Angewandte Chemie (International ed. in English)最新文献_第6页

Strain-Buffering Layered/Rocksalt Heterostructure Constructed via Oxygen Redox Activation for Durable O3-Type Layered Transition Metal Oxides. 耐久o3型层状过渡金属氧化物通过氧氧化还原活化构建应变缓冲层状/岩盐异质结构

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-19 Epub Date: 2026-08-28 DOI: 10.1002/anie.7544135

You Shi, Dan Sun, Xiaobing Huang, Yan Wang, Zhuomin Liu, Pengcheng Mao, Junjie Tu, Wenbo Wang, Yougen Tang, Haiyan Wang

{"title":"Strain-Buffering Layered/Rocksalt Heterostructure Constructed via Oxygen Redox Activation for Durable O3-Type Layered Transition Metal Oxides.","authors":"You Shi, Dan Sun, Xiaobing Huang, Yan Wang, Zhuomin Liu, Pengcheng Mao, Junjie Tu, Wenbo Wang, Yougen Tang, Haiyan Wang","doi":"10.1002/anie.7544135","DOIUrl":"10.1002/anie.7544135","url":null,"abstract":"Harnessing anionic oxygen redox is pivotal for boosting the capacity of O3-type layered transition metal oxides for sodium ion batteries (SIBs), yet it often triggers severe lattice distortion and irreversible oxygen release. Herein, we propose an in situ electrochemical surface reconstruction strategy to stabilize the O3-type NaNi1/3Fe1/3Mn1/3O2 (NFM) cathode. By strictly controlling the initial anionic redox reactions at an ultra-high potential of 4.6 V, a robust heterostructure comprising an ordered layered core and a disordered rocksalt shell is constructed. This unique surface architecture serves as an isotropic strain buffer that effectively mitigates particle cracking and provides dense surface passivation to suppress interfacial side reactions. Furthermore, the induced rocksalt phase stabilizes the surface TM-O coordination, thereby preventing lattice oxygen loss during subsequent cycling. Consequently, when cycled within 2.0-4.0 V, the electrochemically pretreated cathode (DRS(4.6)@NFM) exhibits significantly reduced lattice distortion and superior electrochemical durability (capacity retention ratio of 90.77% after 300 cycles) with negligible voltage decay (retaining 98.56% of the initial voltage). Even when cycled up to 4.2 V, a capacity retention ratio of 87.4% after 300 cycles is still maintained. This work elucidates the interplay between electrochemical pretreatment and structural evolution, providing a decisive foundation for designing high-voltage and durable sodium-ion cathodes.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e7544135"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148852301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Defect Engineering on Amorphous NiFeB Alloys for the Selective Conversion of KA Oil Into Adipic Acid. KA油选择性转化为己二酸的非晶态NiFeB合金缺陷工程。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-19 Epub Date: 2026-09-02 DOI: 10.1002/anie.3494903

Yanwei Li, Yanli Zhang, Weiming Chen, Cuizhu Ye, Yongfang Zhou, Geoffrey I N Waterhouse, Yi Shen

{"title":"Defect Engineering on Amorphous NiFeB Alloys for the Selective Conversion of KA Oil Into Adipic Acid.","authors":"Yanwei Li, Yanli Zhang, Weiming Chen, Cuizhu Ye, Yongfang Zhou, Geoffrey I N Waterhouse, Yi Shen","doi":"10.1002/anie.3494903","DOIUrl":"10.1002/anie.3494903","url":null,"abstract":"Developing high-performance electrocatalysts for the efficient conversion of KA oil (a mixture of cyclohexanol and cyclohexanone) to adipic acid holds great significance. Herein, a series of Ni-based catalysts, including NiM (M = Fe, Cr, and Mn) layered double hydroxides (LDHs), NiMB LDHs and amorphous NiMB alloys, were synthesized for KA oil conversion. Among the samples, Ni4Fe1B alloy exhibited the highest ECSA-normalized current density of 581.5 mA cm-2 and adipic acid selectivity of 52.7% at 1.6 V. Such superior catalytic performance is attributed to the abundant defects induced by boron incorporation, leading to modified electronic structures of nickel sites and optimized adsorption toward KA oil and intermediates. Operando electrochemical x-ray absorption fine structure analyses, combined with operando Raman spectra, suggested that the oxidation of KA oil by Ni4Fe1B alloy involved the transformation of Ni2+ into higher valence states, indicative of a possible indirect oxidation pathway. In contrast, the valence state of Ni2+ in the Ni4Fe1B and Ni4Fe1 LDHs remained unchanged, suggesting a possible direct oxidation mechanism. Theoretical calculations revealed that the Ni4Fe1B alloy exhibited strong adsorption toward cyclohexanol and cyclohexanone molecules and a low energy barrier (0.76 eV) for the rate-determining step, consistent with the experimental results.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e3494903"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148877096","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

