Angewandte Chemie International Edition最新文献_第2页

Reducing Energetic Disorder for High‐Efficiency Perovskite Solar Cells with Low Urbach Energy by in Situ NH3 Generation 原位NH3生成降低低厄巴赫能高效钙钛矿太阳能电池的能量紊乱

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-04 DOI: 10.1002/anie.202516464

Chuanzhen Shang, Duo Qu, Zheng Bao, Chenyun Wang, Qiangqiang Zhao, Chunsheng Li, Bin Zhou, Xuemeng Wang, Ruilin Han, Shasha Wang, Wenying Zhao, Kai Wang, Jiangang Liu, Xiaoyu Yang, Zhang Lan, Jiang Wu, Weidong Xu, Jihuai Wu, Rui Zhu, Yongguang Tu

{"title":"Reducing Energetic Disorder for High‐Efficiency Perovskite Solar Cells with Low Urbach Energy by in Situ NH3 Generation","authors":"Chuanzhen Shang, Duo Qu, Zheng Bao, Chenyun Wang, Qiangqiang Zhao, Chunsheng Li, Bin Zhou, Xuemeng Wang, Ruilin Han, Shasha Wang, Wenying Zhao, Kai Wang, Jiangang Liu, Xiaoyu Yang, Zhang Lan, Jiang Wu, Weidong Xu, Jihuai Wu, Rui Zhu, Yongguang Tu","doi":"10.1002/anie.202516464","DOIUrl":"https://doi.org/10.1002/anie.202516464","url":null,"abstract":"The high disorder in perovskite materials leads to severe carrier non‐radiative recombination, which directly determines the energy loss of photovoltaic devices. Currently, modulation of energetic disorder in perovskite solar cells and its correlation with open‐circuit voltage losses (VOC, loss) remain insufficiently understood. We regulated the perovskite crystallization process by in situ NH3 generation, thereby enhancing the perovskite degree of energetic order. Density functional theory calculations reveal that lone‐pair electrons on the N atom of the NH3 molecule coordinate with Pb2+, increasing the defect formation energy of lead vacancies (VPb), Pb‐on‐I antisite (PbI), and I‐on‐Pb antisite (IPb) to 5.61, 0.37, and 4.09 eV, respectively. As a result, we obtained energetic ordered perovskite film with an Urbach energy of 23.7 meV. The champion device exhibited a reduced VOC, loss by over than 50 mV and achieved an open‐circuit voltage (VOC) of 1.182 V with a power conversion efficiency (PCE) of 26.26%. Under the ISOS‐D protocols, the device maintains over 95% of its initial efficiency after 1100 h of nitrogen storage and over 90% after 700 h at 65 °C. And the 5 × 5 cm2 mini‐modules achieved a PCE of 21.31%, representing state‐of‐the‐art performance in perovskite photovoltaics.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"99 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215915","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}

引用次数: 0

Photocatalytic Radical Umpolung for Strain‐Release Difunctionalization of (Aza)bicyclo[1.1.0]butanes （Aza）双环[1.1.0]丁烷菌株释放双官能化的光催化自由基研究

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-04 DOI: 10.1002/anie.202517231

Chang‐Yin Tan, Hyewon Ju, Jinwook Jeong, Jaehun Kim, Sungwoo Hong

{"title":"Photocatalytic Radical Umpolung for Strain‐Release Difunctionalization of (Aza)bicyclo[1.1.0]butanes","authors":"Chang‐Yin Tan, Hyewon Ju, Jinwook Jeong, Jaehun Kim, Sungwoo Hong","doi":"10.1002/anie.202517231","DOIUrl":"https://doi.org/10.1002/anie.202517231","url":null,"abstract":"Azetidines and cyclobutanes are increasingly valued as potent bioisosteres of pyridines and benzenes in medicinal chemistry. Herein, we report a radical umpolung strategy for the regioselective difunctionalization of azabicyclo[1.1.0]butanes (ABBs) and bicyclo[1.1.0]butanes (BCBs) that exhibits complementary regioselectivity to conventional polar strain‐release methods. This approach uses photocatalytically generated electrophilic sulfonyl radicals from readily available sulfinates to selectively add to nitrogen in ABBs and electron‐rich sites of BCBs, triggering strain‐release ring‐opening. The resulting radical intermediates are subsequently captured through two pathways: N‐heterocyclic carbene (NHC)‐catalyzed radical–radical cross‐coupling enables efficient acylation, while single‐electron reduction generates carbanions capable of nucleophilic addition to electrophiles such as CO2 and aldehydes. The umpolung reactivity of this protocol enhances synthetic versatility by accommodating diverse azetidine functionalities under mild conditions to afford densely functionalized azetidines and cyclobutanes that are difficult to access through existing methods.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"143 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215872","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}

