Catalyzed activation of CO2 by a Lewis-base site in W–Cu–BTC hybrid metal organic frameworks
Catalyzed activation of CO2 by a Lewis-base site in W–Cu–BTC hybrid metal organic frameworks
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DOI：
10.1039/c2sc20521a
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发表时间：
2012-07
期刊：
影响因子：
8.4
通讯作者：
Qiuju Zhang;Lujie Cao;Baihai Li;Liang Chen
中科院分区：
文献类型：
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作者：
Qiuju Zhang;Lujie Cao;Baihai Li;Liang Chen
基于密度泛函（DFT）计算，通过将高活性W离子杂化到Cu 3（BTC）2（H2O）3（也称为Cu-BTC或HKUST-1，BTC = 1，3，5-三羧酸苯）骨架中，设计了基于金属有机骨架（MOF）的催化剂W-Cu-BTC。根据前线分子轨道理论，我们证明了杂化W-Cu结在活化CO2中起着关键作用。与大多数MOFs中开放金属位点的路易斯酸性质相反，W-Cu-BTC中暴露的W离子被鉴定为路易斯碱位点，由W离子向CO2的大量电子捐赠证明。动力学上，线性CO2分子可以很容易地弯曲，形成CO2-W复合物后，克服了一个可以忽略不计的激活势垒为0.09 eV。此外，我们提出了计算的红外光谱（IR）和X射线光谱（XPS）的参考，在未来的实验研究。
A metal–organic framework (MOF)-based catalyst W–Cu–BTC is designed by hybridizing highly active W ions into Cu3(BTC)2(H2O)3 (also known as Cu–BTC or HKUST-1, BTC = 1,3,5-tricarboxylate benzene) frameworks based on density functional (DFT) calculations. We show that the hybrid W–Cu node plays a pivotal role in activating CO2 according to frontier molecular orbital theory. In contrast to the Lewis-acid nature of open metal sites in most MOFs, the exposed W ion in W–Cu–BTC is identified as a Lewis-base site, evidenced by the substantial electron donation from W ion to CO2. Kinetically, the linear CO2 molecule can be readily bent by forming a CO2–W complex after overcoming a negligible activation barrier of 0.09 eV. In addition, we present calculated infrared spectra (IR) and X-Ray spectra (XPS) for reference in future experimental studies.