Transition metal-based catalysts with high efficiency and stability for overall water splitting (OWS) offer significant potential for reducing green hydrogen production costs. Utilizing sputtering deposition technology, we propose a deposition-diffusion strategy to fabricate heterojunction coatings composed of ultrafine FeCoNi-C-N transition metal interstitial solid solution (TMISS) nanocrystals and amorphous nitrided carbon (NC) on the pre-deposited NC micro column arrays. The diffusion of C and N atoms results in the formation of uniformly distributed TMISS nanocrystals, with an average diameter of ~1.9 nm, thus maximizing atomic utilization. The unique crystalline-amorphous heterojunction interface enhances electrocatalytic stability. Furthermore, the electronic regulation of metal sites by interstitial C and N atoms not only optimizes the adsorption-dissociation process in hydrogen evolution reaction (HER), but also accelerates the surface reconstruction of hydroxyl oxides to enhance the oxygen evolution reaction (OER) activity. As a result, the as-prepared coating achieved overpotentials of only 62 and 237 mV for the HER and OER at 10 mA cm−2 in alkaline electrolytes, and exhibited excellent OWS performance and long-term stability at high current densities. This work presents a new perspective for synthesizing TMISS nanocrystals and promotes their application in bifunctional electrocatalysts.
{"title":"Interstitial Doping in Ultrafine Nanocrystals for Efficient and Durable Water Splitting","authors":"Minming Jiang, Jiang Xu, Yujie Chen, Luqi Wang, Qi Zhou, Paul Munroe, Linlin Li, Zong-Han Xie, Shengjie Peng","doi":"10.1002/anie.202424195","DOIUrl":"https://doi.org/10.1002/anie.202424195","url":null,"abstract":"Transition metal-based catalysts with high efficiency and stability for overall water splitting (OWS) offer significant potential for reducing green hydrogen production costs. Utilizing sputtering deposition technology, we propose a deposition-diffusion strategy to fabricate heterojunction coatings composed of ultrafine FeCoNi-C-N transition metal interstitial solid solution (TMISS) nanocrystals and amorphous nitrided carbon (NC) on the pre-deposited NC micro column arrays. The diffusion of C and N atoms results in the formation of uniformly distributed TMISS nanocrystals, with an average diameter of ~1.9 nm, thus maximizing atomic utilization. The unique crystalline-amorphous heterojunction interface enhances electrocatalytic stability. Furthermore, the electronic regulation of metal sites by interstitial C and N atoms not only optimizes the adsorption-dissociation process in hydrogen evolution reaction (HER), but also accelerates the surface reconstruction of hydroxyl oxides to enhance the oxygen evolution reaction (OER) activity. As a result, the as-prepared coating achieved overpotentials of only 62 and 237 mV for the HER and OER at 10 mA cm−2 in alkaline electrolytes, and exhibited excellent OWS performance and long-term stability at high current densities. This work presents a new perspective for synthesizing TMISS nanocrystals and promotes their application in bifunctional electrocatalysts.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"91 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975552","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}
Huaizheng Ren, Sai Li, Liang Xu, Lei Wang, Xinxin Liu, Lei Wang, Yue Liu, Liang Zhang, Han Zhang, Yuxin Gong, Chade Lv, Dongping Chen, Jianxin Wang, Qiang Lv, Yaqiang Li, Huakun Liu, Dianlong Wang, Tao Cheng, Bo Wang, Dongliang Chao, Shixue Dou
Rechargeable zinc batteries (RZBs) are hindered by two primary challenges: instability of Zn anode and deterioration of the cathode structure in traditional aqueous electrolytes, largely attributable to the decomposition of active H2O. Here, we design and synthesize a non-flammable water-in-dimethyl sulfoxide electrolyte to address these issues. X-ray absorption spectroscopy, in situ techniques and computational simulations demonstrate that the activity of H2O in this electrolyte is extremely compressed, which not only suppresses the side reactions and increases the reversibility of Zn anode, but also diminishes the cathode dissolution and proton intercalation. The hybrid solid-electrolyte interface (SEI), formed in situ, helps Zn-Zn symmetric cell a prolonged lifespan exceeding 10000 h at 0.5 mA cm−2 and 600 h at a 60% discharge depth. The versatility of this electrolyte endows the Zn-VO2 full batteries ultra-stable cycling performance. This work provides insights into electrolyte structure-property relationships, and facilitates the design of high-performance RZBs.