引用次数: 0

Chlorine Radical‐Driven, Oxygen‐Independent Afterglow Nanoplatform for Tumor Microenvironment—Adaptive Imaging and Therapy 用于肿瘤微环境自适应成像和治疗的氯自由基驱动、氧不依赖余辉纳米平台

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-04 DOI: 10.1002/anie.202511731

Peng Liang, Baoli Yin, Zhe Dong, Zhe Li, Xinlin Liu, Yong Tan, Hui Cao, Jinxue Xiang, Hanlin Wei, Dingyou Lu, Xiao‐Bing Zhang, Guosheng Song

{"title":"Chlorine Radical‐Driven, Oxygen‐Independent Afterglow Nanoplatform for Tumor Microenvironment—Adaptive Imaging and Therapy","authors":"Peng Liang, Baoli Yin, Zhe Dong, Zhe Li, Xinlin Liu, Yong Tan, Hui Cao, Jinxue Xiang, Hanlin Wei, Dingyou Lu, Xiao‐Bing Zhang, Guosheng Song","doi":"10.1002/anie.202511731","DOIUrl":"https://doi.org/10.1002/anie.202511731","url":null,"abstract":"Persistent luminescence (afterglow) imaging offers exceptional signal‐to‐background ratios by eliminating tissue autofluorescence, yet most organic systems depend on oxygen‐mediated reactive oxygen species and fail in hypoxic environments such as solid tumors. Herein, we report an oxygen‐independent afterglow mechanism driven by chlorine radicals (·Cl). Hemicyanine‐centered nanoparticles (Hcy@AgCl‐PEG) were prepared by nanoprecipitation, surface‐decorated with AgCl heterostructures for light‐activated ·Cl generation, and stabilized with methoxypolyethylene glycol. Upon irradiation, AgCl produces ·Cl, which adds across the dye's conjugated double bond to form metastable epoxide intermediates; subsequent epoxide decomposition releases stored chemical energy, re‐exciting the dye and yielding intense afterglow emission regardless of O2 concentration. This strategy extends to cyanine and porphyrin fluorophores, underscoring its generality. A pH‐responsive variant (Hcy‐pH@AgCl) further enables afterglow imaging of pH‐responsive. In vivo, Hcy@AgCl‐PEG achieves high‐contrast tumor imaging and leverages the oxidative potency of ·Cl to induce pronounced photodynamic therapy via oxidative stress and DNA single‐electron oxidation. Together, these findings establish a new paradigm for oxygen‐free afterglow systems and deliver a versatile theranostic platform for imaging and treatment in dynamic, hypoxia‐associated pathologies.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"13 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215913","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}

引用次数: 0

Synthesis of Degradable Polyimines Through Deborylative Polycondensation 用波酰缩聚法合成可降解聚酰亚胺

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-04 DOI: 10.1002/anie.202517137

Zhiqiang Xi, Yixiang Chen, Xiaolei Zhang

{"title":"Synthesis of Degradable Polyimines Through Deborylative Polycondensation","authors":"Zhiqiang Xi, Yixiang Chen, Xiaolei Zhang","doi":"10.1002/anie.202517137","DOIUrl":"https://doi.org/10.1002/anie.202517137","url":null,"abstract":"Polyimines are degradable and have found applications in separation techniques, gene delivery, optoelectronics, and porous materials. Conventional methods to synthesize polymines involve dehydrative polycondensation, which requires the addition of acid catalysts and drying reagents and has limited substrate scope. In this work, a boron‐mediated strategy has been developed for the synthesis of polyimines. First, we describe the borylation of diamines at the nitrogen sites to afford N,N’‐bis(boryl)diamines. Due to the N─B bond formation, N,N’‐bis(boryl)diamines react fast, irreversibly, and completely with the dialdehydes via an unusual deborylative polycondensation process. Furthermore, methods for deborylative polycondensation reactions were developed under anhydrous and neutral conditions, yielding polyimines containing both aryl and alkyl backbones at room temperature in good to excellent yields. This polymerization protocol is scalable and reduces the operational difficulty in purifying the polyimines. These results provide a general and efficient polymerization tool for the practical synthesis of degradable polyimines.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"5 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215905","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}

