Liu Lifang, Du Shiwen, Guo Xiangyang, Xiao Yejun, Yin Zixi, Yang Nengcong, Bao Yunfeng, Zhu Xunjin, Jin Shengye, Feng Zhaochi, Zhang Fuxiang
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, The Collaborative Innovation Centre of Chemistry for Energy Materials (iChEM), Dalian National Laboratory for Clean Energy, Chinese Academy of Sciences, Zhongshan Road 457, Dalian 116023, China.
University of Chinese Academy of Sciences, Beijing 100049, China.
J Am Chem Soc. 2022 Feb 16;144(6):2747-2754. doi: 10.1021/jacs.1c12179. Epub 2022 Feb 2.
Development of water-stable metal-organic frameworks (MOFs) for promising visible-light-driven photocatalytic water splitting is highly desirable but still challenging. Here we report a novel p-type nickel-based MOF single crystal (Ni-TBAPy-SC) and its exfoliated nanobelts (Ni-TBAPy-NB) that can bear a wide range of pH environment in aqueous solution. Both experimental and theoretical results indicate a feasible electron transfer from the HTBAPy ligand (light-harvesting center) to the Ni-O cluster node (catalytic center), on which water splitting to produce hydrogen can be efficiently driven free of cocatalyst. Compared to the single crystal, the exfoliated two-dimensional (2D) nanobelts show more efficient charge separation due to its shortened charge transfer distance and remarkably enhanced active surface areas, resulting in 164 times of promoted water reduction activity. The optimal H evolution rate on the nanobelt reaches 98 μmol h (ca. 5 mmol h g) showing benchmarked apparent quantum efficiency (AQE) of 8.0% at 420 nm among water-stable MOFs photocatalysts.
开发用于有前景的可见光驱动光催化水分解的水稳定金属有机框架（MOF）是非常可取的，但仍然具有挑战性。在此，我们报道了一种新型的p型镍基MOF单晶（Ni-TBAPy-SC）及其剥离的纳米带（Ni-TBAPy-NB），它们能够在水溶液中承受广泛的pH环境。实验和理论结果均表明，从HTBAPy配体（光捕获中心）到Ni-O簇节点（催化中心）存在可行的电子转移，在该节点上可以在无共催化剂的情况下有效驱动水分解产生氢气。与单晶相比，剥离的二维（2D）纳米带由于其缩短的电荷转移距离和显著增强的活性表面积而表现出更有效的电荷分离，从而使水还原活性提高了164倍。纳米带上的最佳析氢速率达到98 μmol h（约5 mmol h g），在水稳定的MOF光催化剂中，在420 nm处显示出8.0%的基准表观量子效率（AQE）。