{"title":"Tailoring Water-in-DMSO Electrolyte for Ultra-stable Rechargeable Zinc Batteries","authors":"Huaizheng Ren, Sai Li, Liang Xu, Lei Wang, Xinxin Liu, Lei Wang, Yue Liu, Liang Zhang, Han Zhang, Yuxin Gong, Chade Lv, Dongping Chen, Jianxin Wang, Qiang Lv, Yaqiang Li, Huakun Liu, Dianlong Wang, Tao Cheng, Bo Wang, Dongliang Chao, Shixue Dou","doi":"10.1002/anie.202423302","DOIUrl":"https://doi.org/10.1002/anie.202423302","url":null,"abstract":"Rechargeable zinc batteries (RZBs) are hindered by two primary challenges: instability of Zn anode and deterioration of the cathode structure in traditional aqueous electrolytes, largely attributable to the decomposition of active H2O. Here, we design and synthesize a non-flammable water-in-dimethyl sulfoxide electrolyte to address these issues. X-ray absorption spectroscopy, in situ techniques and computational simulations demonstrate that the activity of H2O in this electrolyte is extremely compressed, which not only suppresses the side reactions and increases the reversibility of Zn anode, but also diminishes the cathode dissolution and proton intercalation. The hybrid solid-electrolyte interface (SEI), formed in situ, helps Zn-Zn symmetric cell a prolonged lifespan exceeding 10000 h at 0.5 mA cm−2 and 600 h at a 60% discharge depth. The versatility of this electrolyte endows the Zn-VO2 full batteries ultra-stable cycling performance. This work provides insights into electrolyte structure-property relationships, and facilitates the design of high-performance RZBs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"42 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975061","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}
Liusheng Chen, Yiran Li, Yuna Guo, Guyu Wang, Nan Feng, Jiahui Sun, Yihong Zhong, Yunyan Yao, Lin Ding, Huangxian Ju
Proximity labeling (PL) has emerged as a powerful technique for the in situ elucidation of biomolecular interaction networks. However, PL methods generally rely on single-biological-hierarchy control of spatial localization at the labeling site, which limits their application in multi-tiered biological systems. Here, we introduced another enzymatic reaction upstream of an enzyme-based PL reaction and targeted the two enzymes to markers indicating different biological hierarchies, establishing a two-level spatially localized proximity labeling (P2L) platform for in situ molecular measurement and manipulation. Using the cellular- and glycan-level as the hierarchical models, we demonstrated the ability of P2L to efficiently execute a two-step logic operation and to discriminate target cells with different levels of glycosylation within mixed cell populations. By mounting clickable handles via P2L, we reprogrammed the robust covalent assembly of cells at designated sites. The combination of P2L with proteomics led to the profiling of the protein microenvironment of specific glycans on target cells, revealing changes in tumor-cell-surface interactions under immune pressure from a glycan perspective. P2L provides not only a solution for revealing the heterogeneity of biological systems, but also new insights in the fields of intelligent logic computation, enzyme engineering, tissue engineering, etc.
