Copper Dimer Anchored in g‐CN Monolayer as an Efficient Electrocatalyst for CO₂ Reduction Reaction: A Computational Study

Abstract

Electrocatalytic CO 2 reduction (CO 2 RR) into value-added energy carriers is of utmost importance due to rising emissions of CO 2 and depleting energy resource. The search and design of effective, stable, and low-cost electrocatalysts are crucial but face huge challenges. Here, the potential of copper dimer anchored in g-CN (Cu 2 @CN) monolayer as electrocatalyst for CO 2 RR is systematically evaluated by means of density functional theory calculations. The computational results indicate that the Cu 2 @CN monolayer possesses superior catalytic activity for the conversion of CO 2 to HCOOH and C 2 H 4 with low limiting potential (−0.16 and −0.52 V, respectively), outperforming the corresponding single-atom counterpart (Cu@CN). Considering the myriad of unexplored dimers anchored in/on g-CN monolayer and their potential catalytic applications, this work provides a useful guidance for future studies.

Transition-metal-atom-pairs deposited on g-CN monolayer for nitrogen reduction reaction: Density functional theory calculations

“…The corresponding lattice parameter is 7.12 Å, and the calculated band gap is 3.22 eV (Fig. S1), which matches well with the experimental data and DFT results [27,38]. In addition, each of the two nitrogen atoms face each other at a distance of 5.46 Å, which is slightly smaller than that of the C2N nanosheet (5.52 Å).…”

Structure-Performance Descriptors and the Role of the Axial Oxygen Atom on M–N4–C Single-Atom Catalysts for Electrochemical CO2 Reduction

“…As depicted in Figure 7a The experimentally synthesized 2D porous graphite-CN material (g-CN) could anchor one or two transition metal atoms, making it being efficient electrocatalysts. 47,72,86,87 To further validate the reliability of the descriptor, we studied the CO 2 RR process of the above 23 transition metal atoms supported on a g-CN monolayer. The values of descriptor φ for the above SACs are calculated and listed in Tables S12 and S13 and Figure S24.…”

Computational Screening of Single and Di-Atom Catalysts for Electrochemical CO2 Reduction

“…Two-dimensional (2D) materials have in the past decade emerged as a promising class of catalysts with unique geometries. − However, for electrocatalytic conversion of CO 2 to C 1 and C 2 products, pristine surfaces of some of the 2D materials such as graphene and graphitic-C 3 N 4 are found to be inert and the introduction of dopants, defect states, or edge sites are needed to activate for electrocatalysis. − Embedding single transition metal atoms on nitrogen-doped defected graphene (MNC) surfaces has been found as efficient electrocatalysts for CO 2 R. − While CO 2 * adsorption is the limiting step for transition and coinage metal surfaces over relevant potentials, on the single atom catalysts (SACs), either the CO 2 * adsorption or COOH* formation is identified as the rate limiting step . Furthermore, the single metal dopants show greater surface-adsorbate dipole–field interactions, due to their narrow d -bands.…”