Angewandte Chemie (International ed. in English)最新文献_第7页

Electrocatalytic Polarity Inversion of Azlactones: Access to α-Quaternary Amino Acids with Electron-Rich SOMOphiles. 氮唑内酯的电催化极性反转：通过富电子亲som亲试剂获得α-季氨基酸。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-12 Epub Date: 2026-08-26 DOI: 10.1002/anie.8095368

Paula Rodríguez, David Buedo, Alberto Vega-Peñaloza, Kian Gosling, Stuart C D Kennington, Bart Limburg, Xavier Companyó

引用次数: 0

A Z-Scheme CuWO₄/Poly(heptazine imide) Interface Coupled With Asymmetric Cu²⁺/Cu⁺ Sites Enables Efficient Photocatalytic CO₂-to-Ethanol Conversion. 不对称Cu2+/Cu+位耦合的Z-Scheme CuWO4/聚七嗪亚胺界面实现了co2 -乙醇的高效光催化转化。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-12 DOI: 10.1002/anie.3155700

Jiaming Wu, Hao Dong, Keyan Li, Lei Luo, Bing Zhou, Rui Li, Chunshan Song, Xinwen Guo

{"title":"A Z-Scheme CuWO4/Poly(heptazine imide) Interface Coupled With Asymmetric Cu2+/Cu+ Sites Enables Efficient Photocatalytic CO2-to-Ethanol Conversion.","authors":"Jiaming Wu, Hao Dong, Keyan Li, Lei Luo, Bing Zhou, Rui Li, Chunshan Song, Xinwen Guo","doi":"10.1002/anie.3155700","DOIUrl":"https://doi.org/10.1002/anie.3155700","url":null,"abstract":"Selective photocatalytic reduction of CO2 into multicarbon products remains challenging because constructing uniform C─C coupling centers while maintaining their stability under reaction conditions is difficult. Here, we report a Z-scheme CuWO4/poly(heptazine imide) heterojunction featuring asymmetric Cu2+/Cu+ dual sites for CO2-to-ethanol conversion. Site-selective oxygen vacancies in CuWO4 trigger generation of structurally identical, charge-asymmetric neighboring Cu sites, which enhance CO2 activation and stabilize adjacent *CO intermediates, thereby facilitating C─C bond formation. Meanwhile, an atomically bonded O─W─N heterointerface enables directional Z-scheme charge transfer, supplying photogenerated electrons to the CuWO4 surface and stabilizing the asymmetric Cu2+/Cu+ dual sites throughout photocatalysis. Consequently, the optimized photocatalyst achieves an ethanol production rate of 244.5 µmol g-1 h-1 in pure water without sacrificial reagents. Advanced synchrotron spectroscopies identify the asymmetric Cu2+/Cu+ dual sites and the chemically bonded heterointerface, while operando spectroscopies record the dynamic evolution of active sites and the *CO─*CO coupling pathways upon illumination. Density functional theory calculations reveal that the synergy between asymmetric catalytic centers and the atomically bonded heterointerface promotes the C─C coupling process. This work establishes a strategy for constructing and stabilizing asymmetric catalytic centers through atomic engineering of crystal structure and heterointerface, providing a photocatalyst design paradigm for selective multicarbon solar fuel synthesis.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e3155700"},"PeriodicalIF":16.9,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149171781","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

In Situ Metal Chelation for Topology Regulation and Single-Site Construction in Covalent Organic Frameworks. 原位金属螯合用于共价有机框架的拓扑调节和单位点构建。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-12 DOI: 10.1002/anie.2910902

