IF 10.3 4区化学

结构化学 Pub Date : 2025-09-01 DOI: 10.1016/j.cjsc.2025.100708

Yangfeifei Ou, Xiao-Liang Zhou, You-Zhao Lan, Jian-Wen Cheng

引用次数: 0

Uniform single-crystal mesoporous metal-organic frameworks with tunable architectures 具有可调结构的均匀单晶介孔金属有机骨架

IF 10.3 4区化学

结构化学 Pub Date : 2025-09-01 DOI: 10.1016/j.cjsc.2025.100655

Xin Chen, Zaiwang Zhao, Yujuan Zhao

引用次数: 0

Engineering optical anisotropy in paramagnetic organic crystals: Dichroism of nitronyl nitroxide radicals 顺磁性有机晶体的工程光学各向异性：硝基氮氧化物自由基的二色性

IF 10.3 4区化学

结构化学 Pub Date : 2025-09-01 DOI: 10.1016/j.cjsc.2025.100653

Matvey K. Shurikov , Yuliana A. Kolesnikova , Darya E. Votkina , Pavel A. Abramov , Taisiya S. Sukhikh , Galina V. Romanenko , Sergey L. Veber , Dmitry E. Gorbunov , Nina P. Gritsan , Giuseppe Resnati , Evgeny V. Tretyakov , Vadim Yu. Kukushkin , Pavel S. Postnikov , Pavel V. Petunin

{"title":"Engineering optical anisotropy in paramagnetic organic crystals: Dichroism of nitronyl nitroxide radicals","authors":"Matvey K. Shurikov , Yuliana A. Kolesnikova , Darya E. Votkina , Pavel A. Abramov , Taisiya S. Sukhikh , Galina V. Romanenko , Sergey L. Veber , Dmitry E. Gorbunov , Nina P. Gritsan , Giuseppe Resnati , Evgeny V. Tretyakov , Vadim Yu. Kukushkin , Pavel S. Postnikov , Pavel V. Petunin","doi":"10.1016/j.cjsc.2025.100653","DOIUrl":"10.1016/j.cjsc.2025.100653","url":null,"abstract":"<div><div><span>Six aryl- and pyridine-substituted nitronyl-nitroxide radicals were synthesized and characterized to investigate their optical anisotropic properties. Single-crystal X-ray diffraction analysis revealed molecular packing organized by either halogen and hydrogen bonding<span><span> or hydrogen bonding alone. Single-crystal electronic </span>absorption spectra<span> in the visible region of three studied radicals exhibit pronounced linear dichroism, while single crystals of other radicals do not demonstrate this property. Time-dependent DFT and </span></span></span><em>ab initio</em><span><span> calculations were employed to determine the transition dipole moment<span> (TDM) vectors corresponding to the long-wavelength absorption bands. For all radicals, these vectors are found to be practically parallel to the O⋯O direction of the nitronyl-nitroxide chromophore. Correlation between the dichroic properties and crystal structure was established through comprehensive analysis of TDM vector orientations relative to the </span></span>crystal surface. The strongest dichroic effect was observed in crystals where all projections of the TDM vectors onto the illuminated face are parallel to each other, while weaker or absent effects correspond to non-parallel arrangements. This study constitutes the first systematic investigation of linear dichroism in paramagnetic organic crystals, thereby establishing new avenues for developing multifunctional materials that respond to both optical and magnetic stimuli.</span></div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 9","pages":"Article 100653"},"PeriodicalIF":10.3,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145289738","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Revisit the classical [Fe4S4(SR)4]2– molecular clusters: The steric effects of ligands and their structural transformations 回顾经典的[Fe4S4(SR)4]2 -分子簇：配体的空间效应及其结构转化

