Carbon-based perovskite solar cells (C-PSCs) have the advantages of high stability and low cost, but their mean efficiency has become an obstacle to commercialization. Defects, which are widely distributed on the surface and bulk of films, are an important factor in C-PSCs for low efficiency. The conventional post-treatment method through forming a low-dimensional (LD) perovskite layer usually fails in manipulating the bulk defects. Herein, we propose a strategy of combining wet film (uncrystallized) treatment with dry film treatment to in situ form LD perovskite throughout the grain boundaries inside of the film and on the surface of the film, thereby simultaneously passivating the bulk and surface defects in the CsPbI3 film. As a result, the photoluminescence lifetime is significantly improved from 22.5 ns to 92.1 ns. The assembled CsPbI3 C-PSCs based on the above strategy deliver a champion efficiency of 19.65%, which is a new record efficiency for inorganic C-PSCs.
{"title":"Comprehensive Passivation of Surface and Bulk Defects in Perovskite for High Efficiency Carbon-Based CsPbI3 Solar Cells","authors":"Jianxin Zhang, Xin Peng, Haosheng Wu, Guizhi Zhang, Yueying Chen, Weizi Cai, Zhenxiao Pan, Huashang Rao, Xinhua Zhong","doi":"10.1002/anie.202423655","DOIUrl":"https://doi.org/10.1002/anie.202423655","url":null,"abstract":"Carbon-based perovskite solar cells (C-PSCs) have the advantages of high stability and low cost, but their mean efficiency has become an obstacle to commercialization. Defects, which are widely distributed on the surface and bulk of films, are an important factor in C-PSCs for low efficiency. The conventional post-treatment method through forming a low-dimensional (LD) perovskite layer usually fails in manipulating the bulk defects. Herein, we propose a strategy of combining wet film (uncrystallized) treatment with dry film treatment to in situ form LD perovskite throughout the grain boundaries inside of the film and on the surface of the film, thereby simultaneously passivating the bulk and surface defects in the CsPbI3 film. As a result, the photoluminescence lifetime is significantly improved from 22.5 ns to 92.1 ns. The assembled CsPbI3 C-PSCs based on the above strategy deliver a champion efficiency of 19.65%, which is a new record efficiency for inorganic C-PSCs.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"17 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975058","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}
Fasten your seat belt! Choose lightning-speed, photoactivated journeys for complexes by selecting the metal, its oxidation state, ligands and geometry. Track complexes through excited singlet (S) states, intersystem crossing (ISC) to triplet (T) states, energy/charge-transfer, luminescence, ligand substitutions and redox reactions. Pathways to novel drugs with new mechanisms of action. Unravelling excited metallomics on the way is challenging.
{"title":"Advances in the Design of Photoactivatable Metallodrugs: Excited State Metallomics","authors":"Huayun Shi, Rafael C. Marchi, Peter J. Sadler","doi":"10.1002/anie.202423335","DOIUrl":"https://doi.org/10.1002/anie.202423335","url":null,"abstract":"Fasten your seat belt! Choose lightning-speed, photoactivated journeys for complexes by selecting the metal, its oxidation state, ligands and geometry. Track complexes through excited singlet (S) states, intersystem crossing (ISC) to triplet (T) states, energy/charge-transfer, luminescence, ligand substitutions and redox reactions. Pathways to novel drugs with new mechanisms of action. Unravelling excited metallomics on the way is challenging.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"89 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975066","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}
Nuwanthaka P. Jayaweera, Shana Havenridge, Ashley R. Bielinski, Kihoon Kim, Niklas B. Thompson, Justin M. Hoffman, Amelia M. Wheaton, Prasenjit Sarkar, Rajesh Pathak, Jeffrey W. Elam, Cong Liu, Karen L. Mulfort, Alex B. F. Martinson
This study introduces a sequential infiltration synthesis (SIS) method to form cadmium sulfide discrete atom clusters within poly(4-vinylpyridine) polymer thin films. By alternating exposures to dimethyl cadmium and hydrogen sulfide, researchers synthesized cubane-type Cd4S4 core clusters. The clusters, capped with methyl, thiol, and hydroxy groups, were structurally validated through spectroscopy, X-ray scattering, and simulations. This SIS technique offers a new pathway for creating precisely structured materials with potential applications in light-absorbing technologies, including solar energy harvesting.
