Angewandte Chemie最新文献_第6页

Rhodium-Catalyzed Intermolecular Arylative [2 + 2 + 1] Annulation–Oxidation to Produce Electron-Deficient Azulene-Embedded Polycyclic Aromatic Hydrocarbons 铑催化的分子间芳基化[2 + 2 + 1]环化氧化制备含缺电子的氮杂烯多环芳烃

Angewandte Chemie Pub Date : 2025-05-19 DOI: 10.1002/ange.202505622

Yoshinobu Kamiya, Yu Sato, Tomohiro Oriki, Yuko Kishida, Dr. Haruki Sugiyama, Dr. Waner He, Dr. Kexiang Zhao, Prof. Dr. Tsuyoshi Michinobu, Prof. Dr. Hidehiro Uekusa, Prof. Dr. Ken Tanaka

{"title":"Rhodium-Catalyzed Intermolecular Arylative [2 + 2 + 1] Annulation–Oxidation to Produce Electron-Deficient Azulene-Embedded Polycyclic Aromatic Hydrocarbons","authors":"Yoshinobu Kamiya, Yu Sato, Tomohiro Oriki, Yuko Kishida, Dr. Haruki Sugiyama, Dr. Waner He, Dr. Kexiang Zhao, Prof. Dr. Tsuyoshi Michinobu, Prof. Dr. Hidehiro Uekusa, Prof. Dr. Ken Tanaka","doi":"10.1002/ange.202505622","DOIUrl":"https://doi.org/10.1002/ange.202505622","url":null,"abstract":"Azulene derivatives have attracted much attention for their application in organic electronic materials and devices because of their large dipole moment and small HOMO–LUMO energy gap. As these physical properties of azulene depend on its substitution and condensation patterns, developing methods to synthesize functionalized and π-extended azulenes is desirable. However, synthesizing π-extended azulenes requires harsh reaction conditions, making it hard to achieve both functionalization and π-extension. Here, we report the synthesis of electron-deficient azulene-embedded polycyclic aromatic hydrocarbons (PAHs) with two alkoxycarbonyl groups by the rhodium-catalyzed intermolecular arylative [2 + 2 + 1] annulation of teraryl diynes with dialkyl acetylenedicarboxylates followed by oxidation at room temperature. Interestingly, for the electron-rich diyne, prolonged oxidation time after the arylative [2 + 2 + 1] annulation yields a helicene-like bis(azulene-embedded PAH) in good yield. Thus, obtained electron-deficient fused azulenes have small HOMO–LUMO energy gaps (up to Egelec = 1.52 and Egtheo = 2.06), resulting in long-wavelength absorption extending into the near-infrared region. Due to bulky electron-withdrawing groups and π-extension, the molecule becomes saddle-shaped and highly polarized, and strong π–π stacking interactions are observed in both the solid and solution states.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 29","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/ange.202505622","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144624790","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

Thermally Gated Covalent Adaptivity in Liquid Crystal Elastomers for Stable Actuation 液晶弹性体中用于稳定驱动的热门控共价自适应

Angewandte Chemie Pub Date : 2025-05-19 DOI: 10.1002/ange.202506571

Yixuan Wang, Enjian He, Huan Liang, Yuting Wang, Zhijun Yang, Shuhan Zhang, Prof. Yen Wei, Guoli Wang, Chao Gao, Prof. Yan Ji

{"title":"Thermally Gated Covalent Adaptivity in Liquid Crystal Elastomers for Stable Actuation","authors":"Yixuan Wang, Enjian He, Huan Liang, Yuting Wang, Zhijun Yang, Shuhan Zhang, Prof. Yen Wei, Guoli Wang, Chao Gao, Prof. Yan Ji","doi":"10.1002/ange.202506571","DOIUrl":"https://doi.org/10.1002/ange.202506571","url":null,"abstract":"Liquid crystal elastomers (LCEs), with reversible actuation of large and anisotropic deformation, have surged in smart materials such as soft robotics, sensors and artificial muscles. LCEs incorporating dynamic covalent bonds (DCBs) endowing network with rearranging ability through reversible bond exchange, facilitating the fabrication of soft actuators with tailored actuation modes and reprogrammability. However, unintended activation of DCBs during actuation, particularly under thermal perturbations, remains a critical challenge, as it damages actuation stability which arises catastrophic failure and potential security risks in practical applications. Present strategies in enhancing actuation stability either achieve only transient stability or sacrificed reprogrammability or actuation performance. Here, we propose a strategy incorporating catalyst-free α-AC/A DCB of high temperature active-threshold to fabricate stable exchangeable LCE actuators with thermally gated behavior. This design exhibits a “thermal gate” at 120 °C with inert bond exchange below this threshold, yet rapidly activated at 160 °C. The integrated permanent crosslinks further prevent unintended chain slippage, ensuring topological stability. The resulting exchangeable LCE could be fabricated to actuators efficiently and exhibiting unprecedented durability at 120 °C (sustaining 10 000 actuation cycles). The switch between reprogrammability and actuation stability are long-standing reversible, meeting the demands of long-term service without compromising its reprogrammability.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 29","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144624789","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

