Gun'ko VM, Zarko VI, Turov VV, Leboda R, Chibowski E, Pakhlov EM, Goncharuk EV, Marciniak M, Voronin EF, Chuiko AA
Institute of Surface Chemistry, 31 Prospect Nauki, Kiev, 252022, Ukraine
J Colloid Interface Sci. 1999 Dec 15;220(2):302-323. doi: 10.1006/jcis.1999.6481.
Fumed oxide alumina/silica/titania was studied in comparison with fumed alumina, silica, titania, alumina/silica, and titania/silica by means of XRD, (1)H NMR, IR, optical, dielectric relaxation, and photon correlation spectroscopies, electrophoresis, and quantum chemical methods. The explored Al(2)O(3)/SiO(2)/TiO(2) consists of amorphous alumina ( approximately 22 wt%), amorphous silica ( approximately 28 wt%), and crystalline titania ( approximately 50 wt%, with a blend of anatase (88%) and rutile (12%)) and has a wide assortment of Brønsted and Lewis acid sites, which provide a greater acidity than that of individual fumed alumina, silica, or titania and an acidity close to that of fumed alumina/silica or titania/silica. The changes in the Gibbs free energy (DeltaG) of interfacial water in an aqueous suspension of Al(2)O(3)/SiO(2)/TiO(2) are close to the DeltaG values of the dispersions of pure rutile but markedly lower than those of alumina, anatase, or rutile covered by alumina and silica. The zeta potential of Al(2)O(3)/SiO(2)/TiO(2) (pH of the isoelectric point (IEP) equals approximately 3.3) is akin to that of fumed titania (pH(IEP(TiO2)) approximately 6) at pH > 6, but it significantly differs from the zeta of fumed alumina (pH(IEP(Al2O3)) approximately 9.8) at any pH value as well as those of fumed silica, titania/silica, and alumina/silica at pH < 6. The particle size distribution in the diluted aqueous suspensions of Al(2)O(3)/SiO(2)/TiO(2) studied by means of photon correlation spectroscopy depends relatively slightly on pH in contrast to the titania/silica or alumina/silica dispersions. Theoretical calculations of oxide cluster interaction with water show a high probability of hydrolysis of Al-O-Ti and Si-O-Ti bonds strained at the interface of alumina/titania or silica/titania due to structural differences in the lattices of the corresponding individual oxides. Ab initio calculated chemical shift delta(H) values of H atoms in different hydroxyl groups at the oxide clusters and in bound water molecules are in agreement with the (1)H NMR data and show a significant impact of charged particles (H(3)O(+) or OH(-)) on the average delta(H) values of water droplets with (H(2)O)(n) at n between 2 and 48. Copyright 1999 Academic Press.
通过X射线衍射(XRD)、核磁共振氢谱(¹H NMR)、红外光谱(IR)、光学光谱、介电弛豫光谱、光子相关光谱、电泳以及量子化学方法,对气相法氧化铝/二氧化硅/二氧化钛与气相法氧化铝、二氧化硅、二氧化钛、氧化铝/二氧化硅和二氧化钛/二氧化硅进行了对比研究。所研究的Al₂O₃/SiO₂/TiO₂由非晶态氧化铝(约22 wt%)、非晶态二氧化硅(约28 wt%)和结晶态二氧化钛(约50 wt%,由88%的锐钛矿和12%的金红石混合而成)组成,并且具有种类繁多的布朗斯台德酸和路易斯酸位点,其酸性比单一的气相法氧化铝、二氧化硅或二氧化钛更强,酸性与气相法氧化铝/二氧化硅或二氧化钛/二氧化硅相近。在Al₂O₃/SiO₂/TiO₂水悬浮液中界面水的吉布斯自由能(ΔG)变化接近于纯金红石分散体的ΔG值,但明显低于氧化铝、锐钛矿或被氧化铝和二氧化硅覆盖的金红石的ΔG值。Al₂O₃/SiO₂/TiO₂的zeta电位(等电点(IEP)的pH值约为3.3)在pH > 6时与气相法二氧化钛的zeta电位(pH(IEP(TiO₂))约为6)相似,但在任何pH值下都与气相法氧化铝的zeta电位(pH(IEP(Al₂O₃))约为9.8)显著不同,并且在pH < 6时与气相法二氧化硅、二氧化钛/二氧化硅和氧化铝/二氧化硅的zeta电位也不同。通过光子相关光谱研究发现,与二氧化钛/二氧化硅或氧化铝/二氧化硅分散体相比,Al₂O₃/SiO₂/TiO₂稀释水悬浮液中的粒径分布对pH的依赖性相对较小。氧化物团簇与水相互作用的理论计算表明,由于相应单一氧化物晶格结构的差异,在氧化铝/二氧化钛或二氧化硅/二氧化钛界面处,Al - O - Ti和Si - O - Ti键发生应变,水解的可能性很高。对氧化物团簇中不同羟基以及结合水分子中的H原子进行从头算计算得到的化学位移δ(H)值与¹H NMR数据一致,并且表明带电粒子(H₃O⁺或OH⁻)对n在2至48之间的(H₂O)ₙ水滴的平均δ(H)值有显著影响。版权所有1999年学术出版社。