d-Glucose Adsorption on the TiO2 Anatase (100) Surface: A Direct Comparison Between Cluster-Based and Periodic Approaches

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.

Gallium Nitride‐based Materials as Promising Catalysts for CO2 Reduction: A DFT Study on the Effect of CO2 Coverage and the Incorporation of Mg Doping or Substitutional In

“…[48][49][50] Therefore, the two use of the two methods is complementarity and crucial for a detailed understanding of the structureproperty relationship. [51] Based on these considerations, in this work, we further extend our DFT investigation performing PBC calculations, and employing a more extended GaN(100) surface which includes six bilayers. This allows us to explore the surface CO 2 coverage, by considering the adsorption of one to nine CO 2 molecules on the pristine GaN(100) surface.…”

“…However, cluster model approaches do not allow for the investigation of extended surfaces and heterojunctions, which can be more conveniently performed by means of PBC calculations [48–50] . Therefore, the two use of the two methods is complementarity and crucial for a detailed understanding of the structure–property relationship [51] …”

Titanium dioxide and table sugar enhance the leaching of silver out of nanosilver packaging

“…These interactions give rise to changes in TiO 2 hydrodynamic diameter, surface charge, colloidal stability, and physicochemical behaviors. [36][37][38][39] TiO 2 can also photocatalyze the degradation of surface-bound carbohydrates (including sucrose) or their conversion into other redox reactive chemicals. 38,[40][41][42] As such, we hypothesized that TiO 2 may act in concert with table sugar or other common redox-active food substances to bring about cooperative effects on Ag migration from AgNP-enabled plastics.…”

DFT Study of GaN Clusters Decorated with Rh and Pt Nanoparticles for the Photochemical Reduction of CO2

“…Moreover, cluster approaches are more appropriate for studying charged systems, thanks to the ability to add/subtract a charge carrier without suffering from interactions with similar charge carriers due to periodic boundary conditions. , Due to their reduced size, cluster approaches can be used to investigate complex reaction mechanisms, allowing for the interception of all the involved stationary points, including the more complex transition states. − However, PBC calculations allow for modeling more extended surfaces and provide an accurate description of the structural properties of the surface and molecular adsorbates. The complementarity of the two computational methods can therefore lead to an in-depth understanding of the structure–property relationship …”

“…The complementarity of the two computational methods can therefore lead to an in-depth understanding of the structure−property relationship. 33 In this work, the selected cluster models, whose stability has also been evaluated and the details are discussed in the Supporting Information, were built using the cluster models presented in our previous study. To mimic the adsorbed NP, the metal atoms (M = Rh, Pt) were added on top of the GaN surface.…”