A-Site Engineering of Aurivillius Bi₄Ti₃O₁₂ for Enhanced Ferroelectric Polarization and Photocatalytic Overall Water Splitting. Bi4Ti3O12型Aurivillius Bi4Ti3O12增强铁电极化和光催化全水分解的A-Site工程

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-19 Epub Date: 2026-09-04 DOI: 10.1002/anie.3932816

Xiaosheng Dang, Tongguang Qiu, Wenjin Zheng, Hangyu Zhuzhang, Wandong Xing, Sibo Wang, Guigang Zhang

{"title":"A-Site Engineering of Aurivillius Bi4Ti3O12 for Enhanced Ferroelectric Polarization and Photocatalytic Overall Water Splitting.","authors":"Xiaosheng Dang, Tongguang Qiu, Wenjin Zheng, Hangyu Zhuzhang, Wandong Xing, Sibo Wang, Guigang Zhang","doi":"10.1002/anie.3932816","DOIUrl":"10.1002/anie.3932816","url":null,"abstract":"Efficient suppression of photogenerated charge recombination remains a central challenge in photocatalytic water splitting. Bi4Ti3O12 is a promising ferroelectric semiconductor for overall water splitting, yet its quantum efficiency is fundamentally constrained by weak polarization and sluggish carrier dynamics. Herein, we demonstrate that isovalent A-site substitution provides an effective route to amplify the intrisinc polarization of Bi4Ti3O12 through lattice regularization. Specifically, Sm substitution suppresses localization disorder by attenuating the stereochemical activity of Bi3+ lone pairs, thereby reducing excessive octahedral tilting and enabling more coherent dipole alignment. The resulting enhanced ferroelectric polarization field markedly facilitates charge separation and carrier migration. In addition, post-synthetic acid treatment tailors the surface termination and suppresses the self-corrosion typically associated with bismuth-based photocatalysts. Upon cocatalyst loading, the optimized Bi4Ti3O12-Sm photocatalyst achieves an efficient overall water splitting with an apparent quantum efficiency of 10.5% at 365 nm. This work establishes structural regularization as a viable design principle for enhancing ferroelectric polarization and advancing high-performance photocatalytic systems.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e3932816"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148893301","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Selective Cancer Cell Killing via a Fluorofoldamer-Based Proton Channel That Triggers Ferroptosis. 通过触发铁下垂的氟聚合物质子通道选择性杀死癌细胞。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-16 DOI: 10.1002/anie.8040741

Zhao-Xi Zhou, Gaiping Cao, Xiyu Yuan, Fei Gou, Wenju Chang, Jingyi Li, Jie Shen, Maolin Yan, LiXian Wu, Huaqiang Zeng

