Engineering polyhedral high entropy oxide with high-index facets via mechanochemistry-assisted strategy for efficient oxidative desulfurization

Chang Deng; Peiwen Wu; Hongping Li; Haonan Zhu; Yanhong Chao; Duanjian Tao; Ziran Chen; Mingqing Hua; Jixing Liu; Jianjun Liu; Wenshuai Zhu

doi:10.1016/j.jcis.2022.09.052

Engineering polyhedral high entropy oxide with high-index facets via mechanochemistry-assisted strategy for efficient oxidative desulfurization

J Colloid Interface Sci. 2023 Jan;629(Pt B):569-580. doi: 10.1016/j.jcis.2022.09.052. Epub 2022 Sep 15.

Authors

Chang Deng¹, Peiwen Wu², Hongping Li¹, Haonan Zhu¹, Yanhong Chao³, Duanjian Tao⁴, Ziran Chen⁵, Mingqing Hua⁶, Jixing Liu¹, Jianjun Liu¹, Wenshuai Zhu⁷

Affiliations

¹ School of Chemistry and Chemical Engineering, Institute for Energy Research, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, China.
² School of Chemistry and Chemical Engineering, Institute for Energy Research, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, China. Electronic address: wupeiwen@ujs.edu.cn.
³ School of Chemistry and Chemical Engineering, Institute for Energy Research, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, China; College of Chemical Engineering and Environment, State Key Laboratory of Heavy Oil Processing, China University of Petroleum-Beijing, Beijing 102249, China.
⁴ College of Chemistry and Chemical Engineering, Jiangxi Normal University, Nanchang 330022, China.
⁵ Department of Architecture and Environment Engineering, Sichuan Vocational and Technical College, Suining, Sichuan 629000, China.
⁶ School of Chemistry and Chemical Engineering, Institute for Energy Research, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, China. Electronic address: huamq840710@163.com.
⁷ School of Chemistry and Chemical Engineering, Institute for Energy Research, Jiangsu University, 301 Xuefu Road, Zhenjiang 212013, China; College of Chemical Engineering and Environment, State Key Laboratory of Heavy Oil Processing, China University of Petroleum-Beijing, Beijing 102249, China. Electronic address: zhuws@ujs.edu.cn.

PMID: 36179577
DOI: 10.1016/j.jcis.2022.09.052

Abstract

High entropy oxides are promising catalysts for numerous catalytic oxidation processes with oxygen as the oxidant. However, most of them often show bulk morphologies, which hinders the full exposure of active sites. In this work, a unique 26-faceted polyhedral high entropy oxide MnNiCuZnCoO_x-1000 (P-HEO) with highly active site exposure is fabricated via a mechanochemistry-assisted strategy. By employing such a strategy, the supersaturation of P-HEO during the crystal growth process is effectively reduced to form high-index facets, which is proved to be beneficial to the formation of high-index facets. Characterization results indicate that more oxygen vacancies are generated in P-HEO compared with the bulk counterparts. Density functional theory calculations reveal that the high-index facets {-211} can facilitate adsorption and activation of O₂ because of the higher adsorption energy -2.23 eV compared with that of (111) surfaces (-1.79 eV), which induces significantly enhanced activity for organic sulfides oxidation. Interestingly, the synthesized P-HEO with high-index facets shows a 98.4% removal rate of dibenzothiophene from model oil within 8 h at 120 °C, which is much higher than that of the bulk counterparts (33.5%).

Keywords: High entropy oxides; High-index facets; Oxidative desulfurization; Oxygen vacancies.