Jas S. Ward Jas S. Ward

Angewandte Chemie Pub Date : 2025-05-19 DOI: 10.1002/ange.202509959

Jas S. Ward

引用次数: 0

An Organic-Inorganic-Integrated Solid Electrolyte Interphase with High-Resilience and Anti-Corrosion for Sustainable Zinc Metal Anode 一种高回弹性和耐腐蚀的有机-无机-集成固体电解质界面用于可持续锌金属阳极

Angewandte Chemie Pub Date : 2025-05-19 DOI: 10.1002/ange.202501702

Maoyu Peng, Zhenjie Liu, Machuan Hou, Ruochen Zhang, Min Cheng, Jiangtao Yu, Yang Feng, Peixin Jiao, Tongrui Zhang, Ziheng Zhang, Prof. Xi Chen, Prof. Zhe Hu, Prof. Kai Zhang

{"title":"An Organic-Inorganic-Integrated Solid Electrolyte Interphase with High-Resilience and Anti-Corrosion for Sustainable Zinc Metal Anode","authors":"Maoyu Peng, Zhenjie Liu, Machuan Hou, Ruochen Zhang, Min Cheng, Jiangtao Yu, Yang Feng, Peixin Jiao, Tongrui Zhang, Ziheng Zhang, Prof. Xi Chen, Prof. Zhe Hu, Prof. Kai Zhang","doi":"10.1002/ange.202501702","DOIUrl":"https://doi.org/10.1002/ange.202501702","url":null,"abstract":"Aqueous zinc metal batteries (AZMBs) are highly regarded for their exceptional safety, low cost, environmental compatibility, and potential as a sustainable alternative to lithium-ion batteries. However, Zn dendrite growth and hydrogen evolution on anode side result in limited lifespan and safety issues. Herein, an organic-inorganic-integrated solid electrolyte interphase (SEI) was in situ formed by adding 4-(trifluoromethyl)-1H-imidazole (TFMI) as an electrolyte additive. The artificial SEI merited higher maximum elastic deformation energy due to relatively high resilience and toughness, which can prevent Zn dendrite penetration and anode self-cracking and pulverization. In addition, N-containing heterocycles in SEI act as a H+ catcher, thereby inhibiting anode corrosion and hydrogen evolution. As a result, the Zn||Zn symmetric cell has delivered stable cycling performance after 1500 h at 5 mA cm−2 with a terminated capacity of 5 mAh cm−2. And an outstanding coulombic efficiency of 99.46% at the 2200th cycle was achieved for a Cu||Zn asymmetric cell. Furthermore, a Zn||PANI full battery presented a stable cycling performance with a high-capacity retention of 97.6% after 200 cycles.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 29","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144624826","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

Co-Regulation of Interface and Bulk for Enhanced Localized High-Concentration Electrolytes in Stable and Practical Zinc Metal Batteries 在稳定实用的锌金属电池中增强局部高浓度电解质的界面和体积协同调节

Angewandte Chemie Pub Date : 2025-05-19 DOI: 10.1002/ange.202501183

Tao Li, Hange Yang, Xinji Dong, Hexian Ma, Jinghua Cai, Chenyu Wei, Tao Zhang, Shicong Zhang, Fuqiang Huang, Tianquan Lin

