Even though excited-state properties play a crucial role in photocatalysis, directly correlating these with photocatalytic activity remains challenging. Herein, we propose a method to elucidate the correlations between the catalytic activity of organic photosensitizers and their rate constants of various excited-state processes through integrating machine learning (ML), quantum chemical calculations, and chemical experiments. This approach was applied to interpolative predictions of the yield of the nickel/photocatalytic formation of C–O bonds and radical additions to alkenes using various organic photosensitizers with satisfactory accuracy (R2 = 0.83 and 0.77 on the test set, respectively). The calculated rate constants obtained through quantum chemical calculations proved to be comparable or even superior to the experimentally measured excited-state lifetimes as descriptors. SHAP-based visual analysis revealed that the rate constants corresponding to transitions from the T1 state provide significant contributions to the interpolative prediction of photocatalytic activity. Additionally, the non-radiative decay process between the S1 and S0 states helps describe the low catalytic activity of poorly emissive photosensitizers. These findings highlight the potential of the proposed method to provide insights into photocatalytic properties that are difficult to obtain using conventional approaches.
{"title":"Data-driven approach to elucidate the correlation between photocatalytic activity and rate constants from excited states","authors":"Naoki Noto, Ryuga Kunisada, Manami Hayashi, Tabea Rohlfs, Taiki Nagano, Koki Sano, Naoto Inai, Takuya Ogaki, Yasunori Matsui, Hiroshi Ikeda, Olga Garcia Mancheño, Takeshi Yanai, Susumu Saito","doi":"10.1039/d5sc06465a","DOIUrl":"https://doi.org/10.1039/d5sc06465a","url":null,"abstract":"Even though excited-state properties play a crucial role in photocatalysis, directly correlating these with photocatalytic activity remains challenging. Herein, we propose a method to elucidate the correlations between the catalytic activity of organic photosensitizers and their rate constants of various excited-state processes through integrating machine learning (ML), quantum chemical calculations, and chemical experiments. This approach was applied to interpolative predictions of the yield of the nickel/photocatalytic formation of C–O bonds and radical additions to alkenes using various organic photosensitizers with satisfactory accuracy (R2 = 0.83 and 0.77 on the test set, respectively). The calculated rate constants obtained through quantum chemical calculations proved to be comparable or even superior to the experimentally measured excited-state lifetimes as descriptors. SHAP-based visual analysis revealed that the rate constants corresponding to transitions from the T1 state provide significant contributions to the interpolative prediction of photocatalytic activity. Additionally, the non-radiative decay process between the S1 and S0 states helps describe the low catalytic activity of poorly emissive photosensitizers. These findings highlight the potential of the proposed method to provide insights into photocatalytic properties that are difficult to obtain using conventional approaches.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"14 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145593880","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}
Manjia Li, Minghao Lu, Lijun Wang, Yuqing Zhang, Long Yan, Shushu Wang, Tao Peng
Site-specific incorporation of photo-responsive unnatural amino acids (UAAs) into proteins via genetic code expansion offers a powerful approach to control and study protein function in biological systems. However, existing UAAs are all sensitive to UV or near-UV light, and no visible-light-responsive UAAs have been reported, limiting our ability to regulate multiple proteins simultaneously. Here, we present the genetic encoding of a green-light-activatable lysine derivative, SCouK, for sequential photocontrol of protein activities in live cells. SCouK, containing a photolabile thiocoumarin moiety at the N εamino group of lysine, can be genetically encoded into proteins in bacterial and mammalian cells. We show that sitespecifically incorporated SCouK can be photoactivated across a broad wavelength range, from UV to green light, to restore the functions of EGFP and luciferase. Notably, SCouK is highly efficiently photodecaged by green light centered at 520 nm within 30 seconds, marking it as the first visible-light-responsive lysine derivative with the longest single-photon activation wavelength for genetically encoded photolabile UAAs. Additionally, we showcase the general capability of SCouK for the optical control of different kinases and temporal control and interrogation of the cGAS-STING pathway in live cells.Moreover, by combing SCouK with a UV-light-activatable tyrosine derivative, we achieve, for the first time, sequential photoactivation of two distinct UAA-modified proteins within a single live-cell sample. Overall, the unique features of SCouK, including site-specific incorporation, green-light-responsiveness, orthogonal activation wavelengths, high decaging efficiency, and general applicability, demonstrate its great potential to non-invasively and precisely manipulate proteins in complex living systems for functional studies and therapeutic applications.
