Lan Guangxu, Li Zhe, Veroneau Samuel S, Zhu Yuan-Yuan, Xu Ziwan, Wang Cheng, Lin Wenbin
Department of Chemistry , The University of Chicago , 929 E 57th Street , Chicago , Illinois 60637 , United States.
College of Chemistry and Chemical Engineering, iCHEM, State Key Laboratory of Physical Chemistry of Solid Surface , Xiamen University , Xiamen 361005 , People's Republic of China.
J Am Chem Soc. 2018 Oct 3;140(39):12369-12373. doi: 10.1021/jacs.8b08357. Epub 2018 Sep 19.
Metal-organic layers (MOLs), a free-standing monolayer version of two-dimensional metal-organic frameworks (MOFs), have emerged as a new class of 2D materials for many potential applications. Here we report the design of a new photosensitizing MOL, Hf-Ru, based on Hf secondary building units (SBUs) and [Ru(bpy)] (bpy = 2,2'-bipyridine) derived dicarboxylate ligands. After modifying the SBU surface of Hf-Ru with M(bpy)(CO)X (M = Re and X = Cl or M = Mn and X = Br) derived capping molecules through carboxylate exchange reactions, the resultant Hf-Ru-Re and Hf-Ru-Mn MOLs possess both [Ru(bpy)] photosensitizers and M(bpy)(CO)X catalysts for efficient photocatalytic CO reduction. The proximity of the MOL skeleton to the capping ligands (1-2 nm) facilitates electron transfer from the reduced photosensitizer [Ru(bpy)] to M(bpy)(CO)X (M = Re, Mn) catalytic centers, resulting in CO reduction turnover numbers of 8613 under artificial visible light and of 670 under sunlight. MOLs thus represent a novel platform to assemble multifunctional materials for studying artificial photosynthesis.
金属有机层（MOLs）是二维金属有机框架（MOFs）的一种独立单层形式，已成为一类具有许多潜在应用的新型二维材料。在此，我们报道了一种基于铪二级构筑单元（SBUs）和[Ru(bpy)]（bpy = 2,2'-联吡啶）衍生的二羧酸配体设计的新型光敏MOL，即Hf-Ru。通过羧酸酯交换反应，用M(bpy)(CO)X（M = Re且X = Cl或M = Mn且X = Br）衍生的封端分子修饰Hf-Ru的SBU表面后，所得的Hf-Ru-Re和Hf-Ru-Mn MOLs同时具备[Ru(bpy)]光敏剂和M(bpy)(CO)X催化剂，用于高效光催化CO还原。MOL骨架与封端配体的接近程度（1-2纳米）有助于电子从还原的光敏剂[Ru(bpy)]转移至M(bpy)(CO)X（M = Re、Mn）催化中心，在人工可见光下CO还原周转数为8613，在阳光下为670。因此，MOLs代表了一个用于组装研究人工光合作用的多功能材料的新型平台。