{"title":"Two-Level Spatially Localized Proximity Labeling for Cross-Biological-Hierarchy Measurement and Manipulation","authors":"Liusheng Chen, Yiran Li, Yuna Guo, Guyu Wang, Nan Feng, Jiahui Sun, Yihong Zhong, Yunyan Yao, Lin Ding, Huangxian Ju","doi":"10.1002/anie.202421448","DOIUrl":"https://doi.org/10.1002/anie.202421448","url":null,"abstract":"Proximity labeling (PL) has emerged as a powerful technique for the in situ elucidation of biomolecular interaction networks. However, PL methods generally rely on single-biological-hierarchy control of spatial localization at the labeling site, which limits their application in multi-tiered biological systems. Here, we introduced another enzymatic reaction upstream of an enzyme-based PL reaction and targeted the two enzymes to markers indicating different biological hierarchies, establishing a two-level spatially localized proximity labeling (P2L) platform for in situ molecular measurement and manipulation. Using the cellular- and glycan-level as the hierarchical models, we demonstrated the ability of P2L to efficiently execute a two-step logic operation and to discriminate target cells with different levels of glycosylation within mixed cell populations. By mounting clickable handles via P2L, we reprogrammed the robust covalent assembly of cells at designated sites. The combination of P2L with proteomics led to the profiling of the protein microenvironment of specific glycans on target cells, revealing changes in tumor-cell-surface interactions under immune pressure from a glycan perspective. P2L provides not only a solution for revealing the heterogeneity of biological systems, but also new insights in the fields of intelligent logic computation, enzyme engineering, tissue engineering, etc.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"6 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975063","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}
Jian He, Liu Luo, Jinchi Li, Shiqi Chen, Shuqi Yu, Liang Zeng, Yao Wang, Yungui Chen
Doping with non-metallic heteroatom is an effective approach to tailor the electronic structure of Ni for enhancing its alkaline hydrogen oxidation reaction (HOR) catalytic performance. However, the modulation of HOR activity of Ni by lattice carbon (LC) atoms has rarely been reported, especially to reveal the rule between the doping effect and activity caused by the content of LC atoms. Here, hydrogen is proposed as a scavenger for LC atoms in the pyrolytic reduction process to finely control the content of LC atoms in Ni. With the removal of LC atoms in Ni lattice, the electronic structure changes from Ni3C-like electronic structure to quasi-Ni structure. Furthermore, a volcanic relationship between the LC content and HOR activity of Ni is established for the first time. The Cless-Ni (LC0.44-Ni) with optimized LC content shows the best activity owing to the weakened hydrogen binding energy (HBE) and optimal hydroxyl binding energy (OHBE). This work provides an inspiration for the design of high-performance catalysts by tailoring the electronic structure of the metal via LC atoms doping.
{"title":"Exploiting Lattice Carbon-Induced Modulation Effect in Nickel towards Efficient Alkaline Hydrogen Oxidation","authors":"Jian He, Liu Luo, Jinchi Li, Shiqi Chen, Shuqi Yu, Liang Zeng, Yao Wang, Yungui Chen","doi":"10.1002/anie.202423647","DOIUrl":"https://doi.org/10.1002/anie.202423647","url":null,"abstract":"Doping with non-metallic heteroatom is an effective approach to tailor the electronic structure of Ni for enhancing its alkaline hydrogen oxidation reaction (HOR) catalytic performance. However, the modulation of HOR activity of Ni by lattice carbon (LC) atoms has rarely been reported, especially to reveal the rule between the doping effect and activity caused by the content of LC atoms. Here, hydrogen is proposed as a scavenger for LC atoms in the pyrolytic reduction process to finely control the content of LC atoms in Ni. With the removal of LC atoms in Ni lattice, the electronic structure changes from Ni3C-like electronic structure to quasi-Ni structure. Furthermore, a volcanic relationship between the LC content and HOR activity of Ni is established for the first time. The Cless-Ni (LC0.44-Ni) with optimized LC content shows the best activity owing to the weakened hydrogen binding energy (HBE) and optimal hydroxyl binding energy (OHBE). This work provides an inspiration for the design of high-performance catalysts by tailoring the electronic structure of the metal via LC atoms doping.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"29 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975096","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}
