Article
Physics, Multidisciplinary
Michael Wagstaffe, Adrian Dominguez-Castro, Lukas Wenthaus, Steffen Palutke, Dmytro Kutnyakhov, Michael Heber, Federico Pressacco, Siarhei Dziarzhytski, Helena Gleissner, Verena Kristin Gupta, Harald Redlin, Adriel Dominguez, Thomas Frauenheim, Angel Rubio, Andreas Stierle, Heshmat Noei
Summary: We investigated the dynamics of charge transfer at the interface of water and anatase TiO2(101) using femtosecond time-resolved optical pump-soft x-ray probe photoemission study. Our observations, combined with molecular dynamics simulations, showed that ultrafast interfacial hole transfer from TiO2 to molecularly adsorbed water is completed within 285 fs. This is facilitated by the formation of a new hydrogen bond between an O2c site at the surface and a physisorbed water molecule. The efficient trapping of the hole at the TiO2 surface by hydroxyl species (-OH) before the hole transfer process was also suggested.
PHYSICAL REVIEW LETTERS
(2023)
Article
Engineering, Environmental
Xinyang Li, Zhen Shen, Hao Zhang, Xiaoyu Li, Yujie Zhou, Hong Yao
Summary: This study proposes a new strategy to enhance ozone adsorption on catalyst surfaces by applying a positive electric field. Using first-principles density functional theory calculations, the enhanced mechanism and the effects of electric field strength, adsorption site type, and adsorption configuration on the adsorption energy were investigated. The results showed that the application of a positive electric field significantly increased the adsorption energy and the adsorption sites and configurations played a crucial role.
CHEMICAL ENGINEERING JOURNAL
(2022)
Article
Chemistry, Physical
Federico A. Soria, Cristiana Di Valentin
Summary: This study investigates the interaction of nucleic acid components with TiO2 surfaces using dispersion-corrected hybrid DFT calculations, finding that phosphate anion and bases can anchor nucleotides collaboratively in adsorption mode, with nucleotides containing guanine base showing the strongest adsorption.
APPLIED SURFACE SCIENCE
(2022)
Article
Chemistry, Inorganic & Nuclear
Fengyang Yu, Xiaohua Wang, Haiyue Lu, Gen Li, Baicheng Liao, Hanqing Wang, Chunying Duan, Yu Mao, Liyong Chen
Summary: Low-cost high-efficiency H2 evolution is essential for large-scale applications. This research aims to build highly active photocatalysts for sunlight-driven H2 production through surface engineering. Single-atom Pt doped TiO2-x nanosheets (NSs) with Pt nanoparticles (NPs) at their edges are prepared by an oxygen vacancy engaged synthetic strategy. The Pt/TiO2-x-SAP exhibits ultrahigh photocatalytic performance with a quantum yield of 90.8% and a H2 generation rate of 607 mmol gcata-1 h-1.
INORGANIC CHEMISTRY
(2023)
Article
Biochemistry & Molecular Biology
Ximena Jaramillo-Fierro, Luis Fernando Capa, Francesc Medina, Silvia Gonzalez
Summary: This study investigated the electronic properties and dye adsorption capacity of ZnTiO3 and TiO2 oxides through computational methods, revealing that ZnTiO3 has significantly higher adsorption energy for dyes compared to TiO2, making it suitable for various technological and environmental applications.
Article
Chemistry, Physical
Takahiro Chiba, Kenji Iida, Shinya Furukawa, Jun-ya Hasegawa
Summary: The study investigates the effect of electric fields on hydrogen or proton transfer through hydroxyl groups on an anatase TiO2 (101) surface using first-principles density functional theory and the modern theory of polarization. Unidirectional surface proton transfer induced by external electric fields at different orientations towards the surface is the focus of this research. The preferred pathway for proton transfer can change depending on the magnitude and direction of the electric field. Detailed analysis reveals that the variation in the energy profile with the electric field is significantly different from the classical electric work of an electric field carrying a point charge. The electric field effect on the energy profile of proton transfer is governed by the rearrangement of the chemical bond network at the interface between water molecules and the surface.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Physical
Lan Jiang, Gongbing Zhou
Summary: The study revealed that the interaction between Ru nanoparticles and TiO2 crystal surfaces in Ru/ATCs catalysts contributes to enhancing activity and selectivity in benzene semi-hydrogenation reactions. Among different support facets, Ru/ATCs-101 showed the lowest density of coordinatively unsaturated atoms and exhibited the best catalytic performance.