引用次数: 0

Intramolecular Noncovalent Interaction‐Driven Syn‐/Anti‐Conformational Regulation in Nonfused‐Ring Electron Acceptors 非熔合环电子受体分子内非共价相互作用驱动的顺/反构象调节

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-04 DOI: 10.1002/anie.202513603

Sixuan Wang, Siying Wang, Rui Zeng, Yuqi Hou, Xiaobin Gu, Ziyang Han, Jikai Lv, Na Yu, Jiawei Qiao, Zheng Tang, Xiaotao Hao, Qian Peng, Feng Liu, Yunhao Cai, Xin Zhang, Hui Huang

{"title":"Intramolecular Noncovalent Interaction‐Driven Syn‐/Anti‐Conformational Regulation in Nonfused‐Ring Electron Acceptors","authors":"Sixuan Wang, Siying Wang, Rui Zeng, Yuqi Hou, Xiaobin Gu, Ziyang Han, Jikai Lv, Na Yu, Jiawei Qiao, Zheng Tang, Xiaotao Hao, Qian Peng, Feng Liu, Yunhao Cai, Xin Zhang, Hui Huang","doi":"10.1002/anie.202513603","DOIUrl":"https://doi.org/10.1002/anie.202513603","url":null,"abstract":"Molecular conformation is a critical structural attribute of organic molecules and polymers in addition to their constitution and configuration, thereby forming the foundation for understanding macroscopic material properties and device functionality. For nonfused‐ring electron acceptors (NFREAs) featuring multiple σ‐bonds with high rotational degrees of freedom, significant challenges remain in precisely regulating molecular conformation, particularly in modulating the syn‐ and anti‐conformation preferences. Here, we demonstrate precise engineering of NFREAs through conformation‐directed molecular design, achieving a syn‐to‐anti‐conformational transition via utilizing intramolecular noncovalent S···F interactions. This conformational regulation strategy enables a systematic investigation of how syn‐/anti‐conformational preferences influence molecular planarity and rigidity, self‐assembly behavior, charge transport properties, and device performance. Our results reveal that the anti‐conformation endows anti‐TT‐F with enhanced crystallinity, reduced reorganization energy, and improved charge carrier mobility compared to its syn‐conformational counterpart. Consequently, binary and ternary devices based on anti‐TT‐F achieve remarkable power conversion efficiencies of 15.08% and 19.88%, respectively. This conformational engineering strategy unveils a previously overlooked dimension in molecular design, providing fundamental guidelines for developing high‐performance organic solar cells through the rational manipulation of conformational landscapes.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"110 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215909","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}

引用次数: 0

From Global Flexibility to Local Flexibility: Enable A–B Stacked Metal–Organic Framework for One‐Step Ethylene Purification from Complex Gas Mixtures 从全局灵活性到局部灵活性：启用A-B堆叠金属-有机框架，用于从复杂气体混合物中一步提纯乙烯

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-04 DOI: 10.1002/anie.202516666

Yanan Wang, Hao Wang, Huiyin Lin, Longsheng Yang, Fengqi Huang, Xing Liu, Hanting Xiong, Jingwen Chen, Zhenyu Zhou, Shixia Chen, Shuguang Deng, Jun Wang