{"title":"Co-Regulation of Interface and Bulk for Enhanced Localized High-Concentration Electrolytes in Stable and Practical Zinc Metal Batteries","authors":"Tao Li, Hange Yang, Xinji Dong, Hexian Ma, Jinghua Cai, Chenyu Wei, Tao Zhang, Shicong Zhang, Fuqiang Huang, Tianquan Lin","doi":"10.1002/ange.202501183","DOIUrl":"https://doi.org/10.1002/ange.202501183","url":null,"abstract":"Rechargeable zinc metal batteries (RZMBs) are promising for energy storage due to their high capacity and cost-effectiveness. However, their commercialization is hindered by challenges including dendrite growth, parasitic reactions, and cathode degradation, particularly under low current densities and negative/positive (N/P) capacity ratios. Localized high-concentration electrolytes offer potential solutions, but their reliance on high salt concentrations to replicate solvation structures of high-concentration electrolytes limits their practicality, due to diluent's inherent inertness that limits its role in interfacial chemistry. Here, we present a co-regulation strategy that integrates bulk and interfacial properties to develop an interfacial-enhanced localized high-concentration electrolyte (ILHCE). By incorporating non-coordinating 1,4-dioxane diluent and 1-ethyl-3-methylimidazolium (emim+) cations into dilute aqueous electrolytes, dioxane molecules are pulled into electric double layer (EDL) through the interaction between emim+ and dioxane, achieving a pronounced dilution effect from bulk electrolyte to the EDL. This generates an anion-rich and water-depleted EDL at both anode and cathode interfaces, enhancing Zn2+ transport dynamics, ensuring cathode stability and deriving a robust anion-derived solid-electrolyte interphase. Full batteries using Mn0.5V6O13 cathodes with a low N/P ratio of 1.77 demonstrate 80% capacity retention over 300 cycles at 0.2 A g−1, highlighting ILHCE as a transformative electrolyte design toward real-world applications.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 29","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144624841","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 Hydrogenation of Phenols to Cyclohexanones Over Hydrotalcite-Supported Pd Single-Atom Catalyst 水滑石负载Pd单原子催化剂上苯酚选择性加氢制环己酮的研究

Angewandte Chemie Pub Date : 2025-05-19 DOI: 10.1002/ange.202504260

Yani Liu, Qinglei Meng, Kaili Zhang, Wanying Han, Xinrui Zheng, Yaqin Wang, Yibo Han, Jingping Wang, Haihong Wu, Mingyuan He, Buxing Han

{"title":"Selective Hydrogenation of Phenols to Cyclohexanones Over Hydrotalcite-Supported Pd Single-Atom Catalyst","authors":"Yani Liu, Qinglei Meng, Kaili Zhang, Wanying Han, Xinrui Zheng, Yaqin Wang, Yibo Han, Jingping Wang, Haihong Wu, Mingyuan He, Buxing Han","doi":"10.1002/ange.202504260","DOIUrl":"https://doi.org/10.1002/ange.202504260","url":null,"abstract":"Cyclohexanones are widely used chemicals and currently produced by the oxidation of the fossil feedstocks. Direct selective hydrogenation of lignin derivatives has great potential for producing these chemicals, but is challenging to obtain high yields. Here, we report that hydrotalcite-supported Pd single-atom (Pd/CHT-800) catalyst enabled the hydrogenation of the benzene ring in the aromatics without the overreaction of carbonyl group, which could afford >99.9% yield of cyclohexanones using water as the reaction medium. The reaction mechanism was systematically studied by the control experiments and detailed in situ characterizations. In the Pd/CHT-800 catalyst, the Pd-O-MgAl sites were formed, and the cooperation of the Pd atoms and calcined CHT material could not only realize the aromatic hydrogenation efficiently, but also inhibit the hydrogenation of the carbonyl group in the reaction effectively. This work provides a novel route for the sustainable production of cyclohexanones.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 29","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-19","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144624827","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