Xiang-Hao Han, Derong Chen, Yiwei Zhao, Kai Leng, Kian Ping Loh

{"title":"In Situ Metal Chelation for Topology Regulation and Single-Site Construction in Covalent Organic Frameworks.","authors":"Xiang-Hao Han, Derong Chen, Yiwei Zhao, Kai Leng, Kian Ping Loh","doi":"10.1002/anie.2910902","DOIUrl":"https://doi.org/10.1002/anie.2910902","url":null,"abstract":"Precise regulation over the dimensionality and topology of covalent organic frameworks (COFs) through metal coordination remains a fundamental challenge. Herein, we report an in situ metal-chelation strategy for topology regulation and single-site construction in COFs using a bifunctional β-hydroxy ketone-functionalized HDBC monomer. Metal-free Schiff-base condensation of HDBC with TAPy affords a one-dimensional covalent ribbon framework, named COF-HDBC. Strikingly, in situ Cu2+ chelation during solvothermal crystallization redirects the assembly pathway toward a two-dimensional bex-type Cu-COF-HDBC containing framework-embedded Cu─O coordination sites. Post-synthetic metalation of preassembled COF-HDBC fails to trigger this transformation, verifying the indispensable structure-directing effect of in situ chelation during nucleation and growth. This strategy is extendable to Ni2+ and Co2+, affording isostructural metal-chelated COFs. Multiscale characterizations and Cu K-edge XAFS collectively support the proposed framework structures and the predominantly isolated nature of the Cu centers. As a functional validation, Cu-COF-HDBC enables selective CO2/CO electroreduction to CH4. This work establishes in situ metal chelation as a synthetic handle for programming COF topology and constructing framework-embedded single-metal sites, offering a versatile route to crystalline porous materials with complex architectures and tunable functions.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e2910902"},"PeriodicalIF":16.9,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149168051","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

Tailoring Backbone Angles of Regioisomeric Covalent Organic Frameworks: Distinct O₂ Adsorption Modes Enabling Efficient H₂O₂ Electrosynthesis. 裁剪区域异构体共价有机框架的主角：不同的O2吸附模式，使H2O2电合成高效。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-12 DOI: 10.1002/anie.5704652

Yali Xing, Shuo Chen, Han Wang, Xue Zhang, Ning Sun, Chengjing Fu, Xiaojing Long

{"title":"Tailoring Backbone Angles of Regioisomeric Covalent Organic Frameworks: Distinct O2 Adsorption Modes Enabling Efficient H2O2 Electrosynthesis.","authors":"Yali Xing, Shuo Chen, Han Wang, Xue Zhang, Ning Sun, Chengjing Fu, Xiaojing Long","doi":"10.1002/anie.5704652","DOIUrl":"https://doi.org/10.1002/anie.5704652","url":null,"abstract":"Covalent organic frameworks (COFs) possess periodic skeletons and well-defined catalytic sites, allowing precise molecular-level regulation of interfacial properties in electrocatalytic oxygen reduction. However, conventional structural modifications fail to systematically tune oxygen adsorption geometry and interfacial electronic coupling. Here, we report a linkage-angle engineering strategy that alters the bonding positions of reactive aldehyde groups to fabricate three regioisomeric COFs with predefined backbone dihedral angles of 180°, 120°, and 60°. The angle‑driven regioisomeric effect induces considerable differences in dipole moments together with uneven charge distribution. These collective structural features remodel oxygen‑surface interactions and modulate the intrinsic catalytic kinetics. Theoretical calculations confirm that the compact 60° framework of o-TPDA-COF reconstructs confined pore interfacial microenvironments. Unlike the Griffiths‑type oxygen adsorption favored in its angular analogues, molecular oxygen preferentially adopts the Pauling configuration within o-TPDA-COF to stabilize OOH* intermediates. Consequently, the optimal o-TPDA-COF reaches an excellent H2O2 productivity of 12.82 mol gcat -1 h-1 and a Faradaic efficiency (FE) of 91.64%. This work realizes controllable modulation of oxygen‑adsorption behaviors in COF‑based 2e- oxygen reduction, delivering a novel geometry‑oriented design paradigm for porous electrocatalytic frameworks.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e5704652"},"PeriodicalIF":16.9,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149168584","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

Hydroxyl Regulation Enables Metal Promoter-Free Iron Catalysts for Highly Efficient CO₂ Hydrogenation to Light Olefins. 羟基调节使无金属促进剂的铁催化剂能够高效地将二氧化碳加氢成轻烯烃。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-12 DOI: 10.1002/anie.5758014

Jiaming Liang, Bowei Meng, Lisheng Guo, Wei Zhou, Qingqing Zhou, Yong Wang, Zeyan Cen, Siyu Lin, Encheng Lin, Zhihao Liu, Teng Li, Hao Chen, Linlin Zhao, Yao Xu, Mi Peng, Meng Wang, Bing Liang, Noritatsu Tsubaki, Ding Ma

