Abstract
The CO(2)/CO electroreduction reaction (CO(2)RR/CORR) to liquid products presents an enticing pathway to store intermittent renewable electricity. However, the selectivity for desirable high-value C(3) products, such as n-propanol, remains unsatisfactory in the CO(2)RR/CORR. Here, we report that *CO enrichment and proton regulation cooperatively enhance C(1)-C(2) coupling by increasing CO pressure and utilizing proton sponge modification, promoting the production of n-propanol over a Cu(0)/Cu(+) nanosheet catalyst in the CORR. We obtain an impressive faradaic efficiency (FE) of 44.0% ± 2.3% for n-propanol at a low potential of -0.44 V vs. reversible hydrogen electrode (RHE) under 3 bar CO. Experimental results demonstrated that *H intermediates could be regulated by proton sponge modification. In situ characterization combined with density functional theory (DFT) calculations validate that Cu(+) species exist stably in proton sponge-modified Cu-based catalysts along with appropriate *CO coverage. This design facilitates the potential-determining C(1)-C(1) and C(1)-C(2) coupling steps and contributes to the n-propanol production.