结构化学最新文献

{"title":"Bismuth-based S-scheme heterojunctions for efficient photocatalytic energy conversion and application","authors":"Wenbo Zheng,&nbsp;Xianfeng Qiao,&nbsp;Shuo Wang,&nbsp;Ying Wang,&nbsp;Zhengxin Ding,&nbsp;Jinlin Long","doi":"10.1016/j.cjsc.2026.100971","DOIUrl":"10.1016/j.cjsc.2026.100971","url":null,"abstract":"<div><div>Photocatalytic technology, which enables the direct conversion of solar energy into chemical energy, presents a compelling and sustainable approach to mitigating the pressing issues of the global energy crisis and environmental degradation. S-scheme heterojunctions have garnered significant attention in photocatalysis due to their exceptional charge separation efficiency and enhanced redox properties. Bi-based semiconductors, characterized by their unique layered structures, tunable electronic band configurations, and responsiveness to visible light, offer substantial advantages in the fabrication of S-scheme heterojunctions. This review systematically summarizes recent advances in Bi-based S-scheme heterojunctions for photocatalytic applications, focusing on the improvement of charge separation and utilization efficiency. We first elucidate the fundamental charge transfer mechanism of S-scheme heterojunctions, followed by a comprehensive overview of construction methods including <em>in situ</em> hydrothermal/solvothermal synthesis, electrospinning, calcination, and electrostatically driven assembly. Advanced characterization techniques such as Kelvin probe force microscopy (KPFM), <em>in situ</em> irradiated X-ray photoelectron spectroscopy (ISI-XPS), and femtosecond transient absorption spectroscopy (fs-TAS) for verifying the S-scheme charge transfer mechanism are discussed in detail. Various modulation strategies to improve photocatalytic performance are thoroughly examined, including electronic structure regulation (element doping and defect engineering), interface structure regulation (electron bridges and crystal facet engineering), and morphology/dimension engineering to optimize the surface reaction. Moreover, the applications of Bi-based S-scheme heterojunctions in photocatalytic water splitting for hydrogen production, CO₂ reduction, pollutant degradation and H₂O₂ generation are comprehensively summarized. Finally, the current challenges and future perspectives for the development of high-performance Bi-based S-scheme heterojunction photocatalysts are presented. This review aims to provide profound theoretical insights and strategic frameworks for the rational design of high-efficiency Bi-based S-scheme photocatalysts.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 9","pages":"Article 100971"},"PeriodicalIF":10.5,"publicationDate":"2026-09-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148949388","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":"Hetero-motif POM molecular junctions enable tandem olefin epoxidation and CO2 fixation","authors":"Yingjie Li,&nbsp;Hailong Hu,&nbsp;Aoqi Wang,&nbsp;Jingru Huang,&nbsp;Shiqi Fu,&nbsp;Zongyin Gao,&nbsp;Shuo Tao,&nbsp;Yalin Zhang,&nbsp;Qingde Zhang,&nbsp;Haitao Wang,&nbsp;Xianqiang Huang","doi":"10.1016/j.cjsc.2026.100946","DOIUrl":"10.1016/j.cjsc.2026.100946","url":null,"abstract":"<div><div>Olefin epoxidation and CO₂ cycloaddition are important catalytic reactions for the preparation of cyclic carbonates, valuable intermediates in chemical industry. The development of a single heterogeneous catalyst capable of efficiently catalyzing both transformations, however, remains a considerable challenge. Herein, two polyoxotungstate-based copper-organic frameworks, [Cu(1-eIM)₄]₃(VW₅O₁₉)₂·2(1-eIM) (<strong>PCF-1</strong>) and [Cu(1-iPIM)₄]₃[VW₁₂O₄₀]·(OH)₃ (<strong>PCF-2</strong>), have been synthesized and structurally characterized. These compounds possess multi-dimensional frameworks with excellent solvent and pH stability, and are covalently assembled through Cu–<em>O</em>–W linkages between polyoxotungstate clusters and imidazole-copper units. Density functional theory calculations reveal that the polyoxometalate (POM) acidic sites are more favorable for styrene adsorption, whereas the Cu sites preferentially interact with CO₂. In catalytic tests, <strong>PCF-2</strong> exhibits superior performance in both reactions, giving yields of 88% for olefin epoxidation and 99% for CO₂ cycloaddition, together with excellent recycling stability. This study provides an effective strategy for constructing POM-based heterogeneous molecular junction catalysts for tandem organic transformations.