Copper-Based Metal-Organic Porous Materials for CO2 Electrocatalytic Reduction to Alcohols.

The electrocatalytic reduction of CO2 has been investigated using four Cu-based metal-organic porous materials supported on gas diffusion electrodes, namely, (1) HKUST-1 metal-organic framework (MOF), [Cu3 (μ6 -C9 H3 O6 )2 ]n ; (2) CuAdeAce MOF, [Cu3 (μ3 -C5 H4 N5 )2 ]n ; (3) CuDTA mesoporous metal-organic aerogel (MOA), [Cu(μ-C2 H2 N2 S2 )]n ; and (4) CuZnDTA MOA, [Cu0.6 Zn0.4 (μ-C2 H2 N2 S2 )]n . The electrodes show relatively high surface areas, accessibilities, and exposure of the Cu catalytic centers as well as favorable electrocatalytic CO2 reduction performance, that is, they have a high efficiency for the production of methanol and ethanol in the liquid phase. The maximum cumulative Faradaic efficiencies for CO2 conversion at HKUST-1-, CuAdeAce-, CuDTA-, and CuZnDTA-based electrodes are 15.9, 1.2, 6, and 9.9 %, respectively, at a current density of 10 mA cm-2 , an electrolyte-flow/area ratio of 3 mL min cm-2 , and a gas-flow/area ratio of 20 mL min cm-2 . We can correlate these observations with the structural features of the electrodes. Furthermore, HKUST-1- and CuZnDTA-based electrodes show stable electrocatalytic performance for 17 and 12 h, respectively.