Interrogation of the Selectivity and Electrokinetics of CO2 Reduction by AgSn Films in the Presence of Protic Organic [DBU–H]+ Cations as judged by Impedance Spectroscopy and Distribution of Relaxation Times Analysis

Abstract

The use of renewable electricity to synthesize high energy and high value chemicals via reduction of CO2 is an attractive strategy for renewable energy storage. Improving our understanding of how heterogeneous CO2 reduction electrocatalysts function is important to designing efficient systems for conversion of CO2 into commodity chemicals such as CO and HCO2H. Both Ag- and Sn-based materials have been previously considered as CO2 reduction catalysts and offer distinct CO2RR selectivities. In this work, we have considered electrodeposited composite film electrodes prepared from electroplating baths with varying ratios of Ag+ and Sn2+ triflates to understand how the performance of such composite materials varies as a function of composition. XPS analysis confirms that for each composite film electrodes, Ag existed in the metallic (Ag0) state, while the Sn was mainly oxidized (Sn2+/4+). The AgSn composite film electrodes studied herein are therefore best considered as AgSnOx cathodes with varying ratios of Ag0:Sn2+/4+. These systems were assessed as CO2RR electrocatalysts and were found to promote the 2e–/2H+ reductions to deliver CO and HCOOH with fast kinetics and high efficiencies from electrolyte solutions containing the protic organic cation [DBU–H]+. While Sn-rich composite films showed poor selectivities for CO versus HCO2H, a significant increase in CO versus HCO2H selectivity (up to 99%) is achieved for composite film electrodes in which the Ag content ranged from 25 - 75%. By tuning the ratio of Ag0 to SnOx we prepared composite film cathode materials that support quantitative current efficiencies for generation of CO with geometric current densities approaching 30 mA/cm2 at applied overpotentials that are less than 750 mV were realized. Additionally, electrochemical impedance spectroscopy (EIS) coupled with analysis of the distribution of relaxation times (DRT) was used to better understand factors important to the composites’ activity under CO2RR conditions. Probing the dynamics with DRT analysis revealed that multiple processes relating to both adsorption and diffusion-controlled events are important to the activity of the electrocatalysts considered in this work. The collection of electroanalytical investigations suggest that synergistic interactions between Ag and SnOx give rise to porous films that support enhanced CO2RR kinetics and that mixing of Ag with SnOx enhances the efficacy of adsorption and stabilization of reduced CO2 intermediates and [DBU–H]+ cations to facilitate CO evolution at the cathode/electrolyte interface.