双金属金属有机骨架：探索路易斯酸位点以进行二氧化碳转化,Small

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双金属金属有机骨架：探索路易斯酸位点以进行二氧化碳转化
Small ( IF 13.0 ) Pub Date : 2016-02-22 , DOI: 10.1002/smll.201503741
Ruyi Zou _{1,

2,

3} , Pei-Zhou Li _{1,

3} , Yong-Fei Zeng _{1,

3} , Jia Liu _{3,

4} , Ruo Zhao ₄ , Hui Duan ₁ , Zhong Luo ₁ , Jin-Gui Wang ₁ , Ruqiang Zou _{3,

4} , Yanli Zhao _{1,

3,

5}

Affiliation

成功地将二聚桨轮（Zn ₂（COO）₄）和四聚体（Zn ₄（O）（CO ₂）₆）两种类型的第二种构建单元（SBU）结合在一起，制成了高度多孔的金属有机框架（MOF）。通过三羧酸盐配体与Zn ^II离子的反应而组装。随后，利用构建的MOF对单晶至单晶金属阳离子交换进行了研究，结果表明Cu ^II和Co ^II可以选择性地将离子引入MOF，而不会影响原始骨架的结晶度。这种金属阳离子可交换的MOF为研究金属对所得MOF的气体吸附和催化活性的影响提供了有用的平台。虽然气体吸附实验表明，在相同条件下，Cu ^II和Co ^II交换的样品显示出与原始Zn ^II基MOF相当的CO ₂吸附能力，但催化研究CO ₂与环氧化物环加成反应成相关碳酸盐与Cu ^II和Co相比，基于^II的MOF具有最高的催化活性^II交换了。进行分子动力学模拟以进一步证实这些构建的MOF对CO ₂化学固定在碳酸盐上的催化性能。这项研究揭示了金属交换如何影响MOF的固有性质。

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Bimetallic Metal‐Organic Frameworks: Probing the Lewis Acid Site for CO2 Conversion

A highly porous metal‐organic framework (MOF) incorporating two kinds of second building units (SBUs), i.e., dimeric paddlewheel (Zn₂(COO)₄) and tetrameric (Zn₄(O)(CO₂)₆), is successfully assembled by the reaction of a tricarboxylate ligand with Zn^II ion. Subsequently, single‐crystal‐to‐single‐crystal metal cation exchange using the constructed MOF is investigated, and the results show that Cu^II and Co^II ions can selectively be introduced into the MOF without compromising the crystallinity of the pristine framework. This metal cation‐exchangeable MOF provides a useful platform for studying the metal effect on both gas adsorption and catalytic activity of the resulted MOFs. While the gas adsorption experiments reveal that Cu^II and Co^II exchanged samples exhibit comparable CO₂ adsorption capability to the pristine Zn^II‐based MOF under the same conditions, catalytic investigations for the cycloaddition reaction of CO₂ with epoxides into related carbonates demonstrate that Zn^II‐based MOF affords the highest catalytic activity as compared with Cu^II and Co^II exchanged ones. Molecular dynamic simulations are carried out to further confirm the catalytic performance of these constructed MOFs on chemical fixation of CO₂ to carbonates. This research sheds light on how metal exchange can influence intrinsic properties of MOFs.

更新日期：2016-02-22

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