Prospective CO<Subscript>2</Subscript> emissions from energy supplying systems: photovoltaic systems and conventional grid within Spanish frame conditions

Background, aim, and scope  

In order to assess the environmental sustainability of a novel wastewater treatment process based on power an electrochemical reactor by photovoltaic solar modules (photovoltaic solar electrochemical oxidation), a life cycle approach was considered to quantify the CO₂ equivalent (CO₂-eq.) emissions coming from the two supplying power systems to the electrochemical process: conventional grid power or photovoltaic solar power under Spain frame conditions.     

Synthesis of Black TiOx Nanoparticles by Mg Reduction of TiO2 Nanocrystals and their Application for Solar Water Evaporation

TiO_x (x < 2) nanoparticles with tunable colors from white to gray to blue–gray to black are synthesized by magnesium (Mg) reduction of white P25 TiO₂ nanocrystals followed by removal of excess Mg with aqueous HCl and distilled water. Increasing amounts of Mg smoothly decrease the oxygen content in TiO_x which is responsible for the gradual increase in light absorption and concomitant darkening of its color from white to black with decreasing values of x. The as‐synthesized TiO_x nanoparticles are spin‐coated onto the surface of a stainless steel mesh followed by surface superhydrophobization in order to test their performance as a solar water evaporator. Results from the tests show that the black TiO_x efficiently generates water vapor with a solar thermal conversion efficiency as high as 50% under solar‐simulated light irradiance at an intensity of 1000 W m^–2 (1 Sun). Moreover, TiO_x nanoparticles have inherent advantages over other materials used for solar water desalination, such as their tunable light absorption, low‐cost, low‐toxicity, superhydrophobicity, and chemical stability.     

Enhanced Photocatalytic Activity for H2 Evolution under Irradiation of UV–Vis Light by Au-Modified Nitrogen-Doped TiO2

Background Purpose

Photocatalytic water splitting for hydrogen evolution is a potential way to solve many energy and environmental issues. Developing visible-light-active photocatalysts to efficiently utilize sunlight and finding proper ways to improve photocatalytic activity for H₂ evolution have always been hot topics for research. This study attempts to expand the use of sunlight and to enhance the photocatalytic activity of TiO₂ by N doping and Au loading.

Methods

Au/N-doped TiO₂ photocatalysts were synthesized and successfully used for photocatalytic water splitting for H₂ evolution under irradiation of UV and UV–vis light, respectively. The samples were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS), UV–vis diffuse reflectance spectroscopy (DRS), photoluminescence spectroscopy (PL), and photoelectrochemical characterizations.

Results

DRS displayed an extension of light absorption into the visible region by doping of N and depositing with Au, respectively. PL analysis indicated electron-hole recombination due to N doping and an efficient inhibition of electron-hole recombination due to the loaded Au particles. Under the irradiation of UV light, the photocatalytic hydrogen production rate of the as-synthesized samples followed the order Au/TiO₂ > Au/N-doped TiO₂ > TiO₂ > N-doped TiO₂. While under irradiation of UV–vis light, the N-TiO₂ and Au/N-TiO₂ samples show higher H₂ evolution than their corresponding nitrogen-free samples (TiO₂ and Au/TiO₂). This inconsistent result could be attributed to the doping of N and the surface plasmonic resonance (SPR) effect of Au particles extending the visible light absorption. The photoelectrochemical characterizations further indicated the enhancement of the visible light response of Au/N-doped TiO₂.

Conclusion

Comparative studies have shown that a combination of nitrogen doping and Au loading enhanced the visible light response of TiO₂ and increased the utilization of solar energy, greatly boosting the photocatalytic activity for hydrogen production under UV–vis light.     