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 8","pages":"Article 100946"},"PeriodicalIF":10.5,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148710140","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":"Sulfur-vacancy engineered SmCoO3/MnCdS S-scheme heterojunction for efficient photothermal-photocatalytic H2 evolution","authors":"Yuanjin He,&nbsp;Hao Yang,&nbsp;Qiwei Guo,&nbsp;Bo Zhou,&nbsp;Xuqiang Hao,&nbsp;Zhiliang Jin","doi":"10.1016/j.cjsc.2026.100965","DOIUrl":"10.1016/j.cjsc.2026.100965","url":null,"abstract":"<div><div>The development of S-scheme photocatalysts has emerged as a promising approach to address the critical bottlenecks of limited light absorption and inefficient charge separation in photocatalytic hydrogen evolution (PHE). Herein, a sulfur-vacancy engineered SmCoO₃/MnCdS-Vs (SMCS) S-scheme heterojunction with photothermal effect was successfully constructed for PHE. The photothermal effect induced by SmCoO₃ can rapidly convert light energy into localized thermal energy, and significantly reduces the reaction energy barriers for H₂O molecule activation and promotes the PHE performance. The S-scheme charge transfer mechanism at the SMCS heterointerface is confirmed by <em>in-situ</em> X-ray photoelectron spectroscopy (XPS), charge density difference, and Bader charge. Additionally, sulfur vacancies accelerate interfacial charge transfer in the S-scheme heterojunction. The synergistic effect of S-scheme charge transfer and photothermal effects significantly enhance charge separation and accelerate surface reactions. Consequently, the optimized SMCS photocatalyst with 5wt% SmCoO₃ achieves a maximum hydrogen evolution rate of 27.03 mmol g⁻¹ h⁻¹, which is 3.55 times higher than that of pristine MnCdS-Vs, and an apparent quantum efficiency (AQE) up to 20.98% at 420 nm. Especially, the H₂ production reaches 174 mmol g⁻¹ over 5SMCS within 2 h under AM 1.5 simulated sunlight irradiation. This work provides an efficient strategy for designing photothermal-assisted MnCdS-based S-scheme photocatalyst for boosting hydrogen evolution.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 8","pages":"Article 100965"},"PeriodicalIF":10.5,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148710151","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":"Recent progress on multi-synergistic charge-transfer strategies for efficient triplet up-conversion in narrowband MR-TADF emitters","authors":"Zeng-Jiang Yue,&nbsp;Zheng-Yin Du,&nbsp;Xunwen Xiao,&nbsp;Xu-Feng Luo","doi":"10.1016/j.cjsc.2026.100945","DOIUrl":"10.1016/j.cjsc.2026.100945","url":null,"abstract":"<div><div>Multiple resonance thermally activated delayed fluorescence (MR-TADF) materials have attracted considerable attention due to their attractive narrowband emission characteristics, high luminescence efficiency, and tunable emission colors, showing great potential for advancing narrowband-emission organic light-emitting diodes (OLEDs). To date, research in this field has progressed beyond simply adjusting emission colors, with nearly full-color narrowband emission already achieved. However, the intrinsic molecular design of MR-TADF materials requires a balance between charge-transfer (CT) and local excited (LE) states, resulting in triplet upconversion efficiencies that are generally lower than those of conventional CT-dominated TADF materials, thereby limiting their further application in OLEDs. Currently, several strategies involving synergistic channel interactions have been proposed to optimize the reverse intersystem crossing (RISC) process, which can be categorized into approaches based on modulated twisted intramolecular charge transfer (TICT), through-space charge transfer (TSCT) and multiple CT channel coupling. This review systematically summarizes the molecular design strategies of MR-TADF materials based on different CT modulation approaches and their progress in OLED applications. Furthermore, it discusses the remaining challenges in this research area and provides an outlook on future development. We believe this review will contribute to accelerating the industrialization of narrowband-emission OLEDs.