结构化学最新文献

{"title":"Structural regulation of alkynyl-based covalent organic frameworks for multi-stimulus fluorescence sensing","authors":"Xinrui Chen,&nbsp;Wenjian Huang,&nbsp;Xiaoyang Zhao,&nbsp;Songyao Zhang,&nbsp;Xinrui Miao","doi":"10.1016/j.cjsc.2025.100604","DOIUrl":"10.1016/j.cjsc.2025.100604","url":null,"abstract":"<div><div>Stimuli-responsive two-dimensional (2D) covalent organic frameworks (COFs) with precise structures and permanent porosity have been employed as platforms for sensors. The slight change of backbones inside frameworks leads to different electronic states by external stimuli, such as solvent, pH, and water. Herein, we introduced an alkynyl-based building block (ETBA) with high planarity to synthesize two imine-based alkynyl-COFs (ETBA-TAPE-COF and ETBA-PYTA-COF) with high yield, good crystallinity, and chemical stability. Due to the presence of acetylene bonds, ETBA-TAPE-COF does not adopt the completely overlapping AA stacking mode. Slight interlayer displacement occurs along the parallel direction relative to the acetylene linkages, which facilitates lower configurational energy. Additionally, the introduction of pyrene group contributes to high π-electron mobility of ETBA-PYTA-COF. The interactions between electron-withdrawing group (ETBA) and electron-donating group (PYTA) during the processes of protonation and intramolecular charge transfer (ICT) endow ETBA-PYTA-COF with excellent acidochromic and solvatochromic properties, respectively. Based on this, a fluorescence sensor is successfully established, which can be used for rapid response to trace amounts of water in organic solvents. In contrast, ETBA-TAPE-COF does not exhibit these photophysical properties due to its higher HOMO–LUMO gap compared to ETBA-PYTA-COF. This work proposes a new strategy for designing and preparing COFs with unique photophysical properties without introducing additional functional groups.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 7","pages":"Article 100604"},"PeriodicalIF":10.3,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724110","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}

{"title":"Strategic metal substitution for enhanced visible-light-driven oxygen evolution in heterometallic MOFs","authors":"Cui Luo ,&nbsp;Peng-Hui Li ,&nbsp;Wei-Ming Liao ,&nbsp;Qia-Chun Lin ,&nbsp;Xiao-Xiang Zhou ,&nbsp;Jun He","doi":"10.1016/j.cjsc.2025.100621","DOIUrl":"10.1016/j.cjsc.2025.100621","url":null,"abstract":"<div><div>Oxygen evolution reaction (OER), a critical half-reaction in photocatalytic overall water splitting for producing hydrogen, is a key step toward sustainable energy conversion. Conventional photocatalysts often suffer from limited light absorption and rapid charge recombination, hindering their further applications. To address these challenges, we have designed and synthesized a novel series of self-sensitized metal-organic frameworks (MOFs), Fe₂MCDDB (M = Ni, Mn, or Co). By incorporating photosensitive ligands, we have achieved efficient charge separation and promoted the transfer of photogenerated electrons to the active metal sites for water oxidation. Among the series, Fe₂NiCDDB exhibits exceptional OER activity, achieving an oxygen evolution rate of 125.3 μmol g⁻¹ h⁻¹ under visible light irradiation. Experimental and theoretical results reveal that the optimized electronic structure and prolonged excited-state lifetime of Fe₂NiCDDB contribute to its enhanced catalytic performance. This work provides a promising strategy for designing two-in-one MOF photocatalysts for water oxidation.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 7","pages":"Article 100621"},"PeriodicalIF":10.3,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724113","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}