UV‐Inert ZnTiO3 Electron Selective Layer for Photostable Perovskite Solar Cells

Although planar‐structured perovskite solar cells (PSCs) have power conversion efficiencies exceeding 24%, the poor photostability, especially with ultraviolet irradiance (UV) severely limits commercial application. The most commonly‐used TiO₂ electron selective layer has a strong photocatalytic effect on perovskite/TiO₂ interface when TiO₂ is excited by UV light. Here a UV‐inert ZnTiO₃ is reported as the electron selective layer in planar PSCs. ZnTiO₃ is a perovskite‐structured semiconductor with excellent chemical stability and poor photocatalysis. Solar cells are fabricated with a structure of indium doped tin oxide (ITO)/ZnTiO₃/Cs_0.05FA_0.81MA_0.14PbI_2.55Br_0.45/Sprio‐MeOTAD/Au. The champion device exhibits a stabilized power conversion efficiency of 19.8% with improved photostability. The device holds 90% of its initial efficiency after 100 h of UV soaking (365 nm, 8 mW cm^?2), compared with 55% for TiO₂‐based devices. This work provides a new class of electron selective materials with excellent UV stability in perovskite solar cell applications.     

Bactericidal Performance of Visible-Light Responsive Titania Photocatalyst with Silver Nanostructures

Background

Titania dioxide (TiO₂) photocatalyst is primarily induced by ultraviolet light irradiation. Visible-light responsive anion-doped TiO₂ photocatalysts contain higher quantum efficiency under sunlight and can be used safely in indoor settings without exposing to biohazardous ultraviolet light. The antibacterial efficiency, however, remains to be further improved.

Methodology/Principal Findings

Using thermal reduction method, here we synthesized silver-nanostructures coated TiO₂ thin films that contain a high visible-light responsive antibacterial property. Among our tested titania substrates including TiO₂, carbon-doped TiO₂ [TiO₂ (C)] and nitrogen-doped TiO₂ [TiO₂ (N)], TiO₂ (N) showed the best performance after silver coating. The synergistic antibacterial effect results approximately 5 log reductions of surviving bacteria of Escherichia coli, Streptococcus pyogenes, Staphylococcus aureus and Acinetobacter baumannii. Scanning electron microscope analysis indicated that crystalline silver formed unique wire-like nanostructures on TiO₂ (N) substrates, while formed relatively straight and thicker rod-shaped precipitates on the other two titania materials.

Conclusion/Significance

Our results suggested that proper forms of silver on various titania materials could further influence the bactericidal property.     

Sample processing for DNA chip array-based analysis of enterohemorrhagic <Emphasis Type="Italic">Escherichia coli</Emphasis> (EHEC)

Background  

Exploitation of DNA-based analyses of microbial pathogens, and especially simultaneous typing of several virulence-related genes in bacteria is becoming an important objective of public health these days.     

Antibacterial performance of nanoscaled visible-light responsive platinum-containing titania photocatalyst in vitro and in vivo

Background

Traditional antibacterial photocatalysts are primarily induced by ultraviolet light to elicit antibacterial reactive oxygen species. New generation visible-light responsive photocatalysts were discovered, offering greater opportunity to use photocatalysts as disinfectants in our living environment. Recently, we found that visible-light responsive platinum-containing titania (TiO₂–Pt) exerted high performance antibacterial property against soil-borne pathogens even in soil highly contaminated water. However, its physical and photocatalytic properties, and the application in vivo have not been well-characterized.

Methods

Transmission electron microscopy, energy dispersive spectroscopy, X-ray photoelectron spectroscopy, X-ray diffraction, ultraviolet–visible absorption spectrum and the removal rate of nitrogen oxides were therefore analyzed. The antibacterial performance under in vitro and in vivo conditions was evaluated.

Results

The apparent quantum efficiency for visible light illuminated TiO₂–Pt is relatively higher than several other titania photocatalysts. The killing effect achieved approximately 2 log reductions of pathogenic bacteria in vitro. Illumination of injected TiO₂–Pt successfully ameliorated the subcutaneous infection in mice.

Conclusions

This is the first demonstration of in vivo antibacterial use of TiO₂–Pt nanoparticles. When compared to nanoparticles of some other visible-light responsive photocatalysts, TiO₂–Pt nanoparticles induced less adverse effects such as exacerbated platelet clearance and hepatic cytotoxicity in vivo.

General significance

These findings suggest that the TiO₂–Pt may have potential application on the development of an antibacterial material in both in vitro and in vivo settings.     