APPLIED SURFACE SCIENCE
(2021)
Article
Chemistry, Physical
Manasi R. Mulay, Natalia Martsinovich
Summary: Understanding the interaction between carboxylic groups and TiO2 is crucial for photocatalytic degradation of pollutants. This study used density functional theory (DFT) calculations to investigate the interaction of several aromatic carboxylic acids with the TiO2 (101) surface. Monodentate adsorbed configurations were found to be more stable than bidentate for all the molecules studied. Dispersion interactions were found to have a significant effect on adsorption energies, stabilizing the tilted monodentate adsorption configuration. Thermodynamic probabilities indicated that the dispersion-stabilized structures were the most abundant. Additionally, the optical absorption of TiO2-acid complexes was found to extend into the visible range.
Article
Chemistry, Physical
Kraen C. Adamsen, Nikolay G. Petrik, Wilke Dononelli, Greg A. Kimmel, Tao Xu, Zheshen Li, Lutz Lammich, Bjork Hammer, Jeppe V. Lauritsen, Stefan Wendt
Summary: The interaction between water and metal oxide surfaces is crucial in various research fields and applications, especially reducible anatase TiO2. This study combines experiments and theory to investigate the dissociation of water on bulk-reduced a-TiO2(101). The results show that after water exposure, point-like protrusions appear on the a-TiO2(101) surface, which originate from hydroxyl pairs (OHt/OHb). The study also provides a comprehensive model of the water/a-TiO2(101) interaction and explains the thermal stability of the hydroxyl pairs up to 480 K.
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
(2023)
Article
Chemistry, Multidisciplinary
Shaoyu Lu, Li Yan, Wen Zhong, Chuanyong Jing
Summary: The hydration of TiO2 facets plays a crucial role in controlling reactions at mineral-water interfaces, affecting the adsorption behavior of arsenite. Different facets of TiO2 exhibit varying degrees of arsenite adsorption, with the hydrated {201} facet showing the highest affinity for arsenite molecules according to DFT calculations. This study provides new insights into facet-dependent interfacial adsorption processes.
Article
Chemistry, Physical
Alex J. Tanner, Robin Kerr, Helen H. Fielding, Geoff Thornton
Summary: This study focuses on the Ti3+ polaronic states in anatase TiO2(101) and demonstrates the ability to tune the excited state resonance of polarons by controlling the chemical environment. Subsurface polarons in anatase TiO2(101) undergo state changes upon subband-gap photoexcitation, with the binding energy influenced by formic acid adsorption. The behavior observed, including significant changes in photoexcitation oscillator strength resonating with states above the Fermi level, is likely due to surface migration of subsurface oxygen vacancies.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Chemistry, Physical
Nur Umisyuhada Mohd Nor, Elham Mazalan, Chad Risko, Mark Crocker, Nor Aishah Saidina Amin
Summary: The photocatalytic activity of C-doped anatase-TiO2 (101) surfaces as a function of layer thickness was investigated using density functional theory methods. Results showed that C-doped O sites (C-O) were more stable in the bulk, while C-doped Ti sites (C-Ti) were more stable on the surface. CO defects introduced impurity states without affecting the band gap energy, enhancing light absorption in the visible and IR spectrum. C-Ti defects induced structural distortions, causing a red-shifted absorption.
APPLIED SURFACE SCIENCE
(2022)
Article
Materials Science, Multidisciplinary
Guangri Jia, Ying Wang, Xiaoqiang Cui, Hengzhong Zhang, Jingxiang Zhao, Lu Hua Li, Lin Gu, Qinghua Zhang, Lirong Zheng, Jiandong Wu, Qiong Wu, David J. Singh, Weiwei Li, Lei Zhang, Weitao Zheng
Summary: The introduction of hydrogen into TiO2 greatly enhances its photocatalytic properties, leading to a 60 times enhancement of photocatalytic hydrogen evolution activity. Hydrogenated TiO2 with switchable defects is synthesized through a one-step wet-chemistry method and controlled annealing. The obtained hydrogenated TiO2 exhibits improved visible light absorption and efficient separation of photogenerated carriers, resulting in significantly enhanced photocatalytic activity.
