Adipic acid-mediated hydrogen bonding network allocation for efficient proton conduction in water-stabilized lamellar MOF membranes

Abstract

The poor water-stability and cross-layer proton transfer property pose a challenge to the lamellar metal–organic frameworks (MOFs) membrane when acting as a promising proton exchange membrane. Herein, we report an adipic acid-mediated strategy to improve the water-stability and the cross-layer proton conductivity of CuTCPP lamellar MOF membrane, which achieves a maximum power density and current density of 112.6 mW cm−2 and 424.4 mA cm−2, respectively. Adipic acid with extra functional groups (–PO3H2, –COOH) stably bridges the adjacent crystal layers via the terminal carboxylic acid anchoring Cu sites. In particular, the extra functional groups introduced into the adipic acid regulate the allocation of hydrogen bonding networks in an umbrella-shape around adipic acid with copper-porphyrin structures as external margin, enriching the coherence of hydrogen bonding network on the proton transport path. Benefiting from the regular pore structure of MOF, the optimized hydrogen bonding networks in adjacent crystal layers construct a more abundant through-plane transfer pathway. The resultant through-plane proton conductivities of CuTCPP-PO3H2/–COOH membranes are up to 108/89 mS cm−1 at 80 °C and 100 % RH, which is ∼ 6-fold higher than that of the pristine CuTCPP membrane (13 mS cm−1), with a conductivity attenuation of < 5 % during a humidity cycling test for 12 times.