Epitaxní materiály a nanostruktury

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d-Glucose Adsorption on the TiO2 Anatase (100) Surface: A Direct Comparison Between Cluster-Based and Periodic Approaches
(Frontiers, 2021-08-31) Butera, Valeria; Massaro, Arianna; Muoz-García, Ana B.; Pavone, Michele; Detz, Hermann
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.
Photochemical CO2 conversion on pristine and Mg-doped gallium nitride (GaN): a comprehensive DFT study based on a cluster model approach
(Royal Society of Chemistry, 2021-11-23) Butera, Valeria; Detz, Hermann
The photochemical reduction of carbon dioxide (CO2) into methanol is very appealing since it requires sunlight as the only energy input. However, the development of highly selective and efficient photocatalysts is still very challenging. It has been reported that CO2 can be spontaneously activated on gallium nitride (GaN). Moreover, the photocatalytic activity for CO2 conversion into methanol can be drastically enhanced by incorporating a small amount of Mg dopant. In this work, density functional theory (DFT) based on a cluster model approach has been applied to further explore the photocatalytic activity of bare GaN towards CO2 adsorption and conversion. We extended the investigation of Mg-doping replacing one Ga atom with Mg on three different sites and evaluated the consequent effects on the band gaps and CO2 adsorption energies. Finally, we explore different routes leading to the production of methanol and evaluate the catalytic activity of bare GaN by applying the energetic span model (ESM) in order to identify the rate-determining states which are fundamental for suggesting modifications that can improve the photocatalytic activity of this promising material.
Cyclic Carbonate Formation from Epoxides and CO2 Catalyzed by Sustainable Alkali Halide-Glycol Complexes: A DFT Study to Elucidate Reaction Mechanism and Catalytic Activity
(AMER CHEMICAL SOC, 2020-07-28) Butera, Valeria; Detz, Hermann
We provide a comprehensive DFT investigation of the mechanistic details of CO2 fixation into styrene oxide to form styrene carbonate, catalyzed by potassium iodide-tetraethylene glycol complex. A detailed view on the intermediate steps of the overall reaction clarifies the role of hydroxyl substances as co-catalysts for the alkali halide-catalyzed cycloaddition. The increase of iodide nucleophilicity in presence of tetraethylene glycol is examined and rationalized by NBO and Hirshfeld charge analysis, and bond distances. We explore how different alkali metal salts and glycols affect the catalytic performance. Our results provide important hints on the synthesis of cyclic carbonates from CO2 and epoxides promoted by alkali halides and glycol complexes, allowing the development of more efficient catalysts.
Beyond Karl Fischer titration: a monolithic quantum cascade sensor for monitoring residual water concentration in solvents
(Royal Society of Chemistry, 2023-03-28) Pilat, Florian; Schwarz, Benedikt; Baumgartner, Bettina; Ristanic, Daniela; Detz, Hermann; Andrews, Aaron Maxwell; Lendl, Bernhard; Strasser, Gottfried; Hinkov, Borislav
Quality control of liquids is an important part of analytical chemistry. The gold standard for measuring residual water in organic solvents and pharmaceutical applications is Karl Fischer titration. It has a high sensitivity, selectivity and accuracy. The downsides are a time-consuming offline analysis, together with the need for toxic reagents producing waste, and it suffers from poor inter-laboratory reproducibility. In this work, we present a high-performance lab-on-a-chip sensor exploiting mid-IR spectroscopy for liquid sensing. It is operating at 6.1 mu m wavelength and is suitable for robust and flexible real-time in situ analysis of the residual water concentration in isopropyl alcohol. This is demonstrated in two experiments. A custom-made 60 mu L flow cell is employed to measure only minute amounts of analyte in an inline configuration. In a second approach, the whole sensor is immersed into the analyte to demonstrate sensitive and rapid in situ operation on the millisecond time scale. This is confirmed by the ability for time resolved single water-droplet monitoring, while they are mixed into the liquid sample. We obtain a limit of detection between 120 ppm and 150 ppm with a concentration coverage spanning three orders of magnitude from 1.2 x 10(-2)%(vol) to 25%(vol) for the flow cell and 1.5 x 10(-2)%(vol) to 19%(vol) in the in situ configuration, respectively.
Structure and mid-infrared optical properties of spin-coated polyethylene films developed for integrated photonics applications
(Optica Publishing Group, 2022-06-01) David, Mauro; Disnan, Davide; Lardschneider, Anna; Wacht, Dominik; Hoang, Hanh T.; Ramer, Georg; Detz, Hermann; Lendl, Bernhard; Schmid, Ulrich; Strasser, Gottfried; Hinkov, Borislav
Polyethylene is a promising polymer for mid-infrared integrated optics due to its broad transparency and optimal refractive index. However, simple fabrication protocols that preserve its optical characteristics are needed to foster a wide range of applications and unlock its full potential. This work presents investigations of the optical and structural properties of spin-coated linear low-density polyethylene films fabricated under humidity-controlled conditions. The film thickness on polymer concentration dependence shows a non-linear behavior, in agreement with previously reported theoretical models and allowing predictive concentration-dependent thickness deposition with high repeatability. The surface roughness is on the nanometer-scale for all investigated concentrations between 1% and 10%. The crystallinity of the films was studied with the Raman spectroscopy technique. Mid-infrared ellipsometry measurements show a broad transparency range as expected for bulk material. Layer exposure to solvents revealed good stability of the films, indicating that the fabricated layers can outlast further fabrication steps. These investigations confirm the excellent properties of spin-coated thin films fabricated with our novel method, creating new opportunities for the use in photonic integrated circuits Published by Optica Publishing Group under the terms of the Creative Commons Attribution 4.0 License. Further distribution of this work must maintain attribution to the author(s) and the published article's title, journal citation, and DOI.

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