IF 10.5 4区化学

结构化学 Pub Date : 2026-08-01 Epub Date: 2026-04-14 DOI: 10.1016/j.cjsc.2026.100946

Yingjie Li, Hailong Hu, Aoqi Wang, Jingru Huang, Shiqi Fu, Zongyin Gao, Shuo Tao, Yalin Zhang, Qingde Zhang, Haitao Wang, Xianqiang Huang

{"title":"Hetero-motif POM molecular junctions enable tandem olefin epoxidation and CO2 fixation","authors":"Yingjie Li, Hailong Hu, Aoqi Wang, Jingru Huang, Shiqi Fu, Zongyin Gao, Shuo Tao, Yalin Zhang, Qingde Zhang, Haitao Wang, Xianqiang Huang","doi":"10.1016/j.cjsc.2026.100946","DOIUrl":"10.1016/j.cjsc.2026.100946","url":null,"abstract":"<div><div>Olefin epoxidation and CO<sub>2</sub> 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)<sub>4</sub>]<sub>3</sub>(VW<sub>5</sub>O<sub>19</sub>)<sub>2</sub>·2(1-eIM) (<strong>PCF-1</strong>) and [Cu(1-iPIM)<sub>4</sub>]<sub>3</sub>[VW<sub>12</sub>O<sub>40</sub>]·(OH)<sub>3</sub> (<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 CO<sub>2</sub>. In catalytic tests, <strong>PCF-2</strong> exhibits superior performance in both reactions, giving yields of 88% for olefin epoxidation and 99% for CO<sub>2</sub> 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}

引用次数: 0

Sulfur-vacancy engineered SmCoO3/MnCdS S-scheme heterojunction for efficient photothermal-photocatalytic H2 evolution 硫空位工程SmCoO3/MnCdS S-scheme异质结用于高效光热-光催化析氢

IF 10.5 4区化学

结构化学 Pub Date : 2026-08-01 Epub Date: 2026-04-24 DOI: 10.1016/j.cjsc.2026.100965

Yuanjin He, Hao Yang, Qiwei Guo, Bo Zhou, Xuqiang Hao, Zhiliang Jin

{"title":"Sulfur-vacancy engineered SmCoO3/MnCdS S-scheme heterojunction for efficient photothermal-photocatalytic H2 evolution","authors":"Yuanjin He, Hao Yang, Qiwei Guo, Bo Zhou, Xuqiang Hao, 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 SmCoO<sub>3</sub>/MnCdS-Vs (SMCS) S-scheme heterojunction with photothermal effect was successfully constructed for PHE. The photothermal effect induced by SmCoO<sub>3</sub> can rapidly convert light energy into localized thermal energy, and significantly reduces the reaction energy barriers for H<sub>2</sub>O 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% SmCoO<sub>3</sub> achieves a maximum hydrogen evolution rate of 27.03 mmol g<sup>−1</sup> h<sup>−1</sup>, 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 H<sub>2</sub> production reaches 174 mmol g<sup>−1</sup> 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}

引用次数: 0

Recent progress on multi-synergistic charge-transfer strategies for efficient triplet up-conversion in narrowband MR-TADF emitters 窄带MR-TADF发射器中高效三重态上转换的多协同电荷转移策略研究进展

IF 10.5 4区化学

结构化学 Pub Date : 2026-08-01 Epub Date: 2026-04-09 DOI: 10.1016/j.cjsc.2026.100945

Zeng-Jiang Yue, Zheng-Yin Du, Xunwen Xiao, Xu-Feng Luo

{"title":"Recent progress on multi-synergistic charge-transfer strategies for efficient triplet up-conversion in narrowband MR-TADF emitters","authors":"Zeng-Jiang Yue, Zheng-Yin Du, Xunwen Xiao, 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}

引用次数: 0

Metal-incorporated polymeric resists with tunable lithographic performance via complex-specific design 通过复杂的特定设计，具有可调光刻性能的金属结合聚合物抗蚀剂

IF 10.5 4区化学

结构化学 Pub Date : 2026-08-01 Epub Date: 2026-04-13 DOI: 10.1016/j.cjsc.2026.100947

Xi Liang, Mei-Hua Xiong, Er-Xia Chen, Lu-Yao Hao, Jin-Xia Yang, Jian Zhang, Qipu Lin

{"title":"Metal-incorporated polymeric resists with tunable lithographic performance via complex-specific design","authors":"Xi Liang, Mei-Hua Xiong, Er-Xia Chen, Lu-Yao Hao, Jin-Xia Yang, Jian Zhang, 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}

引用次数: 0

Tuning effective conjugation via B←N orientation: High-mobility n-type isoindigo polymers for organic field-effect transistors 通过B←N取向调谐有效共轭：用于有机场效应晶体管的高迁移率N型等靛蓝聚合物

IF 10.5 4区化学

结构化学 Pub Date : 2026-08-01 Epub Date: 2026-04-06 DOI: 10.1016/j.cjsc.2026.100943

Jingshu Tian, Haofeng Sun, Jiarui Li, Cheng Wang, Kun Yang, Qinqi Zhou, Kai-Kai Liu, Maning Liu, Haichang Zhang