{"title":"From Global Flexibility to Local Flexibility: Enable A–B Stacked Metal–Organic Framework for One‐Step Ethylene Purification from Complex Gas Mixtures","authors":"Yanan Wang, Hao Wang, Huiyin Lin, Longsheng Yang, Fengqi Huang, Xing Liu, Hanting Xiong, Jingwen Chen, Zhenyu Zhou, Shixia Chen, Shuguang Deng, Jun Wang","doi":"10.1002/anie.202516666","DOIUrl":"https://doi.org/10.1002/anie.202516666","url":null,"abstract":"Flexible metal–organic framework (MOF) adsorbents can achieve exceptional separation performances under appropriate stimuli, especially for complex gas mixtures. However, their intrinsic global flexibility often leads to unsatisfactory separation selectivity, which hampers the practical applications. Herein, we propose a “rotor‐locker” strategy to convert an A–B stacked Cd‐MOF‐GF (GF = global flexibility) into Cd‐MOF‐LF (LF = local flexibility) for efficient one‐step C2H4 separation from multiple complex gas mixtures. The grafted methyl groups serve as lockers to suppress global flexibility while preserving local stimulus‐responsive behavior. As a result, Cd‐MOF‐LF exhibits a 10‐fold increase in C2H2 uptake (1.95 mmol g−1) compared to Cd‐MOF‐GF (0.19 mmol g−1) at 0.1 bar and 298 K, yielding a record selectivity of 9.2 for C2H2/C2H4 (50/50) among similar adsorbents. Moreover, the selective capture of C2H6 and CO2 impurities is also significantly enhanced. Dynamic breakthrough experiments demonstrate that the Cd‐MOF‐LF column enables direct separation of polymer‐grade C2H4 (>99.9%) with a high productivity of 0.79 mmol g−1 from a quaternary C2H2/C2H6/CO2/C2H4 (1v/33v/33v/33v) gas mixture. Density functional theory calculations reveal a lower deformation energy (−3.99 kJ mol−1) and specific adsorption sites for Cd‐MOF‐LF.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"1 1","pages":""},"PeriodicalIF":16.6,"publicationDate":"2025-10-04","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145215541","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}

引用次数: 0

Regio-, Stereo-, and Enantioselective Copper-Catalyzed Allylation of Sulfinylamines with Allenes. 区域、立体和对映选择性铜催化亚胺与烯烯的烯丙化反应。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-03 DOI: 10.1002/anie.202515183

Jie Zhu,Yue Zhao,Shengming Ma,Minyan Wang

引用次数: 0

Observation of Near-Infrared Photothermal and Photoacoustic Effects in a Metallosupramolecular Trefoil Knot. 金属超分子三叶草结的近红外光热和光声效应观察。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-03 DOI: 10.1002/anie.202518415

Ye Lu,Zhi-Jie Li,Yi Li,Lu An,Shi-Ping Yang,F Ekkehardt Hahn

{"title":"Observation of Near-Infrared Photothermal and Photoacoustic Effects in a Metallosupramolecular Trefoil Knot.","authors":"Ye Lu,Zhi-Jie Li,Yi Li,Lu An,Shi-Ping Yang,F Ekkehardt Hahn","doi":"10.1002/anie.202518415","DOIUrl":"https://doi.org/10.1002/anie.202518415","url":null,"abstract":"Coordination-driven self-assembly is a facile and powerful strategy for the construction of metallosupramolecular mechanically interlocked molecules (MIMs). However, the limited stability of most MIMs constitutes a challenge with respect to the evaluation of their practical applications. Herein, we demonstrate a rational strategy to control the self-assembly outcome for selected metallosupramolecular structures. The reaction of a biphenyl-bridged bisimidazole ligand with dinuclear building blocks of varying lengths leads, depending on the size of the dinuclear building block, to a simple [1+1] metallacycle, a twisted [2+2] three-dimensional trapezoidal structure, or an intricate [3+3] metallosupramolecular trefoil knot. The trefoil knot exhibits exceptional structural stability, resisting decomposition upon dilution in polar solvent. Its knotted topology enforces strong intramolecular π⋅⋅⋅π stacking interactions, which red-shift the absorption band into the near-infrared (NIR) region. Benefiting from its stability and NIR absorption, the trefoil knot displays a high photothermal conversion efficiency (η = 73.5%) and a potent photoacoustic (PA) effect in water, even at low concentrations.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"98 1","pages":"e202518415"},"PeriodicalIF":16.6,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209335","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}

引用次数: 0

Corrosion-Driven Ni3S4 Gradient in NiFe-LDH Enables Durable Industrial-Scale Water Electrolysis. NiFe-LDH中腐蚀驱动的Ni3S4梯度实现持久的工业规模水电解。

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-03 DOI: 10.1002/anie.202516894

Yi Liu,Junpo Guo,Xupo Liu,Zhihan Liu,Tian Li,Shuang Wang,Congcong Zhang,Kailun Wang,Tianwen Xu,Weijie Kong,Zijun Chen,Jintao Huang,Junwu Xiao,Hongfang Liu,Huaiyu Shao,Deli Wang