Cheng-Xia Chen, Haiping Wang, Hassan Rabaâ, Yang-Yang Xiong, Peter VanNatta, Zhang-Wen Wei, Abdullah M. Al-Enizi, Ayman Nafady, Shengqian Ma
Converting CO2 to high-value fine chemicals represents one of the most promising approaches to combat global warming and subsequently achieve a sustainable carbon cycle. Herein, we contribute an organoboron functionalized ultra-thin metal-organic nanosheet (MON), termed TCPB-Zr-NS, featuring an abundance of exposed Lewis acidic B and formate sites, which can effectively promote CO2 conversion upon the addition of Lewis basic o-phenylenediamines. Compared with the prototypical 3D analogue TCPB-Zr-3D, the resultant TCPB-Zr-NS showcases dramatically improved catalytic activity for the cyclization of o-phenylenediamine as a result of the highly exposed active sites and efficient substrates/products diffusion. Strikingly, the incorporation of Lewis acidic B sites into ultra-thin Zr-based MON (Zr-MON) not only promotes the highly efficient CO2 conversion, but also enhances the recyclability/durability of catalysts. Additionally, the underlying catalytic mechanism has been well established by the comprehensive experiments and theoretical calculations, unveiling a formate-assisted frustrated Lewis pairs (FLP) mediated catalytic pathway. This work opens up a new avenue to heterogeneous FLP-based catalysts for small molecule activation and beyond.
{"title":"Organoboron-Functionalized Metal-organic Nanosheets for Highly Efficient CO2 Fixation Mediated by Frustrated Lewis Pairs","authors":"Cheng-Xia Chen, Haiping Wang, Hassan Rabaâ, Yang-Yang Xiong, Peter VanNatta, Zhang-Wen Wei, Abdullah M. Al-Enizi, Ayman Nafady, Shengqian Ma","doi":"10.1002/anie.202416497","DOIUrl":"https://doi.org/10.1002/anie.202416497","url":null,"abstract":"Converting CO2 to high-value fine chemicals represents one of the most promising approaches to combat global warming and subsequently achieve a sustainable carbon cycle. Herein, we contribute an organoboron functionalized ultra-thin metal-organic nanosheet (MON), termed TCPB-Zr-NS, featuring an abundance of exposed Lewis acidic B and formate sites, which can effectively promote CO2 conversion upon the addition of Lewis basic o-phenylenediamines. Compared with the prototypical 3D analogue TCPB-Zr-3D, the resultant TCPB-Zr-NS showcases dramatically improved catalytic activity for the cyclization of o-phenylenediamine as a result of the highly exposed active sites and efficient substrates/products diffusion. Strikingly, the incorporation of Lewis acidic B sites into ultra-thin Zr-based MON (Zr-MON) not only promotes the highly efficient CO2 conversion, but also enhances the recyclability/durability of catalysts. Additionally, the underlying catalytic mechanism has been well established by the comprehensive experiments and theoretical calculations, unveiling a formate-assisted frustrated Lewis pairs (FLP) mediated catalytic pathway. This work opens up a new avenue to heterogeneous FLP-based catalysts for small molecule activation and beyond.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"16 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968339","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}
Peng Yin, Chunzheng Huang, Li Zhang, Zhenzhen Li, Caijun Zhong, Shi Kuang, Chunyang Lei, Yan Huang, Zhou Nie
Fluorogenic RNA aptamers have revolutionized the visualization of RNAs within complex cellular processes. A representative category of them employs the derivatives of green fluorescent protein chromophore, 4-hydroxybenzlidene imidazolinone (HBI), as chromophores. However, the structural homogeneity of their chromophoric backbones causes severe cross-reactivity with other homologous chromophores. This limitation impairs their multiplexing capabilities, which are essential for the simultaneous visualization of multiple RNA species in live cells. Herein, we rationally designed a series of red-shifted chromophores and employed SELEX-independent engineering to develop a novel fluorogenic RNA aptamer, mSquash. mSquash displays specific and intense fluorescence upon binding with our red-shifted chromophore DFHBFPD (Ex/Em = 501/624 nm). The mSquash/DFHBFPD allows orthogonal imaging of selected RNA targets alongside the established Broccoli/DFHBI-1T (Ex/Em = 472/501 nm), facilitating multiplexed live cell imaging of various targets. Moreover, we expanded the application of fluorescent RNA to photoactive imaging by constructing two genetically encoded photoactivatable fluorescent RNAs for the first time. This innovative approach allows photoactivatable control of fluorescent RNAs via specific light wavelengths (365 nm and 450 nm), enabling spatiotemporal dual-color imaging of RNAs in live cells. Our findings represent a significant advancement in fluorescent RNA-based orthogonal imaging and spatiotemporal analysis of RNAs.
