结构化学最新文献

{"title":"Innovative optothermal-stimulated persistent luminescence nanoparticles for advanced tumor theranostics","authors":"Yuqing Zhang , Xiao Song , Yongsheng Liu , Maochun Hong","doi":"10.1016/j.cjsc.2025.100624","DOIUrl":"10.1016/j.cjsc.2025.100624","url":null,"abstract":"","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 7","pages":"Article 100624"},"PeriodicalIF":10.3,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144722281","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":"Synthesis, separation and structure of zinc coordination clusters: Proposal of an assembly-disassembly-reassembly process observed from ESI-MS","authors":"Huang-Ling Lin ,&nbsp;Meng-Zhen Xu ,&nbsp;Tian-Ying Gu ,&nbsp;Xing-Xing Shi ,&nbsp;Mao Le,&nbsp;Zheng Yin,&nbsp;Ming-Hua Zeng","doi":"10.1016/j.cjsc.2025.100602","DOIUrl":"10.1016/j.cjsc.2025.100602","url":null,"abstract":"<div><div>In mass spectrometry, fragments with a mass higher than the original molecular ion provide valuable insights into the molecular structure and can guide the assembly and disassembly processes for chemical synthesis. Here, we report such an example and following up by modifying the solvothermal reaction conditions (temperature and time) it is possible to isolate the high mass species in crystalline form. [Zn₄L₄Cl₄] (<strong>Zn₄L₄</strong>, L = N-methylbenzimidazole-2-methanolate) has a boat-like Zn₄O₄ core but electrospray ionization mass spectrometry (ESI-MS) of the solution of its crystals shows higher mass peaks of Zn₅L₅, Zn₅L₆ and Zn₆L₆ species. Thus, both disassembly and reassembly are highly probable processes. Consequently, [Zn(HL)₂Cl₂] (<strong>Zn₁</strong>, L = N-methylbenzimidazole-2-methanolate), [Zn₄L₆Cl₂] (<strong>Zn₄L₆</strong>, L = N-methylbenzimidazole-2-methanolate) and [Zn₆L₆Cl₄(CH₃O)₂] (<strong>Zn₆L₆</strong>, L = N-methylbenzimidazole-2-methanolate) were prepared. The results of multistage ESI-MS of their dissolved crystals led to a proposed mechanism of their formation in the gas phase as follows: [Zn₃L₄] through [ZnL] → [ZnL(HL)] → [Zn(HL)₂] → [Zn₂L] → [Zn₂L₂] → [Zn₂L₃]. The mechanism was derived in conjunction with Gibbs free energies calculated using DFT of the fragments observed in the ESI-MS of <strong>Zn₄L₄</strong>, <strong>Zn₄L₆</strong> and <strong>Zn₆L₆</strong>. This work reveals the complex of chemical reactions, involving fragmentation and unexpected combination, under mass spectrometry condition which allows one to synthesize the observed transients, leading to mechanism of formation by correlation of solid-state/solution structural information.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 7","pages":"Article 100602"},"PeriodicalIF":10.3,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724109","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":"Crystal orientation dependent charge transfer dynamics and interfacial water configuration boosting photoelectrocatalytic water oxidation to H2O2","authors":"Yan Zhao ,&nbsp;Zhenming Tian ,&nbsp;Qisen Jia ,&nbsp;Ting Yao ,&nbsp;Jiashu Li ,&nbsp;Yanan Wang ,&nbsp;Xuejing Cui ,&nbsp;Jing Liu ,&nbsp;Xin Chen ,&nbsp;Luhua Jiang","doi":"10.1016/j.cjsc.2025.100619","DOIUrl":"10.1016/j.cjsc.2025.100619","url":null,"abstract":"<div><div>Photoelectrochemical water oxidation reaction (PEC-WOR) as a sustainable route to produce H₂O₂ is attractive but limited by low activity and poor product selectivity of photoanodes due to limited photogenerated charge efficiency and unfavorable thermodynamics. Herein, by crystal orientation engineering, the WO₃ photoanode exposing (200) facets achieves both superior WOR activity (15.4 mA cm⁻² at 1.76 V_RHE) and high selectivity to H₂O₂ (∼70%). Comprehensive experimental and theoretical investigations discover that the high PEC-WOR activity of WO₃-(200) is attributed to the rapid photogenerated charge separation/transfer both in bulk and at interfaces of WO₃-(200) facet, which reduces the charge transfer resistance. This, coupling with the unique defective hydrogen bonding network at the WO₃-(200)/electrolyte interface evidenced by <em>operando</em> PEC Fourier transform infrared spectroscopy, facilitating the outward-transfer of the WOR-produced H⁺, lowers the overall reaction barrier for the PEC-WOR. The superior selectivity of PEC-WOR to H₂O₂ is ascribed to the unique defective hydrogen bonding network alleviated adsorption of ∗OH over the WO₃-(200) facet, which specially lowers the energy barrier of the 2-electron pathway, as compared to the 4-electron pathway. This work addresses the significant role of crystal orientation engineering on photoelectrocatalytic activity and selectivity, and sheds lights on the underlying PEC mechanism by understanding the water adsorption behaviors under illumination. The knowledge gained is expected to be extended to other photoeletrochemical reactions.