Electrochemical Synthesis of Hydroxylamine 羟胺的电化学合成

Angewandte Chemie Pub Date : 2025-05-16 DOI: 10.1002/ange.202509053

Minghao Guo, Yuhan Zhang, Dr. Chengying Guo, Prof. Yifu Yu

{"title":"Electrochemical Synthesis of Hydroxylamine","authors":"Minghao Guo, Yuhan Zhang, Dr. Chengying Guo, Prof. Yifu Yu","doi":"10.1002/ange.202509053","DOIUrl":"https://doi.org/10.1002/ange.202509053","url":null,"abstract":"Hydroxylamine (NH2OH) serves as an important industrial feedstock. The conventional production and transportation of NH2OH requires harsh conditions. Recently, electrochemical hydrogenation of nitrogen-containing oxidative species, such as nitrate, nitrite, and nitric oxide (NO3−/NO2−/NO), into NH2OH has been developed as a sustainable strategy. However, the over-hydrogenation product of ammonia is preferentially obtained under electroreduction condition. Thus, the rational design of catalysts structure is crucial to selective electrosynthesis of NH2OH. In this minireview, we summarize recent advances in electrochemical synthesis of NH2OH with emphasis on the design of catalysts structure. Electrochemical synthesis strategy we discussed is categorized by the existence form of product, including indirect electrosynthesis and direct electrosynthesis. Finally, the techno–economic analysis (TEA) of electrochemical NH2OH production and outlook of performance improvement strategies are carried out to further guide the optimization of reaction system.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 27","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144514558","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

Molecular Design of Polymeric Metal–Organic Nanocapsule Networks for Solid-State Lithium Batteries 固态锂电池用高分子金属-有机纳米胶囊网络的分子设计

Angewandte Chemie Pub Date : 2025-05-16 DOI: 10.1002/ange.202504767

Xin-Yue Ma, Dr. Xiao-Xue Wang, Dr. De-Hui Guan, Cheng-Lin Miao, Huan-Feng Wang, Qing-Yao Zhu, Prof. Ji-Jing Xu

{"title":"Molecular Design of Polymeric Metal–Organic Nanocapsule Networks for Solid-State Lithium Batteries","authors":"Xin-Yue Ma, Dr. Xiao-Xue Wang, Dr. De-Hui Guan, Cheng-Lin Miao, Huan-Feng Wang, Qing-Yao Zhu, Prof. Ji-Jing Xu","doi":"10.1002/ange.202504767","DOIUrl":"https://doi.org/10.1002/ange.202504767","url":null,"abstract":"Solid-state electrolytes (SSEs) have emerged as high-priority materials for ensuring the safe operation of solid-state lithium (Li) batteries. However, current SSEs still face challenges of balancing stability and ionic conductivity, which limits their practical applications in solid-state Li batteries. Here, we report a general strategy for achieving high-performance SSEs by constructing a Li+-conducted polymeric metal–organic nanocapsule (PolyMONC(Li)) network through molecular design. With the unique cage structure and pore size, metal–organic nanocapsule (MONC) can achieve excellent anion confinement effects. The PolyMONC(Li) network with continuous Li+ conduction pathways serves as a solid electrolyte exhibiting a high ionic conductivity (0.18 mS cm−1 at 25 °C) and a high Li+ transference number (0.83). Combining the two superiorities of optimal balance between mechanical strength and excellent Li+ conductivity, the PolyMONC(Li) can still restrain the dendrite growth and prevent Li symmetric batteries from short-circuiting even over 900 h cycling. The PolyMONC(Li)-based SSEs Li-metal batteries achieved a higher specific capacity than common polymer electrolytes such as polyethylene oxide-based SSE. Additionally, taking advantage of the PolyMONC(Li) electrode binder, the solid-state Li–O2 battery achieves a stable cycling over 400 cycles. This work provides a comprehensive guideline for developing porous solids from molecule design to practical application.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 29","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144624326","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 Solid Polymer Electrolyte with Inorganic-Enriched Cathode Electrolyte Interphases Enabling 5.1 V Solid-State Lithium-Ion Batteries 实现5.1 V固态锂离子电池的富无机阴极电解质界面固体聚合物电解质

Angewandte Chemie Pub Date : 2025-05-16 DOI: 10.1002/ange.202505147

Yue Hou, Yiqiao Wang, Zhiquan Wei, Zhuoxi Wu, Dedi Li, Qing Li, Shimei Li, Ze Chen, Yanbo Wang, Guojin Liang, Ke Wang, Chunyi Zhi

