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学者姓名:李建荣

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Unlocking the potential: strategic synthesis of a previously predicted pyrazolate-based stable MOF with unique clusters and high catalytic activity SCIE
期刊论文 | 2024 , 15 (35) , 14425-14430 | CHEMICAL SCIENCE
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Abstract :

The metal-organic framework (MOF) constructed from [Co4Pz8] clusters (Pz = pyrazolate) and 1,3,5-tris(pyrazolate-4-yl) benzene (BTP3-) ligands was structurally predicted many years ago, and expected to be a promising candidate for various applications owing to its unique clusters and highly open 3D framework structure. However, this MOF has not been experimentally prepared yet, despite extensive efforts were made. In this work, we present the successful construction of this MOF, hereinafter referred to as BUT-124(Co), by adopting a two-step synthesis strategy, involving the initial construction of a template framework (BUT-124(Cd)) followed by a post-synthetic metal metathesis process. The effects of various cobalt sources and solvents were systematically investigated, and an innovative stepwise metathesis strategy was employed to optimize the exchange rates and the porosity of the material. BUT-124(Co) demonstrates high catalytic activity in the oxygen evolution reaction (OER), achieving a competitive performance with an overpotential of 393 mV at a current density of 10 mA cm-2, and also affords remarkable long-term stability during potentiostatic electrolysis in 1 M KOH solution, surpassing the durability of many benchmark catalysts. This work not only introduces a novel MOF material with promising properties but also exemplifies a strategic synthesis approach for pyrazolate-based MOFs, paving the way for advancements in diverse application fields. By a two-step synthesis strategy, a previously predicted MOF was experimentally constructed, which shows excellent stability in strong basic aqueous solutions and high catalytic performance in oxygen evolution reactions.

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GB/T 7714 Li, Xiang-Yu , Zhao, Yan-Long , Chen, Su-Nan et al. Unlocking the potential: strategic synthesis of a previously predicted pyrazolate-based stable MOF with unique clusters and high catalytic activity [J]. | CHEMICAL SCIENCE , 2024 , 15 (35) : 14425-14430 .
MLA Li, Xiang-Yu et al. "Unlocking the potential: strategic synthesis of a previously predicted pyrazolate-based stable MOF with unique clusters and high catalytic activity" . | CHEMICAL SCIENCE 15 . 35 (2024) : 14425-14430 .
APA Li, Xiang-Yu , Zhao, Yan-Long , Chen, Su-Nan , Wang, Kecheng , Wang, Shengjun , Xie, Lin-Hua et al. Unlocking the potential: strategic synthesis of a previously predicted pyrazolate-based stable MOF with unique clusters and high catalytic activity . | CHEMICAL SCIENCE , 2024 , 15 (35) , 14425-14430 .
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Recovery of High-Purity SF6 from Humid SF6/N2 Mixture within a Co(II)-Pyrazolate Framework SCIE
期刊论文 | 2024 , 146 (28) , 19303-19309 | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
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Sulfur hexafluoride (SF6) is extensively employed in the power industry. However, its emissions significantly contribute to the greenhouse effect. The direct recovery of high purity SF6 from industrial waste gases would benefit its sustainable use, yet this represents a considerable challenge. Herein, we report the enrichment of SF6 from SF6/N-2 mixtures via adsorptive separation in a stable Co(II)-pyrazolate MOF BUT-53 (BUT: Beijing University of Technology), which features dynamic molecular traps. BUT-53 exhibits an excellent SF6 adsorption uptake of 2.82 mmol/g at 0.1 bar and 298 K, as well as an unprecedented SF6/N-2 (10:90) selectivity of 2485. Besides, the remarkable SF6/N-2 selectivity of BUT-53 enables recovery of high purity (>99.9%) SF6 from a low concentration (10%) mixture through a breakthrough experiment. The excellent SF6/N-2 separation efficiency was also well maintained under humid conditions (RH = 90%) over multiple cycles. Molecular simulation, single-crystal diffraction, and adsorption kinetics studies elucidate the associated adsorption mechanism and water tolerance.

