Surface Selenium Coating Promotes Selective Methanol-to-Formate Electrooxidation on Ni3Se4 Nanoparticles

Yong Zhang; Rong Liu; Yi Ma; Ning Jian; Huan Ge; Huiyan Pan; Yu Zhang; Chaoqi Zhang; Yongliang Liu; Jie Deng; Luming Li; Jun Zhao; Jing Yu; Andreu Cabot; Junshan Li

doi:10.1021/acs.inorgchem.4c03996

Surface Selenium Coating Promotes Selective Methanol-to-Formate Electrooxidation on Ni₃Se₄ Nanoparticles

Inorg Chem. 2024 Nov 20. doi: 10.1021/acs.inorgchem.4c03996. Online ahead of print.

Authors

Yong Zhang^{1

2}, Rong Liu^{1

3}, Yi Ma^{1

2}, Ning Jian^{1

2}, Huan Ge^{1

2}, Huiyan Pan⁴, Yu Zhang⁵, Chaoqi Zhang⁶, Yongliang Liu^{1

2}, Jie Deng², Luming Li², Jun Zhao⁷, Jing Yu⁸, Andreu Cabot^{8

9}, Junshan Li^{1

2}

Affiliations

¹ School of Mechanical Engineering, Chengdu University, Chengdu 610106, China.
² Institute for Advanced Study, Chengdu University, Chengdu 610106, China.
³ School of Preclinical Medicine, Chengdu University, Chengdu 610106, China.
⁴ School of Biological and Chemical Engineering, Nanyang Institute of Science and Technology, Nanyang 473004, China.
⁵ Department of Materials Science and Engineering, Pennsylvania State University, University Park, Pennsylvania 16802, United States.
⁶ College of Materials Science and Engineering, Fuzhou University, Fuzhou, Fujian 350108, China.
⁷ Hebei Key Laboratory of Photoelectric Control on Surface and Interface, College of Science, Hebei University of Science and Technology, Shijiazhuang 050018, China.
⁸ Catalonia Institute for Energy Research - IREC, Sant Adrià de Besòs, 08930 Barcelona, Catalonia, Spain.
⁹ ICREA, Pg. Lluís Companys 23, 08010 Barcelona, Catalonia, Spain.

PMID: 39565610
DOI: 10.1021/acs.inorgchem.4c03996

Abstract

In the quest to replace fossil fuels and reduce carbon dioxide emissions, developing energy technologies based on clean catalytic processes is fundamental. However, the cost-effectiveness of these technologies strongly relies on the availability of efficient catalysts made of abundant elements. Herein, this study presents a one-step hydrothermal method to obtain a series of Ni₃Se₄ nanoparticles with a layer of amorphous selenium on their surface. When employed as electrocatalysts for the methanol oxidation reaction (MOR), the optimized proper surface Se-coated Ni₃Se₄ nanoparticles exhibit a high current density of 160 mA cm^-2 at 1.6 V, achieving a high methanol-to-formate Faradaic efficiency above 97.8% and excellent stability with less than 20% current decay after an 18 h chronoamperometry test. This excellent performance is rationalized using density functional theory calculations, which unveil that the electrochemical recombination of SeO_x results in a reduction of the energy barrier for the dehydrogenation of methanol during the MOR process.