Polymers functionalized with 1,2-benzenedithiolate-bridged model compound of [FeFe]-hydrogenase: Synthesis, characterization and their catalytic activity

Three polymers functionalized with 1,2-benzenedithiolate-bridged diiron carbonyl units, Polymers 1-3, were prepared by using three diazide monomers with different organic frames via click chemistry. These polymers were characterized by IR spectroscopy, thermal gravimetric analysis, scanning electron microscopy and electrochemistry. Their solubility, morphology and catalysis on proton reduction are largely controlled by the organic moieties of the diazides. The presence of carboxylates in Polymer 3 causes significant difference both physically and chemically (electrochemically). It is soluble in water but decomposes rapidly in DMSO. Its stability is much improved after being assembled into membrane electrodes. The electrodes assembled from these polymers are relatively robust,and all operational in water. The carboxylate in Polymer 3 turns out a better proton-relay in catalysis by exhibiting higher catalytic efficiency in both solution and solid state (membrane electrode). (C) 2016 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.