Unravelling the adsorption and electroreduction performance of CO2 and N2 over defective and B, P, Si-doped C3Ns: a DFT study

Dandan Wang; Xueting Liu; Huiru Yang; Ziang Zhao; Yucheng Liu; Xin Qu; Lihua Yang; Ming Feng; Zaicheng Sun

doi:10.1039/d3cp02106h

Unravelling the adsorption and electroreduction performance of CO₂ and N₂ over defective and B, P, Si-doped C₃Ns: a DFT study

Phys Chem Chem Phys. 2023 Jun 28;25(25):16952-16961. doi: 10.1039/d3cp02106h.

Authors

Dandan Wang¹, Xueting Liu¹, Huiru Yang¹, Ziang Zhao¹, Yucheng Liu¹, Xin Qu¹, Lihua Yang¹, Ming Feng¹, Zaicheng Sun²

Affiliations

¹ Key Laboratory of Functional Materials Physics and Chemistry of Ministry of Education, College of Physics, Jilin Normal University, Changchun 130103, China. mingfeng@jlnu.edu.cn.
² Center of Excellence for Environmental Safety and Biological Effects, Beijing Key Lab for Green Catalysis and Separation, Department of Chemistry, Faculty of Environment and Life, Beijing University of Technology, 100 Pingleyuan, Beijing 100124, China. sunzc@bjut.edu.cn.

PMID: 37326588
DOI: 10.1039/d3cp02106h

Abstract

Two-dimensional carbon-based materials have great potential for electrocatalysis. Herein, we screen 12 defective and doped C₃N nanosheets by evaluating their CO₂RR and NRR activity and selectivity vs. the HER based on density functional theory calculations. The calculation results suggest that all 12 C₃Ns can enhance CO₂ adsorption and activation. And P_N-V_C-C₃N is the best electrocatalyst for the CO₂RR towards HCOOH with U_L = -0.17 V, which is much more positive than most of the reported values. B_N-C₃N and P_N-C₃N are also good electrocatalysts that promote the CO₂RR towards HCOOH (U_L = -0.38 V and -0.46 V). Moreover, we find that Si_C-C₃N can reduce CO₂ to CH₃OH, adding an alternative option to the limited catalysts available for the CO₂RR to CH₃OH. Furthermore, B_C-V_C-C₃N, B_C-V_N-C₃N, and Si_C-V_N-C₃N are promising electrocatalysts for the HER with |ΔG_H*| ≤ 0.30 eV. However, only three C₃Ns of B_C-V_C-C₃N, Si_C-V_N-C₃N, and Si_C-V_C-C₃N can slightly improve N₂ adsorption. And none of the 12 C₃Ns are found to be suitable for the electrocatalytic NRR because all the Δe_NNH* values are larger than the corresponding ΔG_H* values. The high performance of C₃Ns in the CO₂RR stems from the altered structure and electronic properties, which result from the introduction of vacancies and doping elements into C₃N. This work identifies suitable defective and doped C₃Ns for excellent performance in the electrocatalytic CO₂RR, which will inspire relevant experimental studies to further explore C₃Ns for electrocatalysis.