Plasma-Initiated Graft Polymerization of Acrylic Acid onto Fluorine-Doped Tin Oxide as a Platform for Immobilization of Water-Oxidation Catalysts.

The discovery of new and versatile strategies for the immobilization of molecular water-oxidation catalysts (WOCs) is crucial for developing clean energy conversion devices [e.g., (photo)electrocatalytic cells for water splitting]. The traditional approach for surface attachment to transparent conductive oxides [e.g., fluorine doped tin oxide (FTO)] is via synthetic modification of the ligand architecture to incorporate functional groups such as carboxylic acids (-COOH) or phosphonates (-POH) prior to immobilization. However, challenges arising from desorption and the cumbersome derivatizations steps have limited the scope and applications of surface-bound WOCs. Herein, we report the successful immobilization of underivatized Ru(II)-based WOCs ( = [Ru(tpy) (bpy) (HO)] (tpy = 2,2':6'2″-terpyridine and bpy = 2,2'-bipyridine) and = [Ru(Mebimpy) (bpy) (HO)] (Mebimpy = 2,6-bis(1-methylbenzimidazol-2-yl) pyridine)) and the Ru(II) polypyridyl chromophore = [Ru(bpy)] onto a FTO plasma-grafted poly(acrylic acid) surface (PAA|FTO). Various characterization techniques such as attenuated total reflectance Fourier transform infrared spectroscopy, scanning electron microscopy, atomic force microscopy, and cyclic voltammetry measurements provide evidence for the plasma-induced grafted PAA|FTO film and immobilization. Surface stability and electrocatalytic properties of these new hybrid composite films upon cycling were investigated at different pH values. Immobilized and onto PAA|FTO displayed pH-dependent (Ru/Ru) couples and onset potentials indicative of PCET (proton-coupled electron transfer) reactions. Based on cyclic voltammetry results and spectroscopic monitoring, the immobilized WOCs and exhibited a higher surface stability in neutral aqueous solutions relative to upon electrochemical oxidation. We attribute the surface PCET and stability to the presence of a water ligand in the coordination sphere of immobilized and which can H-bond with negatively charged carboxylate groups of the cross-linked PAA brushes. Our findings demonstrate that the plasma-grafted polymeric network onto FTO offers a versatile platform to directly anchor unmodified homogeneous WOCs or chromophores for potential applications in solar-to-fuel energy conversion.