Spatial-confinement induced electroreduction of CO and CO(2) to diols on densely-arrayed Cu nanopyramids

The electroreduction of carbon dioxide (CO(2)) and carbon monoxide (CO) to liquid alcohol is of significant research interest. This is because of a high mass-energy density, readiness for transportation and established utilization infrastructure. Current success is mainly around monohydric alcohols, such as methanol and ethanol. There exist few reports on converting CO(2) or CO to higher-valued diols such as ethylene glycol (EG; (CH(2)OH)(2)). The challenge to producing diols lies in the requirement to retain two oxygen atoms in the compound. Here for the first time, we demonstrate that densely-arrayed Cu nanopyramids (Cu-DAN) are able to retain two oxygen atoms for hydroxyl formation. This results in selective electroreduction of CO(2) or CO to diols. Density Functional Theory (DFT) computations highlight that the unique spatial-confinement induced by Cu-DAN is crucial to selectively generating EG through a new reaction pathway. This structure promotes C–C coupling with a decreased reaction barrier. Following C–C coupling the structure facilitates EG production by (1) retaining oxygen and promoting the *COH–CHO pathway, which is a newly identified pathway toward ethylene glycol production; and, (2) suppressing the carbon–oxygen bond breaking in intermediate *CH(2)OH–CH(2)O and boosting hydrogenation to EG. Our findings will be of immediate interest to researchers in the design of highly active and selective CO(2) and CO electroreduction to diols.