{"title":"Genetically Encoded Green-light-responsive Photocaged Lysine for Sequential Control of Protein Function","authors":"Manjia Li, Minghao Lu, Lijun Wang, Yuqing Zhang, Long Yan, Shushu Wang, Tao Peng","doi":"10.1039/d5sc08317f","DOIUrl":"https://doi.org/10.1039/d5sc08317f","url":null,"abstract":"Site-specific incorporation of photo-responsive unnatural amino acids (UAAs) into proteins via genetic code expansion offers a powerful approach to control and study protein function in biological systems. However, existing UAAs are all sensitive to UV or near-UV light, and no visible-light-responsive UAAs have been reported, limiting our ability to regulate multiple proteins simultaneously. Here, we present the genetic encoding of a green-light-activatable lysine derivative, SCouK, for sequential photocontrol of protein activities in live cells. SCouK, containing a photolabile thiocoumarin moiety at the N εamino group of lysine, can be genetically encoded into proteins in bacterial and mammalian cells. We show that sitespecifically incorporated SCouK can be photoactivated across a broad wavelength range, from UV to green light, to restore the functions of EGFP and luciferase. Notably, SCouK is highly efficiently photodecaged by green light centered at 520 nm within 30 seconds, marking it as the first visible-light-responsive lysine derivative with the longest single-photon activation wavelength for genetically encoded photolabile UAAs. Additionally, we showcase the general capability of SCouK for the optical control of different kinases and temporal control and interrogation of the cGAS-STING pathway in live cells.Moreover, by combing SCouK with a UV-light-activatable tyrosine derivative, we achieve, for the first time, sequential photoactivation of two distinct UAA-modified proteins within a single live-cell sample. Overall, the unique features of SCouK, including site-specific incorporation, green-light-responsiveness, orthogonal activation wavelengths, high decaging efficiency, and general applicability, demonstrate its great potential to non-invasively and precisely manipulate proteins in complex living systems for functional studies and therapeutic applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"35 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145593884","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}
Despite impressive advances in the field of defluorinative alkylation of polyfluoroarenes, the corresponding asymmetric counterpart has remained a formidable challenge. Herein, we present the first example of asymmetric defluorinative alkylation of polyfluoroarenes with readily accessible alkenes, 1,3-dienes, and even (Z/E)-mixed 1,3-dienes as potential nucleophiles in the presence of a chiral CuH catalyst, avoiding the conventional utilization of highly reactive organometallics. This method enables the efficient construction of the challenging chiral Csp3–CArF bond with outstanding stereocontrol (up to 99% ee in most cases). This reaction proceeds under mild reaction conditions, demonstrating excellent functional group compatibility and high regio- and stereoselectivity. Experimental studies in conjunction with density functional theory (DFT) calculations were carried out to unravel the plausible mechanism and elucidate the origins of excellent enantioselectivity.
