Renewable Power for Electrocatalytic Generation of Syngas: Tuning the Syngas Ratio by Manipulating the Active Sites and System Design

Achieving decarbonization through zero net CO2 emissions requires commercially viable application of waste CO2, throughout the transition to renewable and low‐carbon energy sources. A promising approach is the electrochemical carbon dioxide reduction reaction (CO2RR), which when powered with renewable electricity sources, provides a pathway for the conversion of intermittent renewable energy and waste CO2 into value‐added chemicals and fuels. However, as CO2RR is accompanied by the competing hydrogen evolution reaction (HER) due to the presence of water, an opportunity is presented to generate a mixture of CO and H2, also known as synthesis gas or syngas – the building block of various oxy‐hydrocarbon products. The aim of this review is to analyze both Power‐to‐CO and Power‐to‐Syngas studies, in order to classify and discuss the active sites for both CO and H2 generation through a new lens, providing insights into the structure‐activity correlations and facilitating the design of more active syngas electrocatalysts in the future. Through an evaluation of the economic viability of syngas generation, we determine that the carbon capture cost is a key parameter, with improvements in catalyst activity, catalyst impurity tolerance, and electrolyzer technology necessary for significant improvement in the economics of electrocatalytic syngas generation. Electrocatalysis: This review explores the recent efforts to synthesize electrocatalysts and utilize high throughput electrolyzer systems for the selective one‐step electrochemical reduction of CO2 and water to industrially applicable syngas ratios (CO and H2). In addition, we undertake an economic analysis of the performance requirements for improving the viability of electrochemical syngas production.