CO2 electroreduction by transition metal-embedded two-dimensional C3N: A theoretical study. Issue 43 (January 2021)

• Record Type: Journal Article
• Authors: Zhang, Jing; Xu, Tongshuai; Yuan, Di; Tian, Junlong; Ma, Dongwei
• Is Part Of: Journal of CO₂ utilization. Issue 43(2021)
• Publication Date: 2021-01
• Subjects: First-principles calculation -- Electrocatalytic CO2 reduction -- TM-C-N -- Single-atom catalyst; Carbon dioxide -- Periodicals; Carbon dioxide -- Environmental aspects -- Periodicals; Carbon dioxide mitigation -- Periodicals; Carbon dioxide; Carbon dioxide -- Environmental aspects; Carbon dioxide mitigation; Periodicals; 628.53205
• DOI: 10.1016/j.jcou.2020.101367
• Languages: English
• ISSNs: 2212-9820

Abstract

Graphical abstract: C3 N are predicted to be promising two-dimensional material platforms to realize transition-metal single-atom catalysts for efficiently electrocatalytic CO2 reduction. Highlights: The C3 N monolayers embedded with the TM single atoms at the C-C double vacancy (M-CC) have been evaluated for CO2 RR by using the first-principles calculation. All M-CCs exhibit high thermal stability, metallic conductivity, and excellent selectivity toward CO2 RR versus HER. Cu-, Co-, Fe-, and Mn-CC are identified as efficient candidates for the CO2 RR to produce HCOOH, CH2 O, CH3 OH, and CH4, respectively. The underlying mechanisms for the high activity have been revealed based on the electronic structure analyses. Abstract: Transition metal (TM) and nitrogen co-doped carbon (T M-N -C) materials have emerged as the promising single-atom catalyst (SAC) for the electrocatalytic CO2 reduction reaction (CO2 RR), for which the coordination environment of the anchored single atom plays an important role. Inspired by this, the C3 N monolayers embedded with the TM single atoms at the CC double vacancy, denoted as M-CC (MTi, V, Cr, Mn, Fe, Co, Ni, Cu, Mo, Ru, Rh, Pd, Ag, Os, Ir, Pt, and Au), have been evaluated for CO2 RR by using the first-principles calculation. We find that the M-CC SACs are of high stability and metallic conductivity, beneficial for the electron transport during the electrocatalytic process. More importantly, all M-CC have high selectivity toward CO2 RR versus the hydrogen evolution reaction. Especially, Cu-, Co-, Fe-, and Mn-CC have acceptable or ultra-low limiting potentials of −0.68, −0.48, −0.83, and −0.24 V to produce HCOOH, CH2 O, CH3 OH, and CH4, respectively. The catalytic activities of M-CC are correlated with the adsorption strength of the key intermediates, further rationalized by the bonding/antibonding population analysis. Our work proposes a new material platform to realize TM-C-N SACs for efficiently electrocatalytic CO2 RR, which could provide useful insights into the design of such catalysts.