Two Novel Schiff Base Manganese Complexes as Bifunctional Electrocatalysts for CO2 Reduction and Water Oxidation

One mononuclear Mn(III) complex [MnIIIL(H2O)(MeCN)](ClO4) (1) and one hetero-binuclear complex [(CuIILMnII(H2O)3)(CuIIL)2](ClO4)2·CH3OH (2) have been synthesized with the Schiff base ligand (H2L= N,N′-bis(3-methoxysalicylidene)-1,2-phenylenediamine). Single crystal X-ray structural analysis manifests that the Mn(III) ion in1has an octahedral coordination structure, whereas the Mn(II) ion in2possesses a trigonal bipyramidal configuration and the Cu(II) ion in2is four-coordinated with a square-planar geometry. Electrochimerical catalytic investigation demonstrates that the two complexes can electrochemically catalyze water oxidation and CO2reduction simultaneously. The coordination environments of the Mn(III), Mn(II), and Cu(II) ions in1and2were provided by the Schiff base ligand (L) and labile solvent molecules. The coordinately unsaturated environment of the Cu(II) center in2can perfectly facilitate the catalytic performance of2. Complexes1and2display that the over potentials for water oxidation are 728 mV and 216 mV, faradaic efficiencies (FEs) are 88% and 92%, respectively, as well as the turnover frequency (TOF) values for the catalytic reduction of CO2to CO are 0.38 s−1at −1.65 V and 15.97 s−1at −1.60 V, respectively. Complex2shows much better catalytic performance for both water oxidation and CO2reduction than that of complex1, which could be owing to a structural reason which is attributed to the synergistic catalytic action of the neighboring Mn(III) and Cu(II) active sites in2. Complexes1and2are the first two compounds coordinated with Schiff base ligand for both water oxidation and CO2reduction. The finding in this work can offer significant inspiration for the future development of electrocatalysis in this area.Keywords:electrocatalysis;carbon dioxide reduction;water oxidation;hetero-binuclear complex;cooperative catalytic effect