, Deli Jiang, Yanhong Liu, Qitao Chen, Lei Xing, Hui Huang, Wei Zhang, Weidong Shi, Zhenhui Kang, Baodong Mao","doi":"10.1002/anie.2242110","DOIUrl":"https://doi.org/10.1002/anie.2242110","url":null,"abstract":"Modern electrocatalysis typically involves multi-species cascade systems, imposing stringent requirements on catalysts to exhibit multi-component and multifunctional characteristics. Such complexity poses great challenges for identifying and understanding the structural and functional nature of the true active phase. Herein, we report the formation of Cu<sub>111</sub> nanolaminates confined within the interface of Cu<sub>1.94</sub>S/In<sub>2</sub>S<sub>3</sub> heterojunction via in situ electrochemical reconstruction. The synthesized Cu<sub>111</sub> nanolaminates act as a single-phase co-activating nanoreactor to preferentially adsorb carbon dioxide (CO<sub>2</sub>) and cascade N-intermediates, enabling C─N coupling for urea synthesis within an ultra-low and distinct potential window. The optimized Cu<sub>1.94</sub>S/Cu<sub>111</sub>/In<sub>2</sub>S<sub>3</sub> catalyst achieves a urea yield rate of 11823.65 µg h<sup>−1</sup> mg<sub>Cu111</sub><sup>−1</sup> and an exceptionally high Faradaic efficiency of 69.34% at -0.35 V versus the reversible hydrogen electrode in a flow cell, surpassing all previously reported transition metal electrocatalysts. In situ spectroscopic analyses and theoretical calculations reveal a favorable reaction pathway and nanoconfined synergy on the Cu<sub>111</sub> nanolaminates, where CO<sub>2</sub> is initially anchored and reduced to *CO and cascaded *NO<sub>2</sub> undergoes C─N coupling to form the key *CONO<sub>2</sub> intermediate toward urea. This study unveils the true active phase within a complex heterostructure electrocatalyst, which also provides new insights into the rational design of advanced electrocatalysts for other energy and environmental applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"7 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139071","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}
Yulan Han, Jiayan Xu, Jiawei Wu, Chenyu Wu, Xiran Cheng, Wenbo Xie, Xiulian Pan, Xinhe Bao, P. Hu
Discovering next-generation heterogeneous catalysts calls for embracing the full complexity of active site formation under realistic conditions. Here, we develop a robust machine learning potential (MLP)-aided computational framework that integrates realistic preparation and reaction conditions to effectively track the formation of active sites and decipher structure-activity relationships. Using syngas conversion over the ZnxCryOz system as a demonstration, we identified that the system preferentially segregates into ZnO and ZnCr2O4 phases, with ZnO forming a monolayer on ZnCr2O4 surfaces under preparation conditions. Under reaction conditions, by deploying CH─O bond dissociation as a descriptor, we found that the ZnO/ZnCr2O4(100) surface is the active surface. Crucially, we pinpoint geometrically linked oxygen vacancy pairs as the true active sites. Full microkinetic analyses conducted on these active sites yield kinetic results that align well with experimental observations. Beyond elucidating the active structure, a model for designing oxide/oxide catalysts to achieve high activity is generalized, opening new pathways for accelerating catalyst discovery across a wide range of reactions.
