Advanced Materials最新文献_第4页

Efficient H2O2 Electrosynthesis in Acidic media via Multiscale Catalyst Optimization

IF 29.4 1区材料科学

Advanced Materials Pub Date : 2025-03-18 DOI: 10.1002/adma.202418489

Jaehyuk Shim, Jaewoo Lee, Heejong Shin, Dong Hyeon Mok, Sungeun Heo, Vinod K Paidi, Byoung-Hoon Lee, Hyeon Seok Lee, Juhyun Yang, Dongho Shin, Jaeho Moon, Kang Kim, Muho Jung, Eungjun Lee, Megalamane S. Bootharaju, Jeong Hyun Kim, Subin Park, Mi-Ju Kim, Pieter Glatzel, Sung Jong Yoo, Seoin Back, Kug-Seung Lee, Yung-Eun Sung, Taeghwan Hyeon

{"title":"Efficient H2O2 Electrosynthesis in Acidic media via Multiscale Catalyst Optimization","authors":"Jaehyuk Shim, Jaewoo Lee, Heejong Shin, Dong Hyeon Mok, Sungeun Heo, Vinod K Paidi, Byoung-Hoon Lee, Hyeon Seok Lee, Juhyun Yang, Dongho Shin, Jaeho Moon, Kang Kim, Muho Jung, Eungjun Lee, Megalamane S. Bootharaju, Jeong Hyun Kim, Subin Park, Mi-Ju Kim, Pieter Glatzel, Sung Jong Yoo, Seoin Back, Kug-Seung Lee, Yung-Eun Sung, Taeghwan Hyeon","doi":"10.1002/adma.202418489","DOIUrl":"https://doi.org/10.1002/adma.202418489","url":null,"abstract":"Electrochemically generating hydrogen peroxide (H2O2) from oxygen offers a more sustainable and cost-effective alternative to conventional anthraquinone process. In alkaline conditions, H2O2 is unstable as HO2−, and in neutral electrolytes, alkali cation crossover causes system instability. Producing H2O2 in acidic electrolytes ensures enhanced stability and efficiency. However, in acidic conditions, the oxygen reduction reaction mechanism is dominated by the inner-sphere electron transfer pathway, requiring careful consideration of both reaction and mass transfer kinetics. These stringent requirements limit H2O2 production efficiency, typically below 10–20% at industrial-relevant current densities (>300 mA cm−2). Using a multiscale approach that combines active site tuning with macrostructure tuning, this work presents an octahedron-like cobalt structure on interconnected hierarchical porous nanofibers, achieving a faradaic efficiency exceeding 80% at 400 mA cm−2 and stable operation for over 120 h at 100 mA cm−2. At 300 mA cm−2, the optimized catalyst demonstrates a cell potential of 2.14 V, resulting in an energy efficiency of 26%.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"9 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143641024","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A 2D/3D Heterostructure Perovskite Solar Cell with a Phase-Pure and Pristine 2D Layer

IF 29.4 1区材料科学

Advanced Materials Pub Date : 2025-03-18 DOI: 10.1002/adma.202416672

Meng-Chen Shih, Shaun Tan, Yongli Lu, Tim Kodalle, Do-Kyoung Lee, Yifan Dong, Bryon W. Larson, Soyeon Park, Ruiqi Zhang, Matthias J. Grotevent, Tara Sverko, Hua Zhu, Yu-Kuan Lin, Carolin M. Sutter-Fella, Kai Zhu, Matthew C. Beard, Vladimir Bulović, Moungi G. Bawendi