{"title":"Nickel phosphide modified TiO2 nanotube arrays for efficient PEC water splitting H2 generation","authors":"Yang Yang ,&nbsp;Yan-Xin Chen ,&nbsp;Ao-Sheng She ,&nbsp;Hao-Yan Shi ,&nbsp;Wen Chen ,&nbsp;Wei Wang ,&nbsp;Hai-Long Wang ,&nbsp;Ke-Xian Li ,&nbsp;Yi-Hu Pu ,&nbsp;Wei-Hua Yang ,&nbsp;Xiu-Mei Lin ,&nbsp;Can-Zhong Lu","doi":"10.1016/j.cjsc.2025.100623","DOIUrl":"10.1016/j.cjsc.2025.100623","url":null,"abstract":"<div><div>Photoelectrochemical (PEC) hydrogen production holds great promise for applications in energy production. A novel strategy characterized by simplicity, stability, and high efficiency is developed to significantly boost the PEC performance of TiO₂ (anatase) nanotube arrays (TNTAs). This strategy entails a series of treatments, including a conventional anodic oxidation (etching) process, a primary annealing treatment, and a secondary annealing treatment via impregnation. As a result, nickel phosphide (Ni₂P) is composited onto well-ordered titanium dioxide (anatase) nanotube array photoanodes (Ni₂P/TNTAs), which exhibit hugely improved PEC H₂ generation performance. A thorough and systematic investigation is conducted to comprehensively analyze the morphology, semiconductor band-gap structure, and PEC H₂ production performance of the Ni₂P/TNTAs composites. The experimental results demonstrate that under identical experimental circumstances, the measured photocurrent density of the Ni₂P/TNTAs photoanode exhibits a 6.63-fold increase relative to that of TNTAs. The H₂ production rate of Ni₂P/TNTAs reaches 182.96 μmol/cm², 6.10 times higher than that of pure TNTAs. The excellent interfacial charge transfer pathway at the Ni₂P/TiO₂ interface promotes photogenerated carrier separation and electron transfer from TiO₂ to Ni₂P. This method offers a valuable reference for designing highly efficient PEC H₂-production catalysts.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 7","pages":"Article 100623"},"PeriodicalIF":10.3,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724116","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}

{"title":"Functionally graded materials based on porous poly(ionic liquid)s: Design strategies and applications","authors":"Xiao-Yu Han ,&nbsp;Si-Hua Liu ,&nbsp;Su-Yun Zhang ,&nbsp;Jian-Ke Sun","doi":"10.1016/j.cjsc.2025.100601","DOIUrl":"10.1016/j.cjsc.2025.100601","url":null,"abstract":"<div><div>Functionally graded materials (FGMs) are innovative materials distinguished by gradual variations in composition and structure, offering exceptional properties for diverse applications. Poly(ionic liquid)s (PILs), merging the characteristics of polymers and ionic liquids, have emerged as viable options for the development of FGMs given their tunable skeleton, ionic conductivity, and compatibility with various functional materials. This review highlights the latest advancements in the design strategies of FGMs based on porous PILs, focusing on single and multi-gradient structures. Furthermore, we also highlight their emerging applications in molecular recognition, sensing, adsorption, separation, and catalysis. By exploring the interplay between porosity, ionic functionality, and gradient architecture, this review offers perspectives on the prospects of PIL-based FGMs for tackling global challenges in energy, environment, and healthcare.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 7","pages":"Article 100601"},"PeriodicalIF":10.3,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724117","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}

{"title":"Neodymium-doped hollow Ir/IrO2 nanospheres with low geometric iridium density enable excellent acidic water oxidation performance","authors":"Xiaoqian Wei ,&nbsp;Hanyu Gao ,&nbsp;Tiantian Wang ,&nbsp;Zijian Li ,&nbsp;Yanru Geng ,&nbsp;Guiping Zheng ,&nbsp;Min Gyu Kim ,&nbsp;Haeseong Jang ,&nbsp;Xien Liu ,&nbsp;Qing Qin","doi":"10.1016/j.cjsc.2025.100600","DOIUrl":"10.1016/j.cjsc.2025.100600","url":null,"abstract":"<div><div>Reducing the Ir loading while preserving catalytic performance and mechanical robustness in anodic catalyst layers remains a critical challenge for the large-scale implementation of proton exchange membrane water electrolysis (PEMWE). Herein, we present a structural engineering strategy involving neodymium-doped Ir/IrO₂ (Nd–Ir/IrO₂) hollow nanospheres with precisely adjustable shell thickness and cavity dimensions. The optimized catalyst demonstrates excellent oxygen evolution reaction (OER) performance in acidic media, achieving a remarkably low overpotential of 259 mV at a benchmark current density of 10 mA cm⁻² while exhibiting substantially enhanced durability compared to commercial IrO₂ and Ir/IrO₂ counterparts. Notably, the Nd–Ir/IrO₂ catalyst delivers a mass activity of 541.6 A g_Ir⁻¹ at 1.50 V <em>vs</em><em>.</em> RHE, representing a 74.5-fold enhancement over conventional IrO₂. Comprehensive electrochemical analysis and advanced characterization techniques reveal that the hierarchical hollow architecture simultaneously addresses multiple critical requirements: (i) abundant exposed active sites enabled by an enhanced electrochemical surface area, (ii) optimized mass transport pathways through engineered porosity, and (iii) preserved structural integrity via a continuous conductive framework, collectively enabling significant Ir loading reduction without compromising catalytic layer performance. Fundamental mechanistic investigations further disclose that Nd doping induces critical interfacial Nd–O–Ir configurations that stabilize lattice oxygen, together with intensified electron effect among mixed valent Ir that inhibits the overoxidation of Ir active sites during the OER process, synergistically ensuring enhanced catalytic durability. Our work establishes a dual-modulation paradigm integrating nanoscale architectural engineering with atomic-level heteroatom doping, providing a viable pathway toward high-performance PEMWE systems with drastically reduced noble metal requirements.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 7","pages":"Article 100600"},"PeriodicalIF":10.3,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724108","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}

