A perspective on the electrocatalytic conversion of carbon dioxide to methanol with metallomacrocyclic catalysts

Electrocatalytic carbon dioxide reduction (CO₂R) presents a promising route to establish zero-emission carbon cycle and store intermittent renewable energy into chemical fuels for steady energy supply. Methanol is an ideal energy carrier as alternative fuels and one of the most important commodity chemicals. Nevertheless, methanol is currently mainly produced from fossil-based syngas, the production of which yields tremendous carbon emission globally. Direct CO₂R towards methanol poses great potential to shift the paradigm of methanol production. In this perspective, we focus our discussions on producing methanol from electrochemical CO₂R, using metallomacrocyclic molecules as the model catalysts. We discuss the motivation of having methanol as the sole CO₂R product, the documented application of metallomacrocyclic catalysts for CO₂R, and recent advance in catalyzing CO₂ to methanol with cobalt phthalocyanine-based catalysts. We attempt to understand the key factors in determining the activity, selectivity, and stability of electrocatalytic CO₂-to-methanol conversion, and to draw mechanistic insights from existing observations. Finally, we identify the challenges hindering methanol electrosynthesis directly from CO₂ and some intriguing directions worthy of further investigation and exploration.