{"title":"A 2D/3D Heterostructure Perovskite Solar Cell with a Phase-Pure and Pristine 2D Layer","authors":"Meng-Chen Shih, Shaun Tan, Yongli Lu, Tim Kodalle, Do-Kyoung Lee, Yifan Dong, Bryon W. Larson, Soyeon Park, Ruiqi Zhang, Matthias J. Grotevent, Tara Sverko, Hua Zhu, Yu-Kuan Lin, Carolin M. Sutter-Fella, Kai Zhu, Matthew C. Beard, Vladimir Bulović, Moungi G. Bawendi","doi":"10.1002/adma.202416672","DOIUrl":"https://doi.org/10.1002/adma.202416672","url":null,"abstract":"Interface engineering plays a critical role in advancing the performance of perovskite solar cells. As such, 2D/3D perovskite heterostructures are of particular interest due to their optoelectrical properties and their further potential improvements. However, for conventional solution-processed 2D perovskites grown on an underlying 3D perovskite, the reaction stoichiometry is normally unbalanced with excess precursors. Moreover, the formed 2D perovskite is impure, leading to unfavorable energy band alignment at the interface. Here a simple method is presented that solves both issues simultaneously. The 2D formation reaction is taken first to completion, fully consuming excess PbI2. Then, isopropanol is utilized to remove excess organic ligands, control the 2D perovskite thickness, and obtain a phase-pure, n = 2, 2D perovskite. The outcome is a pristine (without residual 2D precursors) and phase-pure 2D perovskite heterostructure with improved surface passivation and charge carrier extraction compared to the conventional solution process. PSCs incorporating this treatment demonstrate a notable improvement in both stability and power conversion efficiency, with negligible hysteresis, compared to the conventional process.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"1 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640935","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Organic Photoelectrochemical Multisensory Integration

IF 29.4 1区材料科学

Advanced Materials Pub Date : 2025-03-18 DOI: 10.1002/adma.202503030

Yu-Ting Huang, Zheng Li, Cheng Yuan, Yuan-Cheng Zhu, Wei-Wei Zhao, Jing-Juan Xu

引用次数: 0

Functional Groups-Regulated Organic Semiconductors for Efficient Artificial Photosynthesis of Hydrogen Peroxide

IF 29.4 1区材料科学

Advanced Materials Pub Date : 2025-03-18 DOI: 10.1002/adma.202501494

Xiaohui Yu, Zhen Wei, Yuanshen Qin, Xu Zhang, Derek Hao, Lin Jing, Yuxi Liu, Hongxing Dai, Jiguang Deng, Yongfa Zhu

{"title":"Functional Groups-Regulated Organic Semiconductors for Efficient Artificial Photosynthesis of Hydrogen Peroxide","authors":"Xiaohui Yu, Zhen Wei, Yuanshen Qin, Xu Zhang, Derek Hao, Lin Jing, Yuxi Liu, Hongxing Dai, Jiguang Deng, Yongfa Zhu","doi":"10.1002/adma.202501494","DOIUrl":"https://doi.org/10.1002/adma.202501494","url":null,"abstract":"Hydrogen peroxide (H2O2) is an environmentally friendly reagent, and organic semiconductors (OSCs) are ideal photocatalysts for the synthesis of H2O2 due to their well-defined molecular structure, strong donor-acceptor interactions, and efficient charge separation. This review discusses the regulatory mechanisms of functional group modifications in tuning the photocatalytic performance of OSCs, highlighting the relationship between functional group structure and catalytic performance. For example, electron-regulating groups, such as cyano and halogen, induce molecular dipoles, facilitating the migration of photogenerated electrons. Fluorine groups optimize the band structure and prolong carrier lifetime due to their high electronegativity. π-Conjugated extension groups, like anthraquinone and thiophene, expand conjugation, improve visible light capture, and stabilize intermediates through redox cycles. Hydroxyl groups enhance surface hydrophilicity and promote H2O activation, while imine bond protonation adjusts charge distribution and improves selectivity and cycle stability. Multi-active site functional groups, such as sulfonic acid and amide, accelerate reaction kinetics and inhibit H2O2 decomposition. Functional groups enhance light absorption, charge separation, and surface reactions through electronic structure regulation, intermediate adsorption optimization, and proton-electron transfer. Future work should integrate machine learning to identify optimal functional group combinations and develop green functionalization strategies for efficient H2O2 photocatalyst synthesis.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"17 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640931","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Enhanced Reversibility of Iron Metal Anode with a Solid Electrolyte Interphase in Concentrated Chloride Electrolytes

IF 29.4 1区材料科学

Advanced Materials Pub Date : 2025-03-18 DOI: 10.1002/adma.202419664

Min Soo Jung, Sungjin Yang, Cheng Chen, Sathya Narayanan Jagadeesan, Weiyin Chen, Guangxia Feng, Yiming Sui, Ziang Jiang, Emmanuel N. Musa, Nan-Chieh Chiu, Hunter Maclennan, Elliot Holden, Kyriakos C. Stylianou, Ju Li, Chong Fang, Xueli Zheng, Xiulei Ji