{"title":"Developing Orthogonal Fluorescent RNAs for Photoactive Dual-color Imaging of RNAs in Live Cells","authors":"Peng Yin, Chunzheng Huang, Li Zhang, Zhenzhen Li, Caijun Zhong, Shi Kuang, Chunyang Lei, Yan Huang, Zhou Nie","doi":"10.1002/anie.202424060","DOIUrl":"https://doi.org/10.1002/anie.202424060","url":null,"abstract":"Fluorogenic RNA aptamers have revolutionized the visualization of RNAs within complex cellular processes. A representative category of them employs the derivatives of green fluorescent protein chromophore, 4-hydroxybenzlidene imidazolinone (HBI), as chromophores. However, the structural homogeneity of their chromophoric backbones causes severe cross-reactivity with other homologous chromophores. This limitation impairs their multiplexing capabilities, which are essential for the simultaneous visualization of multiple RNA species in live cells. Herein, we rationally designed a series of red-shifted chromophores and employed SELEX-independent engineering to develop a novel fluorogenic RNA aptamer, mSquash. mSquash displays specific and intense fluorescence upon binding with our red-shifted chromophore DFHBFPD (Ex/Em = 501/624 nm). The mSquash/DFHBFPD allows orthogonal imaging of selected RNA targets alongside the established Broccoli/DFHBI-1T (Ex/Em = 472/501 nm), facilitating multiplexed live cell imaging of various targets. Moreover, we expanded the application of fluorescent RNA to photoactive imaging by constructing two genetically encoded photoactivatable fluorescent RNAs for the first time. This innovative approach allows photoactivatable control of fluorescent RNAs via specific light wavelengths (365 nm and 450 nm), enabling spatiotemporal dual-color imaging of RNAs in live cells. Our findings represent a significant advancement in fluorescent RNA-based orthogonal imaging and spatiotemporal analysis of RNAs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"16 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968488","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 Han, Pingxia Zhang, Heng Zhou, Tong Zhao, Karin Odelius, Minna Hakkarainen
The plastic waste accumulation requires facile yet effective solutions. Currently mechanical recycling typically leads to downcycling, while the environmental footprint of chemical recycling is often unacceptable. Here, we introduce a dual circularity concept, where rational molecular design paves the way for complementary closed‐loop mechanical and chemical recyclability under mild conditions. Very small changes in macromolecular structures, thermal and mechanical properties were observed, after as many as six repeated mechanical recycling cycles, showing that a wide processing window could be the key for closing the mechanical recycling loop. Facile, time and energy efficient closed‐loop chemical recycling into products with identical performance to original ones was also realized, thanks to the abundant free volume and accessible ester‐functionalities. With these design criteria at hand, dual circulation in recyclability can be realized; proceeding with mechanical recycling when we can, and switching to chemical recycling when we must.