{"title":"Sequential Infiltration Synthesis of Cadmium Sulfide Discrete Atom Clusters","authors":"Nuwanthaka P. Jayaweera, Shana Havenridge, Ashley R. Bielinski, Kihoon Kim, Niklas B. Thompson, Justin M. Hoffman, Amelia M. Wheaton, Prasenjit Sarkar, Rajesh Pathak, Jeffrey W. Elam, Cong Liu, Karen L. Mulfort, Alex B. F. Martinson","doi":"10.1002/anie.202421259","DOIUrl":"https://doi.org/10.1002/anie.202421259","url":null,"abstract":"This study introduces a sequential infiltration synthesis (SIS) method to form cadmium sulfide discrete atom clusters within poly(4-vinylpyridine) polymer thin films. By alternating exposures to dimethyl cadmium and hydrogen sulfide, researchers synthesized cubane-type Cd<sub>4</sub>S<sub>4</sub> core clusters. The clusters, capped with methyl, thiol, and hydroxy groups, were structurally validated through spectroscopy, X-ray scattering, and simulations. This SIS technique offers a new pathway for creating precisely structured materials with potential applications in light-absorbing technologies, including solar energy harvesting.","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":"142968344","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}
Integrating enzymes with reticular frameworks offers promising avenues for access to functionally tailorable biocatalysis. This Minireview explores recent advances in enzyme-reticular frameworks hybrid biocomposites, focusing on the utilization of porous reticular frameworks, including metal-organic frameworks, covalent-organic frameworks, and hydrogen-bonded organic frameworks, to regulate the reactivity of an enzyme encapsulated inside mainly by pore infiltration and in situ encapsulation strategies. We highlight how pore engineering and host-guest interfacial interactions within reticular frameworks create tailored microenvironments that substantially impact the mass transfer and enzyme’s conformation, leading to biocatalytic rate enhancement, or imparting enzyme with non-native biocatalytic functions including substrate-selectivity and new activity. Additionally, the feasibility of leveraging framework’s photothermal effect to optimize local reaction temperature and photoelectric effect to elicit diverse photoenzyme-coupled reactions are also detailed summarized, which can expand the functional repertoire of biocatalytic transformations under lighting. This Minireview underscores the potential of reticular framework as tunable and reliable platforms to govern biocatalysis, offering pathways for engineering sustainable, efficient, and selective biocatalytic reactors in pharmaceutical, environmental, and energy-related applications.
