Abstract
Titanium dioxide (TiO2) has been extensively studied as a suitable material for a wide range of fields including catalysis and sensing. For example, TiO2-based nanoparticles are active in the catalytic conversion of glucose into value-added chemicals, while the good biocompatibility of titania allows for its application in innovative biosensing devices for glucose detection. A key process for efficient and selective biosensors and catalysts is the interaction and binding mode between the analyte and the sensor/catalyst surface. The relevant features regard both the molecular recognition event and its effects on the nanoparticle electronic structure. In this work, we address both these features by combining two first-principles methods based on periodic boundary conditions and cluster approaches (CAs). While the former allows for the investigation of extended materials and surfaces, CAs focus only on a local region of the surface but allow for using hybrid functionals with low computational cost, leading to a highly accurate description of electronic properties. Moreover, the CA is suitable for the study of reaction mechanisms and charged systems, which can be cumbersome with PBC. Here, a direct and detailed comparison of the two computational methodologies is applied for the investigation of d-glucose on the TiO2 (100) anatase surface. As an alternative to the commonly used PBC calculations, the CA is successfully exploited to characterize the formation of surface and subsurface oxygen vacancies and to determine their decisive role in d-glucose adsorption. The results of such direct comparison allow for the selection of an efficient, finite-size structural model that is suitable for future investigations of biosensor electrocatalytic processes and biomass conversion catalysis.
Highlights
Titanium dioxide has been the focus of intense research in materials science over the past few decades, thanks to the wide range of technological applications, from biomedicine (Paunesku et al, 2003; Wu et al, 2014) to environment (Kapilashrami et al, 2014; Bella et al, 2017; Bella et al, 2018; Massaro et al, 2020) and photochemistry (Bai et al, 2014; Lettieri et al, 2020)
The results reported in his work underline that the glucose molecule prefers an orientation normal to the titania surface, but the dihedral angle can vary depending on the constraints imposed by the particular hydroxyl group(s) involved in the adsorption
We considered the formation of surface and subsurface oxygen vacancies in our cluster model approach
Summary
Titanium dioxide has been the focus of intense research in materials science over the past few decades, thanks to the wide range of technological applications, from biomedicine (Paunesku et al, 2003; Wu et al, 2014) to environment (Kapilashrami et al, 2014; Bella et al, 2017; Bella et al, 2018; Massaro et al, 2020) and photochemistry (Bai et al, 2014; Lettieri et al, 2020). D-Glucose Adsorption on the TiO2 Surface of TiO2-based materials at the nanoscale level is enabled by the high stability they exhibit under extreme conditions. The most common polymorphs are as follows: 1) rutile, which is the most thermodynamically stable bulk phase, 2) anatase, which is found to be more stable at the nanoscale (Zhang and Banfield, 1998; Ranade et al, 2002), and 3) brookite. Anatase is the most catalytically active mineral and, the most interesting one for both research and industrial applications, especially related to heterogeneous photo-(electro)-catalysis (Linsebigler et al, 1995; Guo et al, 2019; Piccolo et al, 2020). TiO2 nanoparticles have been found highly effective for the selective catalytic conversion of biomass to value-added products. Glucose produced from cellulose through hydrolysis in an aqueous medium can be transformed into useful molecules such as alkyl glucosides, 5-hydroxymethylfurfural, levulinic acid, and gluconic acid (van Putten et al, 2013; Kuo et al, 2014)
Sign-in/Register to view highlights & summary Talk to us
Join us for a 30 min session where you can share your feedback and ask us any queries you have
Schedule a callDisclaimer: All third-party content on this website/platform is and will remain the property of their respective owners and is provided on "as is" basis without any warranties, express or implied. Use of third-party content does not indicate any affiliation, sponsorship with or endorsement by them. Any references to third-party content is to identify the corresponding services and shall be considered fair use under The CopyrightLaw.