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GB/T 7714 Zhang, Xin , Zhao, Yan-Long , Li, Xiang-Yu et al. Recovery of High-Purity SF6 from Humid SF6/N2 Mixture within a Co(II)-Pyrazolate Framework [J]. | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY , 2024 , 146 (28) : 19303-19309 .
MLA Zhang, Xin et al. "Recovery of High-Purity SF6 from Humid SF6/N2 Mixture within a Co(II)-Pyrazolate Framework" . | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY 146 . 28 (2024) : 19303-19309 .
APA Zhang, Xin , Zhao, Yan-Long , Li, Xiang-Yu , Bai, Xuefeng , Chen, Qiancheng , Li, Jian-Rong . Recovery of High-Purity SF6 from Humid SF6/N2 Mixture within a Co(II)-Pyrazolate Framework . | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY , 2024 , 146 (28) , 19303-19309 .
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Reversible Co(II)-Co(III) Transformation in a Family of Metal-Dipyrazolate Frameworks SCIE
期刊论文 | 2024 | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
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Transformation between oxidation states is widespread in transition metal coordination chemistry and biochemistry, typically occurring in solution. However, air-induced oxidation in porous crystalline solids with retention of crystallinity is rare due to the dearth of materials with high structural stability that are inherently redox active. Herein, we report a new family of such materials, four isostructural cobalt-pyrazolate frameworks of face-centered cubic, fcu, topology, fcu-L-Co, that are sustained by Co8 molecular building blocks (MBBs) and dipyrazolate ligands, L. fcu-L-Co were observed to spontaneously transform from Co(II)8 to Co(III)8 MBBs in air with retention of crystallinity, marking the first such instance in metal-organic frameworks (MOFs). This transformation can also be achieved through water vapor sorption cycling, heating, or chemical oxidation. The reverse reactions were conducted by exposure of fcu-L-Co(III) to aqueous hydrazine. fcu-L-Co(II) exhibited high gravimetric water vapor uptakes of 0.55-0.68 g(-1) at 30% relative humidity (RH), while in fcu-L-Co(III) the inflection point shifted to lower RH and framework stability improved. Insight into the transformation between fcu-L-Co(II) and fcu-L-Co(III) was gained from single crystal X-ray diffraction and in situ spectroscopy. Overall, the crystal engineering approach we adopted has afforded a new family of MOFs that exhibit cobalt redox chemistry in a confined space coupled with high porosity.

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GB/T 7714 Kong, Xiang-Jing , He, Tao , Bezrukov, Andrey A. et al. Reversible Co(II)-Co(III) Transformation in a Family of Metal-Dipyrazolate Frameworks [J]. | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY , 2024 .
MLA Kong, Xiang-Jing et al. "Reversible Co(II)-Co(III) Transformation in a Family of Metal-Dipyrazolate Frameworks" . | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2024) .
APA Kong, Xiang-Jing , He, Tao , Bezrukov, Andrey A. , Darwish, Shaza , Si, Guang-Rui , Zhang, Yong-Zheng et al. Reversible Co(II)-Co(III) Transformation in a Family of Metal-Dipyrazolate Frameworks . | JOURNAL OF THE AMERICAN CHEMICAL SOCIETY , 2024 .
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Rare-Earth Metal-Organic Framework with Nonplanar Porphyrin Groups for High-Efficiency Photocatalysis SCIE
期刊论文 | 2024 , 63 (16) , 7412-7421 | INORGANIC CHEMISTRY
WoS CC Cited Count: 1
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Abstract :