{"title":"Integrating Enzymes with Reticular Frameworks To Govern Biocatalysis","authors":"Linjing Tong, Siming Huang, Guosheng Chen, Gangfeng Ouyang","doi":"10.1002/anie.202421192","DOIUrl":"https://doi.org/10.1002/anie.202421192","url":null,"abstract":"Integrating enzymes with reticular frameworks offers promising avenues for access to functionally tailorable biocatalysis. This Minireview explores recent advances in enzyme-reticular frameworks hybrid biocomposites, focusing on the utilization of porous reticular frameworks, including metal-organic frameworks, covalent-organic frameworks, and hydrogen-bonded organic frameworks, to regulate the reactivity of an enzyme encapsulated inside mainly by pore infiltration and in situ encapsulation strategies. We highlight how pore engineering and host-guest interfacial interactions within reticular frameworks create tailored microenvironments that substantially impact the mass transfer and enzyme’s conformation, leading to biocatalytic rate enhancement, or imparting enzyme with non-native biocatalytic functions including substrate-selectivity and new activity. Additionally, the feasibility of leveraging framework’s photothermal effect to optimize local reaction temperature and photoelectric effect to elicit diverse photoenzyme-coupled reactions are also detailed summarized, which can expand the functional repertoire of biocatalytic transformations under lighting. This Minireview underscores the potential of reticular framework as tunable and reliable platforms to govern biocatalysis, offering pathways for engineering sustainable, efficient, and selective biocatalytic reactors in pharmaceutical, environmental, and energy-related applications.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"36 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975099","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}
: Camptothecin (CPT), a chemotherapeutic agent, demonstrates significant potential in cancer therapy. However, as a drug, CPT molecule suffers from poor water solubility, limited bioavailability, and insufficient immune response. Herein, we construct CPT nanofibers (CNF) with a right‐handed chiral property via supramolecular self‐assembly, which significantly overcomes the solubility barriers associated with bioavailability and improves tumor immune prognosis. The CNF exhibits high chiral asymmetry factor (gabs) (~ 0.11) and remarkable structure stability under pH 6.5 condition. By formulating chiral CNF with mitochondrial‐targeted DSPE‐PEG‐TPP, CNF accumulates specifically in the mitochondria of cancer cells, leading to mitochondrial dysfunction and a 3.42‐fold increase in reactive oxygen species (ROS) generation compared to the CPT molecule. This ROS amplification activates the caspase‐1/gasdermin D (GSDMD) pathway, inducing pyroptosis that promotes M1 macrophage polarization and enhences CD8+ T‐cell‐dependent antitumor immunity. Consequently, CNF achieves 1.8‐fold greater growth inhibition of distant tumor and reduces tumor metastasis compared to the CPT molecule. Our innovative platform, assembling CPT molecules into chiral CNF structure, is highly anticipated to overcome the current clinical limitations of CPT molecules and offer a new direction for the development of next‐generation immunotherapy strategies.
{"title":"Chiral Nanofibers of Camptothecin Trigger Pyroptosis for Enhanced Immunotherapy","authors":"Chuan Liang Feng, Fengli Gao, Xiaxin Qiu, Sravan Baddi, Sijia He, Shuting Wang, Changli Zhao, Xiaoqiu Dou","doi":"10.1002/anie.202423446","DOIUrl":"https://doi.org/10.1002/anie.202423446","url":null,"abstract":": Camptothecin (CPT), a chemotherapeutic agent, demonstrates significant potential in cancer therapy. However, as a drug, CPT molecule suffers from poor water solubility, limited bioavailability, and insufficient immune response. Herein, we construct CPT nanofibers (CNF) with a right‐handed chiral property via supramolecular self‐assembly, which significantly overcomes the solubility barriers associated with bioavailability and improves tumor immune prognosis. The CNF exhibits high chiral asymmetry factor (gabs) (~ 0.11) and remarkable structure stability under pH 6.5 condition. By formulating chiral CNF with mitochondrial‐targeted DSPE‐PEG‐TPP, CNF accumulates specifically in the mitochondria of cancer cells, leading to mitochondrial dysfunction and a 3.42‐fold increase in reactive oxygen species (ROS) generation compared to the CPT molecule. This ROS amplification activates the caspase‐1/gasdermin D (GSDMD) pathway, inducing pyroptosis that promotes M1 macrophage polarization and enhences CD8+ T‐cell‐dependent antitumor immunity. Consequently, CNF achieves 1.8‐fold greater growth inhibition of distant tumor and reduces tumor metastasis compared to the CPT molecule. Our innovative platform, assembling CPT molecules into chiral CNF structure, is highly anticipated to overcome the current clinical limitations of CPT molecules and offer a new direction for the development of next‐generation immunotherapy strategies.","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":"142968212","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}