{"title":"Hydroxyl Regulation Enables Metal Promoter-Free Iron Catalysts for Highly Efficient CO2 Hydrogenation to Light Olefins.","authors":"Jiaming Liang, Bowei Meng, Lisheng Guo, Wei Zhou, Qingqing Zhou, Yong Wang, Zeyan Cen, Siyu Lin, Encheng Lin, Zhihao Liu, Teng Li, Hao Chen, Linlin Zhao, Yao Xu, Mi Peng, Meng Wang, Bing Liang, Noritatsu Tsubaki, Ding Ma","doi":"10.1002/anie.5758014","DOIUrl":"https://doi.org/10.1002/anie.5758014","url":null,"abstract":"The efficient hydrogenation of CO2 to light olefins over Fe-based catalysts typically relies on the metal promoters, such as alkali or transition metals. In this study, we find that the intrinsic hydroxyl environments may be the crucial but long-overlooked factor governing the activity of Fe species. With the assistance of low-concentration guar gum, hydrogen-bond networks formed by dense hydroxyls are disrupted to generate isolated or terminal hydroxyl groups, which increase the active sites and significantly facilitate the product desorption. The resulting metal promoter-free Fe achieves a CO2 conversion of 30.1% and a light olefin selectivity of 38.1% at an ultra-high gas hourly space velocity of 300 000 mL gcat -1 h-1. Meanwhile, the space-time yield of light olefins reaches 3.3 kg kgcat -1 h-1, which outperforms all of the reported Fe-based catalysts modified by various promoters. These findings redefine hydroxyls as intrinsic promoters in Fe catalysts for CO2 hydrogenation and can potentially be extended to other heterogeneous catalytic systems and reactions.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e5758014"},"PeriodicalIF":16.9,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149169775","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

Ultrasound-Triggered Heterojunction Helices With Inverted Supramolecular Chirality and Significantly Amplified Circularly Polarized Luminescence. 具有反超分子手性的超声触发异质结螺旋和显著放大的圆极化发光。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-12 Epub Date: 2026-08-26 DOI: 10.1002/anie.7074723

Jinqi Li, Jingxiao Ren, Qi Feng, Jie Lu, Tianyi Li, Li Zhang, Guanghui Ouyang, Huajie Zhu, Minghua Liu

{"title":"Ultrasound-Triggered Heterojunction Helices With Inverted Supramolecular Chirality and Significantly Amplified Circularly Polarized Luminescence.","authors":"Jinqi Li, Jingxiao Ren, Qi Feng, Jie Lu, Tianyi Li, Li Zhang, Guanghui Ouyang, Huajie Zhu, Minghua Liu","doi":"10.1002/anie.7074723","DOIUrl":"10.1002/anie.7074723","url":null,"abstract":"Developing circularly polarized luminescence (CPL) materials with large luminescent dissymmetry factors (glum) through hierarchical self-assembly remains a significant challenge. Herein, we report an ultrasound-triggered hierarchical assembly strategy that enables the construction of heterojunction helices exhibiting inverted supramolecular chirality and substantially amplified CPL. A tetraphenylethylene-alanine derivative forms chiral nanohelices upon heating-cooling in DMSO. The addition of MeCN promotes the growth of nanohelices along with residual monomers into microhelices. Notably, ultrasound following MeCN addition induces reorganization at the termini of the nanohelices, leading to heterojunction helices composed of core and dendritic helical subunits with opposite handedness. These heterojunction helices display inverted and amplified CPL, with a glum value of 0.2 and a fluorescence quantum yield of 50%. Experimental and density functional theory calculations suggest that the ultrasound mechanical force changes the types of hydrogen bonds within extended monomers, thereby redirecting the self-assembly pathway from the ends of nanohelices and newly generated folded monomers. Enhanced interchromophoric interactions and well-ordered dendritic helices contribute to the inversion and amplification of CPL. This study not only presents the first example of heterojunction helices derived from the same chiral molecule but also provides new insights into an ultrasound-triggered pathway for amplifying CPL via hierarchical assembly.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e7074723"},"PeriodicalIF":16.9,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148820884","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

Synchronous Interfacial Chemistry via a Fluorine-Free Bifunctional Additive for Ultrastable Aqueous Zinc-Iodine Batteries. 用无氟双功能添加剂制备超稳定水锌-碘电池的同步界面化学。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-12 Epub Date: 2026-08-26 DOI: 10.1002/anie.7649417

Jiatong Li, Jian Qin, Minhao Dai, Yi Chen, Wei Xiao, Wenbin Li, Jingjing Wang, Xifei Li