Nonplanar porphyrins play crucial roles in many biological processes and chemical reactions as catalysts. However, the preparation of artificial nonplanar porphyrins suffers from complicated organic syntheses. Herein, we present a new rare-earth porphyrinic metal-organic framework (RE-PMOF), BUT-233, which is a three-dimensional (3D) framework structure with the flu topology consisting of 4-connected BBCPPP-Ph ligands H4BBCPPP-Ph = 5 ',5 ''''-(10,20-diphenylporphyrin-5,15-diyl)bis([1,1 ':3 ',1 ''-terphenyl]-4,4 '' dicarboxylic acid) and 8-connected Eu-6 clusters. Noteworthily, the porphyrin cores of the BBCPPP-Ph ligands in BUT-233 are nonplanar with a ruffle-like conformation. In contrast, the porphyrin core in the free ligand H4BBCPPP-Ph is in a nearly ideally planar conformation, as confirmed by its single-crystal structure. BUT-233 is microporous with 6-8 angstrom pores and a Brunauer-Emmett-Teller (BET) surface area of 649 m(2)/g, as well as high stability in common solvents. The MOF was used as a photocatalyst for the oxidation degradation of a chemical warfare agent model molecule CEES (CEES = 2-chloroethyl ethyl sulfide) under the light-emitting diode (LED) irradiation and an O-2 atmosphere at room temperature. CEES was almost completely converted into its nontoxic light-oxidized product CEESO (CEESO = 2-chloroethyl ethyl sulfoxide) in only 5 min with t(1/2) = 2 min (t(1/2): half-life). Moreover, the toxic deep-oxidized product 2-chloroethyl ethyl sulfone (CEESO2) was not detected. The catalytic activity of BUT-233 was high in comparison with those of some previously reported MOF catalysts. The results of photo/electrochemical property studies suggested that the high catalytic activity of BUT-233 was benefited from the presence of nonplanar porphyrin rings on its pore surface.

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GB/T 7714 Wu, Wei , He, Tao , Zhang, Xin et al. Rare-Earth Metal-Organic Framework with Nonplanar Porphyrin Groups for High-Efficiency Photocatalysis [J]. | INORGANIC CHEMISTRY , 2024 , 63 (16) : 7412-7421 .
MLA Wu, Wei et al. "Rare-Earth Metal-Organic Framework with Nonplanar Porphyrin Groups for High-Efficiency Photocatalysis" . | INORGANIC CHEMISTRY 63 . 16 (2024) : 7412-7421 .
APA Wu, Wei , He, Tao , Zhang, Xin , Xie, Lin-Hua , Si, Guang-Rui , Xie, Yabo et al. Rare-Earth Metal-Organic Framework with Nonplanar Porphyrin Groups for High-Efficiency Photocatalysis . | INORGANIC CHEMISTRY , 2024 , 63 (16) , 7412-7421 .
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Enhanced Catalytic Activity of Crystalline Phosphorus Nanosheets Fabricated via Solvothermal Phase Transformation SCIE
期刊论文 | 2024 , 63 (25) , 11860-11869 | INORGANIC CHEMISTRY
WoS CC Cited Count: 1
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The newly reported crystalline phosphorus nanosheets (cryst-P NSs) exhibit promising features for industrial applications, including outstanding air-water stability and facile large-scale production. However, their complex crystallization impedes a priori tailoring. Herein, the temporal evolution of cryst-P NSs was investigated with the optimized synthesis parameters. The occurrence of self-assembly and solid-state rearrangement unveiled the existence of an intermediate phase as the bulk crystalline precursor and the predominance of nonclassical crystallization pathway(s). With the upgraded synthesis protocol simultaneously strengthening the merits of cryst-P NSs, their catalytic performances were evaluated in various electro- and/or photocatalytic reactions spanning hydrogen and oxygen evolution, full water splitting, CO2 reduction, and organic pollutant decomposition. Superior catalytic activities and orders of magnitude longer lifetimes were consistently discerned compared with the widely employed black phosphorus nanosheets with similar size and thickness. The exciting discoveries in both fundamental crystallization and catalytic applications drastically thrust the comprehension of elemental phosphorus, shedding light on the encouraging capabilities of solvothermal synthesis strategies in the design and systematic tailoring of phosphorus materials.

