Intrinsic intermediate gap states of TiO₂ materials and their roles in charge carrier kinetics

Titanium dioxide (TiO 2 ) is regarded as an important prototype photocatalytic material for several decades. The charge carrier kinetics determines the photocatalytic properties of TiO 2 materials; this is found to be greatly dependent on electronic structures. It has been revealed that the intrinsic intermediate gap states (intrinsic GSs) play a significant role in charge carrier kinetics that drive the photocatalytic processes of TiO 2 materials, which are not well summarized until now. Motivated by this thought, the purpose of this review focuses on physiochemical science of the intrinsic GSs of TiO 2 materials and their important role in charge carrier kinetics. We first give a summary on the chemical resources of the intrinsic GSs in TiO 2 and their physiochemical nature. Their general energy distribution, charge carrier population, and the associated thermodynamic properties are also elaborated from an overall viewpoint. We further carefully summarize and compare the experimental studies on the energy and the density distribution of the intrinsic GSs and discuss the associated chemical resources and charge carrier localizations. Trapping is the dominant function of intrinsic GSs in the charge carrier kinetics of TiO 2 materials. The significant effect of trapping on the transport, recombination, and interfacial transfer of charge carriers are also comprehensive summarized. Furthermore, the effects of charge carrier kinetics on photocatalytic performances are also discussed to some extents. Because of the importance of intrinsic GSs in modulating charge carrier kinetics, it is expected to increase the photocatalytic activity by engineering the intrinsic GSs, not only for TiO 2 materials, but also for the other semiconductor photocatalysts

TiO2‐Based Photocatalysis at the Interface with Biology and Biomedicine

This is the peer reviewed version of the following article: M. Tomás-Gamasa, J. L. Mascareñas, ChemBioChem 2020, 21, 294, which has been published in final form at https://doi.org/10.1002/cbic.201900229. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived VersionsThe conversion of sunlight into chemical energy by using photosynthetic machinery is at the heart of nature and life. Scientists have also learned to use light energy to promote a great variety of chemical reactions, most of which are based on redox processes involving electron‐transfer steps. Indeed, the area of photoredox catalysis has recently emerged as one of the hottest fields in synthetic chemistry. Many of the photoredox reactions discovered so far take place in homogeneous phases, and rely on the use of soluble photoresponsive catalysts. However, in recent years, there have been many advances in the area of heterogeneous photocatalysis, most of which are based on the use of semiconductor materials, such as TiO2, as a key photocatalytic system. These technologies have found different applications, especially in the field of sustainable chemistry and therapy. Herein, some of these applications, and the potential of TiO2‐based photocatalysts in biology and biomedicine, are reviewedThis work has received financial support from the Spanish Government (SAF2016‐76689‐R, Orfeo‐cinqa network CTQ2016‐81797‐REDC); the Consellería de Cultura, Educación e Ordenación Universitaria (2015‐CP082, ED431C 2017/19); the Centro Singular de Investigación de Galicia accreditation 2016–2019, ED431G/09); the European Union (European Regional Development Fund‐ERDF); and the European Research Council (Advanced Grant No. 340055). M.T.G. thanks the Ministerio de Economía y Competitividad for the Juan de la Cierva‐Incorporación (IJCI‐2015‐23210)S

Robustness of a local Fermi Liquid against Ferromagnetism and Phase Separation

We study the properties of Fermi Liquids with the microscopic constraint of a local self-energy. In this case the forward scattering sum-rule imposes strong limitations on the Fermi-Liquid parameters, which rule out any Pomeranchek instabilities. For both attractive and repulsive interactions, ferromagnetism and phase separation are suppressed. Superconductivity is possible in an s-wave channel only. We also study the approach to the metal-insulator transition, and find a Wilson ratio approaching 2. This ratio and other properties of Sr_{1-x}La_xTiO_3 are all consistent with the local Fermi Liquid scenario.Comment: 4 pages (twocolumn format), can compile with or without epsf.sty latex style file -- Postscript files: fig1.ps and fig2.p

Growth behavior of titanium dioxide thin films at different precursor temperatures