IF 10.3 4区化学

结构化学 Pub Date : 2025-09-01 DOI: 10.1016/j.cjsc.2025.100660

Yuhao Jin, Zheng Zhou, Haixiang Han

{"title":"Revisit the classical [Fe4S4(SR)4]2– molecular clusters: The steric effects of ligands and their structural transformations","authors":"Yuhao Jin, Zheng Zhou, Haixiang Han","doi":"10.1016/j.cjsc.2025.100660","DOIUrl":"10.1016/j.cjsc.2025.100660","url":null,"abstract":"<div><div>The synthesized molecular clusters featuring the cubic [4Fe–4S] core have been studied for several decades, as they serve as true analogs of the active components in ferritin within biological systems. Such a model cluster has been extensively investigated in various fields, including structural modulation, catalysis, and self-assembly under laboratory conditions, with the aim of gaining an in-depth understanding of their roles in biological functions. Herein, we revisited three well-known [Fe<sub>4</sub>S<sub>4</sub>(SR)<sub>4</sub>]<sup>2</sup><sup>–</sup> molecules, namely [Me<sub>4</sub>N]<sub>2</sub>[Fe<sub>4</sub>S<sub>4</sub>(SR)<sub>4</sub>] (R = <em>o</em>-MBT, <em>m</em>-MBT, <em>p</em>-MBT), and successfully established their single crystal structures that remain unknown prior to this work. Interestingly, it is revealed that the position of the substituent methyl group has an obvious steric effect on the arrangement of the ligand around the [4Fe–4S] core, which further influences their overall packing patterns in single crystals. In addition, this work unveils two new structure transformation behaviors for the [Fe<sub>4</sub>S<sub>4</sub>(SR)<sub>4</sub>]<sup>2</sup><sup>–</sup> system: i) the monomeric [Fe(SR)<sub>4</sub>]<sup>2</sup><sup>–</sup> and tetrameric [Fe<sub>4</sub>S<sub>4</sub>(SR)<sub>4</sub>]<sup>2</sup><sup>–</sup> can be interconverted, and ii) [Fe<sub>4</sub>S<sub>4</sub>(SR)<sub>4</sub>]<sup>2</sup><sup>–</sup> can be transferred into an intriguing iron-oxide complex Na<sub>2</sub>Fe<sub>6</sub>O(OMe)<sub>18</sub>·6MeOH in a well-controlled oxidizing environment.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 9","pages":"Article 100660"},"PeriodicalIF":10.3,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145289743","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Dynamic tuning of d-p orbital hybridization during sulfur vacancy evolution in Co9S8 toward efficient overall water splitting Co9S8中硫空位演化过程中d-p轨道杂化的动态调谐

IF 10.3 4区化学

结构化学 Pub Date : 2025-09-01 DOI: 10.1016/j.cjsc.2025.100661

Weilong Liu , Jipeng Dong , Luyao Zhang , Ning Li , Yangqin Gao , Lei Ge

{"title":"Dynamic tuning of d-p orbital hybridization during sulfur vacancy evolution in Co9S8 toward efficient overall water splitting","authors":"Weilong Liu , Jipeng Dong , Luyao Zhang , Ning Li , Yangqin Gao , Lei Ge","doi":"10.1016/j.cjsc.2025.100661","DOIUrl":"10.1016/j.cjsc.2025.100661","url":null,"abstract":"<div><div>Defect engineering significantly enhances electrocatalytic performance by modulating electronic structures and interfacial coordination, yet the dynamic correlation between defect evolution and catalytic activity during reactions remains unclear. Herein, density functional theory (DFT) calculations first reveal the modulation of sulfur vacancy concentrations on Co<sub>9</sub>S<sub>8</sub> electronic structures, predicting that optimized vacancy concentrations enable highly efficient electrocatalytic water splitting. Experimentally fabricated Co<sub>9</sub>S<sub>8</sub> with appropriate sulfur vacancies exhibits superior bifunctional activity (HER: 164 mV@<em>η</em><sub>10</sub>; OER: 297 mV@<em>η</em><sub>100</sub>). The MCS-assembled overall water splitting system demonstrates stable operation at 1.57 V (10 mA cm<sup>−2</sup>) for over 60 h. Experimental studies illustrate that sulfur vacancies preferentially adsorb OH<sup>−</sup> during reactions, inducing the formation of CoOOH active phases. DFT analysis further indicates that OH<sup>−</sup> adsorption weakens <em>d-p</em> orbital hybridization, optimizing hydrogen/oxygen intermediate adsorption energy barriers and ultimately enhancing catalytic performance. This work establishes novel paradigms for systematic development of catalysts through synergistic analysis of defect dynamics, electronic structures and catalytic performance.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 9","pages":"Article 100661"},"PeriodicalIF":10.3,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145289744","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Highly active transition metal phosphides for urea oxidation: Design strategies, application advances, and perspectives 尿素氧化用高活性过渡金属磷化物：设计策略、应用进展与展望

