Single-Atom Catalysts for CO2 Electroreduction with Significant Activity and Selectivity Improvements
Authors: Back Seoin , Lim Juhyung , Kim Na-Young , Kim Yong-Hyun , Jung Yousung 
Published: February 2020

Single-atom catalyst (SAC) has an electronic structure that is very different from its bulk counterparts, and has shown unexpectedly high specific activity with a significant reduction of noble metal usages although physical origins of such performance enhancements are still poorly understood. Herein, by means of density functional theory calculations, we for the first time investigate the great potential of single atom catalyst for CO2 electroreduction applications. In particular, we study a single transition metal atom anchored on the defective graphene with single or double vacancies, denoted as M@sv-Gr or M@dv-Gr, where M are various transition metals, as a CO2 reduction catalyst. Many SACs are indeed shown to be highly selective for CO2 reduction reaction over a competitive H2 evolution reaction due to a favorable adsorption of carboxyl or formate over hydrogen on the catalysts. On the basis of free energies, we found that the Pt@dv-Gr catalyst shows a remarkable reduction in the limiting potential for CH3OH production compared to any existing catalysts, synthesized or predicted (Figure 1).
We focus on the Pt@dv-Gr to investigate the origin of improvement on the SACs compared to the transition metal. As shown in Figure 1, with the Pt@dv-Gr catalyst, all the intermediates are destabilized compared to those on Pt (211), but most importantly, the destabilization of *CO (0.98 eV) is much more noticeable than that of *CHO (0.42 eV), leading to a 0.49 V reduction in the limiting potential. We also observe that with SACs, the conventional scaling relation between the *CO binding and *CHO binding established for the bulk transition metal significantly deviates from linearity (Figure 2).
We discuss features of SACs which contribute to the breakdown of scaling relation between *CO and *CHO, namely, the lack of atomic ensemble for adsorbates binding and the metal-support interactions that lead to the electronic structures conducive to the catalysis.
Atomic Ensemble:
The optimized geometries of the bare catalysts are shown for Pt@dv-Gr and Pt (211) in Figure 3. One can see that, for Pt (211), two surface Pt atoms are involved in the *CO bonding while only one Pt atom is bonding with *CHO, leading to a large destabilization in the relative free energies when going from *CO to *CHO. On the other hand, for Pt@dv-Gr, only one Pt atom is utilized for both *CO and *CHO binding, resulting in a much more moderate destabilization in relative free energies compared to Pt (211). Thus, the lack of Pt ensemble in the Pt@dv-Gr is responsible for a significantly weaker binding of *CO on the Pt@dv-Gr compared to the Pt (211) surface.
Electronic Structure:
The strong metal-support interaction affects the electronic structure of a metal atom in the SACs greatly. In Figure 4A, the Pt 5d density of states (DOS) in Pt@dv-Gr shows a significant orbital overlap with the C 2p orbitals of the graphene. The electron density isosurfaces (Figure 4B) illustrate that electron clouds of four carbon atoms surrounding the Pt atom are significantly hybridized with the Pt atom. The differential charge density map (Figure 4C) between the defective graphene and Pt@dv-Gr also suggests that the Pt atom is positively charged by electron transfer from the Pt atom to the defective graphene support.
In this paper, we investigated the single atom catalysts (SACs) as a promising CO2 electroreduction catalyst using DFT calculations. The main findings of this work are as follows.
(i) By comparing the free energies of the initial protonation steps for the CRR and HER, we found that all SACs can selectively reduce CO2 rather than producing H2. In particular, the predicted limiting potential for Pt@dv-Gr (-0.27 V) for CH3OH production is considerably less negative than the conventional transition metal catalysts.
(ii) To understand the origin of the improvements in SACs, we investigated two aspects of the Pt@dv-Gr that affect the relative stability of *CO vs. *CHO. A one-fold bonding of *CO on Pt@dv-Gr due to a lack of atomic ensemble, as compared to the two-fold *CO bonding on the Pt (211) is responsible for the significant weakening of *CO binding on the Pt@dv-Gr.
(iii) We investigated the electronic structure of Pt atom in the SAC to find the origin of the deviation of SACs from the conventional scaling relation of transition metals, which arises from the d-band center theory. We suggest that the strong electronic interaction between the d-orbital of metal atom and the p-orbital of graphene is responsible for the different behavior from the transition metal surfaces, as evidenced by the electron transfer and the overlap in the DOS.

Figure 1