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Highly Ordered Mesoporous Hydroxide Thin Films through Self-Assembly of Size-Tailored Nanobuilding Blocks: A Theoretical-Experimental Approach
journal contribution
posted on 2018-12-27, 00:00 authored by Naoki Tarutani, Yasuaki Tokudome, Matías Jobbágy, Galo J. A. A. Soler-Illia, Qiyun Tang, Marcus Müller, Masahide TakahashiMesoporous
crystalline (hydr)oxides of low-valence metal ions (M(II)
and M(III)) are highly demanded in the context of various applications.
In this study, we demonstrate key factors to the successful formation
of ordered mesoporous films through the assembly of nanobuilding block
(ANBB) approach using a colloidal solution of crystalline M(OH)2 (M = Mn, Fe, Co, Ni, and Cu). The colloidal system of α-Ni(OH)2 is presented in depth as a typical example. Crystal growth
and aggregation kinetics of the NBB were tuned by synthetic parameters.
Nanometer-sized NBBs of tailored size between oligomer scale to over
20 nm were obtained. The films prepared from α-Ni(OH)2 NBBs with a diameter of ≤7.5 nm showed ordered mesostructures
through evaporation-induced self-assembly in the presence of supramolecular
templates. Coarse-grained simulations suggest that there is a threshold
diameter of NBB toward the formation of well-ordered mesostructures.
It was found that, as well as limiting the diameter of NBB, inhibition
of an aggregation of NBBs by using coordinative additives or diluting
the NBB colloidal solution was essential to control the assembly of
NBBs and templates into the ordered mesostructures. The results obtained
here open up the synthesis of ordered mesoporous materials with a
crystalline wall of variety of chemical compositions containing low-valence
metal elements.
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Theoretical-Experimental Approach MesoporousNiNanometer-sized NBBsthreshold diameterlow-valence metal ionschemical compositionscrystal growthCoarse-grained simulationsMesoporous Hydroxidelow-valence metal elements20 nmmesoporous materialsaggregation kineticsoligomer scaleevaporation-induced self-assemblySize-Tailored Nanobuilding Blocksmesoporous filmscoordinative additiveswell-ordered mesostructuresnanobuilding blockANBBsupramolecular templates
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