Article
Engineering, Environmental
Zehua Wang, Guochun Lv, Chenxi Zhang, Xiaomin Sun
Summary: Theoretical study on the selective catalytic oxidation of NO to form HNO3 on different TiO2 surfaces found that HNO3 is easier to generate on certain surfaces, with the addition of extra NO molecules affecting the reaction pathway and product formation. This research provides deeper insight into the mechanism of NO oxidation and its potential atmospheric significance.
JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING
(2021)
Article
Chemistry, Physical
Nikolay G. Petrik, Yang Wang, Bo Wen, Yiqing Wu, Runze Ma, Arjun Dahal, Feng Gao, Roger Rousseau, Yong Wang, Greg A. Kimmel, Annabella Selloni, Zdenek Dohnalek
Summary: The study investigates thermal-induced reactions of formic acid on metal oxide surfaces, particularly on single-crystalline and nanocrystalline anatase TiO2(101). Various techniques including STM, TPD, IRAS, DRIFTS, and DFT were used to analyze surface intermediates and reaction products. The primary reaction products were identified as molecular water, carbon monoxide, and formaldehyde, with bidentate formate and bridging hydroxyl as central intermediates. Bridging oxygen vacancies were also found to be potential participants despite their low stability.
JOURNAL OF PHYSICAL CHEMISTRY C
(2021)
Article
Chemistry, Physical
Luigi Genovese, William Dawson, Takahito Nakajima, Viviana Cristiglio, Valerie Vallet, Michel Masella
Summary: We propose a hybrid, multi-method computational scheme for protein/ligand systems, suitable for use on modern and forthcoming parallel computing systems. This scheme combines a multi-scale polarizable molecular modeling approach with an efficient Density Functional Theory (DFT) linear scaling method for simulation analysis. Using this scheme, we investigate α-ketoamide inhibitors targeting the main protease of SARS-CoV-2, and compare the results with high-end ab initio computations. The DFT approach allows for fragmentation of the system and investigation of interaction strength between identified fragment pairs, highlighting the importance of considering multiple protease/inhibitor conformations for reliable interaction data.
JOURNAL OF CHEMICAL PHYSICS
(2023)
Article
Computer Science, Interdisciplinary Applications
Ivan Duchemin, Luigi Genovese, Eloise Letournel, Antoine Levitt, Simon Ruget
Summary: We present a novel numerical approach for computing resonances induced by localized defects in crystals. This method utilizes an integral equation in the defect region to determine the analytic continuations of resolvents. By expressing the resonance in terms of a localized resonance source, the integral equation can be efficiently solved using the Green function of the perfect crystal computed through a complex deformation of the Brillouin zone, known as Brillouin Complex Deformation (BCD), extending the concept of complex coordinate transformations to reciprocal space.
JOURNAL OF COMPUTATIONAL PHYSICS
(2023)
Article
Chemistry, Physical
Carmelo Corsaro, Marcello Condorelli, Antonio Speciale, Francesco Cimino, Giuseppe Forte, Francesco Barreca, Salvatore Spadaro, Claudia Muscara, Manuela D'Arrigo, Giovanni Toscano, Luisa D'Urso, Giuseppe Compagnini, Fortunato Neri, Antonina Saija, Enza Fazio
Summary: The synthesis of contaminant-free silver@linear carbon chains (Ag@LCCs) nanohybrid systems, at different Ag/LCCs ratios, by pulsed laser ablation was investigated. The ablation products were characterized using UV-Vis optical absorption, micro-Raman spectroscopy, and transmission mode scanning electron microscopy. The experimental results were supported by theoretical simulations. Moreover, the bioproperties of the Ag@LCCs nanosystems were studied for wound-healing activity, and it was found that Ag@LCC nanohybrids exhibited good antibacterial properties and had enhanced interaction with mammalian cells, suggesting their potential application in wound healing.