{"title":"A shape-memory hydrogen-bonded organic framework for flue gas desulfurization","authors":"Wenlei Yang,&nbsp;Lingyao Wang,&nbsp;Yuanbin Zhang","doi":"10.1016/j.cjsc.2025.100574","DOIUrl":"10.1016/j.cjsc.2025.100574","url":null,"abstract":"","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 6","pages":"Article 100574"},"PeriodicalIF":5.9,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144335915","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}

{"title":"Investigation of water structure and proton transfer within confined graphene by ab initio molecule dynamics and multiscale data analysis","authors":"Heng-Su Liu ,&nbsp;Xi-Ming Zhang ,&nbsp;Ge-Hao Liang ,&nbsp;Shisheng Zheng ,&nbsp;Jian-Feng Li","doi":"10.1016/j.cjsc.2025.100596","DOIUrl":"10.1016/j.cjsc.2025.100596","url":null,"abstract":"<div><div>The structure of water and proton transfer under nanoscale confinement has garnered significant attention due to its crucial role in elucidating various phenomena across multiple scientific disciplines. However, there remains a lack of consensus on fundamental properties such as diffusion behavior and the nature of hydrogen bonding in confined environments. In this work, we investigated the influence of confinement on proton transfer in water confined within graphene sheets at various spacings by <em>ab initio</em> molecule dynamic and multiscale analysis with time evolution of structural properties, graph theory and persistent homology. We found that reducing the graphene interlayer distance while maintaining water density close to that of bulk water leads to a decrease in proton transfer frequency. In contrast, reducing the interlayer distance without maintaining bulk-like water density results in an increase in proton transfer frequency. This difference is mainly due to the confinement conditions: when density is unchanged, the hydrogen bond network remains similar with significant layering, while compressive stress that increases density leads to a more planar hydrogen bond network, promoting faster proton transfer. Our findings elucidate the complex relationship between confinement and proton transfer dynamics, with implications for understanding proton transport in confined environments, relevant to energy storage and material design.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 6","pages":"Article 100596"},"PeriodicalIF":5.9,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144335909","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}

{"title":"All-sputtered proton-conductive fuel cells based on flashlight-sintered thin-film Y:BaZrO3–δ electrolyte","authors":"Jiwon Baek ,&nbsp;Junseo Youn ,&nbsp;Hyoun-Myoung Oh ,&nbsp;Jonghyuk Lee ,&nbsp;Haesu Lee ,&nbsp;Nguyen Q. Minh ,&nbsp;Young-Beom Kim ,&nbsp;Yoon Ho Lee ,&nbsp;Taehyun Park","doi":"10.1016/j.cjsc.2025.100598","DOIUrl":"10.1016/j.cjsc.2025.100598","url":null,"abstract":"<div><div>In this work, we present an innovative method for fabricating high-performance proton-conductive fuel cells (PCFCs) by combining magnetron sputtering and flashlight sintering (FLS) techniques. BaZr_0.8Y_0.2O₃_–_<em>δ</em> (BZY20) electrolyte thin-films are successfully prepared by improving the crystallinity while maintaining the stoichiometry. All components of PCFC, Ni-YSZ anode, BZY20 electrolyte and Pt-GDC cathode are fabricated by sequentially sputtering them onto an AAO substrate. Electrolytic sintering is performed at 550 and 650 V conditions using FLS, effectively solving the Ba evaporation problem encountered in conventional thermal sintering methods. XRD analysis confirms that the perovskite structure is retained, and crystallinity is improved in the FLS samples. Furthermore, FE-SEM and EDS analyses confirm the uniform elemental distribution and consistent thickness of the FLS-treated electrolyte. An optimized PCFC unit cell with FLS-treated electrolyte exhibits a peak power density of 200.0 mW cm⁻² at 500 °C and an ohmic resistance of 376.0 mΩ cm⁻². These results suggest that the combination of magnetron sputtering and FLS techniques is a promising approach for fabricating high-performance thin-film PCFCs.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 6","pages":"Article 100598"},"PeriodicalIF":5.9,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144335910","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}