IF 10.3 4区化学

结构化学 Pub Date : 2025-09-01 DOI: 10.1016/j.cjsc.2025.100651

Qimeng Zhu , Juan Xiao , Changyi Deng , Tingting Huang , Hui Ding , Li Zhang , Guancheng Xu

{"title":"Highly active transition metal phosphides for urea oxidation: Design strategies, application advances, and perspectives","authors":"Qimeng Zhu , Juan Xiao , Changyi Deng , Tingting Huang , Hui Ding , Li Zhang , Guancheng Xu","doi":"10.1016/j.cjsc.2025.100651","DOIUrl":"10.1016/j.cjsc.2025.100651","url":null,"abstract":"<div><div><span>In recent years, the discharge of urea-containing wastewater from industrial and domestic sources has posed a continuing threat to aquatic ecosystems and human health. In this context, the urea oxidation reaction (UOR) has attracted significant attention due to its low thermodynamic potential of 0.37 V (</span><em>vs.</em><span> RHE). Compared with oxygen evolution reaction (OER), this reaction can significantly reduce the energy consumption of electrolysis while realizing wastewater treatment, and has the dual functions of hydrogen energy preparation and wastewater purification. However, UOR involves complex six-electron transfer and intermediate adsorption/desorption processes, resulting in slow reaction kinetics. Therefore, the development of economical and efficient catalysts has become a research focus, among which transition metal phosphides (TMPs) stand out due to their low cost, excellent activity and adjustable electronic structure. Compared with other non-noble metal systems, TMPs have unique electronic structure and surface properties that can adsorb and activate urea molecules more efficiently. However, there is still a lack of systematic reviews on TMP catalysts at present. Therefore, this review aims to deeply and systematically elaborate the design strategies of TMP catalysts and their applications in UOR, thoroughly discuss the current progress, challenges and future directions, and provide theoretical support and design ideas for the development of a new generation of efficient and stable UOR catalysts.</span></div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 9","pages":"Article 100651"},"PeriodicalIF":10.3,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145289798","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Lanthanide nitric oxides (LnNO, Ln = La–Lu) present unique trend in bonding structure and oxidation states of Ln 镧系氮氧化物（LnNO, Ln = La-Lu）在成键结构和氧化态上呈现出独特的趋势

IF 10.3 4区化学

结构化学 Pub Date : 2025-09-01 DOI: 10.1016/j.cjsc.2025.100675

Zhi-Yu Wei , Shu-Xian Hu

引用次数: 0

A comprehensive review: MOFs and their derivatives as high-performance supercapacitor electrodes mof及其衍生物作为高性能超级电容器电极的综述

IF 10.3 4区化学

结构化学 Pub Date : 2025-09-01 DOI: 10.1016/j.cjsc.2025.100676

Malaika Arshad , Zia Ul Haq Khan , Swera Talib , Sana Sabahat , Noor Samad Shah , Huma Ajab , Farooq Ahmad , Syed Khasim , M.A. Diab , Heba A. El-Sabban