{"title":"Enantioselective copper-catalysed defluorinative alkylation of polyfluoroarenes with alkenes and 1,3-dienes","authors":"Dazhen Shi, Lihan Zhu, Ying Jiang, Simin Wang, Jianjun Yin, Xiuping Yuan, Shucheng Ma, Xiaoyu Li, Jiaqiong Sun, Qian Zhang, Tao Xiong","doi":"10.1039/d5sc08090h","DOIUrl":"https://doi.org/10.1039/d5sc08090h","url":null,"abstract":"Despite impressive advances in the field of defluorinative alkylation of polyfluoroarenes, the corresponding asymmetric counterpart has remained a formidable challenge. Herein, we present the first example of asymmetric defluorinative alkylation of polyfluoroarenes with readily accessible alkenes, 1,3-dienes, and even (<em>Z</em>/<em>E</em>)-mixed 1,3-dienes as potential nucleophiles in the presence of a chiral CuH catalyst, avoiding the conventional utilization of highly reactive organometallics. This method enables the efficient construction of the challenging chiral Csp<small><sup>3</sup></small>–C<small><sub>ArF</sub></small> bond with outstanding stereocontrol (up to 99% ee in most cases). This reaction proceeds under mild reaction conditions, demonstrating excellent functional group compatibility and high regio- and stereoselectivity. Experimental studies in conjunction with density functional theory (DFT) calculations were carried out to unravel the plausible mechanism and elucidate the origins of excellent enantioselectivity.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"166 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145593879","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}
Jiarong Jin, Xin Li, Yicheng Luo, Jian-Fu Chen, Wenjun Tang, Kang Du
Oxyallenes are valuable building blocks in organic synthesis, most commonly exploited as π-allyl metal precursors in transition-metal-catalyzed allylation reactions. In contrast, their engagement in radical processes remain largely unexplored. Herein, we disclose a Giese-type radical addition protocol in which acyl-substituted oxyallenes function as in situ precursors to α, β-unsaturated ketones, enabling efficient coupling with 2-azaallyl radicals. This metal-free method delivers a wide range of γ-amino ketones in high yields with broad functional group tolerance, mild conditions, and scalability to gram quantities. Mechanistic studies, including radical trapping and isotopic labeling, support a pathway involving radical addition of 2-azaallyl radical to transient α, β-enone intermediates. These findings establish a new reactivity mode of oxyallenes in radical chemistry and provide an efficient route to synthetically and pharmaceutically valuable amino ketones.
{"title":"Acyl-oxyallenes as α, β-Unsaturated Ketone Surrogates for Giese Radical Addition","authors":"Jiarong Jin, Xin Li, Yicheng Luo, Jian-Fu Chen, Wenjun Tang, Kang Du","doi":"10.1039/d5sc08002a","DOIUrl":"https://doi.org/10.1039/d5sc08002a","url":null,"abstract":"Oxyallenes are valuable building blocks in organic synthesis, most commonly exploited as π-allyl metal precursors in transition-metal-catalyzed allylation reactions. In contrast, their engagement in radical processes remain largely unexplored. Herein, we disclose a Giese-type radical addition protocol in which acyl-substituted oxyallenes function as <em>in situ</em> precursors to <em>α</em>, <em>β</em>-unsaturated ketones, enabling efficient coupling with 2-azaallyl radicals. This metal-free method delivers a wide range of <em>γ</em>-amino ketones in high yields with broad functional group tolerance, mild conditions, and scalability to gram quantities. Mechanistic studies, including radical trapping and isotopic labeling, support a pathway involving radical addition of 2-azaallyl radical to transient <em>α</em>, <em>β</em>-enone intermediates. These findings establish a new reactivity mode of oxyallenes in radical chemistry and provide an efficient route to synthetically and pharmaceutically valuable amino ketones.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"18 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145594246","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}
Estefanía Sucre-Rosales, Suiying Ye, Yinyin Bao, Eric Vauthey
Electron donor-acceptor (D-A) polymers are emerging as promising candidates for the development of solid materials with tunable emission. Herein, we investigate the excited-state dynamics of polymers consisting of a central naphthalenediimide (NDI) acceptor with two polystyrene donor chains and copolymers with various secondary donors incorporated. We find strong differences in the dynamics when going from diluted polymer solutions to pure polymer films. In liquids, ultrafast intrachain electron transfer from a styrenic donor to the excited NDI, followed by sub-nanosecond charge recombination to the ground state is observed. Because of the tight packing in the film, ultrafast electron transfer occurs between donor and acceptors of different polymer chains. Emission is found to originate from the most strongly coupled D-A pairs, for which electron transfer is so fast that it leads to a lifetime broadening of the NDI absorption band. Because of this, these highly coupled pairs can be photoselected upon red-edge excitation. The charge-transfer state decays on the tens of ns timescale via radiative and non-radiative charge recombination to the ground state as well as via charge recombination to the triplet state of NDI. This latter pathway, which is detrimental to the fluorescence quantum yield, is almost suppressed with the strongest secondary donor. Finally, we show that excitation of the secondary donor instead of the NDI acceptor does not lead to the population the charge-transfer state and thus does not contribute to the luminescence of the films.