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GB/T 7714 Batur, Jenaidullah , Duan, Zunbin , Jin, Ruipeng et al. Enhanced Catalytic Activity of Crystalline Phosphorus Nanosheets Fabricated via Solvothermal Phase Transformation [J]. | INORGANIC CHEMISTRY , 2024 , 63 (25) : 11860-11869 .
MLA Batur, Jenaidullah et al. "Enhanced Catalytic Activity of Crystalline Phosphorus Nanosheets Fabricated via Solvothermal Phase Transformation" . | INORGANIC CHEMISTRY 63 . 25 (2024) : 11860-11869 .
APA Batur, Jenaidullah , Duan, Zunbin , Jin, Ruipeng , Li, Rui , Xie, Yabo , Yu, Xue-Feng et al. Enhanced Catalytic Activity of Crystalline Phosphorus Nanosheets Fabricated via Solvothermal Phase Transformation . | INORGANIC CHEMISTRY , 2024 , 63 (25) , 11860-11869 .
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Reticular Rare-Earth Metal-Organic Frameworks with High Stability and Defective Sites: Post-Functionalization for Hydrogen Peroxide Detection SCIE
期刊论文 | 2024 , 6 (5) , 1977-1983 | ACS MATERIALS LETTERS
WoS CC Cited Count: 1
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Rare-earth metal-organic frameworks (RE-MOFs), which are composed of polynuclear RE clusters of high connection, are gaining prominent attention in MOF chemistry, due to their tremendous structure diversity. The vulnerability of RE-MOFs to moisture and acid/alkaline conditions, however, has limited their modification and application. Herein, based on MOF reticular chemistry, we utilize a ditopic linker of distinct spatial configuration to construct a series of RE(III)-MOFs with bcu topology, BUT-47(M) (M = Tb3+, Y3+, Yb3+ and Tm3+; BUT = Beijing University of Technology), featuring the rare 8-connected RE6 clusters and defective sites. BUT-47(Tb) shows high chemical stability in a wide pH range (2-12). The functionalized BUT-47(Tb) through post-modification in the defective RE6 clusters demonstrates to be capable of selective fluorescence detection of hydrogen peroxide. This work not only highlights the strength of reticular chemistry principles in designing stable RE-MOFs with intriguing structures but also offers smart platforms to tailor properties for specific applications.

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GB/T 7714 Zhao, Jia-Teng , Si, Guang-Rui , He, Tao et al. Reticular Rare-Earth Metal-Organic Frameworks with High Stability and Defective Sites: Post-Functionalization for Hydrogen Peroxide Detection [J]. | ACS MATERIALS LETTERS , 2024 , 6 (5) : 1977-1983 .
MLA Zhao, Jia-Teng et al. "Reticular Rare-Earth Metal-Organic Frameworks with High Stability and Defective Sites: Post-Functionalization for Hydrogen Peroxide Detection" . | ACS MATERIALS LETTERS 6 . 5 (2024) : 1977-1983 .
APA Zhao, Jia-Teng , Si, Guang-Rui , He, Tao , Kong, Xiang-Jing , Li, Jian-Rong . Reticular Rare-Earth Metal-Organic Frameworks with High Stability and Defective Sites: Post-Functionalization for Hydrogen Peroxide Detection . | ACS MATERIALS LETTERS , 2024 , 6 (5) , 1977-1983 .
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Evaluation of Open-Source Large Language Models for Metal-Organic Frameworks Research SCIE
期刊论文 | 2024 , 64 (13) , 4958-4965 | JOURNAL OF CHEMICAL INFORMATION AND MODELING
WoS CC Cited Count: 6
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Along with the development of machine learning, deep learning, and large language models (LLMs) such as GPT-4 (GPT: Generative Pre-Trained Transformer), artificial intelligence (AI) tools have been playing an increasingly important role in chemical and material research to facilitate the material screening and design. Despite the exciting progress of GPT-4 based AI research assistance, open-source LLMs have not gained much attention from the scientific community. This work primarily focused on metal-organic frameworks (MOFs) as a subdomain of chemistry and evaluated six top-rated open-source LLMs with a comprehensive set of tasks including MOFs knowledge, basic chemistry knowledge, in-depth chemistry knowledge, knowledge extraction, database reading, predicting material property, experiment design, computational scripts generation, guiding experiment, data analysis, and paper polishing, which covers the basic units of MOFs research. In general, these LLMs were capable of most of the tasks. Especially, Llama2-7B and ChatGLM2-6B were found to perform particularly well with moderate computational resources. Additionally, the performance of different parameter versions of the same model was compared, which revealed the superior performance of higher parameter versions.

