Selective Heterogeneous CO₂ Electroreduction to Methanol

Catalytic electroreduction of carbon dioxide to useful chemical feedstocks is an environmentally and technologically important process, yet the low energy efficiency and difficulty in controlling product selectivity are great challenges. The reason for part of the latter is that there are presently no catalyst design principles to selectively control CO₂ electroreduction toward a desired product. In this work, as a first attempt, we suggest combining a few criteria (CO binding energy, OH binding energy, and H binding energy) that can be collectively used as activity- and selectivity-determining descriptors to preferentially produce methanol over methane from CO₂ electroreduction. We then apply these concepts to near-surface alloys (NSAs) to propose efficient and selective CO₂ electrochemical reduction catalysts to produce methanol. The W/Au alloy is identified as a promising candidate to have increased catalyst efficiency (decreased CO₂ reduction overpotential and increased overpotential for unwanted hydrogen evolution) as well as improved product selectivity toward methanol, in comparison to conventional Cu catalyst