{"title":"Tuning effective conjugation via B←N orientation: High-mobility n-type isoindigo polymers for organic field-effect transistors","authors":"Jingshu Tian, Haofeng Sun, Jiarui Li, Cheng Wang, Kun Yang, Qinqi Zhou, Kai-Kai Liu, Maning Liu, 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 cm<sup>2</sup> V<sup>−1</sup> s<sup>−1</sup> in organic field-effect transistors,substantially exceeding that of <strong>P2</strong> (0.86 cm<sup>2</sup> V<sup>−1</sup> s<sup>−1</sup>). 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}

引用次数: 0

Spin-state switching driven by divergent structural evolutions in a 3D spin-crossover material 三维自旋交叉材料中发散结构演化驱动的自旋态切换

IF 10.5 4区化学

结构化学 Pub Date : 2026-08-01 Epub Date: 2026-04-04 DOI: 10.1016/j.cjsc.2026.100941

Meng-Ling Wu, Jun-Hui Liang, Yan-Ru Chen, Kang Chen, Ze-Yu Ruan, Si-Guo Wu, Wei-Zhao Cai, Ming-Liang Tong

{"title":"Spin-state switching driven by divergent structural evolutions in a 3D spin-crossover material","authors":"Meng-Ling Wu, Jun-Hui Liang, Yan-Ru Chen, Kang Chen, Ze-Yu Ruan, Si-Guo Wu, Wei-Zhao Cai, 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)<sub>2</sub>}<sub>2</sub>(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}

引用次数: 0

Synergistic modulation of steric hindrance and isomerization space for enhanced photo-regulated performance of metal-organic polyhedra 空间位阻和异构化空间协同调制增强金属有机多面体光调控性能

IF 10.5 4区化学

结构化学 Pub Date : 2026-08-01 Epub Date: 2026-04-21 DOI: 10.1016/j.cjsc.2026.100962

Shu Shi, Mu-Yi Xu, Yang Liu, Yu-Xia Li, Lin-Bing Sun

{"title":"Synergistic modulation of steric hindrance and isomerization space for enhanced photo-regulated performance of metal-organic polyhedra","authors":"Shu Shi, Mu-Yi Xu, Yang Liu, Yu-Xia Li, 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 C<sub>3</sub>H<sub>6</sub>. 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}

引用次数: 0

Defect-enhanced charge separation in ZnCdS/WS2 S-scheme heterojunctions: Engineering sulfur vacancies to facilitate photocatalytic H2 production ZnCdS/WS2 S-scheme异质结中缺陷增强电荷分离：工程硫空位促进光催化制氢

IF 10.5 4区化学

结构化学 Pub Date : 2026-08-01 Epub Date: 2026-04-20 DOI: 10.1016/j.cjsc.2026.100960

Tuo Guo, Guojing Hu, Jiaxin Liu, Li Chen, Guangmin Ren, Qingjie Guo

{"title":"Defect-enhanced charge separation in ZnCdS/WS2 S-scheme heterojunctions: Engineering sulfur vacancies to facilitate photocatalytic H2 production","authors":"Tuo Guo, Guojing Hu, Jiaxin Liu, Li Chen, Guangmin Ren, 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 WS<sub>2</sub> (Vs-WS<sub>2</sub>) 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 H<sub>2</sub> evolution rate of 84.63 mmol g<sup>−1</sup> h<sup>−1</sup>, 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}

引用次数: 0

Ultramicroporous metal-incorporated HOF with tailored pore confinement for high-efficiency C2H2/CO2 sieving separation 具有定制孔限制的超微孔金属复合HOF，用于高效C2H2/CO2筛分分离

IF 10.5 4区化学

结构化学 Pub Date : 2026-08-01 Epub Date: 2026-04-04 DOI: 10.1016/j.cjsc.2026.100942

Yingzhi He, Guangzu Xiong, Wenlei Yang, Yunjia Jiang, Jianbo Hu, Lingyao Wang, Chaoqun Bian, Yuanbin Zhang

{"title":"Ultramicroporous metal-incorporated HOF with tailored pore confinement for high-efficiency C2H2/CO2 sieving separation","authors":"Yingzhi He, Guangzu Xiong, Wenlei Yang, Yunjia Jiang, Jianbo Hu, Lingyao Wang, Chaoqun Bian, 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 (C<sub>2</sub>H<sub>2</sub>) from carbon dioxide (CO<sub>2</sub>) 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 Å<sup>2</sup>) lined with H<sub>2</sub>PO<sub>4</sub><sup>−</sup> 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 C<sub>2</sub>H<sub>2</sub> uptake (63.7 cm<sup>3</sup>/g) and significantly suppressed CO<sub>2</sub> adsorption (5.6 cm<sup>3</sup>/g), leading to an exceptional ideal adsorbed solution theory (IAST) selectivity of 121 for an equimolar C<sub>2</sub>H<sub>2</sub>/CO<sub>2</sub> 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 C<sub>2</sub>H<sub>2</sub> compared to CO<sub>2</sub>, 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}

引用次数: 0

Advances in copper-based catalysts for selective CO2 electroreduction to C1 and C2 products 铜基选择性CO2电还原制C1和C2产品催化剂的研究进展

IF 10.5 4区化学

结构化学 Pub Date : 2026-08-01 Epub Date: 2026-04-21 DOI: 10.1016/j.cjsc.2026.100944

Shen Wang, Yi Wei, Weijie Li, Chao Han

引用次数: 0

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