大连理工大学侯军刚团队报道了在半导体光阳极上设计单原子Ni-N4-O位用于高性能光电化学水分解。相关研究成果发表在2021年11月16日出版的国际知名学术期刊《美国化学会杂志》。

直接光电化学（PEC）分解水是一种很有前途的太阳能转换解决方案；然而，为了提高PEC的性能，存在一个迫切的瓶颈来解决固有电荷传输问题。

该文中，开发了一种通用的耦合策略，以设计原子分散的Ni-N4位点，并与在析氧助催化剂（OEC）和半导体光阳极之间结合的轴向氧原子（Ni-N4-O）进行协调，从而促进光生电子-空穴分离，提高PEC活性。该最先进的OEC/Ni-N4-O/BiVO4光阳极与可逆氢电极（vs RHE）相比，在1.23 V下表现出创纪录的6.0 mA cm^–2高光电流密度，约为BiVO4的3.97倍，实现了卓越的长期光稳定性。

通过X射线吸收精细结构分析和密度泛函理论计算，增强的PEC性能归因于OEC/BiVO4中单原子Ni-N4-O部分的构建，促进空穴转移，降低自由能垒，并加速反应动力学。该研究工作使人们能够开发一种有效的途径来设计和制造高效、稳定的光阳极，用于可行的PEC水分解应用。

附：英文原文

Title: Engineering Single-Atomic Ni-N4-O Sites on Semiconductor Photoanodes for High-Performance Photoelectrochemical Water Splitting

Author: Xiaomeng Zhang, Panlong Zhai, Yanxue Zhang, Yunzhen Wu, Chen Wang, Lei Ran, Junfeng Gao, Zhuwei Li, Bo Zhang, Zhaozhong Fan, Licheng Sun, Jungang Hou

Issue&Volume: November 16, 2021

Abstract: Direct photoelectrochemical (PEC) water splitting is a promising solution for solar energy conversion; however, there is a pressing bottleneck to address the intrinsic charge transport for the enhancement of PEC performance. Herein, a versatile coupling strategy was developed to engineer atomically dispersed Ni-N4 sites coordinated with an axial direction oxygen atom (Ni-N4-O) incorporated between oxygen evolution cocatalyst (OEC) and semiconductor photoanode, boosting the photogenerated electron–hole separation and thus improving PEC activity. This state-of-the-art OEC/Ni-N4-O/BiVO4 photoanode exhibits a record high photocurrent density of 6.0 mA cm–2 at 1.23 V versus reversible hydrogen electrode (vs RHE), over approximately 3.97 times larger than that of BiVO4, achieving outstanding long-term photostability. From X-ray absorption fine structure analysis and density functional theory calculations, the enhanced PEC performance is attributed to the construction of single-atomic Ni-N4-O moiety in OEC/BiVO4, facilitating the holes transfer, decreasing the free energy barriers, and accelerating the reaction kinetics. This work enables us to develop an effective pathway to design and fabricate efficient and stable photoanodes for feasible PEC water splitting application.

DOI: 10.1021/jacs.1c07391

Source: https://pubs.acs.org/doi/10.1021/jacs.1c07391