Changes in water content and distribution in <Emphasis Type="Italic">Quercus ilex</Emphasis> leaves during progressive drought assessed by <Emphasis Type="Italic">in vivo</Emphasis><Superscript>1</Superscript>H magnetic resonance imaging

Background  

Drought is a common stressor in many regions of the world and current climatic global circulation models predict further increases in warming and drought in the coming decades in several of these regions, such as the Mediterranean basin. The changes in leaf water content, distribution and dynamics in plant tissues under different soil water availabilities are not well known. In order to fill this gap, in the present report we describe our study withholding the irrigation of the seedlings of Quercus ilex, the dominant tree species in the evergreen forests of many areas of the Mediterranean Basin. We have monitored the gradual changes in water content in the different leaf areas, in vivo and non-invasively, by ¹H magnetic resonance imaging (MRI) using proton density weighted (ρ_w) images and spin-spin relaxation time (T₂) maps.     

Spatial temperature distribution in human hairy and glabrous skin after infrared CO<Subscript>2</Subscript> laser radiation

Background  

CO₂ lasers have been used for several decades as an experimental non-touching pain stimulator. The laser energy is absorbed by the water content in the most superficial layers of the skin. The deeper located nociceptors are activated by passive conduction of heat from superficial to deeper skin layers.     

Interaction of <Emphasis Type="Italic">legionella pneumophila</Emphasis> and <Emphasis Type="Italic">helicobacter pylori</Emphasis> with bacterial species isolated from drinking water biofilms

Background  

It is well established that Legionella pneumophila is a waterborne pathogen; by contrast, the mode of Helicobacter pylori transmission remains unknown but water seems to play an important role. This work aims to study the influence of five microorganisms isolated from drinking water biofilms on the survival and integration of both of these pathogens into biofilms.     

Multifunctional Coatings from Scalable Single Source Precursor Chemistry in Tandem Photoelectrochemical Water Splitting

The straightforward and inexpensive fabrication of stabilized and activated photoelectrodes for application to tandem photoelectrochemical (PEC) water splitting is reported. Semiconductors such as Si, WO₃, and BiVO₄ can be coated with a composite layer formed upon hydrolytic decomposition of hetero­bimetallic single source precursors (SSPs) based on Ti and Ni, or Ti and Co in a simple single‐step process under ambient conditions. The resulting 3d‐transition metal oxide composite films are multifunctional, as they protect the semiconductor electrode from corrosion with an amorphous TiO₂ coating and act as bifunctional electrocatalysts for H₂ and O₂ evolution based on catalytic Ni or Co species. Thus, this approach enables the use of the same precursors for both photoelectrodes in tandem PEC water splitting, and SSP chemistry is thereby established as a highly versatile low‐cost approach to protect and activate photoelectrodes. In an optimized system, SSP coating of a Si photocathode and a BiVO₄ photoanode resulted in a benchmark noble metal‐free dual‐photoelectrode tandem PEC cell for overall solar water splitting with an applied bias solar‐to‐hydrogen conversion efficiency of 0.59% and a half‐life photostability of 5 h.     

Fullerene as a Photoelectron Transfer Promoter Enabling Stable TiO2‐Protected Sb2Se3 Photocathodes for Photo‐Electrochemical Water Splitting

Understanding the degradation mechanisms of photoelectrodes and improving their stability are essential for fully realizing solar‐to‐hydrogen conversion via photo‐electrochemical (PEC) devices. Although amorphous TiO₂ layers have been widely employed as a protective layer on top of p‐type semiconductors to implement durable photocathodes, gradual photocurrent degradation is still unavoidable. This study elucidates the photocurrent degradation mechanisms of TiO₂‐protected Sb₂Se₃ photocathodes and proposes a novel interface‐modification methodology in which fullerene (C₆₀) is introduced as a photoelectron transfer promoter for significantly enhancing long‐term stability. It is demonstrated that the accumulation of photogenerated electrons at the surface of the TiO₂ layer induces the reductive dissolution of TiO₂, accompanied by photocurrent degradation. In addition, the insertion of the C₆₀ photoelectron transfer promoter at the Pt/TiO₂ interface facilitates the rapid transfer of photogenerated electrons out of the TiO₂ layer, thereby yielding enhanced stability. The Pt/C₆₀/TiO₂/Sb₂Se₃ device exhibits a high photocurrent density of 17 mA cm^?2 and outstanding stability over 10 h of operation, representing the best PEC performance and long‐term stability compared with previously reported Sb₂Se₃‐based photocathodes. This research not only provides in‐depth understanding of the degradation mechanisms of TiO₂‐protected photocathodes, but also suggests a new direction to achieve durable photocathodes for photo‐electrochemical water splitting.     

