Issue 10, 2019

Interplay between the amphipathic polyoxometalate interactions in solution and at solid–liquid interfaces: a toolbox for the technical application

Abstract

The far-reaching interplay between the speciation of polyoxometalates (POMs) in the liquid phase and the POM adsorption characteristics on substrate surfaces yet remains to be understood. The significance of this interplay is however paramount because it indicates the degree of technical applicability of solvent-processable POM molecules. Herein, we target this fundamentally important issue, shedding light on the “POM–counterion–solvent” and “POM–counterion–solvent–substrate” processes. We effectively combine the results from small-angle X-ray scattering in solution with surface sensitive scanning tunneling microscopy and X-ray photoelectron spectroscopy measurements and present on this basis a semi-quantitative analysis which provides an excellent correlation between both approaches. The MeCN-solution speciation of a tris(alkoxo)-ligated Wells–Dawson-type polyoxoanion – explored as a representative of commonly negatively charged POM-based inorganic–organic nanostructures – is strikingly connected with the growth of porous two-dimensional molecular layers on highly oriented pyrolytic graphite (HOPG). Low water amounts dramatically transform intermolecular relationships toward hierarchical agglomeration that inhibits the layer formation on HOPG. The obtained findings lay the groundwork for a mechanistic study of controlled nucleation and growth of POM nanostructures on weakly interacting surfaces.

Graphical abstract: Interplay between the amphipathic polyoxometalate interactions in solution and at solid–liquid interfaces: a toolbox for the technical application

Supplementary files

Article information

Article type
Paper
Submitted
02 Oct 2018
Accepted
03 Dec 2018
First published
04 Dec 2018

Nanoscale, 2019,11, 4267-4277

Interplay between the amphipathic polyoxometalate interactions in solution and at solid–liquid interfaces: a toolbox for the technical application

M. Glöβ, R. Pütt, M. Moors, E. Kentzinger, W. Pyckhout-Hintzen and K. Yu. Monakhov, Nanoscale, 2019, 11, 4267 DOI: 10.1039/C8NR08008A

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