{"title":"Photoinduced Charge-Transfer Dynamics in Fluorescent Electron Donor-Acceptor Polymers","authors":"Estefanía Sucre-Rosales, Suiying Ye, Yinyin Bao, Eric Vauthey","doi":"10.1039/d5sc07237a","DOIUrl":"https://doi.org/10.1039/d5sc07237a","url":null,"abstract":"Electron donor-acceptor (D-A) polymers are emerging as promising candidates for the development of solid materials with tunable emission. Herein, we investigate the excited-state dynamics of polymers consisting of a central naphthalenediimide (NDI) acceptor with two polystyrene donor chains and copolymers with various secondary donors incorporated. We find strong differences in the dynamics when going from diluted polymer solutions to pure polymer films. In liquids, ultrafast intrachain electron transfer from a styrenic donor to the excited NDI, followed by sub-nanosecond charge recombination to the ground state is observed. Because of the tight packing in the film, ultrafast electron transfer occurs between donor and acceptors of different polymer chains. Emission is found to originate from the most strongly coupled D-A pairs, for which electron transfer is so fast that it leads to a lifetime broadening of the NDI absorption band. Because of this, these highly coupled pairs can be photoselected upon red-edge excitation. The charge-transfer state decays on the tens of ns timescale via radiative and non-radiative charge recombination to the ground state as well as via charge recombination to the triplet state of NDI. This latter pathway, which is detrimental to the fluorescence quantum yield, is almost suppressed with the strongest secondary donor. Finally, we show that excitation of the secondary donor instead of the NDI acceptor does not lead to the population the charge-transfer state and thus does not contribute to the luminescence of the films.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"120 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145594245","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}
Guo-Quan Huang, Hu Yang, Ri-Qin Xia, Kun Wu, Yong-Liang Huang, De-Bo Hao, Shun-Bo Li, Weigang Lu, Ji Zheng, Xiao-Ping Zhou, Dan Li
Achieving chirality transfer and amplification through controlled supramolecular aggregation has long been a challenge in chemistry. This study presents the self-assembly of homochiral triple-helical aggregates (P- and M-type) with enantiomerically pure Cu(I) cyclic trinuclear complexes (CTCs) through metallophilic and hydrogen-bonding interactions. Both P- and M-type aggregates exhibit bright orange-red phosphorescence and circularly polarized luminescence (CPL) emission with exceptional luminescence dissymmetry factor (glum) of approximately ±1×10−2. These values are the highest among coinage metal-based complexes with emissions across red and near-infrared. Experimental results and computational simulations reveal that the extensive overlap of chiral and luminescent centers is key to enabling CPL activity. Further installing naphthyl chromophore in the pyrazolate ligands results in isostructural triple-helical aggregates with rarely observed dual CPL emission behavior. Overall, this study showcases the successful construction of homochiral triple-helical aggregates by incorporating chiral centers and hydrogen-bonding sites into the peripheral pyrazolate ligands of Cu(I) CTCs, allowing for chirality transfer and amplification evidenced by large glum values of CPL emission. These findings may facilitate the bottom-up design of homochiral supramolecular aggregates for CPL-related applications.