{"title":"Corrosion-Driven Ni3S4 Gradient in NiFe-LDH Enables Durable Industrial-Scale Water Electrolysis.","authors":"Yi Liu,Junpo Guo,Xupo Liu,Zhihan Liu,Tian Li,Shuang Wang,Congcong Zhang,Kailun Wang,Tianwen Xu,Weijie Kong,Zijun Chen,Jintao Huang,Junwu Xiao,Hongfang Liu,Huaiyu Shao,Deli Wang","doi":"10.1002/anie.202516894","DOIUrl":"https://doi.org/10.1002/anie.202516894","url":null,"abstract":"Designing low-cost yet highly efficient oxygen evolution reaction (OER) electrocatalysts is essential to enable sustainable green hydrogen generation. However, synthesis complexity, slow kinetics, and poor durability hinder industrial use. In this study, we present a corrosion-driven gradient engineering approach for the rapid, energy-free synthesis of Ni3S4/NiFe-LDH heterostructures on iron foam (IF) under ambient conditions. During spontaneous IF corrosion, a compositional and gradient structure forms, with Ni3S4 dominating the surface and NiFe-LDH enriching the core, establishing a continuous pathway for rapid electron transport. The catalyst exhibits superior OER performance, achieving low overpotentials of 297 mV in 1 M KOH and 326 mV in simulated seawater at 500 mA cm-2. Notably, in pure-water anion exchange membrane water electrolyzer, the catalyst demonstrates industrial-grade performance, sustaining 1 A cm-2 at 1.85 V with remarkable stability over 1,000 h of continuous operation. Operando spectroscopic studies unveil that SO4 2- leaching from surface Ni3S4 in the gradient structure provides dual protection against metal dissolution and chloride corrosion. Furthermore, the in situ formation of FeOOH synergistically stabilizes the catalytically critical Ni3+ species in NiOOH through strong Fe─O─Ni interfacial bonding, contributing to the exceptional durability. This work provides fundamental insights into corrosion-mediated catalyst design, offering a scalable pathway for developing industrial-grade electrocatalysts.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"214 1","pages":"e202516894"},"PeriodicalIF":16.6,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209312","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}

引用次数: 0

Synergistic Enhancement of Electron and Hole Transport by Pd Single Atoms and Gradient-Distributed Ti3+ Species for High-Performance Photocatalytic Oxidation of CH4 to Oxygenates. Pd单原子和梯度分布Ti3+物质协同增强CH4高效光催化氧化制氧合物的电子和空穴输运

IF 16.6 1区化学

Angewandte Chemie International Edition Pub Date : 2025-10-03 DOI: 10.1002/anie.202517585

Kai Sun,Xinya Pei,Shengyao Wang,Xu-Sheng Wang,Panzhe Qiao,Defa Wang,Lequan Liu,Jinhua Ye,Hui Song

{"title":"Synergistic Enhancement of Electron and Hole Transport by Pd Single Atoms and Gradient-Distributed Ti3+ Species for High-Performance Photocatalytic Oxidation of CH4 to Oxygenates.","authors":"Kai Sun,Xinya Pei,Shengyao Wang,Xu-Sheng Wang,Panzhe Qiao,Defa Wang,Lequan Liu,Jinhua Ye,Hui Song","doi":"10.1002/anie.202517585","DOIUrl":"https://doi.org/10.1002/anie.202517585","url":null,"abstract":"Photocatalytic oxidation of methane to liquid oxygenates offers a sustainable strategy for utilizing natural gas and reducing carbon emissions. However, the efficiency of current photocatalysts remains limited by poor charge carrier utilization, particularly the ineffective migration of holes that are crucial for C─H bond activation. Herein, we report a rationally engineered TiO2 photocatalyst incorporating atomically dispersed Pd and a gradient distribution of Ti3+ species, achieving a remarkable C1 oxygenates yield of 8.14 mmol·gcat -1·h-1 with 91.3% selectivity at room temperature, surpassing most state-of-the-art photocatalysts. Comprehensive characterizations and theoretical calculations reveal that Pd single atoms accelerate electron transfer and facilitate O2 dissociation, while the gradient-distributed Ti3+ species promote hole migration from the bulk to the surface, enabling efficient CH4 activation. These spatially separated charge pathways synergistically promote the formation of •CH3 and •OOH radicals, which couple to generate CH3OOH and subsequently convert into methanol and formaldehyde.","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"44 1","pages":"e202517585"},"PeriodicalIF":16.6,"publicationDate":"2025-10-03","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145209318","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}

引用次数: 0