Sulfophenylated centimeter-sized graphene membrane in a direct methanol fuel cell.

An ideal proton exchange membrane should only allow protons to pass and remain impermeable to fuels, as required in fuel cell applications. In methanol fuel cells, high proton conductivity enables high power density, whereas methanol crossover between the electrodes degrades the catalyst activity and lowers efficiency. In conventional polymer membranes, however, conductivity and selectivity are often antagonistic: long transport pathways are needed to achieve selectivity, but these introduce additional ionic resistance. Graphene, a two-dimensional material consisting of a single atomic layer of carbon, intrinsically addresses both requirements. Its basal plane is impermeable to water and other molecules, while still exhibiting a measurable degree of proton conductivity. Here, we show that chemical functionalization of monolayer graphene with sulfophenyl groups significantly enhances its proton transport properties. The conductance increases from 6.9 ± 1.1 to 30.9 ± 2.3 S·cm-2, while the energy barrier for proton transport is reduced to 6.9 kJ·mol-1. These findings propose functionalized graphene as an alternative to polymer membranes for electrochemical energy devices.