Natural Assembly of Electroactive Metallopolymers on the Electrode Surface: Enhanced Electrocatalytic Production of Hydrogen by [2Fe-2S] Metallopolymers in Neutral Water

A molecular catalyst attached to an electrode surface can offer the advantages of both homogeneous and heterogeneous catalysis. Unfortunately, some molecular catalysts constrained to a surface lose much or all of their solution performance. In contrast, we found that when a small molecule [2Fe-2S] catalyst is incorporated into metallopolymers of the form PDMAEMA-g-[2Fe-2S] (PDMAEMA = poly(2-dimethylamino)ethyl methacrylate) and adsorbed to the surface, the observed rate of hydrogen production increases to k_obs > 10⁵ s^-1 per active site with lower overpotential, increased lifetime, and tolerance to oxygen. Herein, the electrocatalytic performances of these metallopolymers with different length polymer chains are compared to reveal the factors that lead to this high performance. It was anticipated that smaller metallopolymers would have faster rates due to faster electron and proton transfers to more accessible active sites, but the experiments show that the rates of catalysis per active site are independent of the polymer size. Molecular dynamics modeling reveals that the high performance is a consequence of adsorption of these metallopolymers on the surface with natural assembly that brings the [2Fe-2S] catalytic sites into close contact with the electrode surface while maintaining exposure of the sites to protons in solution. The assembly is conducive to fast electron transfer, fast proton transfer, and a high rate of catalysis regardless of the polymer size. These results offer a guide to enhancing the performance of other electrocatalysts with incorporation into a polymer that provides an optimal interaction of the catalyst with the electrode and solution.