Layer-by-Layer Construction of a Nanoarchitecture by Polyoxometalates and Polymers: Enhanced Electrochemical Hydrogen...

In this contribution, a nanoarchitectural approach was employed to produce a nanolayer of polyoxometalate (POM) on the surface of a glassy carbon electrode (GCE) to achieve a higher surface area with higher electrocatalytic activity toward the electrochemical hydrogen evolution reaction (HER). To accomplish this, the well-known layer-by-layer (LbL) technique was employed, which involved the alternate adsorption of the POM, Na_0.3[N(C₄H₉)₄]_7.7 [(Mo₃O₈)₄(O₃PC(O)(C₃H₆NH₂CH₂C₄H₃S)PO₃)₄], abbreviated as [(TBA)Mo₁₂(AleThio)₄], and polyethyleneimine (PEI) polymer. This nanolayered electrode exhibited catalytic properties toward the HER in 0.5 M H₂SO₄ with the resulting polarization curves indicating an increase in the HER activity with the increasing number of POM layers, and the overpotential required for this reaction was lowered by 0.83 V when compared with a bare GCE. The eighth PEI/[(TBA)Mo₁₂(AleThio)₄] bilayer exhibited a significantly lower HER overpotential of -0.077 V at a current density of 10 mA cm^-2. Surface characterization of the LbL-assembled nanolayers was carried out using X-ray photoelectron spectroscopy, atomic force microscopy, and scanning electron microscopy. We believe that the synergetic effect of the positively charged PEI polymer and the catalytically active molybdate POM is the cause for the successful response to the electrochemical HER.