Yan Zhi-Hao, Ma Bo, Li Shu-Rong, Liu Junxue, Chen Rong, Du Ming-Hao, Jin Shengye, Zhuang Gui-Lin, Long La-Sheng, Kong Xiang-Jian, Zheng Lan-Sun
Collaborative Innovation Center of Chemistry for Energy Materials, State Key Laboratory of Physical Chemistry of Solid Surface and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen 361005, China.
State Key Laboratory of Molecular Reaction Dynamics and Collaborative Innovation Center of Chemistry for Energy Materials, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, China.
Sci Bull (Beijing). 2019 Jul 30;64(14):976-985. doi: 10.1016/j.scib.2019.05.014. Epub 2019 May 18.
Photocatalytic reduction of CO to CO is a promising strategy for reducing atmospheric CO levels and storing solar radiation as chemical energy. Here, we demonstrate that a molecular catalyst [Ni(bpet)(HO)] successfully encapsulated into a highly robust and visible-light responsive metal-organic framework (Ru-UiO-67) to fabricate composite catalysts for photocatalytic CO reduction. The composite Ni@Ru-UiO-67 photocatalysts show efficient visible-light-driven CO reduction to CO with a TON of 581 and a selectivity of 99% after 20-h illumination, because of the facile electron transfer from Ru-photosensitizer to Ni(II) active sites in Ni@Ru-UiO-67 system. The mechanistic insights into photoreduction of CO have been studied based on thermodynamical, electrochemical, and spectroscopic investigation, together with density functional theory (DFT) calculations. This work shows that encapsulating molecular catalyst into photoactive MOF highlights opportunities for designing efficient, stable and recyclable photocatalysts.
光催化将CO还原为CO是降低大气中CO水平并将太阳能辐射储存为化学能的一种有前景的策略。在此，我们证明了一种分子催化剂[Ni(bpet)(HO)]成功封装到一种高度稳健且对可见光有响应的金属有机框架（Ru-UiO-67）中，以制备用于光催化CO还原的复合催化剂。复合Ni@Ru-UiO-67光催化剂在光照20小时后显示出高效的可见光驱动的CO还原为CO，TON为581，选择性为99%，这是因为在Ni@Ru-UiO-67体系中，电子能够从Ru光敏剂轻松转移到Ni(II)活性位点。基于热力学、电化学和光谱研究以及密度泛函理论（DFT）计算，对CO光还原的机理进行了深入研究。这项工作表明，将分子催化剂封装到光活性MOF中为设计高效、稳定和可回收的光催化剂提供了机会。
