Angewandte Chemie (International ed. in English)最新文献_第9页

Synthesis of Isoquinolines Through Isochromenylium Intermediates Captured by Nitriles and a CO-to-CN Switch. 利用腈捕获的等色胺中间体和CO-to-CN开关合成异喹啉。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-19 Epub Date: 2026-08-28 DOI: 10.1002/anie.5898322

Xu-Dong Hu, Gui-Feng Ding, Yu-Qing Zheng, Wen-Bo Liu

{"title":"Synthesis of Isoquinolines Through Isochromenylium Intermediates Captured by Nitriles and a CO-to-CN Switch.","authors":"Xu-Dong Hu, Gui-Feng Ding, Yu-Qing Zheng, Wen-Bo Liu","doi":"10.1002/anie.5898322","DOIUrl":"10.1002/anie.5898322","url":null,"abstract":"Isochromenylium ions have emerged as versatile intermediates for the rapid construction of molecular complexity through cascade reactions. However, their application in catalytic annulation processes with nitriles to form isoquinolines remains largely unexplored, despite the prevalence of nitrile motifs and isoquinoline frameworks in bioactive molecules and functional materials. Here we report a catalytic cascade strategy for the efficient synthesis of isoquinolines, including enantioenriched variants, from readily available substrates. The reaction includes palladium-catalyzed cyclization of ortho-alkynylaryl aldehydes to generate an isochromenylium palladium species, which is captured by indium-promoted 1,2-addition of nitriles. Subsequent water-assisted ring opening furnishes a Zincke-type intermediate, followed by intramolecular condensation to deliver the isoquinoline products. This cascade process achieves a net conversion of a carbonyl (CO) unit into a nitrile-derived carbon-nitrogen (CN) linkage at an intermediate-stage in a single operation. Notably, the use of malononitrile-tethered substrates enables the synthesis of enantioenriched isoquinolines with high enantioselectivity. Mechanistic studies indicate a cooperative role of palladium and indium in promoting the 1,2-addition of isochromenylium palladium species to the nitrile. The method exhibits excellent atom economy, good functional group tolerance, and scalability, highlighting its potential application for heterocycle synthesis.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e5898322"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148852317","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

Light-Gated Chirality in a Supramolecular Cavitand. 超分子空腔中的光门控手性。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-19 Epub Date: 2026-09-04 DOI: 10.1002/anie.9254918

Hang Yu, Aiyou Hao, Pengyao Xing

{"title":"Light-Gated Chirality in a Supramolecular Cavitand.","authors":"Hang Yu, Aiyou Hao, Pengyao Xing","doi":"10.1002/anie.9254918","DOIUrl":"10.1002/anie.9254918","url":null,"abstract":"Achieving precise and modulable chiral expression on molecular platforms is of great significance for the design and synthesis of chiroptical materials. Herein, we construct a supramolecular cavitand platform that enables programmable locking, switching, and rewriting of chiral information gated by light. A resorcin[4]arene-based cavitand integrates multiple photoisomeriable stilbenes and alternating imidazole segments. By employing an outer-wall binding strategy to bind multiple chiral carboxylic acids, it achieves efficient chirality transfer and enables the construction of a supramolecular chiral cavitand. Photoisomerization of embedded stilbene units, drives pathway-dependent conformational transformations that govern chirality induction, retention, and erasure. Notably, different light channels (365/254 nm) enable distinct outcomes, including preservation of chiral host-guest complexes, disruption of propeller chirality, and complete guest release. Furthermore, chirality can be locked and retained in a propeller form after removing the chiral acids, demonstrating a light-regulated chiral construction. The system further functions as a read-write chiral information platform, allowing visualization, encryption, decryption, and erasure of chiroptical signals through programmable photochemical inputs. This work establishes a strategy for coupling photochemical control with supramolecular confinement, providing a proof-of-concept study of significant importance in chiral informatics.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e9254918"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148893276","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

Host-Directed Discovery of Dynamic-Covalent Guests From Dynamic Combinatorial Libraries. 动态组合库中动态共价来宾的主定向发现。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-19 Epub Date: 2026-09-04 DOI: 10.1002/anie.7195803

