Selective CO<sub>2</sub>-to-HCOOH Electroreduction on Graphdiyne-Supported Bimetallic Single-Cluster Catalysts
Bin Chen, Yafei Jiang, Hai Xiao, Jun Li
Abstract
The oxophilic elements may stabilize the O-intermediate in electrochemical CO 2 reduction reaction (eCO 2 RR), yet their applications for formic acid (HCOOH) production may be limited by the Sabatier principle. Here we explore the bimetallic M 1 Ti 3 (M = Ni, Pd, Pt, Cu, Ag, Au) single-cluster catalysts (SCCs) anchored on graphdiyne (GDY) for eCO 2 RR to produce HCOOH. First-principles calculations show that the M 1 Ti 3 /GDY SCCs prefer to activate and hydrogenate CO 2 to the *OCHO intermediate (*denotes the active site of the catalyst) due to the oxophilic Ti sites, while the M 1 site plays a key role in suppressing the adsorption of *H and tuning the adsorption of *OCHO and *HCOOH for the HCOOH production, which is attributed to the modulation of Ti–O bonding strength by the M 1 atom. We predict that the Au 1 Ti 3 /GDY SCC is an efficient electrocatalyst for the selective eCO 2 RR to produce HCOOH. The directions for further improvements for the selective eCO 2 RR to produce HCOOH are discussed.