Scanning Tunneling Microscopy and Tunneling Spectroscopy of Nano-structured H<SUB>6</SUB>P<SUB>2</SUB>Mo<SUB><I>x</I></SUB>W<SUB>18−<I>x</I></SUB>O<SUB>62</SUB> (<I>x</I> = 0, 3, 9, 15, 18) Wells-Dawson Heteropolyacids

Abstract

Scanning tunneling microscopy (STM) and tunneling spectroscopy studies of nano-structured H6P2MoxW(18-x)O62 (x = 0, 3, 9, 15, 18) Wells-Dawson heteropolyacids (HPAs) were carried out to examine redox properties of the HPAs. STM images of H6P2MoxW(18-x)O62 HPAs clearly showed self-assembled and well-ordered 2-dimensional arrays on graphite surface. Tunneling spectroscopy measurements revealed that all H6P2MoxW(18-x)O62 HPAs exhibited a negative differential resistance (NDR) behavior in their tunneling spectra. NDR peak voltage of H6P2MoxW(18-x)O62 HPAs appeared at less negative applied voltage with increasing molybdenum substitution. Reduction potential of H6P2MoxW(18-x)O62 HPAs measured by an electrochemical method increased and absorption edge energy determined by UV-visible spectroscopy shifted to lower value with increasing molybdenum substitution. In other words, NDR peak voltage of H6P2MoxW(18-x)O62 HPAs appeared at less negative applied voltage with increasing reduction potential and with decreasing absorption edge energy of the HPAs; more reducible H6P2MoxW(18-x)O62 HPAs showed NDR behavior at less negative applied voltage. These results indicate that NDR peak voltage of nano-structured HPAs measured by STM could be utilized as a correlating parameter for the redox properties of bulk HPAs.