Zhenye Qiu, Ruirui Gu, He Tian, Jean-Marie Lehn, Da-Hui Qu

{"title":"Host-Directed Discovery of Dynamic-Covalent Guests From Dynamic Combinatorial Libraries.","authors":"Zhenye Qiu, Ruirui Gu, He Tian, Jean-Marie Lehn, Da-Hui Qu","doi":"10.1002/anie.7195803","DOIUrl":"10.1002/anie.7195803","url":null,"abstract":"Dynamic covalent chemistry and host-guest recognition are complementary tools for constructing adaptive molecular systems and functional materials, yet their integration has been hindered by the lack of general strategies for efficiently discovering host-compatible dynamic-covalent guests. Here we report a host-directed screening strategy that directly identifies optimal imine guests from dynamic combinatorial libraries. Upon addition of the macrocyclic host, selective host-guest binding drives thermodynamically controlled library redistribution, leading to significant constitutional amplification of the preferred guests. A one-pot workflow involving activation, complexation, deactivation, displacement, and readout enables precise quantification of this redistribution by simple one-dimensional NMR spectroscopy. While 1H NMR readout is well suited to smaller libraries, 19F NMR offers clear advantages for more complex libraries, as demonstrated with a [5× 5] library. [2×n] library architecture further improves screening robustness by directing the major antagonistic response toward a channel excluded from candidate ranking. Although pillararene-imine complexes have rarely been reported because of their weak binding, stepwise screening of three library sets identified imine guests for ethyl pillar[5]arene with association constants of up to (2.2 ± 0.1) × 103 M-1. These findings establish host-directed selection as a practical strategy for coupling molecular recognition with constitutional dynamics in adaptive systems and materials.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e7195803"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148893322","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 Plasmonic S-Scheme Heterojunction Achieves Broadband Response and Ultralow Overpotential of Photo-Assisted Li─O₂ Batteries. 等离子体s型异质结实现光辅助锂氧电池的宽带响应和超低过电位。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-19 Epub Date: 2026-08-28 DOI: 10.1002/anie.2006350

Xingyu Yu, Yunyun Xu, Hao Gong, Zhixin Liu, Xingxu Gao, Kun Chang, Tao Wang, Jianping He, Zhong-Shuai Wu

{"title":"A Plasmonic S-Scheme Heterojunction Achieves Broadband Response and Ultralow Overpotential of Photo-Assisted Li─O2 Batteries.","authors":"Xingyu Yu, Yunyun Xu, Hao Gong, Zhixin Liu, Xingxu Gao, Kun Chang, Tao Wang, Jianping He, Zhong-Shuai Wu","doi":"10.1002/anie.2006350","DOIUrl":"10.1002/anie.2006350","url":null,"abstract":"Li─O2 batteries (LOBs) offer an ultrahigh theoretical energy density but suffer from a large overpotential. Photocathodes can lower this overpotential, but most of them cannot achieve efficient charge separation, sufficient redox capability, and broadband photoresponse at the same time. Here, a plasmonic S-scheme heterojunction photocathode (W18O49/g-C3N4, WOCN) is constructed. W18O49 serves as the oxidation semiconductor of the heterojunction and a noble-metal-free plasmonic absorber, forming a continuous plasmonic heterointerface with g-C3N4. The intrinsic localized surface plasmon resonance (LSPR) of W18O49 originates from periodically arranged lattice-localized electrons in W5+ clusters. Photogenerated carriers with strong redox capability and LSPR-generated hot electrons are separated by the S-scheme carrier transfer pathway. Under AM 1.5G illumination, the WOCN-based LOBs exhibit an ultralow overpotential of 0.04 V and a round-trip efficiency of 98.75%. Even under NIR illumination, an overpotential of 0.34 V and a round-trip efficiency of 90.12% are achieved, demonstrating an effective NIR response in photo-assisted LOBs for the first time. This work opens a new avenue for designing plasmonic S-scheme heterojunctions toward next-generation energy storage systems with full solar spectrum utilization.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e2006350"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148852129","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

Identification of Senescence-Associated β-Galactosidase With Single-Molecule Resolution. 衰老相关β-半乳糖苷酶的单分子分辨鉴定。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-19 Epub Date: 2026-08-28 DOI: 10.1002/anie.5443283

Guangwei Wang, Xi Chen, Yihao Ge, Kaixuan Duan, Shaowei Wu, Qinglong Qiao, Donglei Shi, Ji-Wei Shen, Jianjian Zhang, Tony D James, Zhaochao Xu, Yuan Guo

{"title":"Identification of Senescence-Associated β-Galactosidase With Single-Molecule Resolution.","authors":"Guangwei Wang, Xi Chen, Yihao Ge, Kaixuan Duan, Shaowei Wu, Qinglong Qiao, Donglei Shi, Ji-Wei Shen, Jianjian Zhang, Tony D James, Zhaochao Xu, Yuan Guo","doi":"10.1002/anie.5443283","DOIUrl":"10.1002/anie.5443283","url":null,"abstract":"The majority of human senescent cells exhibit overexpression of senescence-associated β-galactosidase (SA-β-gal), rendering this enzyme the most extensively utilized biomarker of senescence and a key prodrug target for intervening in aging. However, strategies for the authentic in situ identification of SA-β-gal with single-molecule resolution have not been established, limiting the accuracy of senescence targeting. Here we present an unprecedented molecular approach to identify SA-β-gal in a manner that avoids dissociation from the target enzyme, which integrates the atomic hybridization of SA-β-gal substrates with protein-environment-sensitive fluorescence technology. Using this design principle, we created nine fluorescent probes with distinct working modes for the single-molecule (target enzyme)-resolved identification of SA-β-gal. Five of them formed crystal complexes with the wild-type β-galactosidase by binding at the active site, clearly evidencing their single-molecule resolution capability. Our strategy, capable of both identifying and locating SA-β-gal, facilitated its application in dynamic single-molecule localization microscopic imaging, achieving the in situ tracking of SA-β-gal in living cells at the nanoscale. Significantly, the probing of SA-β-gal with high fidelity enabled the precise evaluation of the aging degree in mice. As such, our research provides a promising method for the authentic in situ identification of this senescence-associated protein with single-molecule resolution.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e5443283"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148852273","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

