Insight into the Active Sites of N,P-Codoped Carbon Materials for Electrocatalytic CO2 Reduction

Jingsheng Zhou; Beibei An; Zhiyong Zhu; Li Wang; Jinglai Zhang

doi:10.1021/acs.inorgchem.2c00148

Insight into the Active Sites of N,P-Codoped Carbon Materials for Electrocatalytic CO₂ Reduction

Inorg Chem. 2022 Apr 25;61(16):6073-6082. doi: 10.1021/acs.inorgchem.2c00148. Epub 2022 Apr 12.

Authors

Jingsheng Zhou^{1

2

3}, Beibei An^{1

2

3}, Zhiyong Zhu^{1

2

3}, Li Wang^{1

2

3}, Jinglai Zhang^{1

2

3}

Affiliations

¹ Henan Province Engineering Research Center of Green Anticorrosion Technology for Magnesium Alloys, Henan University, Kaifeng, Henan 475004, PRChina.
² Henan Engineering Research Center of Corrosion and Protection for Magnesium Alloys, Henan University, Kaifeng, Henan 475004, PRChina.
³ College of Chemistry and Chemical Engineering, Henan University, Kaifeng, Henan 475004, PRChina.

PMID: 35412819
DOI: 10.1021/acs.inorgchem.2c00148

Abstract

Doping heteroatoms in carbon materials is a promising method to prepare the robust electrocatalysts for the carbon dioxide reduction reaction (CO₂RR), which is beneficial for sustainable energy storage and environmental remediation. However, the obscure recognition of active sites is the obstacle for further development of high-efficiency electrocatalysts, especially for the N,P-codoped carbon materials. Herein, a series of N,P-codoped carbon materials (CNP) is prepared with different N and P contents to explore the relationship between the N/P configuration and the CO₂RR activity. As compared with the N-doped carbon materials, the additional P doping is helpful to improve the activity. The optimum N,P-codoped carbon materials (CNP-900) achieve 80.8% CO Faradaic efficiency (FE_CO) at a mild overpotential of 0.44 V. On the basis of the X-ray photoelectron spectroscopy results, the suitable ratio between pyridinic N and graphitic N and the least P-N content are beneficial for CO₂RR. The density functional theory calculations further illustrate that two elementary steps to form *COOH and *CO in CO₂RR are determined by the graphitic N and pyridinic N configurations, respectively. The existence of the P-N configuration breaks the equilibrium between graphitic N and pyridinic N to suppress the activity.