Interplay between the amphipathic polyoxometalate interactions in solution and at solid-liquid interfaces: a toolbox for the technical application.
Interplay between the amphipathic polyoxometalate interactions in solution and at solid-liquid interfaces: a toolbox for the technical application.
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DOI：
10.1039/c8nr08008a
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发表时间：
2019-03
期刊：
影响因子：
6.7
通讯作者：
Maria Glöβ;Ricarda Pütt;M. Moors;E. Kentzinger;W. Pyckhout-Hintzen;K. Monakhov
中科院分区：
文献类型：
--
作者：
Maria Glöβ;Ricarda Pütt;M. Moors;E. Kentzinger;W. Pyckhout-Hintzen;K. Monakhov
多金属氧酸盐（POM）在液相中的形态与POM在基质表面的吸附特性之间的相互作用仍有待进一步研究。然而，这种相互作用的重要性是至关重要的，因为它表明了可溶剂加工的聚甲醛分子的技术适用性程度。在此，我们针对这一根本性的重要问题，阐明了“pom -反离子-溶剂”和“pom -反离子-溶剂-衬底”工艺。我们将溶液中的小角x射线散射结果与表面敏感扫描隧道显微镜和x射线光电子能谱测量结果有效地结合起来，并在此基础上提出了半定量分析，提供了两种方法之间良好的相关性。三（烷氧基）连接的wells - dawson型多氧阴离子（作为通常带负电荷的pom基无机-有机纳米结构的代表）的men溶液形态与高取向热解石墨（HOPG）上多孔二维分子层的生长密切相关。低水量显著地改变了分子间的分层团聚关系，抑制了HOPG上的层形成。这些发现为弱相互作用表面上POM纳米结构的可控成核和生长机理研究奠定了基础。
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.