Created Ex Nihilo: A Near-Infrared Afterglow Luminescent Framework of Imidazole Derivatives for Bioimaging. 创建的无氧：用于生物成像的咪唑衍生物的近红外余辉发光框架。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-19 Epub Date: 2026-09-02 DOI: 10.1002/anie.9929915

Zihan Wu, Liping Zhang, Ziwei Wang, Yachao Wang, Gelin Xu, Feng Chi, Dongxia Zhu, Martin R Bryce, Ben Zhong Tang, Lijie Ren

{"title":"Created Ex Nihilo: A Near-Infrared Afterglow Luminescent Framework of Imidazole Derivatives for Bioimaging.","authors":"Zihan Wu, Liping Zhang, Ziwei Wang, Yachao Wang, Gelin Xu, Feng Chi, Dongxia Zhu, Martin R Bryce, Ben Zhong Tang, Lijie Ren","doi":"10.1002/anie.9929915","DOIUrl":"10.1002/anie.9929915","url":null,"abstract":"Afterglow luminescence probes are limited by (i) a lack of new afterglow scaffolds; (ii) a dependence on initial external light activation, and (iii) aggregation-caused quenching. Herein, we demonstrate for the first time that Ir(III) complexes of general formula Ir(C^N)2(N^N)+ PF6 - with an imidazole-based N^N ligand exhibit bright afterglow luminescence in the presence of reactive oxygen and nitrogen species (RONS) or under ultrasound (US) irradiation. A series of Ir(III) complexes (Ir-1-Ir-4) establish a new afterglow luminescence mechanism based on experimental data and theoretical calculations. The key feature of the present mechanism is the reaction of the ─N═C─N─H unit of the imidazole ligands with various RONS. After modification of the luminescent framework by quinolyl-triphenylamine C^N ligands, Ir-4 is endowed with aggregation induced emission (AIE) properties and with enhanced near-infrared afterglow luminescence. When assembled into water-soluble nanoparticles (NPs) with the aid of an amphiphilic polymer, Ir-4@R NPs demonstrated excellent afterglow luminescence imaging and effective sonodynamic therapy in vitro and in vivo. These Ir(III) complexes represent the first examples of an afterglow luminescent molecular framework based on readily available and versatile imidazole ligands, breaking through the existing limitation of molecular structures with afterglow luminescence.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e9929915"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.ncbi.nlm.nih.gov/pmc/articles/PMC13676407/pdf/","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148877072","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":0,"RegionCategory":"","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Unconventional Dendrite-Free Deposition of Mg Metal Anodes at Low Temperatures. 低温下非常规无枝晶沉积Mg金属阳极。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-19 Epub Date: 2026-08-26 DOI: 10.1002/anie.2311794

Yuan Wang, Shiyang Wang, Junbo Cui, Kangyu Yi, Kewei Wang, Ke Wang, Zixu He, Yijiang Bao, Junpeng Yan, Yulin Jie, Dongsheng Xu, Xuefeng Wang, Ruiguo Cao, Shuhong Jiao

{"title":"Unconventional Dendrite-Free Deposition of Mg Metal Anodes at Low Temperatures.","authors":"Yuan Wang, Shiyang Wang, Junbo Cui, Kangyu Yi, Kewei Wang, Ke Wang, Zixu He, Yijiang Bao, Junpeng Yan, Yulin Jie, Dongsheng Xu, Xuefeng Wang, Ruiguo Cao, Shuhong Jiao","doi":"10.1002/anie.2311794","DOIUrl":"10.1002/anie.2311794","url":null,"abstract":"Temperature plays a critical role in governing the plating behavior of metallic anodes by regulating ionic conductivity of the electrolyte, desolvation energy, and charge transfer processes in the solid-electrolyte interphase (SEI). While low temperature commonly triggers dendritic growth on metallic anodes (e.g., Li, Na, and Zn), the temperature effect on Mg plating/stripping behaviors remains unknown thus far. Herein, we report an unconventional temperature-dependent deposition behavior of Mg anodes that tends to form dendrite-free deposits at low temperatures. Integration of cryo-transmission electron microscopy, atomic force microscopy, and x-ray photoelectron spectroscopy reveals that the SEI layer formed at low temperatures has an ultrathin thickness (∼2-3 nm) and is enriched in high-modulus inorganic compounds, which facilitates the uniform deposition of Mg anodes. As a result, the Mg metal anode realizes an exceptional average Coulombic efficiency up to 99.92% over 2000 cycles at -20°C. This study demonstrates the unconventional deposition behavior of Mg metal anodes at low temperatures, underpinning their potential for low-temperature applications and advancing the fundamental understanding of metal deposition.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e2311794"},"PeriodicalIF":16.9,"publicationDate":"2026-10-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148820893","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

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