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 8","pages":"Article 100945"},"PeriodicalIF":10.5,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148710153","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":"Metal-incorporated polymeric resists with tunable lithographic performance via complex-specific design","authors":"Xi Liang,&nbsp;Mei-Hua Xiong,&nbsp;Er-Xia Chen,&nbsp;Lu-Yao Hao,&nbsp;Jin-Xia Yang,&nbsp;Jian Zhang,&nbsp;Qipu Lin","doi":"10.1016/j.cjsc.2026.100947","DOIUrl":"10.1016/j.cjsc.2026.100947","url":null,"abstract":"<div><div>The continued scaling of extreme ultraviolet (EUV) lithography demands photoresists whose key parameters, such as resolution, sensitivity, and contrast, can be independently tailored to meet the specific requirements of advanced nanofabrication. Herein, we introduce a series of non-chemically amplified negative-tone photoresists based on metal-incorporated polymers, denoted as BP-M (M = Sn, Sb, Bi). The resists are constructed by covalently embedding heavy-metal complexes into a sulfonium-functionalized polymer backbone. Even at low metal loadings, the high EUV absorption and distinct photoreactivity of the metal centers enable efficient patterning without chemical amplification. Despite comparable EUV absorption coefficients, each metal imparts a unique lithographic signature: BP-Sb exhibits the highest sensitivity, BP-Bi achieves the finest resolution, and BP-Sn delivers the sharpest contrast. Lithographic performance can thus be predictably modulated through simple metal substitution. Mechanistic studies uncover a dual-action pathway wherein cleavage of metal-carbon bonds generates cross-linking radicals, while decomposition of sulfonium moieties induces polarity reversal, synergistically driving a pronounced solubility switch. This \"complex-polymer synergistic design\" establishes a rational platform for resist engineering, positioning antimony and bismuth as sustainable alternatives to conventional tin-based systems.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 8","pages":"Article 100947"},"PeriodicalIF":10.5,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148710141","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":"Tuning effective conjugation via B←N orientation: High-mobility n-type isoindigo polymers for organic field-effect transistors","authors":"Jingshu Tian,&nbsp;Haofeng Sun,&nbsp;Jiarui Li,&nbsp;Cheng Wang,&nbsp;Kun Yang,&nbsp;Qinqi Zhou,&nbsp;Kai-Kai Liu,&nbsp;Maning Liu,&nbsp;Haichang Zhang","doi":"10.1016/j.cjsc.2026.100943","DOIUrl":"10.1016/j.cjsc.2026.100943","url":null,"abstract":"<div><div>The incorporation of electron-withdrawing B←N coordination units has emerged as an effective strategy to enhance n-type charge transport in conjugated polymers. However, the orientation of these units, whether perpendicular or parallel to the polymer backbone, profoundly influences effective conjugation, molecular packing, and ultimately charge transport properties. To address this structure-property relationship systematically, we designed the IIDG-AB chromophore with precisely controlled polymerization sites, yielding two isomeric polymers: <strong>P1</strong> with perpendicular B←N orientation and <strong>P2</strong> with parallel orientation. Integrated theoretical and experimental investigations reveal that <strong>P1</strong>, despite having a shorter geometric conjugation length, achieves a more extended effective π-system, stronger intramolecular charge transfer (ICT), tighter solution-phase aggregation, closer π-π stacking, and more delocalized electron excitation. These collective attributes result in a deeper lowest unoccupied molecular orbital level and superior electron transport, with <strong>P1</strong> exhibiting an electron mobility of 1.77 cm² V⁻¹ s⁻¹ in organic field-effect transistors,substantially exceeding that of <strong>P2</strong> (0.86 cm² V⁻¹ s⁻¹). This work demonstrates that chromophore twist and intrinsic dihedral angles can distort backbone conformation, limit effective conjugation and weaken packing efficiency. We highlight that orienting B←N coordination perpendicular to the backbone is critical, establishing a key design principle for high-performance n-type polymers. The concept of “conformation-driven performance” offers a valuable paradigm for the rational development of organic electronic materials.