{"title":"Enhanced Reversibility of Iron Metal Anode with a Solid Electrolyte Interphase in Concentrated Chloride Electrolytes","authors":"Min Soo Jung, Sungjin Yang, Cheng Chen, Sathya Narayanan Jagadeesan, Weiyin Chen, Guangxia Feng, Yiming Sui, Ziang Jiang, Emmanuel N. Musa, Nan-Chieh Chiu, Hunter Maclennan, Elliot Holden, Kyriakos C. Stylianou, Ju Li, Chong Fang, Xueli Zheng, Xiulei Ji","doi":"10.1002/adma.202419664","DOIUrl":"https://doi.org/10.1002/adma.202419664","url":null,"abstract":"Iron is a promising candidate for a cost-effective anode for large-scale energy storage systems due to its natural abundance and well-established mass production. Recently, Fe-ion batteries (FeIBs) that use ferrous ions as the charge carrier have emerged as a potential storage solution. The electrolytes in FeIBs are necessarily acidic to render the ferrous ions more anodically stable, allowing a wide operation voltage window. However, the iron anode suffers severe hydrogen evolution reaction with a low Coulombic efficiency (CE) in an acidic environment, shortening the battery cycle life. Herein, a hybrid aqueous electrolyte that forms a solid-electrolyte interphase (SEI) layer on the Fe anode surface is introduced. The electrolyte mainly comprises FeCl2 and ZnCl2 as cosalts, where the Zn-Cl anionic complex species of the concentrated ZnCl2 allows dimethyl carbonate (DMC) to be miscible with the aqueous ferrous electrolyte. SEI derived from DMC's decomposition passivates the iron surface, which leads to an average CE of 98.3% and much-improved cycling stability. This advancement shows the promise of efficient and durable FeIBs.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"22 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143641020","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Oriented Assembly of 2D Metal-Pyridylporphyrinic Framework to Regulate the Redox Kinetics in Li−S Batteries

IF 29.4 1区材料科学

Advanced Materials Pub Date : 2025-03-18 DOI: 10.1002/adma.202501869

Yan Zhao, Ziyun Shang, Muti Feng, Hongxia Zhong, Yu Du, Weijie Chen, Yu Wang, Jiaxing Zou, Yulin Chen, Hai Wang, Ye Wang, Jia-Nan Zhang, Gan Qu

{"title":"Oriented Assembly of 2D Metal-Pyridylporphyrinic Framework to Regulate the Redox Kinetics in Li−S Batteries","authors":"Yan Zhao, Ziyun Shang, Muti Feng, Hongxia Zhong, Yu Du, Weijie Chen, Yu Wang, Jiaxing Zou, Yulin Chen, Hai Wang, Ye Wang, Jia-Nan Zhang, Gan Qu","doi":"10.1002/adma.202501869","DOIUrl":"https://doi.org/10.1002/adma.202501869","url":null,"abstract":"Developing the highly efficient catalysts is a great challenge for accelerating the redox reactions in Li−S batteries. Inspired by the single-atom catalysts and metalloproteins, it makes full use of the advantages of metal–organic frameworks (MOFs) as electrocatalysts. Herein, a series of 2D metal-bonded metalloporphyrin MOFs are prepared with 5,10,15,20-tetrakis(4-pyridyl) cobalt porphyrin (CoTPyP) as building blocks and transition metals (M═Mn, Fe, Co, Ni, and Cu) as nodes, respectively. The crystalline structures of the bimetallic 2D MOFs are confirmed by UV–vis spectra and X-ray diffraction analyses. According to DFT calculation, the peripheral metal nodes optimize the electronic state of Co in porphyrin core. Especially, CoTPyP-Mn facilitates the cleavage of S−S bond from both ends and promotes their conversion kinetics through Co−S and Li−N bonds. The Li−S cells with CoTPyP-Mn show the initial specific capacity of 1339 mA h g−1 at 0.2 C. The capacity decay rate is only 0.0442% per cycle after 1000 cycles at 2 C. This work achieves the rational control of the central Co d electron state through the peripheral regulation and enriches the application of MOFs in accelerating the redox kinetics in Li−S batteries.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"43 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143641026","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Manipulating Interfacial Water Via Metallic Pt1Co6 Sites on Self-Adaptive Metal Phosphides to Enhance Water Electrolysis

