Zhang Lijun, Jin Zhiliang, Tsubaki Noritatsu
Department of Applied Chemistry, Graduate School of Engineering, University of Toyama, Gofuku 3190, Toyama 930-8555, Japan.
School of Chemistry and Chemical Engineering, North Minzu University, Yinchuan 750021, P. R. China.
ACS Appl Mater Interfaces. 2021 Nov 3;13(43):50996-51007. doi: 10.1021/acsami.1c14987. Epub 2021 Oct 22.
As a part of photocatalytic water splitting, the design of low-cost, high-activity catalysts plays an essential role in the development of photocatalytic water splitting. Metal oxides have the advantages of a wide range of sources, many varieties, and easy preparation. Doping engineering on their surface can construct new active sites and adjust their catalytic activity. In this work, a new strategy was developed through anion hybridization to regulate electron delocalization. Using one of the cobalt-based zeolitic imidazole skeletons (ZIF-67) as a precursor material, a two-step calcination method was used to prepare a P-doped CoO mixed anion composite photocatalyst. The hydrogen production rate of P@CoO is 39 times that of ZIF-67 and 6.8 times that of CoO. Through density functional theory (DFT) calculations, the electron delocalization state of the sample surface is predicted and the reaction energy barrier is reduced to promote the process of the hydrogen evolution reaction (HER). The special O(δ-)-Co(δ+)-P(δ-) surface bonding state promotes the bridging of isolated electronic states and provides active sites for the adsorption and activation of reaction substrates. The improved electron transport pathway and the synergy between the catalytic sites under the high electron transport rate are the main reasons for the enhanced photocatalytic hydrogen evolution activity. This strategy, including changing the surface bond state and optimizing the structure and composition of the catalyst not only provides a new method for preparing other MOF-derived nanomaterials with porous structures but also inspires the reasonable development of other MOF-based advanced photocatalysts.
作为光催化水分解的一部分，低成本、高活性催化剂的设计在光催化水分解的发展中起着至关重要的作用。金属氧化物具有来源广泛、种类繁多、易于制备的优点。在其表面进行掺杂工程可以构建新的活性位点并调节其催化活性。在这项工作中，通过阴离子杂化开发了一种新策略来调节电子离域。以一种钴基金属有机骨架（ZIF-67）作为前驱体材料，采用两步煅烧法制备了P掺杂的CoO混合阴离子复合光催化剂。P@CoO的产氢速率是ZIF-67的39倍，是CoO的6.8倍。通过密度泛函理论（DFT）计算，预测了样品表面的电子离域状态，并降低了反应能垒以促进析氢反应（HER）的进行。特殊的O(δ-)-Co(δ+)-P(δ-)表面键合状态促进了孤立电子态的桥连，并为反应底物的吸附和活化提供了活性位点。改善的电子传输途径以及在高电子传输速率下催化位点之间的协同作用是光催化析氢活性增强的主要原因。这种策略，包括改变表面键合状态以及优化催化剂的结构和组成，不仅为制备其他具有多孔结构的MOF衍生纳米材料提供了一种新方法，也为其他基于MOF的先进光催化剂的合理开发提供了启发。