{"title":"Selective Cancer Cell Killing via a Fluorofoldamer-Based Proton Channel That Triggers Ferroptosis.","authors":"Zhao-Xi Zhou, Gaiping Cao, Xiyu Yuan, Fei Gou, Wenju Chang, Jingyi Li, Jie Shen, Maolin Yan, LiXian Wu, Huaqiang Zeng","doi":"10.1002/anie.8040741","DOIUrl":"https://doi.org/10.1002/anie.8040741","url":null,"abstract":"We report a new class of aromatic foldamer-based artificial proton channels incorporating fluorinated building blocks, which exhibit high proton transport efficiency and selectivity. The lead channel, 2, shows outstanding proton transport activity (EC50 = 13.1-14.7 nM) and high selectivity (H+/Cl- = 249.7; H+/Na+ = 23.9; H+/K+ = 45.0), forming transmembrane channels without compromising membrane integrity or facilitating the transport of competing ions. By exploiting the unique acidic tumor microenvironment, 2 mediates proton influx to acidify the intracellular environment of cancer cells, inducing cell death via ferroptosis. This is evidenced by the downregulation of AKR1B1 and GPX4, corresponding increases in reactive oxygen species (ROS) and malondialdehyde (MDA) levels, and lipid remodeling. Accordingly, 2 exhibits potent cytotoxicity across multiple cancer cell lines (IC50 < 10 µM) and significantly suppresses tumor growth in vivo without observable systemic toxicity. This work establishes the first artificial proton channel (APC) that induces ferroptosis via channel-mediated intracellular acidification, offering a membrane-targeted anticancer strategy with low propensity for drug resistance.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e8040741"},"PeriodicalIF":16.9,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149198815","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Catalytic Asymmetric Synthesis of Spiro[3.3]heptane-Based Axially Chiral α-Amino Acids. 催化不对称合成螺旋[3.3]庚烷基轴向手性α-氨基酸。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-16 DOI: 10.1002/anie.7366839

Yu-Ping Tang, Liang Chen, Qingqin Huang, Yu-Cheng Lei, Lei Dai

{"title":"Catalytic Asymmetric Synthesis of Spiro[3.3]heptane-Based Axially Chiral α-Amino Acids.","authors":"Yu-Ping Tang, Liang Chen, Qingqin Huang, Yu-Cheng Lei, Lei Dai","doi":"10.1002/anie.7366839","DOIUrl":"https://doi.org/10.1002/anie.7366839","url":null,"abstract":"Natural α-amino acids are fundamental to virtually all forms of life, and their unnatural analogues are indispensable building blocks in synthetic chemistry and pharmaceutical science. Current research predominantly focuses on centrally chiral unnatural α-amino acids, while α-amino acids featuring other chirality types are yet to be disclosed. We therefore sought to expand the chemical space of α-amino acids by introducing the concept of axially chiral α-amino acid. Here, we rationally design a prochiral α-amino acid substrate derived from a spiro[3.3]heptane scaffold, an emerging Fsp3-enriched isostere in medicinal chemistry, and subsequent catalytic asymmetric synthesis of axially chiral α-amino acids is realized via a reductive amination enabled by chiral phosphoric acid catalysis. A wide array of spiro[3.3]heptane-based axially chiral α-amino acids are obtained in generally high yields and enantioselectivities, and are readily incorporated into complex peptides by both solution-phase and solid-phase peptide synthesis. As conformationally constrained L-lysine mimetics, these amino acids can enhance inhibitory activities against PD-1/PD-L1 and improve physicochemical properties. Experimental and computational studies elucidate the reaction mechanism, the origin of enantioselectivity, and the structural basis for the improved biological activities. This work expands the accessible chemical space of α-amino acids and establishes valuable building blocks for complex peptide synthesis.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e7366839"},"PeriodicalIF":16.9,"publicationDate":"2026-10-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149198738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Peptidomimetic Polymer With Conformation-Coded Hierarchical Assembly for Visualizing Biodistribution. 具有构象编码分层组装的仿生肽聚合物用于生物分布可视化。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-15 DOI: 10.1002/anie.1895737

Yeqiang Zhou, Shuangyan Li, Danqi Yang, Yiwei Wang, Jiayu Zou, Minghao Wang, Chuan Peng, Yang Liu, Hong Tan, Mingming Ding

