| Abstract |
Using the technique of solid-state hydride synthesis, which is based on the reduction of solid compounds of metals in a flow-type reactor with volatile element-hydrogen compounds in the region of thermal stability of the latter, the authors obtained dispersed 3D metal products applied to silica substrates. The surface of such products contains chemosorbed molecules of various silicon hydride reducing agents. For the first time the reduction properties of silicon hydride reagents were correlated with their nucleophilic properties, which were analyzed on the basis of quantum-chemical calculations, performed with the help of HyperChem. The study confirmed a symbatic relationship at the initial stage of NiCl2 reduction between the nucleophilic properties of the studied reagents with a Si – H bond in the molecule structure and the degree of reduction reached. It was found that, with all the other conditions being equal and depending on the type of the reducing agent, the degree of reduction rises in the following row: vapour of methyldichlorosilane, vapour of methyl hydride siloxane, vapour of ethyl hydride siloxane, monosilane. The experiments revealed a much greater efficiency of methyldichlorosilane rather than monosilane for the reduction of oxide material. The former chlorinates the oxide and thus makes its reduction easier and more efficient. Depending on the type of metal and the initial solid-phase material, reduction in the methyldichlorosilane vapour helps control the specific surface of the metal product in the range of 40 to 120 m2/g. It is demonstrated that a metal product (M = Cu, Ni, Fe) with a highly hydrophobic surface is formed as the result of consecutive reduction of the initial compounds (material) in the methyldichlorosilane vapour and in methane. This paper describes the first consistent study that relied on X-ray photoelectron spectroscopy to understand the adjustability of the electron binding energy of the characteristic level of metal (M2p3/2) reduced by solid-state hydride synthesis on silica substrates. Depending on the type of reducing agent used, the binding energy of the M2p3/2 level of metal on silica gel, which reflects the degree of stabilization on substrate, rises following the sequence H2, CH4, NH3, CH3SiHCl2, SiH4. Silica gel samples coated with nickel by solid-state hydride synthesis were found to manifest the strongest hydrophobic properties, comparable to the properties of the superhydrophobic organosilicon adsorbent of polymethylsiloxane. Samples of porous glass coated with copper in the same conditions have a good hydrophobicity, stability and improved emission characteristics and can compete with nanocarbon structures as an innovative material for cold cathodes. |
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Inorganic synthesis of highly hydrophobic metals containing
surface compounds with electron acceptor modifiers: process features
