Chen Hai-Hang, Ji Yongfei, Fan Ting
School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510641, P. R. China.
School of Chemistry and Chemical Engineering, Guangzhou University, Guangzhou 510006, P. R. China.
Phys Chem Chem Phys. 2022 Oct 27;24(41):25347-25355. doi: 10.1039/d2cp02671f.
Designing highly active and earth-abundant oxygen evolution reaction (OER) electrocatalysts for electrochemical water splitting remains a challenge. Recently, Cl-doped CuO has emerged as a very promising non-noble-metal electrocatalyst candidate for the OER. However, the mechanism of the OER catalyzed by Cl-doped CuO has not been explored systematically. Herein, a comprehensive density functional theory (DFT) study is employed to study the role of Cl doping comparing the OER on pure and Cl-doped CuO surfaces with/without Cu vacancies. Our results reveal that Cl doping increases the adsorption ability of CuO(111) by providing an excess electron, while a Cu vacancy decreases its adsorption ability by changing the geometric structure of the adsorption sites and the electronic structures. Cl-CuO(111) ( = 0.58 V) and V-Cl-CuO(111) ( = 0.46 V) have comparable or even better OER activity than those of widely used OER electrocatalysts such as the IrO catalyst ( = 0.56 V). It is facile to have a Cu vacancy when CuO(111) is doped with Cl because of a large strain introduced by Cl doping. Thus, V-Cl-CuO(111) should be the most feasible catalyst for the OER catalyzed by Cl-doped CuO material. The dual role of Cl doping is that it not only increases the OER activity but also helps to form a Cu vacancy. The results show that CuO(111) activity can be greatly enhanced electronic and geometric structure modulation, which is helpful for the design of more efficient CuO-based catalysis.
设计用于电化学水分解的高活性且储量丰富的析氧反应（OER）电催化剂仍然是一项挑战。最近，Cl掺杂的CuO已成为一种非常有前途的用于OER的非贵金属电催化剂候选物。然而，Cl掺杂的CuO催化OER的机理尚未得到系统研究。在此，采用全面的密度泛函理论（DFT）研究来研究Cl掺杂的作用，比较有无Cu空位的纯CuO和Cl掺杂的CuO表面上的OER。我们的结果表明，Cl掺杂通过提供一个额外电子来提高CuO(111)的吸附能力，而Cu空位则通过改变吸附位点的几何结构和电子结构来降低其吸附能力。Cl-CuO(111)（ = 0.58 V）和V-Cl-CuO(111)（ = 0.46 V）具有与广泛使用的OER电催化剂（如IrO催化剂， = 0.56 V）相当甚至更好的OER活性。当CuO(111)被Cl掺杂时，由于Cl掺杂引入的大应变，很容易产生Cu空位。因此，V-Cl-CuO(111)应该是Cl掺杂的CuO材料催化OER最可行的催化剂。Cl掺杂的双重作用是它不仅提高了OER活性，还有助于形成Cu空位。结果表明，通过电子和几何结构调制可以大大提高CuO(111)的活性，这有助于设计更高效的基于CuO的催化剂。
