ABSTRACT
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, Na0.3[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.
ABSTRACT
The Dawson-type sulfate polyoxometalate (POM) [S2W18O62]4- has successfully been entrapped in polypyrrole (PPy) films on glassy carbon electrode (GCE) surfaces through pyrrole electropolymerization. Films of varying POM loadings (i.e., thickness) were grown by chronocoulometry. Film-coated electrodes were then characterized using voltammetry, revealing POM surface coverages ranging from 1.9 to 11.7 × 10-9 mol·cm-2, and were stable over 100 redox cycles. Typical film morphology and composition were revealed to be porous using atomic force microscopy, scanning electron microscopy, and X-ray photoelectron spectroscopy, and the effects of this porosity on POM redox activity were probed using AC impedance. The hybrid organic-inorganic films exhibited a good electrocatalytic response toward the reduction of iodate with a sensitivity of 0.769 µA·cm-2·µM-1.
