PHOTOCATALYTIC ACTIVITY OF MESOPOROUS TiO2 (ANATAS) IN THE REACTION OF HYDROGEN RELEASE FROM AQUEOUS-ETHANOLIC MIXTURE

N. Ermokhina, A. Korzhak, D. Klymchuk, Alexander M Puziy, V. Grebennikov, N. Romanovska, Olexandr Shulzhenko, P. Manorik
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Abstract

Samples of mesoporous nanocrystalline titanium dioxide (anatase with a crystallite size of about 10 nm) were obtained by a modified sol-gel method in the presence of a template of dibenzo-18-crown-6 and small additives of surfactant (dodecylmethylethylammonium bromide) or ions of lanthanum (III) in butyl alcohol in combination with hydrothermal treatment at 175 °C for 24 hours followed by calcination in air at 500 °C for 4 hours. The photocatalytic activity of the obtained TiO2 samples was investigated in a model reaction of the photocatalytic release of H2 from an aqueous-ethanol mixture. It was found that in all cases the use of hydrothermal treatment significantly increases the photoactivity of the obtained sample, which in some cases is more than 3-4 times higher than the corresponding characteristic for commercial photocatalyst Evonik P25. The key effect of hydrothermal treatment on the increase of photoactivity of the samples is probably the consequence of a drastic increase in the treated samples of pore volume and diameter, as well as a decrease in the size of anatase crystallites. These changes (along with a significant increase in the specific surface area) are greater for samples obtained in the presence of La3+ ions. It is shown that samples of TiO2 microspheres obtained at the same concentrations of reagents in the reaction mixture show slightly higher photocatalytic activity than the corresponding lanthanum-stabilized samples of mesoporous TiO2 powders (micrometer-scale particles are not formed in the presence of lanthanum (III) ions). However, with an increasing concentration of reagents in the reaction mixture, the photocatalytic activity has the sample containing lanthanum. Probably, this can be explained by the high textural characteristics of the TiO2 sample in combination with the peculiarities of its morphology - the formation of secondary nanoparticles of agglomerated formations and the influence of La3+ ions. It is worth noting that the photocatalytic activity of TiO2 samples prepared in the presence of La3+ ions reduces as their specific surface area decreases.
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介孔二氧化钛(ANATAS)在水-乙醇混合物释氢反应中的光催化活性
在二苯并-18-冠-6模板和少量表面活性剂(十二烷基甲基乙基溴化铵)或正丁醇镧离子的存在下,采用改进的溶胶-凝胶法,在175℃水热处理24小时后,在500℃空气中煅烧4小时,获得了介孔纳米二氧化钛(晶粒尺寸约为10 nm的锐钛矿)样品。在水-乙醇混合物中光催化释放H2的模型反应中,研究了所得TiO2样品的光催化活性。研究发现,在所有情况下,水热处理都显著提高了所得样品的光活性,在某些情况下,其光活性比商用光催化剂赢创P25的相应特性高3-4倍以上。水热处理对样品光活性提高的关键作用可能是处理后样品的孔隙体积和孔径急剧增加,锐钛矿晶体尺寸减小的结果。在La3+离子存在下获得的样品中,这些变化(以及比表面积的显著增加)更大。结果表明,在反应混合物中相同浓度的试剂下得到的TiO2微球样品的光催化活性略高于相应的镧稳定的介孔TiO2粉末样品(在镧(III)离子存在下不会形成微米级颗粒)。然而,随着反应混合物中试剂浓度的增加,光催化活性对含有镧的样品有影响。可能,这可以解释为TiO2样品的高结构特征及其形态的特殊性-形成凝聚形成的次级纳米颗粒和La3+离子的影响。值得注意的是,在La3+离子存在下制备的TiO2样品的光催化活性随着其比表面积的减小而降低。
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