{"title":"Peptidomimetic Polymer With Conformation-Coded Hierarchical Assembly for Visualizing Biodistribution.","authors":"Yeqiang Zhou, Shuangyan Li, Danqi Yang, Yiwei Wang, Jiayu Zou, Minghao Wang, Chuan Peng, Yang Liu, Hong Tan, Mingming Ding","doi":"10.1002/anie.1895737","DOIUrl":"https://doi.org/10.1002/anie.1895737","url":null,"abstract":"Directly encoding local physicochemical information into an intrinsically self-referenced fluorescence signal remains a major challenge in bioimaging. Here, we report an aliphatic peptidomimetic polymer system whose luminescence is programmed through conformation-directed hierarchical assembly. β-sheet-like and random-coil conformations direct self-assembly into rigid nanotubes and isotropic vesicles, respectively, with distinct emission profiles. At elevated local concentrations, the nanotubes undergo higher-order assembly into spherical superstructures exhibiting a J-aggregate-like red-shifted optical response, with a pronounced blue-to-orange color transition and emission extending into the near-infrared region. We exploit this intrinsic concentration-dependent color response for multicolor organelle imaging in living cells and for noninvasive, visually interpretable, semiquantitative mapping of polymer biodistribution in living animals. By converting local concentration into emission hue rather than absolute intensity, this work establishes a new design principle for self-referenced optical imaging, with potential applications in biosensing, quantitative bioimaging, and drug delivery.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e1895737"},"PeriodicalIF":16.9,"publicationDate":"2026-10-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149198774","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Engineering Polar Nanoregions in COFs via Controlled Symmetry Breaking Toward Piezocatalysis. 基于可控对称破缺的COFs纳米极区工程研究。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-12 DOI: 10.1002/anie.3994811

Ge Yan, Yixuan Wang, Xiaodong Sun, Liberty L Mguni, Shuai Zhang, Shiyuan Liu, Xue Zhou, Lingfeng Zhu, Yali Yao, Hongwei Huang, Liqun Ye, Xinyi Yang, Bo Zou, Tianyi Ma

{"title":"Engineering Polar Nanoregions in COFs via Controlled Symmetry Breaking Toward Piezocatalysis.","authors":"Ge Yan, Yixuan Wang, Xiaodong Sun, Liberty L Mguni, Shuai Zhang, Shiyuan Liu, Xue Zhou, Lingfeng Zhu, Yali Yao, Hongwei Huang, Liqun Ye, Xinyi Yang, Bo Zou, Tianyi Ma","doi":"10.1002/anie.3994811","DOIUrl":"https://doi.org/10.1002/anie.3994811","url":null,"abstract":"To address the limited piezocatalytic activity of covalent organic frameworks (COFs) arising from high structural symmetry and rapid charge recombination, an imine-linked COFs (TFB-TAPT) is synthesized by Schiff-base condensation of 1,3,5-triformylbenzene (TFB) and 2,4,6-tri(4-aminophenyl)-1,3,5-triazine (TAPT), followed by partial substitution of amino ligands with 1H,1H-undecafluorohexylamine (UFHA) through a building-block exchange strategy to afford TFB-TAPT-FA. This approach achieves controlled symmetry breaking with precise polar group distribution, without the lattice disruption caused by asymmetric monomers in one-pot methods. The resulting randomly oriented polar nanoregions exhibit relaxation behavior, collectively generating a strong piezoelectric response under external stimuli. Piezoresponse force microscopy (PFM) measurements indicate that TFB-TAPT-FA has a piezoelectric coefficient of 140 pm/V, 2.5 times that of TFB-TAPT. This amplification of the electromechanical response arises from the polar nanoregions, as evidenced by its higher calculated dipole moment (5.68 Debye). Consequently, TFB-TAPT-FA achieves an impressive piezocatalytic hydrogen production rate of 3.8 mmol g-1 h-1, marking a 17-fold improvement over TFB-TAPT. Notably, TFB-TAPT-FA enables efficient hydrogen production without cocatalysts or heterojunctions. More broadly, the introduction of polar nanoregions similarly enhances the performance of other imine-linked COFs, demonstrating a potentially general strategy for designing piezocatalysts through nanoscale polarization engineering in COFs.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e3994811"},"PeriodicalIF":16.9,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149169417","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Discovery of a Potent and Selective First-In-Class Antagonist of GPR15 With In Vivo Anti-Obesity Activity. 具有体内抗肥胖活性的GPR15有效和选择性的一流拮抗剂的发现。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-12 DOI: 10.1002/anie.6947632

