A Close Look at the Structure of the TiO2-APTES Interface in Hybrid Nanomaterials and Its Degradation Pathway: An Experimental and Theoretical Study

详细信息    查看全文

• 作者：Daniela Meroni ; Leonardo Lo PrestiGiovanni Di Liberto ; Michele Ceotto ; Robert G. Acres ; Kevin C. PrinceRoberto Bellani ; Guido Soliveri ; Silvia Ardizzone
• 刊名：Journal of Physical Chemistry C
• 出版年：2017
• 出版时间：January 12, 2017
• 年：2017
• 卷：121
• 期：1
• 页码：430-440
• 全文大小：663K
• ISSN：1932-7455

文摘

The surface functionalization of TiO₂-based materials with alkylsilanes is attractive in several cutting-edge applications, such as photovoltaics, sensors, and nanocarriers for the controlled release of bioactive molecules. (3-Aminopropyl)triethoxysilane (APTES) is able to self-assemble to form monolayers on TiO₂ surfaces, but its adsorption geometry and solar-induced photodegradation pathways are not well understood. We here employ advanced experimental (XPS, NEXAFS, AFM, HR-TEM, and FT-IR) and theoretical (plane-wave DFT) tools to investigate the preferential interaction mode of APTES on anatase TiO₂. We demonstrate that monomeric APTES chemisorption should proceed through covalent Si–O–Ti bonds. Although dimerization of the silane through Si–O–Si bonds is possible, further polymerization on the surface is scarcely probable. Terminal amino groups are expected to be partially involved in strong charge-assisted hydrogen bonds with surface hydroxyl groups of TiO₂, resulting in a reduced propensity to react with other species. Solar-induced mineralization proceeds through preferential cleavage of the alkyl groups, leading to the rapid loss of the terminal NH₂ moieties, whereas the Si-bearing head of APTES undergoes slower oxidation and remains bound to the surface. The suitability of employing the silane as a linker with other chemical species is discussed in the context of controlled degradation of APTES monolayers for drug release and surface patterning.