Controlled manipulation of TiO 2 nanoclusters inside mesochannels of core-shell silica particles as stationary phase for
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ORIGINAL PAPER
Controlled manipulation of TiO2 nanoclusters inside mesochannels of core-shell silica particles as stationary phase for HPLC separation Wanying Li 1 & Hui Qian 1 & Rui Liu 2 & Xiaoli Zhao 3 & Zhi Tang 3 & Xianhuai Huang 2 & Weihua Li 2 & Xiaoming Chen 1 & Fazhi Xie 1 & Wensheng Zou 1 & Qishu Qu 1,2 Received: 11 November 2019 / Accepted: 10 April 2020 # Springer-Verlag GmbH Austria, part of Springer Nature 2020
Abstract Based on a detailed study of the hydrolysis process of tetrabutyl orthotitanate (TBOT), TiO2 nanoclusters were modified inside the pores of SiO2 core-shell particles instead of the outside. The pore size distribution of SiO2 core-shell spheres modified with TiO2 (SiO2@dSiO2@TiO2) was analyzed by Barrett-Joyner-Halenda (BJH) method and density functional theory (DFT) method, respectively. The results of the DFT calculations demonstrate that the TiO2 nanoclusters are always first formed in bulk solution and then enter the pores. By regulating the rate of hydrolysis of TBOT, almost all of the TiO2 nanoclusters are modified into the pores and the structure of the original SiO2 core-shell sphere is hardly affected. The morphology of the particles was characterized by scanning electron microscopy and transmission electron microscopy. The crystal phase of TiO2 was measured by XRD. SiO2@dSiO2@TiO2 spheres functionalized with C18 were packed into a stainless steel column. The chemical stability of SiO2@dSiO2@TiO2 spheres under alkaline was tested by flushing of a mobile phase at pH 13 for 7 days. The efficiency of the column after the alkali solution treatment still reaches 98,430 plates m−1, which is only about 1.6% lower than that before the alkali solution treatment. A series of basic and acidic analytes were also separated on the column. Keywords Dendritic . Modification . Nanocomposites . Mesoporous materials . SiO2/TiO2 core-shell particles . Titania . Anatase
Introduction Among a large number of inorganic materials, TiO2 has excellent chemical and thermal stability, and can be used in the range of pH 1–14 [1]. The surface of Electronic supplementary material The online version of this article (https://doi.org/10.1007/s00604-020-04268-w) contains supplementary material, which is available to authorized users. * Zhi Tang [email protected] * Qishu Qu [email protected]; [email protected] 1
Key Laboratory of Functional Molecule Design and Interface Process, School of Materials Science and Chemical Engineering, Anhui Jianzhu University, Hefei 230601, China
2
Anhui Provincial Key Laboratory of Environmental Pollution Control and Resource Reuse, School of Environment and Energy Engineering, Anhui Jianzhu University, Hefei 230601, China
3
State Key Laboratory of Environmental Criteria and Risk Assessment, Chinese Research Academy of Environmental Sciences, Beijing, China
TiO2 also has special amphoteric ion exchange groups so that they can be either cation or anion exchangers depending on pH, while SiO2 behaves only as a cation exchanger. Another unique advantage of using TiO2 as a support
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