{"title":"Triple-Helical Aggregates of Copper(I) Cyclic Trinuclear Complexes for Circularly Polarized Luminescence","authors":"Guo-Quan Huang, Hu Yang, Ri-Qin Xia, Kun Wu, Yong-Liang Huang, De-Bo Hao, Shun-Bo Li, Weigang Lu, Ji Zheng, Xiao-Ping Zhou, Dan Li","doi":"10.1039/d5sc04965b","DOIUrl":"https://doi.org/10.1039/d5sc04965b","url":null,"abstract":"Achieving chirality transfer and amplification through controlled supramolecular aggregation has long been a challenge in chemistry. This study presents the self-assembly of homochiral triple-helical aggregates (<em>P</em>- and <em>M</em>-type) with enantiomerically pure Cu(I) cyclic trinuclear complexes (CTCs) through metallophilic and hydrogen-bonding interactions. Both <em>P</em>- and <em>M</em>-type aggregates exhibit bright orange-red phosphorescence and circularly polarized luminescence (CPL) emission with exceptional luminescence dissymmetry factor (g<small><sub>lum</sub></small>) of approximately ±1×10<small><sup>−2</sup></small>. These values are the highest among coinage metal-based complexes with emissions across red and near-infrared. Experimental results and computational simulations reveal that the extensive overlap of chiral and luminescent centers is key to enabling CPL activity. Further installing naphthyl chromophore in the pyrazolate ligands results in isostructural triple-helical aggregates with rarely observed dual CPL emission behavior. Overall, this study showcases the successful construction of homochiral triple-helical aggregates by incorporating chiral centers and hydrogen-bonding sites into the peripheral pyrazolate ligands of Cu(I) CTCs, allowing for chirality transfer and amplification evidenced by large g<small><sub>lum</sub></small> values of CPL emission. These findings may facilitate the bottom-up design of homochiral supramolecular aggregates for CPL-related applications.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"93 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145593882","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}
Zinc is a crucial element in cellular processes, and its homeostasis has intricate relationships with the initiation, progression, and therapeutic intervention of cancer. Activation of the cyclic GMP-AMP synthase (cGAS)-stimulator of interferon genes (STING) pathway has been proven to be an effective strategy for cancer immunotherapy. Herein, we report four phosphorescent iridium complexes (Ir1–Ir4) with zinc chelating ligands. Among them, Ir1 can bind and image mitochondrial chelatable zinc ions via phosphorescent-lifetime responses, consequently modulating the expression of zinc-regulatory proteins. Furthermore, the in-situ formed heteronuclear metal complex Ir1-Zn2 shows nuclease mimetic activities, capable of hydrolyzing mitochondrial DNA (mtDNA) to release mtDNA fragments for the activation of cGAS-STING pathway. In conclusion, we designed a mitochondria-targeting phosphorescent Ir(III) complex with dual functions in dysregulation of zinc homeostasis and generation of nuclease in situ, which provides an innovative approach to stimulate the cGAS-STING pathway.
{"title":"Phosphorescent Iridium Complexes Activated by Endogenous Zinc as Mitochondrial DNA Nuclease for Stimulation of cGAS-STING Pathway","authors":"Zhi-Yuan Li, Long-Bo Yu, Qing-Hua Shen, Liang Hao, Peng Wang, Xiao-Xiao Chen, Yu-Yi Ling, Cai-Ping Tan","doi":"10.1039/d5sc07181j","DOIUrl":"https://doi.org/10.1039/d5sc07181j","url":null,"abstract":"Zinc is a crucial element in cellular processes, and its homeostasis has intricate relationships with the initiation, progression, and therapeutic intervention of cancer. Activation of the cyclic GMP-AMP synthase (cGAS)-stimulator of interferon genes (STING) pathway has been proven to be an effective strategy for cancer immunotherapy. Herein, we report four phosphorescent iridium complexes (Ir1–Ir4) with zinc chelating ligands. Among them, Ir1 can bind and image mitochondrial chelatable zinc ions via phosphorescent-lifetime responses, consequently modulating the expression of zinc-regulatory proteins. Furthermore, the in-situ formed heteronuclear metal complex Ir1-Zn2 shows nuclease mimetic activities, capable of hydrolyzing mitochondrial DNA (mtDNA) to release mtDNA fragments for the activation of cGAS-STING pathway. In conclusion, we designed a mitochondria-targeting phosphorescent Ir(III) complex with dual functions in dysregulation of zinc homeostasis and generation of nuclease in situ, which provides an innovative approach to stimulate the cGAS-STING pathway.