Enhancing Ru-Cl interaction via orbital hybridization effect in Ru0.4Sn0.3Ti0.3 electrode for efficient chlorine evolution

Dianzhi Zhang; Fei Xie; Haiming Gong; Tao Liu; Panyong Kuang; Jiaguo Yu

doi:10.1016/j.jcis.2023.12.028

Enhancing Ru-Cl interaction via orbital hybridization effect in Ru_0.4Sn_0.3Ti_0.3 electrode for efficient chlorine evolution

J Colloid Interface Sci. 2024 Mar 15:658:127-136. doi: 10.1016/j.jcis.2023.12.028. Epub 2023 Dec 12.

Authors

Dianzhi Zhang¹, Fei Xie¹, Haiming Gong¹, Tao Liu¹, Panyong Kuang², Jiaguo Yu³

Affiliations

¹ Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, 68 Jincheng Street, Wuhan 430078, China.
² Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, 68 Jincheng Street, Wuhan 430078, China. Electronic address: kuangpanyong@cug.edu.cn.
³ Laboratory of Solar Fuel, Faculty of Materials Science and Chemistry, China University of Geosciences, 68 Jincheng Street, Wuhan 430078, China. Electronic address: yujiaguo93@cug.edu.cn.

PMID: 38100969
DOI: 10.1016/j.jcis.2023.12.028

Abstract

Chlorine evolution reaction (CER) is a commercially valuable electrochemical reaction used at an industrial scale. However, oxygen evolution reaction (OER) during the electrolysis process inevitably leads to the decreased efficiency of CER. It is necessary to improve the selectivity of CER by minimizing or even eliminating the occurrence of OER. Herein, a ternary metal oxide (Ru_0.4Sn_0.3Ti_0.3) electrode was fabricated and employed as an active and robust anode for CER. The Ru_0.4Sn_0.3Ti_0.3 electrode exhibits an excellent CER performance in 6.0 M NaCl solution, with a low potential of 1.17 V (vs. saturated calomel electrode, SCE) at 200 mA cm^-2 current density, a high Cl₂ selectivity of over 90 %, and robust durability after consecutive operation for 160 h under 100 mA cm^-2. The maximum O₂-Cl₂ potential difference between OER and CER further demonstrates the high Cl₂ selectivity of Ru_0.4Sn_0.3Ti_0.3 electrode. Theoretical studies show that the strong Ru 3d-Ti 3d orbitals hybridization effect makes the d-band center (ε_d) of Ru 3d and Ti 3d orbitals positively and negatively shifted, respectively, endowing Ru site with enhanced Cl adsorption ability (i.e. enhanced Ru-Cl interaction) and Ru_0.4Sn_0.3Ti_0.3 electrode with superior CER activity. This work offers valuable insights into the development of advanced electrodes for CER in practical application.

Keywords: Chlorine evolution reaction; Orbital hybridization effect; Ru(0.4)Sn(0.3)Ti(0.3) electrode; Selectivity; d-band center.