Proton conductors, particularly hydrated solid membranes,
have
various applications in sensors, fuel cells, and cellular biological
systems. Unraveling the intrinsic proton transfer mechanism is critical
for establishing the foundation of proton conduction. Two scenarios
on electrical conduction, the Grotthuss and the vehicle mechanisms,
have been reported by experiments and simulations. But separating
and quantifying the contributions of these two components from experiments
is difficult. Here, we present the conductive behavior of a two-dimensional
layered proton conductor, graphene oxide membrane (GOM), and find
that proton hopping is dominant at low water content, while ion diffusion
prevails with increasing water content. This change in the conduction
mechanism is attributable to the layers of water molecules in GOM
nanosheets. The overall conductivity is greatly improved by forming
one layer of water molecules. It reaches the maximum with two layers
of water molecules, resulting from creating a complete hydrogen-bond
network within GOM. When more than two layers of water molecules
enter the GOM nanosheets, inducing the breakage of the ordered lamellar
structure, protons spread in both in-plane and out-of-plane directions
inside the GOM. Our results validate the existence of two conduction
mechanisms and show their distinct contributions to the overall conductivity.
Furthermore, these findings provide an optimization strategy for the
design of realizing the fast proton transfer in materials with water
participation.