{"title":"Synchronous Interfacial Chemistry via a Fluorine-Free Bifunctional Additive for Ultrastable Aqueous Zinc-Iodine Batteries.","authors":"Jiatong Li, Jian Qin, Minhao Dai, Yi Chen, Wei Xiao, Wenbin Li, Jingjing Wang, Xifei Li","doi":"10.1002/anie.7649417","DOIUrl":"10.1002/anie.7649417","url":null,"abstract":"The simultaneous interfacial instability at both electrodes of aqueous zinc-iodine (Zn-I2) batteries remains a fundamental challenge, as conventional compartmentalized strategies often overlook their shared electrolyte environment. Here, maltol is employed as a fluorine-free bifunctional additive to synchronize interfacial chemistry. At the zinc anode, maltol associates with water and preferentially adsorbs on the surface in a planar, cooperative configuration, reconstructing the inner Helmholtz plane (IHP) to suppress water-/sulfate-induced side reactions and regulate Zn nucleation/growth. At the iodine cathode, its multidentate oxygen sites anchor and destabilize I3 -, restricting polyiodide migration and promoting reversible I2/I- conversion. The strategy is validated in two complementary Zn-I2 models. An I- catholyte cell achieved over 35,000 cycles with only 0.0007% capacity decay per cycle. In the solid iodine-loaded porous carbon (I2@PC) model, a high-loading cell delivered an areal capacity of approximately 2 mAh cm-2 and retained 83.8% capacity after 11,000 cycles. Moreover, a 0.54 Ah pouch cell provided over 250 Ah cumulative output at 5.4 mAh cm-2 and an N/P ratio of 5.37. This work demonstrates a sustainable molecular-design strategy that synchronously stabilizes both electrodes, offering a holistic solution beyond conventional single-electrode approaches for long-lived, high-performance aqueous Zn-I2 batteries.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e7649417"},"PeriodicalIF":16.9,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148820950","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

Carbodicarbene σ/π-Donation Enables a Reactive Two-Coordinate Germanium(II) Dication. carbodicarbenσ /π-给体使得双坐标锗（II）的反应成为可能。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-12 DOI: 10.1002/anie.5172217

Yin-Zhi Weng, Lei Qin, Ting-Hsuan Wang, Glenn P A Yap, Bamlaku Semagne Aweke, Lili Zhao, Tiow-Gan Ong

{"title":"Carbodicarbene σ/π-Donation Enables a Reactive Two-Coordinate Germanium(II) Dication.","authors":"Yin-Zhi Weng, Lei Qin, Ting-Hsuan Wang, Glenn P A Yap, Bamlaku Semagne Aweke, Lili Zhao, Tiow-Gan Ong","doi":"10.1002/anie.5172217","DOIUrl":"10.1002/anie.5172217","url":null,"abstract":"All previously reported Ge(II) dications have remained chemically dormant, their reactivity confined to simple coinage metal coordination-a consequence of cationization-induced lone pair contraction that renders the Ge center inaccessible to substrates. We report that dual σ/π-donating carbodicarbene (CDC) ligands directly counteract this contraction, yielding [(CDC)2Ge][OTf]2 (4), the first two-coordinate Ge(II) dication to display broad reactivity beyond coinage metal coordination. Crystallographic and computational analysis reveal a delocalized 3c-4e C-Ge-C moiety and a less contracted Ge lone pair with retained Ge-centered LUMO, underpinning an unprecedented reactivity profile encompassing 1,1-oxidative addition, [1 + 4] cycloaddition, selenium insertion, and cooperative C-S bond activation. As a Ge-donor ligand, 4 coordinates to Rh, Ir, and Ag with donor strength comparable to that of IMes and forms geminal bimetallic complex 8, featuring a rare noncluster Ag-Ge-Ag three-center two-electron bonding motif. These results establish CDC-based low-coordination stabilization as a productive strategy for accessing structurally simple yet reactive main-group dications.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e5172217"},"PeriodicalIF":16.9,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149171490","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

From Passive Cocoon to Active Metamorphosis: High-Current-Driven Evolution of Silicon for Ultrastable Anodes. 从被动茧到主动变形：高电流驱动的超稳定阳极硅的演变。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-12 Epub Date: 2026-08-26 DOI: 10.1002/anie.3879325

