Surface-Directed Fabrication of Integrated Membrane-Electrode Interfaces
In the past five years, we have established a research program to investigate the integration of electrode/catalyst support, gas diffusion pathways, and ionomer into a single network based on a bottom-up, surface-directed approach. Here, the porous electrode surface provides the common foundation for both catalyst deposition and ionomer growth to develop a highly controlled process. Our efforts have focused on (1) the preparation of surface-initiated ionomer that can be grown from electrodes of essentially any geometry and is chemisorbed to the active electrode surface, and (2) the integration of this ionomer with both planar and 3-D electrodes that are atomically modified by Pt catalysts. Figure 1 shows a schematic of a single pore of such an integrated cathode where a catalytic Pt atomic layer is supported along the pores of a nanoporous gold electrode. The catalyst layer is electronically accessible from the metal cathode and in contact with proton-conducting ionomer to yield extremely high utilization efficiencies of the catalyst (approaching 100%) with the ultralow loadings expected from atomic overlayers. We have introduced a new class of ionomer film that is grown from the catalyst/electrode interface to develop proton conducting pathways throughout the 3-D electrode and to the adsorbed catalyst particles. This ionomer is a comb polymer designed to contain sulfonate-lined channels for rapid proton conduction as well as hydrophobic domains (fluorocarbon or hydrocarbon) to promote O 2 solubility and transfer. This interfacial ionomer is designed to interface with a bulk membrane (such as Nafion) and an anode that could be engineered in a similar way. A key conclusion thus far is that ionomer and Pt catalyst can be integrated at a single interface (both 2-D and 3-D) to provide a high level of control over the construction of electrodes. To expand our efforts to date, we seek to utilize the materials chemistry we have developed to investigate how the depth-dependent structure of an ionomer film affects its performance in transferring protons and oxygen to accelerate the rate of the oxygen reduction reaction. By correlating structure and composition to performance and identifying barriers that limit efficiency, we seek to design ultra high performance ionomer films that are customized for the oxygen reduction reaction.