Active Sites in Copper-Based Metal-Organic Frameworks: Understanding Substrate Dynamics, Redox Processes, and Valence-Band Structure
Active Sites in Copper-Based Metal-Organic Frameworks: Understanding Substrate Dynamics, Redox Processes, and Valence-Band Structure
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DOI：
10.1021/acs.jpcc.5b08053
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发表时间：
2015-12-10
影响因子：
3.7
通讯作者：
Shustova, Natalia B.
中科院分区：
文献类型：
--
作者：
Duke, Audrey S.;Dolgopolova, Ekaterina A.;Shustova, Natalia B.
我们已经开发了一种综合的方法，结合合成，X射线光电子能谱（XPS）的研究，和理论计算的活性不饱和金属网站（UMS）在铜基金属有机框架（MOFs）的调查。具体地，在MOP金属节点处实现了Cu+2到Cu+1的大量还原。引入混合价铜位点导致价带结构的显著变化和费米边缘附近态密度的增加，从而改变了铜基框架的电子性质。混合价态的MOFs的发展也允许调谐的选择性吸附结合作为UMS氧化态的函数。所提出的研究可能会显著影响MOF在多相催化和气体净化中的应用，并预示着控制典型绝缘MOF材料电导率的新途径。
We have developed an integrated approach that combines synthesis, X-ray photoelectron spectroscopy (XPS) studies, and theoretical calculations for the investigation of active unsaturated metal sites (UMS) in copper-based metal organic frameworks (MOFs). Specifically, extensive reduction of Cu+2 to Cu+1 at the MOP metal nodes was achieved. Introduction of mixed valence copper sites resulted in significant changes in the valence band structure and an increased density of states near the Fermi edge, thereby altering the electronic properties of the copper-based framework. The development of mixed-valence MOFs also allowed tuning of selective adsorbate binding as a function of the UMS oxidation state. The presented studies could significantly impact the use of MOFs for heterogeneous catalysis and gas purification as well as foreshadow a new avenue for controlling the conductivity of typically insulating MOF materials.