Na Chen, Ruichen Shen, Tianpei He, Na Du, Jing Xi, Yangbing Yang, Lilei Yu, Quan Yuan
“Cell factory” strategy based on microbial anabolism pathways offers an intriguing alternative to relieve the dependence on fossil fuels, which are recognized as the main sources of CO2 emission. Typically, anabolism of intracellular substance in cell factory requires the consumption of sufficient reduced nicotinamide adenine dinucleotide phosphate (NADPH) and adenosine triphosphate (ATP). However, it is of great challenge to modify the natural limited anabolism and to increase the insufficient level of NADPH and ATP to optimum concentrations without causing metabolic imbalance. Inspired by the natural photosynthesis process in which NADPH and ATP can both be produced through the coupled electron-proton transfer processes driven by sunlight, herein we designed a light-driven bionic system composed of three modules including photo-induced electron module, electron transfer channel module and proton gradient module. The proposed strategy of light-driven bionic system enables for achieving simultaneous and controllable supplies of NADPH and ATP, thus facilitating both highly efficient CO2 fixation and biomanufacturing. The proposed light-driven bionic system design strategy in this work might pave new sustainable ways for reducing power and energy regeneration to optimize microbial metabolism, offering intriguing alternatives for CO2 emission reduction and high value-added chemical biomanufacturing.
{"title":"A photosynthesis-derived bionic system for sustainable biosynthesis","authors":"Na Chen, Ruichen Shen, Tianpei He, Na Du, Jing Xi, Yangbing Yang, Lilei Yu, Quan Yuan","doi":"10.1002/anie.202414981","DOIUrl":"https://doi.org/10.1002/anie.202414981","url":null,"abstract":"“Cell factory” strategy based on microbial anabolism pathways offers an intriguing alternative to relieve the dependence on fossil fuels, which are recognized as the main sources of CO2 emission. Typically, anabolism of intracellular substance in cell factory requires the consumption of sufficient reduced nicotinamide adenine dinucleotide phosphate (NADPH) and adenosine triphosphate (ATP). However, it is of great challenge to modify the natural limited anabolism and to increase the insufficient level of NADPH and ATP to optimum concentrations without causing metabolic imbalance. Inspired by the natural photosynthesis process in which NADPH and ATP can both be produced through the coupled electron-proton transfer processes driven by sunlight, herein we designed a light-driven bionic system composed of three modules including photo-induced electron module, electron transfer channel module and proton gradient module. The proposed strategy of light-driven bionic system enables for achieving simultaneous and controllable supplies of NADPH and ATP, thus facilitating both highly efficient CO2 fixation and biomanufacturing. The proposed light-driven bionic system design strategy in this work might pave new sustainable ways for reducing power and energy regeneration to optimize microbial metabolism, offering intriguing alternatives for CO2 emission reduction and high value-added chemical biomanufacturing.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"32 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142975065","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}
Xue Zhang, Yi Zhou, Zhi-Xiang Yu, Chen-Ho Tung, Zhenghu Xu
Planar chirality found tremendous use in many fields, such as chemistry, optics, and materials science. In particular, planar chiral [2.2]paracyclophanes (PCPs) are a type of structurally interesting and practically useful chiral compounds bearing unique electronic and photophysical properties and thus have been widely used in π-stacking polymers, organic luminescent materials, and as a valuable toolbox for developing chiral ligands or organocatalysts. However, the synthesis of chiral PCP derivatives remains a longstanding challenge. Current synthetic methods primarily rely on chiral preparative liquid chromatography separation or chemical and kinetic resolution reactions. Here, we report an enantioconvergent alkynylation of an in situ-formed dehydro-[2,2]-paracyclophane intermediate by asymmetric copper(I) catalysis. This approach enables the efficient synthesis of valuable planar chiral PCP building blocks and heterocycles with good yields and excellent enantioselectivity. The success of this reaction lies in the development of a practical route to access strained dehydro-[2,2]-paracyclophane intermediates, which can also be utilized in various strain-release nucleophilic or cycloaddition reactions to synthesize diverse functionalized PCPs. DFT calculations of this reaction suggest that the enantioselectivity is determined by the aryne complexation with chiral copper(I) acetylide and the subsequent insertion reaction.