Chong Huang, Jingxin Qiao, Mengqiu Zhou, Xin Yang, Lengjing Zhu, Jinxiao Ru, Le Du, Wuxin Liu, Yan Chen, Anjie Xia, Linli Li, Shengyong Yang

{"title":"Discovery of a Potent and Selective First-In-Class Antagonist of GPR15 With In Vivo Anti-Obesity Activity.","authors":"Chong Huang, Jingxin Qiao, Mengqiu Zhou, Xin Yang, Lengjing Zhu, Jinxiao Ru, Le Du, Wuxin Liu, Yan Chen, Anjie Xia, Linli Li, Shengyong Yang","doi":"10.1002/anie.6947632","DOIUrl":"https://doi.org/10.1002/anie.6947632","url":null,"abstract":"GPR15 (G Protein-coupled Receptor 15), an atypical chemokine receptor, is implicated in the pathogenesis of multiple diseases, yet small-molecule GPR15 antagonists remain undeveloped. Herein, we identify and characterize YL410, the first-in-class potent and selective GPR15 antagonist. In the cAMP-GloSensor assay, YL410 inhibits GPR15 with an IC50 of 0.027 ± 0.005 µM, and displays high selectivity against a panel of related GPCRs and kinases. It suppresses GPR15L-induced Jurkat T-cell migration, and exhibits favorable pharmacokinetics and acceptable safety. Molecular docking, replicated molecular dynamics simulations, quantitative contact analyses, and mutagenesis experiments support a plausible orthosteric binding model for YL410, maintained by a reproducible network of polar and hydrophobic contacts, which rationalizes its potent antagonism and observed structure-activity relationships (SAR). Complementary AI-based structure predictions (AlphaFold3, Chai-1, and Boltz) recapitulated the energetically accessible orthosteric poses but not the dynamically stable pose selected by the MD simulations, underscoring the importance of kinetic-stability validation in antagonist pose selection. Notably, in a diet-induced obesity (DIO) mouse model, YL410 administration induced significant weight loss and exerted blood glucose-lowering effects. Collectively, this study presents the first potent, selective, and in vivo efficacious GPR15 antagonist, providing new insights into the development of therapeutics for the treatment of obesity.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e6947632"},"PeriodicalIF":16.9,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149172040","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Microdroplet Interfacial Electric Field Triggers Hydroxyl Radical Coupling Toward Efficient H₂O₂ Photosynthesis. 微滴界面电场触发羟基自由基偶联实现高效H2O2光合作用。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-12 Epub Date: 2026-08-25 DOI: 10.1002/anie.9181115

