Oriented polyoxometalate–polycation multilayers on a carbon substrate

Abstract

In this paper, a new method of fabricating multilayers on a carbon substrate is presented. First, a uniformly charged carbon surface was prepared through molecular design. Then an ultrathin film consisting of layer-pairs of oppositely charged polymeric cationic poly(diallyldimethylammonium chloride) (PDDA) and silicotungstate, SiW12O404− (SiW12), was grown layer-by-layer onto the grafted carbon substrate using a molecular self-assembly technique and an electrochemical method. The technique allows one to prepare highly adherent, dense and smooth films of polyoxometalates with special properties. By combining cyclic voltammetry (CV) and X-ray (XR) reflectometry, it was determined that the average surface density of SiW12 was 2.10 × 10−10 mol cm−2, and the thickness increase per adsorption of PDDA–SiW12 was 1.7 ± 0.2 nm, indicating that the amount of SiW12 anion per one layer adsorption corresponded to a monolayer coverage. Atomic force microscopy (AFM) was also used to examine the surface morphology and determine the grain size distribution and roughness for multilayer films. An increase in root-mean-square (RMS) surface roughness from 7 to 9 Å was observed as the number of layer-pairs in the film increased from 2 to 6. FTIR results showed that the good stability of the multilayer films was due to Coulomb interactions between the SiW12 anion and the polymeric cations PDDA. Moreover, the multilayer films, in acidic aqueous solution, showed good electrocatalytic activity toward the reduction of NO2−, and the catalytic currents increased with increasing the layer numbers of SiW12 adsorption. These characteristics of the multilayer films might find potential applications in the field of sensors and microelectronics devices.