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    张建军

    • 教授     博士生导师   硕士生导师
    • 性别:男
    • 毕业院校:南京大学
    • 学位:博士
    • 所在单位:化学学院
    • 学科:无机化学
    • 办公地点:化工综合楼D411
    • 联系方式:0411-84986036
    • 电子邮箱:zhangjj@dlut.edu.cn

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    Metal-ion-dependent, Solvent-mediated Structural Transformation and Simultaneous Partial Transmetalation of ansrsFramework into Desulfurization-efficient Co-Cu-HKUST-1

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    论文类型:期刊论文

    发表时间:2021-03-26

    发表刊物:ZEITSCHRIFT FUR ANORGANISCHE UND ALLGEMEINE CHEMIE

    卷号:646

    期号:17

    页面范围:1437-1443

    ISSN号:0044-2313

    关键字:Metal-organic framework; Metal-organic framework; Structural transformation; Metal-organic framework; Structural transformation; Transmetalation; Metal-organic framework; Structural transformation; Transmetalation; HKUST-1; Metal-organic framework; Structural transformation; Transmetalation; HKUST-1; Desulfurization

    摘要:[Co-2(BTC)(Cl)(DMA)(3)] (1) (BTC3-= benzene-1,3,5-tricarboxylate, DMA =N,N-dimethylacetamide) obtained from the reaction between Co(2+)and H3BTC in DMA features a three-dimensionalsrsframework built of 3-connected {Co-2(COO)(3)} as secondary building units and BTC(3-)as spacers. When exposed to DMA solution of Cu(NO3)(2),1was progressively transformed into the first heterometallic Co-Cu-HKUST-1 ([Co0.14Cu2.86(BTC)(2)]) (2) of such kind via unusually solvent-mediated structural transformation and simultaneous partial transmetalation. While the mechanism for such conversion is proposed based on systematic studies,2was revealed to be an equally efficient desulfurization adsorbent as the homometallic Cu-HKUST-1 in removing thiophene (0.142 mmol S per gram of adsorbent). However, when exposed to Zn(NO3)(2)solution in DMA for longer time,1retained its framework with limited metal-ion exchange, resulting in the formation of [Co1.93Zn0.07(BTC)(Cl)(DMA)(3)] (3). Possible reasons responsible for the formation of2and3through different routes could be due to the less solubility and more thermodynamic stability of2in comparison with those of1, and the different coordination geometries which Co2+, Zn(2+)and Cu(2+)prefer.