{"title":"A comprehensive review: MOFs and their derivatives as high-performance supercapacitor electrodes","authors":"Malaika Arshad , Zia Ul Haq Khan , Swera Talib , Sana Sabahat , Noor Samad Shah , Huma Ajab , Farooq Ahmad , Syed Khasim , M.A. Diab , Heba A. El-Sabban","doi":"10.1016/j.cjsc.2025.100676","DOIUrl":"10.1016/j.cjsc.2025.100676","url":null,"abstract":"<div><div>An expanding human population and technological progress demand clean and effective energy-storing systems. Within the realm of energy-storing devices, supercapacitors (SCs) have grabbed huge focus owing to their high-power density, unique cycling stability, and fast charging discharging capabilities. Electrode material has a prominent impact on the effectiveness of SCs. Several types of electrode materials have been used, encompassing varied metal oxides, activated carbon, conducting polymers, and MOFs. Metal organic frameworks (MOFs) are considered emerging electrode candidates, which could be ascribed to the tunable porosity, large surface areas, and designed morphology. This review shows a detailed analysis of various mono-, bi-, and tri-metallic MOFs along with derivatives in SC applications, their structural characteristics, and synthetic strategies. It also critically evaluates MOFs potential to boost the SC's energy density, power density, stability, and conductivity. Also, it underscores their significance in the establishment of future-oriented energy storage applications.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 9","pages":"Article 100676"},"PeriodicalIF":10.3,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145289732","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

Novel vinylene-linked COF ruthenium catalyst design achieves record performance in proton exchange membrane water electrolyzers 新型乙烯链COF钌催化剂设计在质子交换膜水电解槽中实现了创纪录的性能

IF 10.3 4区化学

结构化学 Pub Date : 2025-09-01 DOI: 10.1016/j.cjsc.2025.100656

Jianhong Jiang, Xianming Xia, Hongbo He

引用次数: 0

Convenient transformation of FAU zeolites to IWV aluminosilicates with adjustable Al sites for Baeyer-Villiger oxidation FAU沸石为Baeyer-Villiger氧化用铝位可调IWV铝硅酸盐的便捷转化

IF 10.3 4区化学

结构化学 Pub Date : 2025-09-01 DOI: 10.1016/j.cjsc.2025.100654

Meichen Jiao , Sitong Liu , Chunmin Jia , Hao Xu , Zhiguo Zhu , Peng Wu , Xian-Ming Zhang

{"title":"Convenient transformation of FAU zeolites to IWV aluminosilicates with adjustable Al sites for Baeyer-Villiger oxidation","authors":"Meichen Jiao , Sitong Liu , Chunmin Jia , Hao Xu , Zhiguo Zhu , Peng Wu , Xian-Ming Zhang","doi":"10.1016/j.cjsc.2025.100654","DOIUrl":"10.1016/j.cjsc.2025.100654","url":null,"abstract":"<div><div>The Baeyer-Villiger (BV) oxidation of cyclohexanone is explored using IWV-type aluminosilicates with different Al sites as heterogeneous catalysts. The IWV framework exhibits a two-dimensional 12-membered ring (MR) pore system intersected by 14-MR supercages, resembling typical beta zeolite. To address the constraints associated with hydrothermal synthesis, IWV aluminosilicates were synthesized via interzeolite transformation of various FAU-type zeolites. HF-assisted transformation of dealuminated FAU zeolite resulted in the formation of a high-silica IWV aluminosilicate (Si/Al = 54.6), whereas the incorporation of aluminum isopropoxide enables the tuning of Si/Al ratio down to 18.7. The alkaline conversion of protonated FAU zeolites, utilizing Na<sup>+</sup> ions as mineralizing agents, produces high-Al content IWV derivatives in just four days. Catalytic evaluation demonstrates that the high-silica IWV catalyst exhibits a higher turnover number than the other IWV catalysts, along with enhanced <em>ε</em>-caprolactone (CL) selectivity relative to that of high-silica beta zeolite. Facile modifications are performed to adjust Al sites, as characterized by pyridine-adsorbed infrared spectroscopy. Experimental evidence confirms that Al Brønsted acid sites improves the selective oxidation of cyclohexanone, while concurrently enhancing CL hydrolysis.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 9","pages":"Article 100654"},"PeriodicalIF":10.3,"publicationDate":"2025-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145289741","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

引用次数: 0

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