{"title":"A stable scandium(III) metal-organic framework with introduced nitrate ions for enhancing C2H6/C2H4 selectivity in the separation of MTO products","authors":"Yajun Gao ,&nbsp;Xinyu Yang ,&nbsp;Jian Su ,&nbsp;Zhizhong Li","doi":"10.1016/j.cjsc.2025.100576","DOIUrl":"10.1016/j.cjsc.2025.100576","url":null,"abstract":"<div><div>Based upon the thiophene-2,5-dicarboxylic acid (H₂Tdc), a novel [Sc₃(<em>μ</em>₂-OH)₃(CO₂)₄O₆]_<em>n</em> inorganic chain-based Sc-MOF with decorated nitrate ions, {[Sc₃(OH)₂(Tdc)₃(NO₃)]⋅H₂O}_∞ (<strong>AEU-1</strong>; AEU for Army Engineering University of PLA), was synthesized, which shows good water and chemical stabilities. Significantly, due to channel constriction accompanied by the polar window caused by introducing nitrate ions, <strong>AEU-1</strong> exhibits high C₂H₆/C₂H₄ adsorption selectivity comparable to many famous C₂H₆-selective MOFs, making it a promising candidate for the purification of methanol-to-olefin (MTO) products. Furthermore, theoretical investigations reveal that the introduced nitrate ions in <strong>AEU-1</strong> as the main adsorption sites could provide strong interactions between the framework and C₂H₆/C₃H₆ in the full-contacting mode, leading to an increase in the adsorption enthalpies (<em>Q</em>_st) of C₂H₆ and C₃H₆, and thus further improving the C₂H₆/C₂H₄ and C₃H₆/C₂H₄ adsorption selectivity. Our work could open up a new avenue for constructing MOFs with inorganic polar moieties as adsorption sites for one-step C₂H₄ purification and C₃H₆ recovery from MTO mixtures with high selectivity.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 6","pages":"Article 100576"},"PeriodicalIF":5.9,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144335908","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}

{"title":"Single-atom catalysts for electrocatalytic nitrogen reduction to ammonia: A review","authors":"Qiaorui Wang ,&nbsp;Dingyun Liang ,&nbsp;Zhongwen Zhang ,&nbsp;Yalan Yang ,&nbsp;Yunran Zhang ,&nbsp;Yirong Wang ,&nbsp;Lei Liu ,&nbsp;Wenfeng Jiang ,&nbsp;Muneerah Alomar ,&nbsp;Li-Long Zhang","doi":"10.1016/j.cjsc.2025.100599","DOIUrl":"10.1016/j.cjsc.2025.100599","url":null,"abstract":"<div><div>The electrochemical nitrogen reduction reaction (eNRR) presents a sustainable alternative to the energy-intensive Haber-Bosch process for ammonia (NH₃) production. This review examines the fundamental principles of eNRR, emphasizing the critical roles of proton-exchange membranes and electrolytes in facilitating efficient nitrogen (N₂) reduction. Special attention is given to single-atom catalysts (SACs), highlighting their unique structural and electronic properties that contribute to enhanced catalytic performance. The discussions encompass SACs based on precious metals, non-precious metals, and non-metallic materials, delving into their synthesis methods, coordination environments, and activity in the eNRR. This review also elucidates current challenges in the field and proposes future research directions aimed at optimizing SACs design to enhance eNRR efficiency.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 6","pages":"Article 100599"},"PeriodicalIF":5.9,"publicationDate":"2025-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144335911","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}