{"title":"Strained Dehydro-[2,2]-paracyclophane Enabled Planar Chirality Construction and [2.2]Paracyclophane Functionalization","authors":"Xue Zhang, Yi Zhou, Zhi-Xiang Yu, Chen-Ho Tung, Zhenghu Xu","doi":"10.1002/anie.202420667","DOIUrl":"https://doi.org/10.1002/anie.202420667","url":null,"abstract":"Planar chirality found tremendous use in many fields, such as chemistry, optics, and materials science. In particular, planar chiral [2.2]paracyclophanes (PCPs) are a type of structurally interesting and practically useful chiral compounds bearing unique electronic and photophysical properties and thus have been widely used in π-stacking polymers, organic luminescent materials, and as a valuable toolbox for developing chiral ligands or organocatalysts. However, the synthesis of chiral PCP derivatives remains a longstanding challenge. Current synthetic methods primarily rely on chiral preparative liquid chromatography separation or chemical and kinetic resolution reactions. Here, we report an enantioconvergent alkynylation of an in situ-formed dehydro-[2,2]-paracyclophane intermediate by asymmetric copper(I) catalysis. This approach enables the efficient synthesis of valuable planar chiral PCP building blocks and heterocycles with good yields and excellent enantioselectivity. The success of this reaction lies in the development of a practical route to access strained dehydro-[2,2]-paracyclophane intermediates, which can also be utilized in various strain-release nucleophilic or cycloaddition reactions to synthesize diverse functionalized PCPs. DFT calculations of this reaction suggest that the enantioselectivity is determined by the aryne complexation with chiral copper(I) acetylide and the subsequent insertion reaction.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"13 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968479","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}
Lei Zhang, Tian Sun, Zhao Zhang, Ziyue Zhang, Yuxi Xu
The Friedel-Crafts reaction has been extensively applied to the preparation of various porous organic polymers because of its simple operation and abundant building blocks. However, due to its poor reversibility and excessive random reactive sites, the synthesis of crystalline organic polymers/frameworks by Friedel-Crafts reaction has never been realized so far. Herein, we develop a molecular confined Friedel-Crafts reaction strategy to achieve rapid preparation (within only 30 minutes) of highly crystalline covalent triazine frameworks (CTFs) with tailorable functionality for the first time. Theoretical calculations and detailed experiments revealed the critical role of carboxyl groups in aromatic benzene monomer during the CTFs crystallization, which can not only effectively cause a suitable activation barrier for the electrophilic attack of 2,4,6-trichloro-1,3,5-triazine through their electron-withdrawing properties, but also introduce anchoring effects (molecular confinement effects) to facilitate the ordered polymerization at specific sites in 2D planar direction. Benefiting from the convenient synthetic route and low-cost raw materials, we could unprecedentedly realize the kilogram-scale fabrication of carboxyl-functionalized high-crystalline CTFs. Moreover, thanks to the hydrophilic and ionizable properties of carboxyl groups, the obtained functionalized CTFs exhibited excellent aqueous dispersibility and superior solution processability.
