High Water-Assisted Proton Conductivities of Two Cadmium(II) Complexes Constructed from Zwitterionic Ligands.

Finding more metal complexes with outstanding water stability and high proton conductivity still has important research significance for the energy field. Herein, two highly proton-conductive complexes, one hydrogen-bonded supramolecular framework (HSF) [Cd(CBIA)2(H2O)4]·2H2O (1) and one coordination polymer (CP), {[Cd2(CBIA)2(4,4'-bipy)2(H2O)2]·(CBIA)·(OH)·2H2O}n (2) (4,4'-bipy = 4,4'-bipyridine), were triumphantly assembled using a zwitterionic organic compound, 2-(1-(carboxymethyl)-1H-benzo[d]imidazol-3-ium-3-yl)acetate (HCBIA). In the structure of HSF 1, there are several coordination and lattice H2O units except for the two monodentate CBIA- anions. CP 2 with a one-dimensional (1D) cylindrical structure has free CBIA- units and free H2O units located in the cavity. Thanks to the ability of the uncoordinated carboxyl groups and coordination/lattice water molecules to construct the rich H-bonding networks, both complexes exhibit super-high proton conductivities, reaching 5.09 × 10-3 and 3.41 × 10-3 S cm-1 under 100 °C/98% relative humidity (RH), respectively. Based on the exploration of crystal structure data, combined with the calculated activation energy, and adsorption/desorption plots of nitrogen and water vapor, the causes and differences in proton conductivity of the two complexes, especially the proton-conductive mechanism, are compared and analyzed. This study again confirms that the zwitterionic ligands can exert important effects on forming organo-inorganic hybrid materials with high proton conductivity.

Proton Conductive Lanthanide-Based Metal-Organic Frameworks: Synthesis Strategies, Structural Features, and Recent Progress.

In the fields of proton exchange membrane fuel cells as well as impedance recognition, molecular sieve, and biochemistry, the development of proton conductive materials is essential. The design and preparation of the next generation of proton conductive materials-crystalline metal-organic framework (MOF) materials with high proton conductivity and excellent water stability-are facing great challenges. Due to the large radius and high positive charge of lanthanides, they often interact with organic ligands to exhibit high coordination numbers and flexible coordination configurations, resulting in the higher stability of lanthanide-based MOFs (Ln-MOFs) than their transition metal analogues, especially regarding water stability. Therefore, Ln-MOFs have attracted considerable attention. This review offers a view of the latest progress of proton conductive Ln-MOFs, including synthesis strategy, structural characteristics, and advantages, proton conductivity, proton conductive mechanism, and applications. More importantly, by discussing structure-property relationships, we searched for and analyzed design techniques and directions of development of Ln-MOFs in the future. The latest progress of synthesis strategy, structural characteristics, proton conductive properties and mechanism and applications on Ln-MOFs. Ln-MOFS Lanthanide-based MOFs, MOF metal-organic framework, PEMFC proton exchange membrane fuel cells.