{"title":"Molecular Design for Dual Circularity: Polyester with Complementary Mechanical and Chemical Recyclability under Mild Conditions","authors":"Yue Han, Pingxia Zhang, Heng Zhou, Tong Zhao, Karin Odelius, Minna Hakkarainen","doi":"10.1002/anie.202421431","DOIUrl":"https://doi.org/10.1002/anie.202421431","url":null,"abstract":"The plastic waste accumulation requires facile yet effective solutions. Currently mechanical recycling typically leads to downcycling, while the environmental footprint of chemical recycling is often unacceptable. Here, we introduce a dual circularity concept, where rational molecular design paves the way for complementary closed‐loop mechanical and chemical recyclability under mild conditions. Very small changes in macromolecular structures, thermal and mechanical properties were observed, after as many as six repeated mechanical recycling cycles, showing that a wide processing window could be the key for closing the mechanical recycling loop. Facile, time and energy efficient closed‐loop chemical recycling into products with identical performance to original ones was also realized, thanks to the abundant free volume and accessible ester‐functionalities. With these design criteria at hand, dual circulation in recyclability can be realized; proceeding with mechanical recycling when we can, and switching to chemical recycling when we must.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"21 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968182","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}
Electrocatalytic oxidation of cyclohexanol/cyclohexanonein water provides a promising strategy for obtaining adipic acid (AA), which is an essential feedstock in the polymer industry. However, this process is impeded by slow kinetics and limited Faradaic efficiency (FE) due to a poor understanding of the reaction mechanism. Herein, NiCo2O4/CeO2 is developed to enable the electrooxidation of cyclohexanol to AA with a 0.0992 mmol h−1 cm−2 yield rate and 87% Faradaic efficiency at a lower potential. Mechanistic investigations demonstrate that cyclohexanol electrooxidation to AA is a gradual oxidation process involving the dehydrogenation of cyclohexanol to cyclohexanone, the generation of 2‐hydroxy cyclohexanone, and subsequent C−C cleavage. Theoretical calculations reveal that electronic interactions between CeO2 and NiCo2O4 decrease the energy barrier of cyclohexanone oxidation to 2‐hydroxy cyclohexanone and inhibit the *OH to *O step, leading to AA electrosynthesis with a high yield rate and FE. Kinetic analysis further elucidates the effect of CeO2 on promoting cyclohexanone adsorption and activation on the electrode surface, thus facilitating the reaction kinetics. Moreover, a two‐electrode flow reactor is constructed to produce 72.1 mmol AA and 10.4 L H2 by using KA oil as the anode feedstock at 2.5 A (200 mA cm−2), demonstrating promising potential.
环己醇/环己酮在水中的电催化氧化反应为获得己二酸（AA）提供了一种前景广阔的策略，而己二酸是聚合物行业的一种重要原料。然而，由于对反应机理的不甚了解，这一过程受到缓慢的动力学和有限的法拉第效率（FE）的阻碍。本文开发的 NiCo2O4/CeO2 能够在较低电位下将环己醇电氧化成 AA，产率为 0.0992 mmol h-1 cm-2，法拉第效率为 87%。机理研究表明，环己醇电氧化成 AA 是一个渐进的氧化过程，包括环己醇脱氢成环己酮、生成 2- 羟基环己酮以及随后的 C-C 裂解。理论计算显示，CeO2 和 NiCo2O4 之间的电子相互作用降低了环己酮氧化成 2-羟基环己酮的能垒，抑制了 *OH 到 *O 的步骤，从而导致 AA 电合成具有高产率和 FE。动力学分析进一步阐明了 CeO2 对促进环己酮在电极表面吸附和活化的作用，从而促进了反应动力学。此外，利用 KA 油作为阳极原料，在 2.5 A（200 mA cm-2）的条件下，构建了一个双电极流动反应器，生产出 72.1 mmol AA 和 10.4 L H2，显示出巨大的潜力。
