Rapid hydrolysis of the CuSO4 salt solution microdroplets deposited on the alkaline solution and the formation of ordered arrays of open microspheres with Cu(OH)2 walls

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Abstract

It was shown for the first time that open microspheres 1–10 µm in size with Cu(OH)2 walls and unique morphology are formed as reactions of rapid hydrolysis of copper (II) cations when microdroplets of aqueous CuSO4 solution are sprayed on the surface of alkaline solution of Na2SO4 at room temperature and without the use of surfactants. It has been shown that the microspheres formed under these conditions have a single hole in their walls with a size ranging from fractions to units of a micrometer and they are oriented on the surface of the alkaline solution with this hole facing towards the air. These microspheres can be transferred to various substrates using a vertical elevator technique, where they are deposited in layers with their holes predominantly oriented in the opposite direction from the substrate. It has been found that the walls of these microspheres are several hundred nanometers thick and are composed of a combination of Cu(OH)2 nanocrystals, and nanorods, with a diameter 5–10 nm and a length up to 500 nm. When the samples are heated in air at 150°C, these nanocrystals lose water and form CuO single crystals without significant changes in their morphology. It was found that applying layers of microspheres to the surfaces of various substrates gives it superhydrophilic properties.

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About the authors

A. A. Golubeva

Saint Petersburg State University

Email: a.meleshko@spbu.ru

Institute of Chemistry

Russian Federation, St. Petersburg, 198504

А. А. Meleshko

Saint Petersburg State University

Author for correspondence.
Email: a.meleshko@spbu.ru

Institute of Chemistry

Russian Federation, St. Petersburg, 198504

V. P. Tolstoy

Saint Petersburg State University

Email: a.meleshko@spbu.ru

Institute of Chemistry

Russian Federation, St. Petersburg, 198504

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Supplementary files

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2. Fig. 1. Schematic representation of the sequence of operations when applying a layer of microspheres with Cu(OH)2 walls to the surface of titanium foil: a - stage of surface treatment of the solution of NaOH and Na2SO4 mixture with microdroplets of aerosol from CuSO4 solution, b - stage of transferring the microsphere array to the substrate using the vertical elevator technique.

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3. Fig. 2. SEM-electron micrographs taken at different magnifications of the Cu(OH)2 microsphere layer deposited on the surface of titanium foil using the vertical elevator technique.

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4. Fig. 3. Electron micrographs of microsphere fragments with Cu(OH)2 wall obtained by SEM at different magnification in light field mode (a-c), and electron micrograph of a wall fragment of a similar sample heated in air at 150℃ obtained in high resolution SEM mode (d).

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5. Fig. 4. Energy-dispersive X-ray spectrum of Cu(OH)2 microsphere (a), X-ray diffractogram (b) and FT-IR transmission spectrum (c) of Cu(OH)2 microspheres before (1) and after (2) heating in air at 150℃.

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6. Fig. 5. Wetting angles of water on silicon surface without a layer (a), with a layer (b) of Cu(OH)2 microspheres obtained by vertical elevator technique, c, d - schematic images of the process of water drop spreading on silicon surface with a layer of Cu(OH)2 microspheres.

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