{"title":"A Solid Polymer Electrolyte with Inorganic-Enriched Cathode Electrolyte Interphases Enabling 5.1 V Solid-State Lithium-Ion Batteries","authors":"Yue Hou, Yiqiao Wang, Zhiquan Wei, Zhuoxi Wu, Dedi Li, Qing Li, Shimei Li, Ze Chen, Yanbo Wang, Guojin Liang, Ke Wang, Chunyi Zhi","doi":"10.1002/ange.202505147","DOIUrl":"https://doi.org/10.1002/ange.202505147","url":null,"abstract":"Manufacturing solid polymer electrolytes (SPEs) is an effective strategy for pursuing safe, energy-dense solid-state lithium-ion batteries (SSLIBs). However, the challenges lie in obtaining high-voltage SSLIBs due to the lack of an electrochemically stable SPE and the degradation of the high-voltage cathode beyond 5 V. Hence, we employed quantum chemical calculations to screen a poly(vinylidene fluoride-co-trifluoroethylene-co-chlorotrifluoroethylene) (PVDF-TrFE-CFE, designated as PVTF) polymer with strong antioxidant capability to fabricate stable SPEs for high-voltage SSLIBs. Furthermore, a sacrificial additive (lithium difluorophosphate, LiDFP) was introduced in PVTF SPE to build a high-quality cathode electrolyte interphase (CEI) layer to stabilize the LiNi0.5Mn1.5O4 (LNMO) cathode, which is denoted as PVTF1.0@LiDFP. The Li|PVTF1.0@LiDFP|LiNi0.5Mn1.5O4 (LNMO) cell operating at 5.1 V sustains excellent cycling performance and remarkable rate performance, maintaining a long cycle life of over 200 cycles and achieving a high-rate capability of up to 2 C. Complementary characterization methods were utilized to dynamically observe the cathode structure and interphase evolution, revealing that the high antioxidant stability of the polymeric PVTF framework and the incorporation of LiDFP additive to form a high-quality CEI enriched with inorganic components realize the superior performance of Li|PVTF1.0@LiDFP|LNMO cell. Overall, the insights gained from our study provide a solid foundation for the development of high-voltage SSLIBs.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 29","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144624327","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

Defective Poly(heptazine imide) Nanosheets for Efficient One-Step Two-Electron Photocatalytic O2 Reduction to Medical-Like H2O2 有缺陷的聚七嗪亚胺纳米片用于一步双电子光催化O2还原为医用类H2O2

Angewandte Chemie Pub Date : 2025-05-16 DOI: 10.1002/ange.202507415

Dr. Laiyu Luo, Qinglong Wu, Dr. Siyu Wang, Haojie Song, Jiaqi Li, Liping Zhang, Prof. Qun Zhang, Prof. Yuanxing Fang, Prof. Baojiang Jiang, Prof. Xinchen Wang

{"title":"Defective Poly(heptazine imide) Nanosheets for Efficient One-Step Two-Electron Photocatalytic O2 Reduction to Medical-Like H2O2","authors":"Dr. Laiyu Luo, Qinglong Wu, Dr. Siyu Wang, Haojie Song, Jiaqi Li, Liping Zhang, Prof. Qun Zhang, Prof. Yuanxing Fang, Prof. Baojiang Jiang, Prof. Xinchen Wang","doi":"10.1002/ange.202507415","DOIUrl":"https://doi.org/10.1002/ange.202507415","url":null,"abstract":"Poly(heptazine imide) (PHI) is a promising photocatalyst for hydrogen peroxide (H2O2) production; however, enhancing its specific surface area to expose internal active sites and understanding their roles in key mechanistic steps for the H2O2 synthesis remain challenging. Here, we utilized organic cations to exfoliate bulk PHI and fabricate PHI nanosheets for producing H2O2 at a rate of 27.35 mmol g−1 h−1 under simulated solar light irradiation, outperforming most of the reported carbon nitride-based catalysts. Importantly, after 36 h of cyclic accumulation reactions in a self-created spiral flow reactor, the H2O2 concentration stabilized at 2.7 wt.%, close to medical sterilization levels. In situ spectroscopic characterizations and density functional theory calculations revealed that the exfoliation results in molecular reconfiguration of the PHI basal planes, forming the active sites to promote charge separation and electron localization. This new structure also creates midgap states, enabling direct H2O2 production via a one-step, two-electron pathway, bypassing the superoxide radical pathway. Theoretical calculations suggest that the localized electronic structure created by the active sites favors the protonation of adsorbed O2 and stabilizes the *OOH species, which converts to H2O2. This study elucidates and underscores the importance of active-site reconfiguration for efficient photocatalytic oxygen reduction reaction (ORR) pathways.","PeriodicalId":7803,"journal":{"name":"Angewandte Chemie","volume":"137 29","pages":""},"PeriodicalIF":0.0,"publicationDate":"2025-05-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144624824","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