Understanding Photocatalytic Activity Dependence on Node Topology in Ti-Based Metal–Organic Frameworks
Understanding Photocatalytic Activity Dependence on Node Topology in Ti-Based Metal–Organic Frameworks
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DOI：
10.1021/acsmaterialslett.2c01115
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发表时间：
2023-04
影响因子：
11.4
通讯作者：
Nikita Kolobov;A. Zaki;Katarzyna Świrk;P. Maity;L. Garzón‐Tovar;G. Angeli;A. Dikhtiarenko;G. Delahay;P. Trikalitis;A. Emwas;A. Cadiau;O. Mohammed;Christopher H. Hendon;K. Adil;J. Gascón
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作者：
Nikita Kolobov;A. Zaki;Katarzyna Świrk;P. Maity;L. Garzón‐Tovar;G. Angeli;A. Dikhtiarenko;G. Delahay;P. Trikalitis;A. Emwas;A. Cadiau;O. Mohammed;Christopher H. Hendon;K. Adil;J. Gascón
尽管开发更高效的Ti基金属有机框架（MOF）光催化剂的动力，但MIL-125-NH 2仍然是基准，并且仅提供了少数设计原则来改善光催化性能。Ti M0 F中的连接体官能化已经显示通过关闭电子带隙而使得能够在可见光下进行光致变色，从而显著改善电荷载流子寿命。受限于已知的Ti基MOFs，节点核性和拓扑结构对光催化活性的作用尚不清楚。在这里，我们报告了一种新的MOF，ICGM-1，一种具有1D Ti-O棒的3D连接框架。光催化析氢揭示了显着的活性差异，我们只归因于节点的几何形状。使用时间分辨光谱和DFT计算，我们将这些差异归因于微妙的电子和几何性质，为Ti-MOF光催化剂的开发铺平了道路。
Despite the drive to develop more efficient Ti-based metal–organic framework (MOF) photocatalysts, MIL-125-NH2is still the benchmark, and only a few design principles have been offered to improve photocatalytic performance. Linker functionalization in Ti MOFs has been shown to enable photocatalysis under visible light by closing the electronic band gap, significantly improving charge carrier lifetimes. Limited by known Ti-based MOFs, the role of node nuclearity and topology on photocatalytic activity remains unclear. Here, we report a new MOF, ICGM-1, a 3D-connected framework featuring 1D Ti–O rods. Photocatalytic hydrogen evolution reveals a significant difference in activity, which we attribute solely to node geometry. Using time-resolved spectroscopy and DFT calculations, we ascribe these differences to subtle electronic and geometric properties, paving the way for the development of Ti-MOF photocatalysts.