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GB/T 7714 Bai, Xuefeng , Xie, Yabo , Zhang, Xin et al. Evaluation of Open-Source Large Language Models for Metal-Organic Frameworks Research [J]. | JOURNAL OF CHEMICAL INFORMATION AND MODELING , 2024 , 64 (13) : 4958-4965 .
MLA Bai, Xuefeng et al. "Evaluation of Open-Source Large Language Models for Metal-Organic Frameworks Research" . | JOURNAL OF CHEMICAL INFORMATION AND MODELING 64 . 13 (2024) : 4958-4965 .
APA Bai, Xuefeng , Xie, Yabo , Zhang, Xin , Han, Honggui , Li, Jian-Rong . Evaluation of Open-Source Large Language Models for Metal-Organic Frameworks Research . | JOURNAL OF CHEMICAL INFORMATION AND MODELING , 2024 , 64 (13) , 4958-4965 .
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Expanding the Structural Topologies of Rare-Earth Porphyrinic Metal-Organic Frameworks through Ligand Modulation SCIE
期刊论文 | 2023 | ACS APPLIED MATERIALS & INTERFACES
WoS CC Cited Count: 7
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Expanding the structural diversity of porphyrinic metal-organic frameworks (PMOFs) is essential to develop functional materials with novel properties or enhanced performance in different applications. Herein, we establish a strategy to construct rare-earth (RE) PMOFs with unprecedented topology via rational functionalization of porphyrinic ligands. By introducing phenyl/pyridyl groups to the meso-positions of the porphyrin core, the symmetries and connectivities of the ligands are tuned, and three RE-PMOFs (BUT 224/-225/-226) with new topologies are successfully obtained. In addition, BUT-225(Co), with both the Lewis basic and acidic sites, exhibits enhanced CO2 uptake and higher catalytic activity for the cycloaddition of CO2 and epoxides under mild conditions. This work reveals that the RE-PMOFs with novel topologies can be rationally designed and constructed through ligand functionalization, which provides insights into the construction of tailored PMOFs for various applications.

Keyword :

heterogeneous catalysis heterogeneous catalysis porphyrin porphyrin rare-earth metals rare-earth metals metal-organic frameworks metal-organic frameworks topology topology

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GB/T 7714 Wu, Wei , Xie, Yabo , Lv, Xiu-Liang et al. Expanding the Structural Topologies of Rare-Earth Porphyrinic Metal-Organic Frameworks through Ligand Modulation [J]. | ACS APPLIED MATERIALS & INTERFACES , 2023 .
MLA Wu, Wei et al. "Expanding the Structural Topologies of Rare-Earth Porphyrinic Metal-Organic Frameworks through Ligand Modulation" . | ACS APPLIED MATERIALS & INTERFACES (2023) .
APA Wu, Wei , Xie, Yabo , Lv, Xiu-Liang , Xie, Lin-Hua , Zhang, Xin , He, Tao et al. Expanding the Structural Topologies of Rare-Earth Porphyrinic Metal-Organic Frameworks through Ligand Modulation . | ACS APPLIED MATERIALS & INTERFACES , 2023 .
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金属有机框架材料对非二氧化碳温室气体捕捉研究进展
期刊论文 | 2023 , 74 (1) , 365-379 | 化工学报
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随着全球暖化研究的深入,非二氧化碳温室气体(非二气体)日益受到重视,其温升效应大,寿命长,能够带来巨大的温室效应,因而成为近年来的研究热点.其中对非二气体的高效捕捉是目前面临的难点和新挑战.多孔材料吸附捕捉是一种低能耗的气体捕集分离技术,关键在于高效的吸附剂开发.金属-有机框架材料(MOFs)因其结构多样,孔道的高度可调控性能,以及具有丰富的开放金属位点等特点为非二气体的分离和捕捉提供了新的机遇.以此为主题,总结了近年来MOF材料在非二气体分离方面的研究成果,分析了各材料的分离机理与性能,展望了未来MOFs材料在非二气体分离领域的挑战与机遇.