{"title":"First Principles Identification of Active Sites in Heterogeneous Catalysis: A Case Study on ZnxCryOz for Syngas Conversion","authors":"Yulan Han, Jiayan Xu, Jiawei Wu, Chenyu Wu, Xiran Cheng, Wenbo Xie, Xiulian Pan, Xinhe Bao, P. Hu","doi":"10.1002/anie.202522416","DOIUrl":"https://doi.org/10.1002/anie.202522416","url":null,"abstract":"Discovering next-generation heterogeneous catalysts calls for embracing the full complexity of active site formation under realistic conditions. Here, we develop a robust machine learning potential (MLP)-aided computational framework that integrates realistic preparation and reaction conditions to effectively track the formation of active sites and decipher structure-activity relationships. Using syngas conversion over the Zn<sub>x</sub>Cr<sub>y</sub>O<sub>z</sub> system as a demonstration, we identified that the system preferentially segregates into ZnO and ZnCr<sub>2</sub>O<sub>4</sub> phases, with ZnO forming a monolayer on ZnCr<sub>2</sub>O<sub>4</sub> surfaces under preparation conditions. Under reaction conditions, by deploying CH─O bond dissociation as a descriptor, we found that the ZnO/ZnCr<sub>2</sub>O<sub>4</sub>(100) surface is the active surface. Crucially, we pinpoint geometrically linked oxygen vacancy pairs as the true active sites. Full microkinetic analyses conducted on these active sites yield kinetic results that align well with experimental observations. Beyond elucidating the active structure, a model for designing oxide/oxide catalysts to achieve high activity is generalized, opening new pathways for accelerating catalyst discovery across a wide range of reactions.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"35 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139086","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}
Traditional heterogeneous photocatalytic systems coupled with oxidant activation hold great promise for environmental remediation but are constrained by radical scavenging and nonselective oxidation. Here, we introduce an overlooked photoswitch-mediated electron transfer (PSMET) mechanism that circumvents reactive oxygen species by enabling direct, ultrafast electron transfer from pollutants to oxidants through a photoactive mediator. Using environmentally benign bismuth oxyiodide as a model catalyst under visible-light irradiation, we achieve unprecedented degradation rates for various electron-rich pollutants such as sulfamethoxazole (t1/2 <2.0 min). This mechanism exhibits pollutant-dependent oxidant utilization mode and selective pollutant degradation characteristics. Mechanistic analyses reveal the formation of a high-potential electron-transfer pathway activated by photoexcitation, directly coupling pollutant oxidation to oxidant reduction within a single electron-transfer cycle. Frontier molecular orbital calculations further demonstrate that the narrow bandgap and p-type semiconductor characteristics selectively facilitate electron extraction from contaminants to oxidants. Remarkably, this PSMET mechanism displays universal applicability with diverse oxidants, maintaining >98% pollutant removals even in complex aqueous matrices and continuous-flow systems. Furthermore, the mechanism allows precise optical control over reaction initiation and termination, offering unparalleled spatiotemporal regulation for sustainable wastewater treatment. Our findings redefine photocatalytic oxidation paradigms and open new pathways toward energy-efficient, optically programmable, and environmentally sustainable remediation technologies.
{"title":"Photoswitch Mediated Electron Highway Driving Direct Pollutant-to-Oxidant Electron Transfer in Ultrafast Fenton-Like Reactions","authors":"Zhi-Quan Zhang, Bin-Bin Zhang, Jing Wang, Chang-Wei Bai, Xin-Jia Chen, Fu-Qiao Yang, Pi-Jun Duan, Fei Chen","doi":"10.1002/anie.202521687","DOIUrl":"https://doi.org/10.1002/anie.202521687","url":null,"abstract":"Traditional heterogeneous photocatalytic systems coupled with oxidant activation hold great promise for environmental remediation but are constrained by radical scavenging and nonselective oxidation. Here, we introduce an overlooked photoswitch-mediated electron transfer (PSMET) mechanism that circumvents reactive oxygen species by enabling direct, ultrafast electron transfer from pollutants to oxidants through a photoactive mediator. Using environmentally benign bismuth oxyiodide as a model catalyst under visible-light irradiation, we achieve unprecedented degradation rates for various electron-rich pollutants such as sulfamethoxazole (t<sub>1/2</sub> <2.0 min). This mechanism exhibits pollutant-dependent oxidant utilization mode and selective pollutant degradation characteristics. Mechanistic analyses reveal the formation of a high-potential electron-transfer pathway activated by photoexcitation, directly coupling pollutant oxidation to oxidant reduction within a single electron-transfer cycle. Frontier molecular orbital calculations further demonstrate that the narrow bandgap and p-type semiconductor characteristics selectively facilitate electron extraction from contaminants to oxidants. Remarkably, this PSMET mechanism displays universal applicability with diverse oxidants, maintaining >98% pollutant removals even in complex aqueous matrices and continuous-flow systems. Furthermore, the mechanism allows precise optical control over reaction initiation and termination, offering unparalleled spatiotemporal regulation for sustainable wastewater treatment. Our findings redefine photocatalytic oxidation paradigms and open new pathways toward energy-efficient, optically programmable, and environmentally sustainable remediation technologies.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"16 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2026-02-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146139068","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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