Covalent attachment of [Ni(alkynyl-cyclam)]2+ catalysts to glassy carbon electrodes.

Surface modification of glassy carbon electrodes (GCEs) with molecular electrocatalysts is an important step towards developing more efficient heterogeneous CO2 reduction materials. Here, we report direct anodic electrografting of [Ni(alkynyl-cyclam)]2+ catalysts to the surface of GCEs in one simple step using inexpensive earth-abundant chemicals. When modified, these electrodes show reversible electrochemistry in organic solvents with zero peak-to-peak separations (ΔE = 0) and non-diffusive I (V) profiles that are typical for heterogeneous redox materials. CPE of these electrodes showed enhanced formation of H2 gas relative to CO compared to homogeneous catalysts.