Physicochemical Analysis of Cu(II)-Driven Electrochemical CO Reduction and its Competition with Proton Reduction.

The reduction of CO has become a key role in reducing greenhouse gas emissions in efforts to search for long-term responses to climate change. We report a couple of CO-reducing molecular catalysts based on earth-abundant copper complexes. These are [Cu(DPA)(PyNAP)] (1) and [Cu(DPA)(PyQl)] (2) (where, DPA=pyridine-2,6-dicarboxylate, PyNAP=2-(pyridin-2-yl)-1,8-naphthyridine, and PyQl=2-(pyridin-2-yl)quinoline). The copper metal-catalysed 2-electron reduction of CO to CO in the presence of 2-protons is challenging. These catalysts exhibit the production of CO gas in DMF/water mixtures, achieving an impressive Faradaic efficiency of 84 % and 72 % for complex 1 and 2 at -1.7 V vs. SCE, respectively, for selective CO reduction. The production of H due to 2H+2e was also observed as a byproduct through the competitive proton reduction reaction. This was cross-verified by online gas and mass analysis. A comprehensive series of electrochemical experiments have substantiated the homogeneous behaviour exhibited by these molecular electrocatalysts. Our investigations confirmed the stability of the electrocatalysts under the electrocatalytic conditions. The mechanistic pathways were proposed to work with the EECC and ECEC (E: electrochemical and C: chemical) mechanisms. A CO insertion into an in-situ generated hydride from the Cu-center generates CO through the favourable path. This critical path kinetically favors excess Faradaic efficiency in 1 than 2, which agrees with the computational investigation.