Improving Proton-Conducting Stability by Regulating Pore Size of MOF Materials through Mixed Grinding

An effective strategy to improve the proton conductivity of metal–organic frameworks (MOFs) is to regulate the pore size of composite materials. In this work, composite materials of MOF-808@MOG-808-X (X is the mass ratios of MOF-808 to MOG-808) was successfully prepared by grinding and blending. MOF-808@MOG-808-1:2 was optimal for its suitable pore structure, which facilitates the practical construction of hydrogen bonding networks, promotes rapid and stable proton conduction, and enables the proton conductivity, achieving a 1 + 1 > 2 effect. At 353 K and 93% relative humidity (RH), the maximum proton conductivity of MOF-808@MOG-808-1:2 reaches 1.08 × 10–1 S·cm–1. Next, MOF-808@MOG-808-1:2 was blended with chitosan (CS) to obtain composite proton exchange membranes (PEMs), namely, CS@MOF-808@MOG-808-1:2-Y (Y = 5%, 10%, or 15%) with the maximum proton conductivity reaching 1.19 × 10–2 S·cm–1 at 353 K and 93% RH for CS@MOF-808@MOG-808-1:2-10% with additional stability. The conductive mechanisms of the composite materials were revealed by activation energy calculation. This investigation not only proposes a simple grinding–blending method for the development of MOF-doped composite materials for proton conductivity but also provides a producting material basis for future applications of MOFs in proton exchange membrane fuel cells (PEMFCs).