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 7","pages":"Article 100619"},"PeriodicalIF":10.3,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724111","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":"Type-I heterojunction photocatalysis: Enhanced activity via ZnIn2S4/MnCo2O4.5 interfacial electric fields","authors":"Qiang Yu ,&nbsp;Shuhan Sun ,&nbsp;Xianming Jin ,&nbsp;Ruiqiang Yan ,&nbsp;Bingjing He ,&nbsp;Nikolay Sirotkin ,&nbsp;Alexander Agafonov ,&nbsp;Xianqiang Xiong ,&nbsp;Kangle Lv","doi":"10.1016/j.cjsc.2025.100620","DOIUrl":"10.1016/j.cjsc.2025.100620","url":null,"abstract":"<div><div>The modulation of charge transfer pathways within type-I heterojunctions through interfacial electric field (IEF) engineering is of critical importance in promoting photocatalytic hydrogen evolution, effectively facilitating the separation of photogenerated charge carriers. In this study, we performed <em>in-situ</em> growth of two-dimensional ZnIn₂S₄ nanosheets on MnCo₂O_4.5 nanorods to construct an ohmic-like type-I ZnIn₂S₄/MnCo₂O_4.5 heterojunction for efficient photocatalytic hydrogen evolution. This ohmic-like charge transfer mechanism effectively addresses the intrinsic limitations inherent to conventional type-I heterojunctions neglecting IEF effects, particularly through IEF-induced enhancement of charge separation efficiency. Consequently, the optimized ZnIn₂S₄/MnCo₂O_4.5 photocatalyst demonstrates an outstanding photocatalytic hydrogen evolution rate of 20.9 mmol g⁻¹ h⁻¹, 14.9 times that of the bare ZnIn₂S₄. Furthermore, the ohmic-like charge transport behavior has been rigorously validated by integrated advanced experimental characterizations, including <em>in-situ</em> X-ray photoelectron spectroscopy (XPS), Kelvin probe force microscopy (KPFM), and surface photovoltage (SPV) measurements, which collectively provide robust evidence for the proposed mechanism. This work offers valuable insights into the design of high-efficient ohmic-like type-I heterojunction catalysts for photocatalytic H₂ evolution.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 7","pages":"Article 100620"},"PeriodicalIF":10.3,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724112","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":"Four tartaric acid-bridged tetra-europium(III)-containing antimonotungstate with catalytic oxidation of thioethers/alcohols","authors":"Yuanping Jiang ,&nbsp;Haoqi Liu ,&nbsp;Jiawei Zhang ,&nbsp;Luying Jiao,&nbsp;Xiaoling Lin,&nbsp;Fuhua Zhang,&nbsp;Guoping Yang","doi":"10.1016/j.cjsc.2025.100603","DOIUrl":"10.1016/j.cjsc.2025.100603","url":null,"abstract":"<div><div>A novel tetra-europium(III)-containing antimonotungstate, Na_8.2[H₂N(CH₃)₂]₉[Na_10.8(tar)₄(H₂O)₂₀(Eu₂Sb₂W₂₁O₇₂)₂]·44.5H₂O (<strong>EuSbW</strong>, H₄tar = <span>dl</span>-tartaric acid), has been synthesized and characterized. The dimeric polyoxoanion of <strong>EuSbW</strong> consists of two Dawson-like {Eu₂Sb₂W₂₁} units bridged by four <span>dl</span>-tartaric acid ligands. The adjacent carboxyl and hydroxy groups in each tartaric acid simultaneously chelate with W and Eu atoms from different {Eu₂Sb₂W₂₁} units, thereby forming the dimeric structure. <strong>EuSbW</strong> represents an extremely rare polyoxometalate where four tartaric acid ligands function as connectors to bridge two {Eu₂Sb₂W₂₁} units. Additionally, <strong>EuSbW</strong> exhibits excellent catalytic activity and reusability in the oxidation of thioethers and alcohols, achieving 100% conversion and &gt; 99% selectivity for various thioethers, and 85–100% conversion with 90–99% selectivity for diverse alcohols under mild conditions.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 7","pages":"Article 100603"},"PeriodicalIF":10.3,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144722279","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":"Photomechanical movements of a coordination polymer-based composite enable a reversible photocontrollable electrical switch","authors":"Qian Ren ,&nbsp;Shu-Fen Zhang ,&nbsp;Dong Liu ,&nbsp;Jian-Ping Lang","doi":"10.1016/j.cjsc.2025.100622","DOIUrl":"10.1016/j.cjsc.2025.100622","url":null,"abstract":"<div><div>Flexible circuit switches have been widely used in electronic devices due to their outstanding flexibility and operability. In order to expand the types of flexible circuit switch materials, we develop a unique composite material, which integrates a photoresponsive flexible substrate derived from a photoreactive coordination polymer (CP) with an elastic conductive adhesive tape (CAT) in this work. The photoreactive CP {[Cd(2,6-bpvn)(3,5-DBB)₂]·DMF}_<em>n</em> (<strong>1</strong>) is prepared through solvothermal reaction of Cd(NO₃)₂·4H₂O with 2,6-bis((<em>E</em>)-2-(pyridin-4-yl)vinyl)naphthalene (2,6-bpvn) and 3,5-dibromobenzoic acid (3,5-HDBB). Upon irradiation with UV light, crystals of <strong>1</strong> can undergo [2 + 2] photocycloaddition reaction and exhibit photomechanical movements. The crystalline powder of <strong>1</strong> can be uniformly distributed in polyvinyl alcohol (PVA) to generate the composite film <strong>1-PVA</strong>. After pasting a piece of CAT on the surface of a <strong>1-PVA</strong> film, a conductive two-layer film of <strong>1-PVA/CAT</strong> can be fabricated. This film bends rapidly upon UV light exposure, connecting the circuit and causing the bulb to light up. When the light source is removed, it reverts to its initial state and the circuit is disconnected and the bulb is extinguished. This process can be cycled at least 100 times, achieving precise turn-on and turn-off performances of the photocontrollable circuit switch.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"44 7","pages":"Article 100622"},"PeriodicalIF":10.3,"publicationDate":"2025-07-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"144724114","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":"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}