Kaixiang Chen, Yujian Shen, Chaolong Yang, Mengqi Ma, Wenhong Ruan

{"title":"From Passive Cocoon to Active Metamorphosis: High-Current-Driven Evolution of Silicon for Ultrastable Anodes.","authors":"Kaixiang Chen, Yujian Shen, Chaolong Yang, Mengqi Ma, Wenhong Ruan","doi":"10.1002/anie.3879325","DOIUrl":"10.1002/anie.3879325","url":null,"abstract":"The commercial viability of silicon anodes in lithium-ion batteries remains heavily impeded by severe volume expansion, unstable solid-electrolyte interphases (SEI), and the necessity for restrictive low-current pre-lithiation. While improving initial Coulombic efficiency (ICE), low-current activation accelerates progressive capacity decay over extended cycling and prevents fast-charging. Furthermore, conventional nanostructuring operates on a paradigm of mere passive containment, leaving root electrochemical instabilities fundamentally unresolved. Inspired by butterfly metamorphosis, we introduce a biomimetic electrochemical paradigm. Analogous to endogenous enzymes driving transformation within a protective cocoon, we employ an initial high current as an \"electrochemical enzyme\" to trigger the controlled size reduction of Si confined within a covalent organic framework (COF) \"cocoon.\" Regulated by this architecture, the high-current pulse drives controlled Si pulverization, synchronously realizing in situ pre-lithiation and generating a stable amorphous Li-Si phase via a comprehensively elucidated synergistic mechanism. Benefiting from this structural evolution, the engineered anode exhibits superior robustness. It retains 74.5% and 71.9% capacity over 2000 cycles at 10 000 and 20 000 mA g-1, respectively, and successfully accommodates extreme fast charging (118 s). By conceptualizing a transition from passive containment to active in situ regulation, this study unveils a transformative design paradigm for high-energy, high-power battery materials.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e3879325"},"PeriodicalIF":16.9,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148820887","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

Charge-Delocalizing sp-Hybridized COFs for Selective H₂O₂ Electrosynthesis. 选择性H2O2电合成的电荷离域sp杂化COFs。

IF 16.9

Angewandte Chemie (International ed. in English) Pub Date : 2026-10-12 DOI: 10.1002/anie.3570658

Changqing Li, Yuqiang Huang, Zilin Lu, Zhao Qiao, Yongxuan Jiang, Zhongping Li, Yucheng Jin, Siliu Lyu, Lipeng Zhai, Jong-Beom Baek, Sang-Young Lee

{"title":"Charge-Delocalizing sp-Hybridized COFs for Selective H2O2 Electrosynthesis.","authors":"Changqing Li, Yuqiang Huang, Zilin Lu, Zhao Qiao, Yongxuan Jiang, Zhongping Li, Yucheng Jin, Siliu Lyu, Lipeng Zhai, Jong-Beom Baek, Sang-Young Lee","doi":"10.1002/anie.3570658","DOIUrl":"https://doi.org/10.1002/anie.3570658","url":null,"abstract":"Hydrogen peroxide (H2O2) is an important oxidant for chemical manufacturing, environmental remediation, and biomedical applications, yet its industrial production still relies mainly on the energy-intensive anthraquinone process. Electrochemical H2O2 synthesis via the two-electron oxygen reduction reaction (2e- ORR) provides a sustainable alternative but is often hindered by sluggish charge transport and insufficient O2 activation. Here, we develop a bond-hybridization strategy by incorporating sp-hybridized acetylene units into the vertex or linker of covalent organic frameworks (COFs). The resulting COFs feature extended π-conjugation, enhanced charge delocalization, and electronically polarized pores, thereby strengthening O2 adsorption and activation. Compared with sp2-dominated analogues, these sp-hybridized COFs show faster charge-transfer kinetics, higher H2O2 selectivity, and improved 2e- ORR activity. In a flow cell, the optimized catalyst delivers an H2O2 production rate of 27.8 mol g-1 h-1 and a peak Faradaic efficiency of 91.7% at 150 mA cm-2. Mechanistic analyses combining electronic-structure calculations and in situ vibrational spectroscopy reveal that sp hybridization reshapes frontier-orbital distributions and local charge density, thereby coupling framework-wide charge delocalization with favorable O2 adsorption and *OOH stabilization. These results establish bond hybridization as a molecular-level design parameter for catalytic selectivity in COFs, extending framework engineering beyond conventional functional-group and building-block modification.","PeriodicalId":520556,"journal":{"name":"Angewandte Chemie (International ed. in English)","volume":" ","pages":"e3570658"},"PeriodicalIF":16.9,"publicationDate":"2026-10-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"149168533","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