Electrocatalytic reduction of CO2, a greenhouse gas, to value-added products such as formate and methanol would be a useful way to recycle our carbon-based fuel emissions. However, accessing complex products like methanol and methane is kinetically challenging. Product selectivity continues to challenge the field. H+ reduction to H2 is a competing reaction for many CO2 reducing catalysts, and a better understanding of how catalyst functionalization may favor one product completely will benefit the field. The metal carbonyl cluster [Fe4N(CO)12]- catalyzes CO2 reduction to formate at -1.2 V vs SCE in 95:5 MeCN/H2O with high efficiency, and produces no H2. Here, we report that after a CO ligand is replaced with a hydroxyl-bearing phosphine, the ligand acts as a classic proton shuttle; the cluster favors H2 production with &gt; 95% efficiency in and yields no formate. If PPh3 is used to replace a carbonyl instead of the hydroxyl ligand, formate is produced. Future experiments will explore the effect of varying ligand charge on product selectivity.

Electrocatalytic H2 production is favored over formate production by including a proton shuttle on [Fe4N(CO)12]-

251st National Meeting (2016)

The official archive and repository for all ACS Meetings & Expositions abstracts and select posters or presentations.