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 8","pages":"Article 100943"},"PeriodicalIF":10.5,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148710089","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Spin-state switching driven by divergent structural evolutions in a 3D spin-crossover material","authors":"Meng-Ling Wu,&nbsp;Jun-Hui Liang,&nbsp;Yan-Ru Chen,&nbsp;Kang Chen,&nbsp;Ze-Yu Ruan,&nbsp;Si-Guo Wu,&nbsp;Wei-Zhao Cai,&nbsp;Ming-Liang Tong","doi":"10.1016/j.cjsc.2026.100941","DOIUrl":"10.1016/j.cjsc.2026.100941","url":null,"abstract":"<div><div>The exploration of structural evolutions in dynamic crystals under multiple stimuli is of high interest. Herein, we develop a cyanide-bridged bimetallic coordination polymer [Fe{Ag(CN)₂}₂(imipz)] (<strong>1-Fe</strong>, imipz = imidazo[1,2-<em>a</em>]pyrazine) featuring one-dimensional zigzag Ag chains with argentophilic interactions. <strong>1-Fe</strong> exhibits an incomplete spin-crossover (SCO) behavior with a hysteresis loop of 19 K. Notably, temperature and pressure drive distinct crystal evolution pathways that lead to divergent spin-state regulation. Under thermal annealing, the intermediate spin-state is achieved mainly through the deflection of the imipz ligand and leads to the formation of non-equivalent SCO-active centers. Under hydrostatic compression, Ag–CN–Fe linkages undergo significant structural deformations, resulting in enhanced argentophilic interactions and anisotropic compressibility in the lattice. Concomitantly, a reversible pressure-induced electronic configuration modulation occurs, transitioning from a high-spin to a low-spin state accompanied by an isostructural phase transition. These results highlighted in this work elucidate the stimuli-responsive mechanisms for spin-state trapping via dynamic structural deformations, and provide a novel perspective for the design of addressable functional crystals.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 8","pages":"Article 100941"},"PeriodicalIF":10.5,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148710139","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":"Synergistic modulation of steric hindrance and isomerization space for enhanced photo-regulated performance of metal-organic polyhedra","authors":"Shu Shi,&nbsp;Mu-Yi Xu,&nbsp;Yang Liu,&nbsp;Yu-Xia Li,&nbsp;Lin-Bing Sun","doi":"10.1016/j.cjsc.2026.100962","DOIUrl":"10.1016/j.cjsc.2026.100962","url":null,"abstract":"<div><div>As an emerging class of smart materials, photoresponsive metal-organic polyhedra (PMOPs) have garnered growing attention owing to their modular architectures, tunable functionality and remote addressability. However, severe aggregation in the solid state compromises the photoresponsiveness; additionally, their photo-regulated performances (e.g. on adsorption) remain to be improved. Here we report a synergistic modulation strategy that concurrently engineers steric hindrance and isomerization space to construct a novel Rh-based PMOP, (<em>t</em>Bu-Azo)(LA)MOP. This cage architecture comprises a sterically hindered azobenzene unit (<em>t</em>Bu-Azo) and a long alkyl-chain spacer (LA), where the <em>tert</em>-butyl groups are designed to enhance the manipulation on open metal sites, while the LA ligands are designed to provide essential intermolecular spacing for efficient photoisomerization. Upon visible-/UV-light irradiation, the photoresponsive units in (<em>t</em>Bu-Azo)(LA)MOP undergo reversible <em>trans</em>-<em>cis</em> isomerization with markedly improved photo-regulated performance. Consequently, a 49.7% change in propylene uptake is achieved, far surpassing that of the comparator (Azo)MOP assembled from unmodified azobenzene ligands in the absence of LA (17.1%). The outstanding photo-regulated performance, combined with high adsorption capacity, positions (<em>t</em>Bu-Azo)(LA)MOP among the top-performing photoresponsive adsorbents reported to date. Density-functional-theory calculations are consistent with the interpretation that the <em>trans</em>-<em>cis</em> isomerization may effectively modulate the binding strength between active sites and C₃H₆. This work offers a viable avenue for the design of high-performance photoresponsive materials with broad applicability.