Uncovering the role of yttrium in a cerium-based binary oxide in the catalytic conversion of carbon dioxide and methanol to dimethyl carbonate

Yizhou Wang; Shuo Geng; Fei Liu; Mengqin Yao; Jun Ma; Jianxin Cao; Ziwei Li

doi:10.1016/j.jcis.2023.09.015

Uncovering the role of yttrium in a cerium-based binary oxide in the catalytic conversion of carbon dioxide and methanol to dimethyl carbonate

J Colloid Interface Sci. 2023 Dec 15;652(Pt B):1984-1993. doi: 10.1016/j.jcis.2023.09.015. Epub 2023 Sep 4.

Authors

Yizhou Wang¹, Shuo Geng¹, Fei Liu², Mengqin Yao¹, Jun Ma¹, Jianxin Cao³, Ziwei Li¹

Affiliations

¹ School of Chemistry and Chemical Engineering, Guizhou University, Guiyang, Guizhou 550025, PR China; Key Laboratory of Green Chemical and Clean Energy Technology, Guizhou University, Guiyang, Guizhou 550025, PR China; Engineering Research Center of Efficient Utilization for Industrial Waste, Guizhou University, Guiyang, Guizhou 550025, PR China.
² School of Chemistry and Chemical Engineering, Guizhou University, Guiyang, Guizhou 550025, PR China; Key Laboratory of Green Chemical and Clean Energy Technology, Guizhou University, Guiyang, Guizhou 550025, PR China; Engineering Research Center of Efficient Utilization for Industrial Waste, Guizhou University, Guiyang, Guizhou 550025, PR China. Electronic address: ce.feiliu@gzu.edu.cn.
³ School of Chemistry and Chemical Engineering, Guizhou University, Guiyang, Guizhou 550025, PR China; Key Laboratory of Green Chemical and Clean Energy Technology, Guizhou University, Guiyang, Guizhou 550025, PR China; Engineering Research Center of Efficient Utilization for Industrial Waste, Guizhou University, Guiyang, Guizhou 550025, PR China. Electronic address: jxcao@gzu.edu.cn.

PMID: 37690306
DOI: 10.1016/j.jcis.2023.09.015

Abstract

Cerium(IV) oxide (CeO₂)-based materials are effective catalysts for the synthesis of dimethyl carbonate (DMC) from carbon dioxide (CO₂) and methanol (CH₃OH). Herein, 5% Y-CeO₂ was synthesized by the co-precipitation method. It forms a solid solution structure, which leads to the highest concentration of oxygen vacancies. The Y-V_O-Ce active site created by Y³⁺ doping enhances the adsorption and activation of CO₂ based on moderately passivating CH₃OH adsorption. Consequently, 5% Y-CeO₂ exhibited the highest CH₃OH conversion rate of 0.8% and a DMC yield of 15 mmol⋅(g cat)^-1, which is 1.4 times of pure CeO₂ (reacting in a stainless-steel autoclave at 140 °C with a stirring speed of 1000 r⋅min^-1 and an initial pressure of 3.0 MPa for 2 h). An adsorption test and in situ diffuse reflectance infrared Fourier transform spectroscopy showed that 5% Y-CeO₂ could effectively inhibit the formation of triple-bonded methoxy species, and promote the formation of bidentate carbonate and bridged methoxy intermediates, which is conducive to the improvement of reaction activity.

Keywords: Competitive adsorption; Dimethyl carbonate; Oxygen vacancy; Solid solution structure; Y–CeO(2) binary oxide.