{"title":"Rapid and Scalable Preparation of High-Crystalline Carboxyl-Functionalized Covalent Triazine Frameworks via Friedel-Crafts Reaction","authors":"Lei Zhang, Tian Sun, Zhao Zhang, Ziyue Zhang, Yuxi Xu","doi":"10.1002/anie.202421251","DOIUrl":"https://doi.org/10.1002/anie.202421251","url":null,"abstract":"The Friedel-Crafts reaction has been extensively applied to the preparation of various porous organic polymers because of its simple operation and abundant building blocks. However, due to its poor reversibility and excessive random reactive sites, the synthesis of crystalline organic polymers/frameworks by Friedel-Crafts reaction has never been realized so far. Herein, we develop a molecular confined Friedel-Crafts reaction strategy to achieve rapid preparation (within only 30 minutes) of highly crystalline covalent triazine frameworks (CTFs) with tailorable functionality for the first time. Theoretical calculations and detailed experiments revealed the critical role of carboxyl groups in aromatic benzene monomer during the CTFs crystallization, which can not only effectively cause a suitable activation barrier for the electrophilic attack of 2,4,6-trichloro-1,3,5-triazine through their electron-withdrawing properties, but also introduce anchoring effects (molecular confinement effects) to facilitate the ordered polymerization at specific sites in 2D planar direction. Benefiting from the convenient synthetic route and low-cost raw materials, we could unprecedentedly realize the kilogram-scale fabrication of carboxyl-functionalized high-crystalline CTFs. Moreover, thanks to the hydrophilic and ionizable properties of carboxyl groups, the obtained functionalized CTFs exhibited excellent aqueous dispersibility and superior solution processability.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"82 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968345","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}
Crystal-facet heterojunction engineering of mesoporous nanoreactors with highly redox-active represents an efficacious strategy for the transformation of CO2 into valuable C2 products (e.g., C2H4). Herein, hollow mesoporous cube-like CuS nanoreactors (~860 nm) with controlled anisotropic crystal-facets are prepared through an interfacial-confined ion dynamic migration-rearrangement strategy. The regulation of the S2- ion concentration facilitates the modulation of the highly active (110) to (100) crystal-facet ratios from 0.119 to 0.288, and induces the formation of anisotropic crystal-facet heterojunctions. The controllable crystal-facet heterojunctions trigger the directional charge carrier migration, and are accompanied with the formation of tandem S-defect sites (Cu0-S1@S3). Both of them promote the efficient electron-hole pair dissociation and attain asymmetric C-C coupling. The hollow mesoporous CuS nanoreactors with optimized crystal-facet ratio of 0.224 (HMe-CuS-3) deliver a high selectivity of 72.7% for the photocatalytic reduction of CO2 to acetylene (C2H2). Further constructed Au-(110) and Co3O4-(100) spatially separated cascade nanoreactors (SS-Au@Co3O4-CuS) achieve CO2-C2H4 photoreduction, in which the Co-sites enhance H2O dissociation to provide protons and the protonation of *CO to *COH. The *COH is further captured by Au-sites to accomplish the asymmetric *CO-*COH coupling and subsequent protonation, ensuring a high C2H4 generation rate of 4.11 μmol/g/h with a selectivity as high as 90.6%.
{"title":"Crystal-Facet Engineering of Mesoporous CuS Cascade Nanoreactors Enhances Photocatalytic C-C Coupling of CO2-to-C2H4","authors":"Jiaming Zhang, Linlin Duan, Wei Zhang, Bing Ma, Jiangwei Zhang, Jinying Li, Aixia Wang, Peiting Guo, Dongyuan Zhao, Yuzhu Ma","doi":"10.1002/anie.202423861","DOIUrl":"https://doi.org/10.1002/anie.202423861","url":null,"abstract":"Crystal-facet heterojunction engineering of mesoporous nanoreactors with highly redox-active represents an efficacious strategy for the transformation of CO2 into valuable C2 products (e.g., C2H4). Herein, hollow mesoporous cube-like CuS nanoreactors (~860 nm) with controlled anisotropic crystal-facets are prepared through an interfacial-confined ion dynamic migration-rearrangement strategy. The regulation of the S2- ion concentration facilitates the modulation of the highly active (110) to (100) crystal-facet ratios from 0.119 to 0.288, and induces the