{"title":"CeO2 Modification Promotes the Oxidation Kinetics for Adipic Acid Electrosynthesis from KA Oil Oxidation at 200 mA cm−2","authors":"Shuoshuo Guo, Changhong Wang, Huizhi Li, Tieliang Li, Cuibo Liu, Ying Gao, Bo-Hang Zhao, Bin Zhang","doi":"10.1002/anie.202423432","DOIUrl":"https://doi.org/10.1002/anie.202423432","url":null,"abstract":"Electrocatalytic oxidation of cyclohexanol/cyclohexanonein water provides a promising strategy for obtaining adipic acid (AA), which is an essential feedstock in the polymer industry. However, this process is impeded by slow kinetics and limited Faradaic efficiency (FE) due to a poor understanding of the reaction mechanism. Herein, NiCo2O4/CeO2 is developed to enable the electrooxidation of cyclohexanol to AA with a 0.0992 mmol h−1 cm−2 yield rate and 87% Faradaic efficiency at a lower potential. Mechanistic investigations demonstrate that cyclohexanol electrooxidation to AA is a gradual oxidation process involving the dehydrogenation of cyclohexanol to cyclohexanone, the generation of 2‐hydroxy cyclohexanone, and subsequent C−C cleavage. Theoretical calculations reveal that electronic interactions between CeO2 and NiCo2O4 decrease the energy barrier of cyclohexanone oxidation to 2‐hydroxy cyclohexanone and inhibit the *OH to *O step, leading to AA electrosynthesis with a high yield rate and FE. Kinetic analysis further elucidates the effect of CeO2 on promoting cyclohexanone adsorption and activation on the electrode surface, thus facilitating the reaction kinetics. Moreover, a two‐electrode flow reactor is constructed to produce 72.1 mmol AA and 10.4 L H2 by using KA oil as the anode feedstock at 2.5 A (200 mA cm−2), demonstrating promising potential.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"43 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968203","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}
A pyrrole‐fused analogue of warped nanographene, designated as deca‐nitrogen doped 'WNG' (azaWNG), was synthesized through the annular fusion of decapyrroylcorannulene. The resulting azaWNG exhibited extremely limited solubility in common organic solvents and was characterized solely by mass spectrometry. Theoretical calculations revealed that azaWNG has a sunflower‐like molecular structure with electron‐deficient corannulene as the core and electron‐rich pyrrole as the petals, demonstrating a significantly narrower energy gap compared to all‐carbon WNG. To improve its solubility and facilitate precise structural characterization, iodine monochloride was utilized for edge‐perchlorination of azaWNG, enabling successful separation and purification of chlorinated azaWNG in solution phase. X‐ray crystallography analysis unequivocally confirmed that edge‐perchlorinated azaWNG contains 5 heptagons and 11 pentagons embedded within the warped π skeleton. Cyclic voltammetry measurements indicated that the first oxidation potential of azaWNG is –0.59 V, representing the lowest value reported for any previously studied aza‐nanographene. Consequently, azaWNG can be readily oxidized by AgPF6 or even atmospheric oxygen to yield stable oxidation states, as corroborated by UV‐visible absorption spectroscopy; this behavior is attributed to the fusion of ten pyrroles around corannulene. This work marks the first instance of nitrogen doping in WNG (C80H30), underscoring the significant modification to electronic structure induced by such doping.