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145593881","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}
Yue Wang, Jianhua Wang, Xueting Feng, Guanzhen Chen, Xusheng Wang, Tao Gan, Xing Fan, Haiping Lin, Yunhu Han
The advancement of rechargeable zinc-air batteries (ZABs) hinges critically on the development of efficient and durable bifunctional oxygen electrocatalysts. Herein, we report an atomically dispersed Fe-Ni bifunctional catalyst loaded on a hollow carbon framework (FeNi-hCN) through a density difference-assisted strategy. This unique architecture, leveraging the synergistic interplay between Fe and Ni atoms and the advantageous properties of the hollow carbon support, endows the catalyst with exceptional bifunctional oxygen electrocatalytic activity: half-wave potential (E1/2) of 0.91 V for the oxygen reduction reaction (ORR) and overpotential of only 330 mV at 10 mA cm-2 for the oxygen evolution reaction (OER). Remarkably, the catalyst demonstrates outstanding stability, retaining its activity after 100,000th accelerated degradation test (ADT) and 240 hours of continuous OER operation. When deployed as the air cathode in aqueous ZABs, this catalyst achieves a high peak power density of 212 mW cm-2 and stable 560 hours cycling, outperforming Pt/C+RuO2 combination. Density functional theory (DFT) calculations elucidate that the Fe-Ni dual sites synergistically lower the adsorption energy of the critical *OOH intermediate, thereby reducing the overall energy barriers for both ORR and OER pathways. This density difference-assisted method also works for other MOFs like UiO-66 and HKUST-1, enabling diverse high-performance carbon-supported catalysts.
高效、耐用的双功能氧电催化剂是锌空气电池发展的关键。在此，我们报告了一种原子分散的Fe-Ni双功能催化剂，通过密度差辅助策略负载在空心碳框架（FeNi-hCN）上。这种独特的结构，利用了铁和镍原子之间的协同相互作用和中空碳载体的优势，赋予催化剂特殊的双功能氧电催化活性：氧还原反应（ORR）的半波电位（E1/2）为0.91 V，氧析反应（OER）的过电位仅为330 mV， 10 mA cm-2。值得注意的是，该催化剂表现出出色的稳定性，在10万次加速降解试验（ADT）和240小时连续OER操作后仍保持其活性。在ZABs水溶液中作为空气阴极时，该催化剂的峰值功率密度达到212 mW cm-2，循环时间稳定在560小时，优于Pt/C+RuO2组合。密度泛函理论（DFT）计算表明，Fe-Ni双位点协同降低了临界*OOH中间体的吸附能，从而降低了ORR和OER途径的总能垒。这种密度差辅助方法也适用于其他mof，如UiO-66和HKUST-1，从而实现多种高性能碳负载催化剂。
{"title":"Synergistic Fe-Ni Dual-Atom Sites on Hollow Carbon Enabling High-Performance Rechargeable Zinc-Air Batteries","authors":"Yue Wang, Jianhua Wang, Xueting Feng, Guanzhen Chen, Xusheng Wang, Tao Gan, Xing Fan, Haiping Lin, Yunhu Han","doi":"10.1039/d5sc07448g","DOIUrl":"https://doi.org/10.1039/d5sc07448g","url":null,"abstract":"The advancement of rechargeable zinc-air batteries (ZABs) hinges critically on the development of efficient and durable bifunctional oxygen electrocatalysts. Herein, we report an atomically dispersed Fe-Ni bifunctional catalyst loaded on a hollow carbon framework (FeNi-<em>h</em>CN) through a density difference-assisted strategy. This unique architecture, leveraging the synergistic interplay between Fe and Ni atoms and the advantageous properties of the hollow carbon support, endows the catalyst with exceptional bifunctional oxygen electrocatalytic activity: half-wave potential (<em>E</em><small><sub>1/2</sub></small>) of 0.91 V for the oxygen reduction reaction (ORR) and overpotential of only 330 mV at 10 mA cm<small><sup>-2</sup></small> for the oxygen evolution reaction (OER). Remarkably, the catalyst demonstrates outstanding stability, retaining its activity after 100,000<small><sup>th</sup></small> accelerated degradation test (ADT) and 240 hours of continuous