Improving Efficiency of TiO<Subscript>2</Subscript>:Ag /Si Solar Cell Prepared by Pulsed Laser Deposition

Titanium dioxide (TiO₂) has been extensively studied and demonstrated to be suitable to enhance the efficiency of solar cell. In this work, TiO₂ is doped with silver nanoparticles (AgNP’s) on glass and the Si substrate by using Pulsed Laser Deposition (PLD) technique. UV–vis spectroscopy, X-ray diffraction (XRD), X-ray fluorescence (XRF), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Atomic Force Microscope (AFM), electrical conductivity (σ _dc), Hall coefficient (R_H), current–voltage (I–V), and capacity–voltage (C–V) characterizations have been used to examine the optical, the morphological, and the electrical properties of the films. It has been found that 5 wt.% (Ag) doped TiO₂ thin film has the most effect on efficiency of TiO₂:Ag /Si solar cell. The (I–V) characteristics showed that the (TiO₂) thin film enhances the efficiency of the (p–n) junction solar cell from 1.26 % pure TiO₂ to 7.19 % with doping of noble metal (Ag) representing improvement in the efficiency of solar cell leading to estimate empirical equations between efficiency, extinction coefficient, and energy band gap which have a total fit with the experimental data.     

Stable coexistence of two <Emphasis Type="Italic">Caldicellulosiruptor</Emphasis> species in a <Emphasis Type="Italic">de novo</Emphasis> constructed hydrogen-producing co-culture

Background  

Mixed culture enrichments have been used frequently for biohydrogen production from different feedstock. In spite of the several advantages offered by those cultures, they suffer poor H₂ yield. Constructing defined co-cultures of known H₂ producers may offer a better performance than mixed-population enrichments, while overcoming some of the limitations of pure cultures based on synergies among the microorganisms involved.     

Effect of a disinfection strategy on the methicillin‐resistant Staphylococcus aureus CC398 prevalence of sows,their piglets and the barn environment

Aims

To assess, in a cleaned and disinfected barn environment, the efficacy of an animal disinfection strategy to reduce the livestock‐associated methicillin‐resistant Staphylococcus aureus (LA‐MRSA) prevalence in sows, their offspring and the barn environment.

Methods and Results

On each farm, six sow rounds were sampled; sows were divided into either a test or control group. Per round, 20 sows and 40 of their piglets were sampled at different time points together with the barn environment. The disinfection strategy of the test groups consisted of washing the sows with a shampoo followed by disinfection of the skin with a solution containing chlorhexidine digluconate and isopropanol. On the first day of disinfection and 6 days after stopping the disinfection, a significant decrease (P < 0·01) of on average 68 and 66% in sow MRSA prevalence was observed on both farms, whereas no decrease was seen in the control groups. Just before weaning, 21–28 days after the end of the disinfection strategy, the difference in MRSA prevalence between both groups was reduced to 4% and no longer significant (P = 0·20). The MRSA prevalence of the piglets in the test groups was significantly lower (26%; P < 0·01) 6 days after the end of disinfection. Just before weaning, this difference was reduced to 5% but still significant (P < 0·01). In the swine nursery unit, no significant difference (P = 0·99) was seen between both groups. Based on semi‐quantitative counts, a relationship (r² > 0·6; P < 0·01) was seen between MRSA contamination in the barn environment and the MRSA prevalence in pigs.

Conclusion

Results show that the tested disinfection strategy reduces temporarily the sow and piglet MRSA status, but does not result in a final reduction in MRSA at weaning or in the nursery unit.

Significance and Impact of the Study

First report on the efficacy of an animal disinfection strategy to reduce LA‐MRSA prevalence in sows, their offspring and the barn environment.     