IF 29.4 1区材料科学

Advanced Materials Pub Date : 2025-03-18 DOI: 10.1002/adma.202419644

Kang Jiang, Zhixiao Liu, Zhen Wang, Feng Xie, Xinyi Yuan, Yongwen Tan

{"title":"Manipulating Interfacial Water Via Metallic Pt1Co6 Sites on Self-Adaptive Metal Phosphides to Enhance Water Electrolysis","authors":"Kang Jiang, Zhixiao Liu, Zhen Wang, Feng Xie, Xinyi Yuan, Yongwen Tan","doi":"10.1002/adma.202419644","DOIUrl":"https://doi.org/10.1002/adma.202419644","url":null,"abstract":"Metallizing active sites to control the structural and kinetic dissociation of water at the catalyst–electrolyte interface, along with elucidating its mechanism under operating conditions, is a pivotal innovation for the hydrogen evolution reaction (HER). Here, a design of singly dispersed Pt–Co sites in a fully metallic state on nanoporous Co2P, tailored for HER, is introduced. An anion-exchange-membrane water electrolyzer equipped with this catalyst can achieve the industrial current densities of 1.0 and 2.0 A cm−2 at 1.71 and 1.85 V, respectively. It is revealed that the singly dispersed Pt–Co sites undergo self-adaptive distortion under operating conditions, which form a Pt1Co6 configuration with a strongly negative charge that optimizes reactant binding and reorganizes the interfacial water structure, resulting in an improved concentration of potassium (K+) ions in the closest ion plane. The K+ ions interact cooperatively with H2O (K·H2O), which strengthens the Pt–H binding interaction and facilitates the polarization of the H─OH bond, leading to improved HER activity. This study not only propels the advancement of cathodic catalysts for water electrolysis but also delineates a metallization strategy and an interface design principle, thereby enhancing electrocatalytic reaction rates.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"7 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640933","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Localized and Controllable Mineral Salts Crystallization Enabled by Dye Modified Gold Nanorods with Enhanced Photothermal Conversion

IF 29.4 1区材料科学

Advanced Materials Pub Date : 2025-03-18 DOI: 10.1002/adma.202417138

Xudong Yan, Yutong Shang, Yi Li, Xiangyi Wang, Yiling Yao, Liping Ding, Taihong Liu, Rong Miao, Yu Fang

{"title":"Localized and Controllable Mineral Salts Crystallization Enabled by Dye Modified Gold Nanorods with Enhanced Photothermal Conversion","authors":"Xudong Yan, Yutong Shang, Yi Li, Xiangyi Wang, Yiling Yao, Liping Ding, Taihong Liu, Rong Miao, Yu Fang","doi":"10.1002/adma.202417138","DOIUrl":"https://doi.org/10.1002/adma.202417138","url":null,"abstract":"Well-designed nanomaterials with favorable photothermal performance are beneficial for exploring fascinating and prospective applications. Herein the facile and effective way is reported to enhance photothermal properties of gold nanorods (GNRs) through immobilizing tailored organic dyes around GNRs. Benefitting from the combination of plasmonic thermalization and nonradiative relaxation, the modified GNRs exhibit a temperature increase of >100 °C under 638 nm laser irradiation in film state, which is double of that of the bare GNRs-doped film under the same condition. The hybrid film also exhibits superior stability and reusability compared to the film only doped with the dyes. Surface temperature of the hybrid film can be adjusted from 31 to 116 °C by tunning either doping materials concentration or light power. Interestingly, the hybrid film serves as a reusable energy converter in confined and controllable photothermal crystallization of mineral salts. NaCl crystals can be arranged into different patterns by moving the laser probe during the crystallization. Microcrystals of CaCO3 (calcite, vaterite, and aragonite), BaCO3, and SrCO3 are successfully obtained. It is believed that the as-prepared materials as well as the demonstrated photothermal crystallization will contribute to the development of function-led photothermal materials.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"49 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640934","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Charge-Directed Nanocellulose Assembly for Interfacial Phase-Transfer Catalysis

IF 29.4 1区材料科学

Advanced Materials Pub Date : 2025-03-18 DOI: 10.1002/adma.202418325

Jaewon Shin, Bokgi Seo, Kyoungho Choi, DaAe Park, Hee Jeong Lee, HoAn Kim, Daehyun Shin, Bum Jun Park, Jin Woong Kim