OER operation. When deployed as the air cathode in aqueous ZABs, this catalyst achieves a high peak power density of 212 mW cm<small><sup>-2</sup></small> and stable 560 hours cycling, outperforming Pt/C+RuO<small><sub>2</sub></small> combination. Density functional theory (DFT) calculations elucidate that the Fe-Ni dual sites synergistically lower the adsorption energy of the critical *OOH intermediate, thereby reducing the overall energy barriers for both ORR and OER pathways. This density difference-assisted method also works for other MOFs like UiO-66 and HKUST-1, enabling diverse high-performance carbon-supported catalysts.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"15 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-11-25","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145594244","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}
jilong Li, Xiang Hao, Jiwu Zhao, Jinyu Li, Bo Su, Zhengxin Ding, Meirong Huang, Zhi-An Lan, Min-Quan Yang, Sibo Wang
Solar-driven dry reforming of methane (DRM) offers a sustainable pathway to convert CH 4 and CO 2 into valuable syngas feedstock, yet the efficiency is hindered by the sluggish lattice oxygen (LO) migration of catalyst and the incomplete understanding of light-enhanced redox cycling. Here, we demonstrate that Ru/LaFeO 3 functions as an highly efficient and durable photothermal catalyst for DRM. The incorporation of Ru not only serves as an electron trap but also modulates the catalyst's electronic structure. Notably, under light irradiation, photoinduced charge redistribution further intensifies this electronic modulation, leading to electron enrichment at Ru, La, and Fe sites, and hole accumulation at LO sites. This interfacial charge dynamics weakens La-O and Fe-O bonds and facilitating LO migration, enabling efficient CH 4 activation and oxidation at Ru sites, accompanied by the generation of oxygen vacancies (OVs). Simultaneously, the in-situ generated OVs promote CO 2 adsorption and activation, facilitating its cleavage into CO and replenishing the OVs, thereby sustaining the redox cycle for continuous catalysis. This study provides key mechanistic insights into photoinduced LO dynamics driven by charge redistribution, and offers valuable guidance for the rational design of advanced photothermal systems that leverage both thermal and photonic effects of solar energy for enhanced catalysis via the LO-mediated pathways.
{"title":"Light-induced electronic structure modulation in perovskite ferrite for efficient photothermal dry reforming of methane","authors":"jilong Li, Xiang Hao, Jiwu Zhao, Jinyu Li, Bo Su, Zhengxin Ding, Meirong Huang, Zhi-An Lan, Min-Quan Yang, Sibo Wang","doi":"10.1039/d5sc05708f","DOIUrl":"https://doi.org/10.1039/d5sc05708f","url":null,"abstract":"Solar-driven dry reforming of methane (DRM) offers a sustainable pathway to convert CH 4 and CO 2 into valuable syngas feedstock, yet the efficiency is hindered by the sluggish lattice oxygen (LO) migration of catalyst and the incomplete understanding of light-enhanced redox cycling. Here, we demonstrate that Ru/LaFeO 3 functions as an highly efficient and durable photothermal catalyst for DRM. The incorporation of Ru not only serves as an electron trap but also modulates the catalyst's electronic structure. Notably, under light irradiation, photoinduced charge redistribution further intensifies this electronic modulation, leading to electron enrichment at Ru, La, and Fe sites, and hole accumulation at LO sites. This interfacial charge dynamics weakens La-O and Fe-O bonds and facilitating LO migration, enabling efficient CH 4 activation and oxidation at Ru sites, accompanied by the generation of oxygen vacancies (OVs). Simultaneously, the in-situ generated OVs promote CO 2 adsorption and activation, facilitating its cleavage into CO and replenishing the OVs, thereby sustaining the redox cycle for continuous catalysis. This study provides key mechanistic insights into photoinduced LO dynamics driven by charge redistribution, and offers valuable guidance for the rational design of advanced photothermal systems that leverage both thermal and photonic effects of solar energy for enhanced catalysis via the LO-mediated pathways.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"16 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145583569","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}