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 8","pages":"Article 100962"},"PeriodicalIF":10.5,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148710150","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":"Defect-enhanced charge separation in ZnCdS/WS2 S-scheme heterojunctions: Engineering sulfur vacancies to facilitate photocatalytic H2 production","authors":"Tuo Guo,&nbsp;Guojing Hu,&nbsp;Jiaxin Liu,&nbsp;Li Chen,&nbsp;Guangmin Ren,&nbsp;Qingjie Guo","doi":"10.1016/j.cjsc.2026.100960","DOIUrl":"10.1016/j.cjsc.2026.100960","url":null,"abstract":"<div><div>The rational construction of active sites on the inner surface of heterojunction can enhance the photocatalyst carrier separation efficiency and photocatalytic activity. Herein, the sulfur-deficient-rich WS₂ (Vs-WS₂) was selected and complexed with ZnCdS to construct a step-scheme (S-scheme) heterojunction (ZCSW-Vs) with good photocatalytic hydrogen evolution reaction (HER) activity. The optimized photocatalyst ZCSW-Vs exhibits excellent H₂ evolution rate of 84.63 mmol g⁻¹ h⁻¹, which is about 14-fold enhanced compared with that of ZCSW. The excellent photocatalytic activity is attributed to S vacancies optimizing the adsorption of hydrogen during the reaction process, according to characterization and density functional theory (DFT) calculations. In addition, the internal electric field of the ZCSW-Vs heterojunction significantly promotes the carrier-directed migration. This work provides insights into the design of efficient photocatalytic materials and the explanation of reaction mechanism through the synergistic effect of vacancies and S-scheme heterojunctions.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 8","pages":"Article 100960"},"PeriodicalIF":10.5,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148710148","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":"Ultramicroporous metal-incorporated HOF with tailored pore confinement for high-efficiency C2H2/CO2 sieving separation","authors":"Yingzhi He,&nbsp;Guangzu Xiong,&nbsp;Wenlei Yang,&nbsp;Yunjia Jiang,&nbsp;Jianbo Hu,&nbsp;Lingyao Wang,&nbsp;Chaoqun Bian,&nbsp;Yuanbin Zhang","doi":"10.1016/j.cjsc.2026.100942","DOIUrl":"10.1016/j.cjsc.2026.100942","url":null,"abstract":"<div><div>The separation of acetylene (C₂H₂) from carbon dioxide (CO₂) is of great importance in industrial chemical processes but remains challenging due to their similar physical properties. Hydrogen-bonded organic frameworks (HOFs) have emerged as promising adsorbents, yet balancing their structural stability with separation performance requires further optimization. Herein, we report two ionic metal-hybrid HOFs (ZNU-29 and ZNU-30) constructed via ligand modulation and metallization strategies. ZNU-30 features one-dimensional (1D) ultramicroporous channels (2.66 × 3.66 Ų) lined with H₂PO₄⁻ groups and electron-rich pyridine rings, creating a confined pore environment that combines molecular sieving and electrostatic interactions. At 298 K, ZNU-30 exhibits high C₂H₂ uptake (63.7 cm³/g) and significantly suppressed CO₂ adsorption (5.6 cm³/g), leading to an exceptional ideal adsorbed solution theory (IAST) selectivity of 121 for an equimolar C₂H₂/CO₂ mixture. Dynamic breakthrough experiments confirm its excellent practical separation capability. Density functional theory (DFT) calculations reveal that the superior performance originates from stronger binding affinity and lower diffusion barriers for C₂H₂ compared to CO₂, enabled by the precisely tailored pore geometry and electronegative pore environment. This work offers an effective strategy for designing stable and highly selective metal-hybrid HOFs for challenging gas separations.</div></div>","PeriodicalId":10151,"journal":{"name":"结构化学","volume":"45 8","pages":"Article 100942"},"PeriodicalIF":10.5,"publicationDate":"2026-08-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"148710088","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}