Yanchi Yao, Chao Zhu, Qile Fang, Shuang Song, Baoliang Chen, Yi Shen

{"title":"Microdroplet Interfacial Electric Field Triggers Hydroxyl Radical Coupling Toward Efficient H2O2 Photosynthesis.","authors":"Yanchi Yao, Chao Zhu, Qile Fang, Shuang Song, Baoliang Chen, Yi Shen","doi":"10.1002/anie.9181115","DOIUrl":"10.1002/anie.9181115","url":null,"abstract":"The two-electron water oxidation reaction (2e- WOR) via ·OH coupling offers a direct route for H2O2 photosynthesis, but conventional bulk systems remain rigidly limited by high thermodynamic barriers, short-lived ·OH, and disordered H-bond networks. Inspired by the potential of reaction microenvironments to drive thermodynamically unfavorable pathways, we developed a microdroplet photocatalytic platform using hydrophilic nitrogen-rich COFs (Tp-DAPd and Tp-DAPm), achieving H2O2 photosynthesis rates of 11.12 and 12.15 mmol·L-1·g-1, with 11.6- and 7.9-fold enhancements over their bulk counterparts, respectively. Product-labeling fluorescence imaging microscopy (PLFIM) at the single-microdroplet scale visualized size-dependent acceleration and inward expansion of the interfacial reactive zone. Multiscale mechanistic investigations reveal that the intrinsic microdroplet interfacial electric field actively regulates the 2e- WOR process by restructuring the H-bond network into a low-entropy state, stabilizing partially solvated ·OH, and inducing a favorable trans-gauche configuration. These effects work together to create a unique microenvironment that promotes water dissociation and ·OH coupling, thereby lowering the thermodynamic barrier for 2e- WOR under operational conditions. This work represents a microenvironment-oriented strategy to overcome intrinsic thermodynamic limitations and inspires new strategies for the rational design of microdroplet-assisted photosynthetic systems.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e9181115"},"PeriodicalIF":16.9,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148820944","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Singlet Oxygen From Lattice Oxygen-Adsorbate Hybridization Drives Highly Selective Electrooxidation of Methallyl Alcohol to Methacrolein. 单线态氧从晶格氧-吸附物杂交驱动高选择性电氧化甲醇为甲基丙烯醛。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-12 Epub Date: 2026-08-25 DOI: 10.1002/anie.7784614

Ximin Zhang, Xiaojun Li, Meiqing Cai, Junhua Li, Wenbiao Wang, Kaibin Chu, Jingjing Qin, Xueying Cao, Youbing Huang, Xingchen Jiao, Xiaohui Xu, Hui Qian, Xinjie Tian, Jun-Ling Song

{"title":"Singlet Oxygen From Lattice Oxygen-Adsorbate Hybridization Drives Highly Selective Electrooxidation of Methallyl Alcohol to Methacrolein.","authors":"Ximin Zhang, Xiaojun Li, Meiqing Cai, Junhua Li, Wenbiao Wang, Kaibin Chu, Jingjing Qin, Xueying Cao, Youbing Huang, Xingchen Jiao, Xiaohui Xu, Hui Qian, Xinjie Tian, Jun-Ling Song","doi":"10.1002/anie.7784614","DOIUrl":"10.1002/anie.7784614","url":null,"abstract":"Selective oxidation of methallyl alcohol (MAO) to methacrolein (MAC) is crucial yet challenged by C═C cleavage and overoxidation in both thermochemical and radical-mediated routes. Herein, we report a Mn-doped NiMoO4 catalyst anchored on partially oxidized copper-foam (M-NMO/Cu2+1O/CF) achieves unprecedented 100% selectivity and Faradaic efficiency for MAO to MAC at a record production rate of 1776 µmol cm-2 h-1 (420 C,1.0 M K2CO3, 1.62 V vs. RHE). The catalyst synergizes lattice-oxygen mechanism (LOM) with adsorbate-evolution mechanism (AEM) to generate singlet oxygen (1O2). This electrophilic 1O2 dominates the selective oxidation of Cα-OH in MAO, preserving its C═C bond via preferential α-hydrogen abstraction. Isotope labeling (H2 18O) and operando Fourier-transform infrared spectroscopy (FT-IR) reveal that 1O2 is generated primarily from lattice-oxygen through critical peroxide-like M-O-O intermediates, with a secondary contribution from adsorbed water. Density functional theory (DFT) reveals Mn-induced asymmetric d-band engineering concurrently lowers the LOM barrier and raises the AEM barrier at Ni centers, establishing a Ni-governed, LOM-dominant dual-pathway for 1O2 generation. The catalyst further enables general furfuryl and benzyl alcohol oxidation, and scale-up in a flow electrolyzer achieves 90% MAO conversion. This work establishes an asymmetric electronic modulation strategy for in situ generation of singlet oxygen via peroxide-like intermediates, enabling highly selective electrooxidation of alcohols.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e7784614"},"PeriodicalIF":16.9,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148820932","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0