Zhongcheng Wang, Fengjuan Guo, Xusheng Zhang, Hongtao Gao, Wenlong Yang
Selective electrochemical oxidation of amine molecules presents a promising approach for synthesizing high-value nitrile products. Nevertheless, its practical implementation is largely impeded by the challenge in activating the dehydrogenation of C(sp3)−H/N(sp3)−H bonds in amines. In this work, borate anions intercalated α-Ni(OH)2 nanosheets (BI-Ni(OH)2) are synthesized via a convenient microwave-assisted synthesis strategy and employed as an exceptional electrocatalyst for the benzylamine (BA) oxidation reaction (BOR). Benefiting from its better wetting behavior, larger electroactive surface area and more favorable reaction kinetics, the BI-Ni(OH)2 catalyst shows a distinctly enhanced activity in electro-oxidation of BA to benzonitrile (BN) compared to pristine α-Ni(OH)2 nanosheets (P-Ni(OH)2), especially giving rise to a Faradaic efficiency exceeding 80% toward BN production under the voltage of 1.55 V when coupled with cathodic hydrogen evolution reaction (HER) in a two-electrode electrolyzer. Experimental measurements and density functional theory calculations conjointly demonstrate that borate intercalation cannot only reduce the energy barrier for generating NiOOH species as active centers, but also promote the adsorption of BA molecules onto the catalyst surface, enabling a significantly optimized electro-oxidation kinetics for the BOR, which is accountable for the enhanced electrocatalytic performance.
{"title":"Borate intercalation optimizes the electro-oxidation kinetics of α-Ni(OH)2 nanosheets for selective electrochemical conversion of benzylamine to benzonitrile","authors":"Zhongcheng Wang, Fengjuan Guo, Xusheng Zhang, Hongtao Gao, Wenlong Yang","doi":"10.1039/d5sc04502a","DOIUrl":"https://doi.org/10.1039/d5sc04502a","url":null,"abstract":"Selective electrochemical oxidation of amine molecules presents a promising approach for synthesizing high-value nitrile products. Nevertheless, its practical implementation is largely impeded by the challenge in activating the dehydrogenation of C(sp3)−H/N(sp3)−H bonds in amines. In this work, borate anions intercalated α-Ni(OH)2 nanosheets (BI-Ni(OH)2) are synthesized via a convenient microwave-assisted synthesis strategy and employed as an exceptional electrocatalyst for the benzylamine (BA) oxidation reaction (BOR). Benefiting from its better wetting behavior, larger electroactive surface area and more favorable reaction kinetics, the BI-Ni(OH)2 catalyst shows a distinctly enhanced activity in electro-oxidation of BA to benzonitrile (BN) compared to pristine α-Ni(OH)2 nanosheets (P-Ni(OH)2), especially giving rise to a Faradaic efficiency exceeding 80% toward BN production under the voltage of 1.55 V when coupled with cathodic hydrogen evolution reaction (HER) in a two-electrode electrolyzer. Experimental measurements and density functional theory calculations conjointly demonstrate that borate intercalation cannot only reduce the energy barrier for generating NiOOH species as active centers, but also promote the adsorption of BA molecules onto the catalyst surface, enabling a significantly optimized electro-oxidation kinetics for the BOR, which is accountable for the enhanced electrocatalytic performance.","PeriodicalId":9909,"journal":{"name":"Chemical Science","volume":"86 1","pages":""},"PeriodicalIF":8.4,"publicationDate":"2025-11-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145583500","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}
京公网安备 11010802042870号
京ICP备2023020795号-1
扫码关注我们
求助内容：
应助结果提醒方式：