Catalytic Potential of Post‐Transition Metal Doped Graphene‐Based Single‐Atom Catalysts for the CO₂ Electroreduction Reaction

Abstract

Catalysts are required to ensure electrochemical reduction of CO2 to fuels proceeds at industrially acceptable rates and yields. As such, highly active and selective catalysts must be developed. Herein, a density functional theory study of p‐block element and noble metal doped graphene‐based single‐atom catalysts in two defect sites for the electrochemical reduction of CO2 to CO and HCOOH is systematically undertaken. It is found that on all of the systems considered, the thermodynamic product is HCOOH. Pb/C3, Pb/N4 and Sn/C3 are identified as having the lowest overpotential for HCOOH production while Al/C3, Al/N4, Au/C3 and Ga/C3 are identified as having the potential to form higher order products due to the strength of binding of adsorbed HCOOH.

Recent Advances in Electrochemical, Photochemical, and Photoelectrochemical Reduction of CO2 to C2+ Products

“…[85,103,105,143] In addition, Ni single atom catalysts are receiving a lot of attention for ECRR converting CO 2 into CO. [144][145][146] Analyzing the characteristics of boron-and single atom-based catalysts for ECRR, it can be seen that they are MOF structured catalysts in which B, P, or transition metal exists in the carbon structure. [100,105,143,[147][148][149] Furthermore, electrocatalysts in which dual-metals atom exists in a carbon structure or 3D carbon structure are fabricated and used for electrochemical reactions. [150,151] If two active sites are applied to the CO 2 ECRR study by combining the carbon structure and transition metal phosphide (TMP) catalysts, the production of C 2+ can be expected.…”

Composite interfaces of g-C3N4 fragments loaded on a Cu substrate for CO2 reduction

“…The hydrogen evolution reaction (HER) is well known as a competitive reaction vs. CO 2 RR, which reduces the efficiency and selection of CO 2 RR. There are two main ways to evaluate the competition between CO 2 RR and HER in the theoretical study: (1) comparing DG* H with DG* OCHO /DG* COOH , 58,59 and (2) using the difference in limiting potentials for the CO 2 RR and HER (U L (CO 2 )-U L (H 2 )). 48,49 For the first method, if the values of DG* H are more negative than DG* OCHO or DG* COOH , HER is more competitive.…”

Recent advances of single-atom catalysts in CO2conversion

“…By contrast, Ga/C 3 , Al/N 4 , Al/C 3 , and Au/C 3 were recognized to generate controllable products because of the sufficiently strongly binding of HCOOH. 288…”