Keyword :

吸附容量 吸附容量 吸附捕集 吸附捕集 选择性 选择性 非二氧化碳温室气体 非二氧化碳温室气体 金属有机框架材料 金属有机框架材料

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GB/T 7714 李沐紫 , 贾国伟 , 赵砚珑 et al. 金属有机框架材料对非二氧化碳温室气体捕捉研究进展 [J]. | 化工学报 , 2023 , 74 (1) : 365-379 .
MLA 李沐紫 et al. "金属有机框架材料对非二氧化碳温室气体捕捉研究进展" . | 化工学报 74 . 1 (2023) : 365-379 .
APA 李沐紫 , 贾国伟 , 赵砚珑 , 张鑫 , 李建荣 . 金属有机框架材料对非二氧化碳温室气体捕捉研究进展 . | 化工学报 , 2023 , 74 (1) , 365-379 .
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Highly Efficient Propyne/Propylene Separation in a "Flexible-Robust" and Hydrolytically Stable Cu(II)-MOF SCIE
期刊论文 | 2023 , 62 (31) , 12329-12336 | INORGANIC CHEMISTRY
WoS CC Cited Count: 6
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Propyne/propylene separation is importantin the petrochemicalindustry but challenging due to their similar physical propertiesand close molecular sizes. Metal-organic frameworks (MOFs)are a class of promising adsorbents for light hydrocarbon separations.Among them, the so-called "flexible-robust" MOFs combinethe advantages of flexibility and rigidity in structure and couldshow enhanced gas separation selectivity as well as improved gas uptakeat low pressure. Interpenetrated MOFs offer a platform to explorethe "flexible-robust" feature of MOFs based on theirsubnetwork displacement in the process of gas adsorption. Herein,we present two hydrolytically stable MOFs (BUT-308 and BUT-309) with interpenetrated structures and fascinating propyne/propyleneseparation performance. BUT-308 is composed of interpenetrated2D Cu(BDC-NH2)BPB layers (H2BDC-NH2 = 2-aminobenzene-1,4-dicarboxylic acid; BPB = 1,4-bis(4-pyridyl)benzene),while BUT-309 consists of twofold interpenetrated 3Dpillared-layer Cu-2(BDC-NH2)(2)(BPB-CF3) nets (BPB-CF3 = 2-trifluoromethyl-1,4-bis(4-pyridyl)benzene).Gas adsorption measurements showed that BUT-309 was a"flexible-robust" adsorbent with multistep adsorptionisotherms for C3H4 rather than C3H6 at a wide temperature range. The guest-dependent pore-openingbehavior endows BUT-309 with high potential in the C3H4/C3H6 separation. The C3H4 adsorption measurements of BUT-309 at 273-323 K showed that the lowering of the temperatureinduced the pore-opening action at lower pressure. Column breakthroughexperiments further confirmed the capability of BUT-309 for the efficient removal of C3H4 from a C3H4/C3H6 binary gas, and theC(3)H(6) processing capacity at 273 K (15.7 cm(3) g(-1)) was higher than that at 298 K (35.2cm(3) g(-1)). This work shows a rare exampleof "flexible-robust" MOFs and demonstrated its highpotential for C3H4/C3H6 separation. A hydrolytically stable Cu-MOF(BUT-309) consisting of twofold interpenetrated 3D pillared-layerCu(2)(BDC-NH2)(2)(BPB-CF3)netswas constructed. Gas adsorption measurements showed that BUT-309 was a "flexible-robust" adsorbent with multistep adsorptionisotherms for C3H4 rather than C3H6 at a wide temperature range. The guest-dependent pore-openingbehavior endows BUT-309 with high potential in C3H4/C3H6 separation. Columnbreakthrough experiments further confirmed the capability of BUT-309 for the efficient removal of C3H4 from a C3H4/C3H6 binarygas.

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GB/T 7714 Xu, Ming-Ming , Liu, Yu-Hui , Zhang, Xin et al. Highly Efficient Propyne/Propylene Separation in a "Flexible-Robust" and Hydrolytically Stable Cu(II)-MOF [J]. | INORGANIC CHEMISTRY , 2023 , 62 (31) : 12329-12336 .
MLA Xu, Ming-Ming et al. "Highly Efficient Propyne/Propylene Separation in a "Flexible-Robust" and Hydrolytically Stable Cu(II)-MOF" . | INORGANIC CHEMISTRY 62 . 31 (2023) : 12329-12336 .
APA Xu, Ming-Ming , Liu, Yu-Hui , Zhang, Xin , Lv, Jia-Ao , Zhao, Rui-Chao , Xie, Lin-Hua et al. Highly Efficient Propyne/Propylene Separation in a "Flexible-Robust" and Hydrolytically Stable Cu(II)-MOF . | INORGANIC CHEMISTRY , 2023 , 62 (31) , 12329-12336 .
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