{"title":"A Pyrrole‐Fused Nanographene and its Edge‐Perchlorinated Derivative Featuring a Corannulene Core and Five N‐doped Heptagons","authors":"Xue-Peng Zhang, Zuo-chang Chen, Han-rui Tian, Wen-xin Zhang, Si-Wei Ying, Peng Du, Bin-wen Chen, Yang-Rong Yao, Yin-Fu Wu, Mei-Lin Zhang, Qianyan Zhang, Shun-Liu Deng, Su-yuan Xie, Lan-Sun Zheng","doi":"10.1002/anie.202420228","DOIUrl":"https://doi.org/10.1002/anie.202420228","url":null,"abstract":"A pyrrole‐fused analogue of warped nanographene, designated as deca‐nitrogen doped 'WNG' (azaWNG), was synthesized through the annular fusion of decapyrroylcorannulene. The resulting azaWNG exhibited extremely limited solubility in common organic solvents and was characterized solely by mass spectrometry. Theoretical calculations revealed that azaWNG has a sunflower‐like molecular structure with electron‐deficient corannulene as the core and electron‐rich pyrrole as the petals, demonstrating a significantly narrower energy gap compared to all‐carbon WNG. To improve its solubility and facilitate precise structural characterization, iodine monochloride was utilized for edge‐perchlorination of azaWNG, enabling successful separation and purification of chlorinated azaWNG in solution phase. X‐ray crystallography analysis unequivocally confirmed that edge‐perchlorinated azaWNG contains 5 heptagons and 11 pentagons embedded within the warped π skeleton. Cyclic voltammetry measurements indicated that the first oxidation potential of azaWNG is –0.59 V, representing the lowest value reported for any previously studied aza‐nanographene. Consequently, azaWNG can be readily oxidized by AgPF6 or even atmospheric oxygen to yield stable oxidation states, as corroborated by UV‐visible absorption spectroscopy; this behavior is attributed to the fusion of ten pyrroles around corannulene. This work marks the first instance of nitrogen doping in WNG (C80H30), underscoring the significant modification to electronic structure induced by such doping.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"29 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968205","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}
Shuhong Liu, Jinchan Liu, Alexander Foote, Hiroaki Ogasawara, Sarah Al Abdullatif, Victor S. Batista, Khalid Salaita
Genetically encoded tension sensors (GETSs) allow for quantifying forces experienced by intracellular proteins involved in mechanotransduction. The vast majority of GETSs are comprised of a FRET pair flanking an elastic “spring-like” domain that gradually extends in response to force. Because of ensemble averaging, the FRET signal generated by such analog sensors conceals forces that deviate from the average, and hence it is unknown if a subset of proteins experience greater magnitudes of force. We address this problem by developing digital GETSs comprised of coiled-coils (CCs) with tunable mechanical thresholds. We validate the mechanical response of CC digital probes using thermodynamic stability prediction, AlphaFold2 modeling, steered molecular dynamics simulations, and single molecule force microscopy. Live cell measurements using optimized CC tension sensors that are inserted into vinculin demonstrate that 13% of this mechanosensor experiences forces > 9.9 pN within focal adhesions. This reveals greater magnitudes of vinculin force than had previously been reported and demonstrates that coiled-coil tension sensors enable more facile and precise tension measurements in living systems.
{"title":"Digital and Tunable Genetically Encoded Tension Sensors Based on Engineered Coiled-Coils","authors":"Shuhong Liu, Jinchan Liu, Alexander Foote, Hiroaki Ogasawara, Sarah Al Abdullatif, Victor S. Batista, Khalid Salaita","doi":"10.1002/anie.202407359","DOIUrl":"https://doi.org/10.1002/anie.202407359","url":null,"abstract":"Genetically encoded tension sensors (GETSs) allow for quantifying forces experienced by intracellular proteins involved in mechanotransduction. The vast majority of GETSs are comprised of a FRET pair flanking an elastic “spring-like” domain that gradually extends in response to force. Because of ensemble averaging, the FRET signal generated by such analog sensors conceals forces that deviate from the average, and hence it is unknown if a subset of proteins experience greater magnitudes of force. We address this problem by developing digital GETSs comprised of coiled-coils (CCs) with tunable mechanical thresholds. We validate the mechanical response of CC digital probes using thermodynamic stability prediction, AlphaFold2 modeling, steered molecular dynamics simulations, and single molecule force microscopy. Live cell measurements using optimized CC tension sensors that are inserted into vinculin demonstrate that 13% of this mechanosensor experiences forces > 9.9 pN within focal adhesions. This reveals greater magnitudes of vinculin force than had previously been reported and demonstrates that coiled-coil tension sensors enable more facile and precise tension measurements in living systems.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"51 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975060","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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