Suppression of the Hydrogen Evolution Reaction Is the Key: Selective Electrosynthesis of Formate from CO2 over Porous In55Cu45 Catalysts.

Direct electrosynthesis of formate through CO2 electroreduction (denoted CO2RR) is currently attracting great attention because formate is a highly valuable commodity chemical that is already used in a wide range of applications (e.g., formic acid fuel cells, tanning, rubber production, preservatives, and antibacterial agents). Herein, we demonstrate highly selective production of formate through CO2RR from a CO2-saturated aqueous bicarbonate solution using a porous In55Cu45 alloy as the electrocatalyst. This novel high-surface-area material was produced by means of an electrodeposition process utilizing the dynamic hydrogen bubble template approach. Faradaic efficiencies (FEs) of formate production (FEformate) never fell below 90% within a relatively broad potential window of approximately 400 mV, ranging from -0.8 to -1.2 V vs the reversible hydrogen electrode (RHE). A maximum FEformate of 96.8%, corresponding to a partial current density of jformate = -8.9 mA cm-2, was yielded at -1.0 V vs RHE. The experimental findings suggested a CO2RR mechanism involving stabilization of the HCOO* intermediate on the In55Cu45 alloy surface in combination with effective suppression of the parasitic hydrogen evolution reaction. What makes this CO2RR alloy catalyst particularly valuable is its stability against degradation and chemical poisoning. An almost constant formate efficiency of ∼94% was maintained in an extended 30 h electrolysis experiment, whereas pure In film catalysts (the reference benchmark system) showed a pronounced decrease in formate efficiency from 82% to 50% under similar experimental conditions. The identical location scanning electron microscopy approach was applied to demonstrate the structural stability of the applied In55Cu45 alloy foam catalysts at various length scales. We demonstrate that the proposed catalyst concept could be transferred to technically relevant support materials (e.g., carbon cloth gas diffusion electrode) without altering its excellent figures of merit.