The hydrophilic TiO2 films were successfully deposited on slide glass substrates using titanium tetraisopropoxide as a single precursor without carriers or bubbling gases by a metal-organic chemical vapor deposition method. The TiO2 films were employed by scanning electron microscopy, Fourier transform infrared spectrometry, UV-Visible [UV-Vis] spectroscopy, X-ray diffraction, contact angle measurement, and atomic force microscopy. The temperature of the substrate was 500°C, and the temperatures of the precursor were kept at 75°C (sample A) and 60°C (sample B) during the TiO2 film growth. The TiO2 films were characterized by contact angle measurement and UV-Vis spectroscopy. Sample B has a very low contact angle of almost zero due to a superhydrophilic TiO2 surface, and transmittance is 76.85% at the range of 400 to 700 nm, so this condition is very optimal for hydrophilic TiO2 film deposition. However, when the temperature of the precursor is lower than 50°C or higher than 75°C, TiO2 could not be deposited on the substrate and a cloudy TiO2 film was formed due to the increase of surface roughness, respectively

Nitrogen doping of TiO2 photocatalyst forms a second eg state in the Oxygen (1s) NEXAFS pre-edge

Close inspection of the pre-edge in oxygen near-edge x-ray absorption fine structure spectra of single step, gas phase synthesized titanium oxynitride photocatalysts with 20 nm particle size reveals an additional eg resonance in the VB that went unnoticed in previous TiO2 anion doping studies. The relative spectral weight of this Ti(3d)-O(2p) hybridized state with respect to and located between the readily established t2g and eg resonances scales qualitatively with the photocatalytic decomposition power, suggesting that this extra resonance bears co-responsibility for the photocatalytic performance of titanium oxynitrides at visible light wavelengths

Double In Situ Approach for the Preparation of Polymer Nanocomposite with Multi-functionality

A novel one-step synthetic route, the double in situ approach, is used to produce both TiO2nanoparticles and polymer (PET), and simultaneously forming a nanocomposite with multi-functionality. The method uses the release of water during esterification to hydrolyze titanium (IV) butoxide (Ti(OBu)4) forming nano-TiO2in the polymerization vessel. This new approach is of general significance in the preparation of polymer nanocomposites, and will lead to a new route in the synthesis of multi-functional polymer nanocomposites

Implementation of earlier antibiotic administration in patients with severe sepsis and septic shock in Japan: a descriptive analysis of a prospective observational study.

BACKGROUND: Time to antibiotic administration is a key element in sepsis care; however, it is difficult to implement sepsis care bundles. Additionally, sepsis is different from other emergent conditions including acute coronary syndrome, stroke, or trauma. We aimed to describe the association between time to antibiotic administration and outcomes in patients with severe sepsis and septic shock in Japan. METHODS: This prospective observational study enrolled 1184 adult patients diagnosed with severe sepsis based on the Sepsis-2 criteria and admitted to 59 intensive care units (ICUs) in Japan between January 1, 2016, and March 31, 2017, as the sepsis cohort of the Focused Outcomes Research in Emergency Care in Acute Respiratory Distress Syndrome, Sepsis and Trauma (FORECAST) study. We compared the characteristics and in-hospital mortality of patients administered with antibiotics at varying durations after sepsis recognition, i.e., 0-60, 61-120, 121-180, 181-240, 241-360, and 361-1440 min, and estimated the impact of antibiotic timing on risk-adjusted in-hospital mortality using the generalized estimating equation model (GEE) with an exchangeable, within-group correlation matrix, with "hospital" as the grouping variable. RESULTS: Data from 1124 patients in 54 hospitals were used for analyses. Of these, 30.5% and 73.9% received antibiotics within 1 h and 3 h, respectively. Overall, the median time to antibiotic administration was 102 min [interquartile range (IQR), 55-189]. Compared with patients diagnosed in the emergency department [90 min (IQR, 48-164 min)], time to antibiotic administration was shortest in patients diagnosed in ICUs [60 min (39-180 min)] and longest in patients transferred from wards [120 min (62-226)]. Overall crude mortality was 23.4%, where patients in the 0-60 min group had the highest mortality (28.0%) and a risk-adjusted mortality rate [28.7% (95% CI 23.3-34.1%)], whereas those in the 61-120 min group had the lowest mortality (20.2%) and risk-adjusted mortality rates [21.6% (95% CI 16.5-26.6%)]. Differences in mortality were noted only between the 0-60 min and 61-120 min groups. CONCLUSIONS: We could not find any association between earlier antibiotic administration and reduction in in-hospital mortality in patients with severe sepsis