formation of anisotropic crystal-facet heterojunctions. The controllable crystal-facet heterojunctions trigger the directional charge carrier migration, and are accompanied with the formation of tandem S-defect sites (Cu0-S1@S3). Both of them promote the efficient electron-hole pair dissociation and attain asymmetric C-C coupling. The hollow mesoporous CuS nanoreactors with optimized crystal-facet ratio of 0.224 (HMe-CuS-3) deliver a high selectivity of 72.7% for the photocatalytic reduction of CO2 to acetylene (C2H2). Further constructed Au-(110) and Co3O4-(100) spatially separated cascade nanoreactors (SS-Au@Co3O4-CuS) achieve CO2-C2H4 photoreduction, in which the Co-sites enhance H2O dissociation to provide protons and the protonation of *CO to *COH. The *COH is further captured by Au-sites to accomplish the asymmetric *CO-*COH coupling and subsequent protonation, ensuring a high C2H4 generation rate of 4.11 μmol/g/h with a selectivity as high as 90.6%.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"11 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-01-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142968614","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}
Jie Li, Yan Guan, Tian-Tian Hao, Jiang Huang, Yi Chen, Heng Li, Pengfei Duan, He-Lou Xie
Efficient circularly polarized luminescence (CPL) optical waveguides have significant potential for advancing photonic and optoelectronic devices. However, the development of CPL optical waveguides materials (OWMs) with low optical loss coefficient remains a considerable challenge. To overcome this, we design and synthesize CPL OWMs based on room‐temperature phosphorescent liquid crystalline polymers (LCPs). Experimental results demonstrate that these LCPs exhibit a nematic liquid crystal phase and a phosphorescence lifetime of approximately 0.145 ms. By introducing a chiral dopant, we induce a chiral arrangement in the LCPs, followed by crosslinking via photo‐cycloaddition and removal of the chiral dopants through solvent soaking. The resulting polymers exhibit stable solvent resistance and highly efficient circularly polarized phosphorescence (CPP) properties, with dissymmetric factors (gRTP) in the range of 0.16 to 0.17. Notably, the CPP‐active OWMs exhibit efficient circularly polarized photonic signal waveguiding, with an optical loss coefficient of approximately 0.175 dB/mm. Ultimately, these CPP‐active OWMs are sucessfully applied in information encryption, decryption, and optical switching, paving the way for advanced photonic and optoelectronic devices.
{"title":"Phosphorescent Liquid Crystalline Polymer‐based Circularly Polarized Luminescence Optical Waveguides for Enhanced Photonic Signal Processing and Information Encryption","authors":"Jie Li, Yan Guan, Tian-Tian Hao, Jiang Huang, Yi Chen, Heng Li, Pengfei Duan, He-Lou Xie","doi":"10.1002/anie.202423395","DOIUrl":"https://doi.org/10.1002/anie.202423395","url":null,"abstract":"Efficient circularly polarized luminescence (CPL) optical waveguides have significant potential for advancing photonic and optoelectronic devices. However, the development of CPL optical waveguides materials (OWMs) with low optical loss coefficient remains a considerable challenge. To overcome this, we design and synthesize CPL OWMs based on room‐temperature phosphorescent liquid crystalline polymers (LCPs). Experimental results demonstrate that these LCPs exhibit a nematic liquid crystal phase and a phosphorescence lifetime of approximately 0.145 ms. By introducing a chiral dopant, we induce a chiral arrangement in the LCPs, followed by crosslinking via photo‐cycloaddition and removal of the chiral dopants through solvent soaking. The resulting polymers exhibit stable solvent resistance and highly efficient circularly polarized phosphorescence (CPP) properties, with dissymmetric factors (gRTP) in the range of 0.16 to 0.17. Notably, the CPP‐active OWMs exhibit efficient circularly polarized photonic signal waveguiding, with an optical loss coefficient of approximately 0.175 dB/mm. Ultimately, these CPP‐active OWMs are sucessfully applied in information encryption, decryption, and optical switching, paving the way for advanced photonic and optoelectronic devices.","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":"142968199","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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