Article
Chemistry, Multidisciplinary
Valentina Arena, Emanuele Smecca, Salvatore Valastro, Corrado Bongiorno, Giuseppe Fisicaro, Ioannis Deretzis, Carlo Spampinato, Giovanni Mannino, Sandro Dattilo, Andrea Antonino Scamporrino, Sabrina Carola Carroccio, Antonino La Magna, Alessandra Alberti
Summary: The importance of lead analysis in environmental matrices is increasing due to human-induced spread of toxic species in nature. A new dry approach for lead detection and measurement is proposed, which involves capturing lead from a liquid solution using a solid sponge and quantifying it through X-ray analyses. Gig-lox TiO2 layers with a branched multi-porosity spongy structure were used to capture lead atoms in a liquid environment. The method is based on the relationship between the electronic density of the solid sponge and the critical angle for total reflection of X-rays.
Article
Green & Sustainable Science & Technology
Salvatore Valastro, Emanuele Smecca, Giovanni Mannino, Corrado Bongiorno, Giuseppe Fisicaro, Stefan Goedecker, Valentina Arena, Carlo Spampinato, Ioannis Deretzis, Sandro Dattilo, Andrea Scamporrino, Sabrina Carroccio, Enza Fazio, Fortunato Neri, Francesco Bisconti, Aurora Rizzo, Corrado Spinella, Antonino La Magna, Alessandra Alberti
Summary: With the projected rapid growth of the market uptake of perovskite solar cells (PSCs), the use of this clean energy technology will play a crucial role in reducing the global carbon footprint. However, the presence of toxic lead (Pb) poses a major barrier to its full commercialization. Researchers have demonstrated that the application of a transparent titanium dioxide (TiO2) sponge can effectively prevent Pb leakage, leading to a more sustainable solution and accelerated practical applications.
NATURE SUSTAINABILITY
(2023)
Article
Chemistry, Physical
E. Schiliro, S. E. Panasci, A. M. Mio, G. Nicotra, S. Agnello, B. Pecz, G. Z. Radnoczi, I. Deretzis, A. La Magna, F. Roccaforte, R. Lo Nigro, F. Giannazzo
Summary: This paper investigates the atomic layer deposition (ALD) of ultra-thin films of Al2O3 and HfO2 on gold-supported monolayer MoS2, providing insights into the nucleation mechanisms in the early stages of the ALD process. The characterization reveals a tensile strain and p-type doping distribution at the micro-scale, local strain variations at the nanoscale, and atomic scale variability in the Mo-Au atomic distances. Ab initio DFT calculations show the significant influence of the Au substrate on the MoS2 energy band structure and the enhanced physisorption of the precursors due to nanoscale morphological effects. The nucleation and growth of Al2O3 and HfO2 films on 1L-MoS2/Au are studied, revealing slower growth rate for HfO2 and formation of continuous films for both materials at higher ALD cycles. The films show different conductive behavior and strain effects, influencing the MoS2 properties.
APPLIED SURFACE SCIENCE
(2023)
Article
Chemistry, Physical
Gaetano Calogero, Domenica Raciti, Damiano Ricciarelli, Pablo Acosta-Alba, Fuccio Cristiano, Richard Daubriac, Remi Demoulin, Ioannis Deretzis, Giuseppe Fisicaro, Jean-Michel Hartmann, Sebastien Kerdils, Antonino La Magna
Summary: This study presents a multiscale computational framework for pulsed laser annealing that can simulate the atom-by-atom kinetics of material transformations under laser interaction, overcoming the limitations of current tools. The method has important implications and potential applications in investigating complex changes in SiGe alloys.
JOURNAL OF PHYSICAL CHEMISTRY C
(2023)
Article
Engineering, Electrical & Electronic
Damiano Ricciarelli, Giovanni Mannino, Ioannis Deretzis, Gaetano Calogero, Giuseppe Fisicaro, Richard Daubriac, Fuccio Cristiano, Remi Demoulin, Pawel P. Michalowski, Pablo Acosta-Alba, Jean-Michel Hartmann, Sebastien Kerdiles, Antonino La Magna
Summary: Ultraviolet nanosecond laser annealing is a powerful tool for optimal heating and melting. The complexity of semiconductor integration schemes has increased the importance of this process. Reliable simulations of laser melting are necessary, especially for 3D nanostructured systems with various shapes and phases. In this study, the laser melting process of Si1-xGex alloys was simulated using a finite element method/phase field approach, highlighting the significance of reproducing the reflectivity of the material interface accurately.
MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING
(2023)
Article
Materials Science, Multidisciplinary
Vikram Gavini, Stefano Baroni, Volker Blum, David R. Bowler, Alexander Buccheri, James R. Chelikowsky, Sambit Das, William Dawson, Pietro Delugas, Mehmet Dogan, Claudia Draxl, Giulia Galli, Luigi Genovese, Paolo Giannozzi, Matteo Giantomassi, Xavier Gonze, Marco Govoni, Francois Gygi, Andris Gulans, John M. Herbert, Sebastian Kokott, Thomas D. Kuehne, Kai-Hsin Liou, Tsuyoshi Miyazaki, Phani Motamarri, Ayako Nakata, John E. Pask, Christian Plessl, Laura E. Ratcliff, Ryan M. Richard, Mariana Rossi, Robert Schade, Matthias Scheffler, Ole Schutt, Phanish Suryanarayana, Marc Torrent, Lionel Truflandier, Theresa L. Windus, Qimen Xu, Victor W-Z Yu, D. Perez
Summary: Electronic structure calculations provide important insights into physical and chemical properties of various systems, and they are crucial in fields like materials science and computational chemistry. As we enter the exascale era, there are new opportunities and challenges in terms of simulation capabilities and efficient use of new architectures. This roadmap discusses the current status, development priorities, and plans of 14 electronic structure codes in tackling these challenges and leveraging the benefits of exascale computing.
MODELLING AND SIMULATION IN MATERIALS SCIENCE AND ENGINEERING
(2023)
Article
Energy & Fuels
Giovanni Mannino, Jesus Sanchez-Diaz, Emanuele Smecca, Salvatore Valastro, Ioannis Deretzis, Rafael S. Sanchez, Juan P. Martinez-Pastor, Ivan Mora-Sero, Alessandra Alberti
Summary: The most promising lead-free option for perovskite solar cells is tin halide perovskite materials. Spectroscopic ellipsometry is used to investigate the dielectric function of FASnI(3) layers with and without additives, revealing a decrease in absorption coefficient in the band gap region and an increase in absorption in the 3-4.5 eV region, suggesting the production of amorphous tin oxide. By adding sodium borohydride and dipropylammonium iodide, the optically active area is preserved and SnO2 production is prevented. Additionally, FASnI(3) is optically durable up to 100°C when additives are used.
Article
Engineering, Electrical & Electronic
Rayhane Zribi, Angelo Ferlazzo, Enza Fazio, Marcello Condorelli, Luisa D'Urso, Giulia Neri, Carmelo Corsaro, Fortunato Neri, Giuseppe Compagnini, Giovanni Neri
Summary: This study fabricated and characterized a sensor based on silver nanoplates colloidal solutions deposited onto screen-printed carbon electrodes. The sensor showed wavelength-dependent and size-tunable electrochemical sensing response towards hydrogen peroxide (H2O2). The study also demonstrated the potential of using Ag nanoparticles with specific nanoplates morphology for electrochemical redox probes.
IEEE TRANSACTIONS ON INSTRUMENTATION AND MEASUREMENT
(2023)
Article
Chemistry, Multidisciplinary
Paola La Magna, Carlo Spampinato, Salvatore Valastro, Emanuele Smecca, Valentina Arena, Giovanni Mannino, Ioannis Deretzis, Giuseppe Fisicaro, Corrado Bongiorno, Alessandra Alberti
Summary: This study explores the potential of a blended material composed of CsPbI3:EuCl3 perovskite and Gig-Lox TiO2 for use in solar cells. The inclusion of EuCl3 in CsPbI3 stabilizes the desired gamma-phase, making it suitable for solar energy conversion. X-ray-based techniques and spectroscopic ellipsometry were used to investigate the structural properties and interfacial behavior of this blended material. The findings reveal a significant quenching of photoluminescence, highlighting the important role of distributed interfaces in facilitating efficient carrier injection.