{"title":"Charge-Directed Nanocellulose Assembly for Interfacial Phase-Transfer Catalysis","authors":"Jaewon Shin, Bokgi Seo, Kyoungho Choi, DaAe Park, Hee Jeong Lee, HoAn Kim, Daehyun Shin, Bum Jun Park, Jin Woong Kim","doi":"10.1002/adma.202418325","DOIUrl":"https://doi.org/10.1002/adma.202418325","url":null,"abstract":"Liquid–liquid interfaces present unique opportunities for sustainable biphasic catalysis, yet concurrent amplification of molecular transport and reactivity at these boundaries remains challenging. Here it is demonstrated that high-aspect-ratio cationic nanocellulose (HNC+) spontaneously self-assembles into mechanically robust nanomesh architectures at oil-water interfaces through charge-directed assembly. This assembly is driven by electrostatic attraction between the cationic nanofibers and the intrinsic negative charge at hydrophobic-aqueous interfaces (σ ≈−0.3 C m−2), generating sufficient excess attractive force (ΔU ≈−1,200 kBT) to overcome image charge repulsion. The resulting nanomesh exhibits uniform “breathing holes” (≈34 nm) and exceptional stability under extreme conditions (pH 2–13, 1.8 m NaCl, and 90 °C). When applied to oxidative desulfurization, the system achieves >90% thiophene removal under ambient conditions with exceptional atom economy (E-factor < 1.1) and catalyst stability through multiple cycles. This breakthrough strategy for interfacial engineering using renewable materials opens new possibilities for green chemical manufacturing while providing fundamental insights into charge-mediated assembly at liquid interfaces. These findings establish a viable pathway for sustainable heterogeneous catalysis that aligns with circular economy principles.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"1 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640930","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

p-π Conjugated Covalent Organic Frameworks Expedite Molecular Triplet Excitons for H2O2 Production Coupled with Biomass Upgrading

IF 29.4 1区材料科学

Advanced Materials Pub Date : 2025-03-18 DOI: 10.1002/adma.202502220

Fan Zhang, Ximeng Lv, Haozhen Wang, Junzhuo Cai, Huining Wang, Shuai Bi, Ruilin Wei, Chao Yang, Gengfeng Zheng, Qing Han

{"title":"p-π Conjugated Covalent Organic Frameworks Expedite Molecular Triplet Excitons for H2O2 Production Coupled with Biomass Upgrading","authors":"Fan Zhang, Ximeng Lv, Haozhen Wang, Junzhuo Cai, Huining Wang, Shuai Bi, Ruilin Wei, Chao Yang, Gengfeng Zheng, Qing Han","doi":"10.1002/adma.202502220","DOIUrl":"https://doi.org/10.1002/adma.202502220","url":null,"abstract":"High-efficiency production of triplet states in covalent organic framework photocatalysts is crucial for high-selectivity oxygen (O2) reduction to hydrogen peroxide (H2O2). Herein, fluorine and partial fluorine atoms are incorporated into an olefin-linked triazine covalent organic framework (F-ol-COF and HF-ol-COF), in which the adjacent fluorine (F) atoms-olefinic bond forms p-π conjugation that induces spin-polarization under irradiation, thus expediting triplet excitons for activating O2 to singlet oxygen (1O2) and contributing to a high H2O2 selectivity (91%). Additionally, the feasibility of coupling H2O2 production with the valorization of 5-hydroxymethylfurfural (HMF) is exhibited. The F-ol-COF demonstrates a highly stable H2O2 yield rate of 12558 µmol g−1 h−1 with the HMF-to-functionalized furan conversion yield of 95%, much higher than the partially fluorinated COF (HF-ol-COF) and the non-fluorinated COF (H-ol-COF). Mechanistic studies reveal that F-incorporation promotes charge separation, intensifies the Lewis acidity of the carbon atoms on the olefinic bond as active sites for O2 adsorption, and provides highly concentrated holes at the triazine unit for HMF oxidation upgrading. This study suggests the attractive potential of rational design of porous-crystalline photocatalysts for high-efficiency photocatalytic O2 reduction to H2O2 and biomass upgrading.","PeriodicalId":114,"journal":{"name":"Advanced Materials","volume":"54 1","pages":""},"PeriodicalIF":29.4,"publicationDate":"2025-03-18","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143640932","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0