A Hierarchically Organized Photoelectrode Architecture for Highly Efficient CdS/CdSe‐Sensitized Solar Cells

A form of photoelectrode architecture suitable for inorganic semiconductor solar cells is reported. The developed architecture consists of hierarchically organized TiO₂ nanostructures with several tens of nanometer‐sized particles that have a large surface area and open channels with several hundred‐nanometer‐gaps perpendicular to the substrate. These are tailored by controlling the kinetic energy of the ablated species during pulsed laser deposition (PLD). To fabricate the solar cells, CdS and CdSe inorganic sensitizers are assembled onto the architecture by successive ionic layer adsorption and reaction and polysulfide solution is used as an electrolyte with lead sulfide counter‐electrodes. The inorganic semiconductor solar cells using the developed architecture (PLD‐TiO₂) show high energy conversion efficiencies of 5.57% compared to a conventional mesoporous TiO₂ film(NP‐TiO₂) (3.84%) with an optical mask at 1 sun of illumination. The improved cell performance of PLD‐TiO₂ is attributed to greater light‐harvesting ability, which results in the enhancement of the J_sc value. PLD‐TiO₂ absorbs more CdS/CdSe because of its larger surface area and excellent adhesion properties with fluorine‐doped tin oxide (FTO) substrates. Additionally, due to its unique channel‐shaped architecture, PLD‐TiO₂ has a longer electron lifetime compared to NP‐TiO₂.     

Acute Toxicity of Intravenously Administered Titanium Dioxide Nanoparticles in Mice

Background

With a wide range of applications, titanium dioxide (TiO₂) nanoparticles (NPs) are manufactured worldwide in large quantities. Recently, in the field of nanomedicine, intravenous injection of TiO₂ nanoparticulate carriers directly into the bloodstream has raised public concerns on their toxicity to humans.

Methods

In this study, mice were injected intravenously with a single dose of TiO₂ NPs at varying dose levels (0, 140, 300, 645, or 1387 mg/kg). Animal mortality, blood biochemistry, hematology, genotoxicity and histopathology were investigated 14 days after treatment.

Results

Death of mice in the highest dose (1387 mg/kg) group was observed at day two after TiO₂ NPs injection. At day 7, acute toxicity symptoms, such as decreased physical activity and decreased intake of food and water, were observed in the highest dose group. Hematological analysis and the micronucleus test showed no significant acute hematological or genetic toxicity except an increase in the white blood cell (WBC) count among mice 645 mg/kg dose group. However, the spleen of the mice showed significantly higher tissue weight/body weight (BW) coefficients, and lower liver and kidney coefficients in the TiO₂ NPs treated mice compared to control. The biochemical parameters and histological tissue sections indicated that TiO₂ NPs treatment could induce different degrees of damage in the brain, lung, spleen, liver and kidneys. However, no pathological effects were observed in the heart in TiO₂ NPs treated mice.

Conclusions

Intravenous injection of TiO₂ NPs at high doses in mice could cause acute toxicity effects in the brain, lung, spleen, liver, and kidney. No significant hematological or genetic toxicity was observed.     

Sterilization effects of a TiO<Subscript>2</Subscript> photocatalytic film against a<Emphasis Type="Italic">Streptococcus mutans</Emphasis> culture

Streptococcus mutans is one of the more significant pathogens involved in the development of dental caries in humans. The purpose of this research was to design a TiO₂-coated dental instrument and to determine the bactericidal effects of the instrument onS. mutants. TiO₂ photocatalytic films were prepared by the low-pressure metal-organic chemical vapor deposition (LPMOCVD) method using titanium tetraisopropoxide (TTIP) as precursor. The photocatalytic reaction was carried out on a TiO₂-coated pyrex petri dish with an ultraviolet (UV) light emitting diode (LED) illuminator or a fluorescent lamp light source. Our data indicates that the relative survival ratio ofS. mutans when plated onto TiO₂ photocatalytic films and under exposure to UV-A light for 15 min was 0.01%. In addition, a fluorescent lamp light source also had bactericidal effects on theS. mutans plated TiO₂ photocatalytic films. These results indicate that TiO₂-coated dental materials or devices may be useful in dental treatments for the prevention of carious or enamel demineralization.     

TiO2 Nanocrystals Synthesized by Laser Pyrolysis for the Up‐Scaling of Efficient Solid‐State Dye‐Sensitized Solar Cells

A crucial issue regarding emerging nanotechnologies remains the up‐scaling of new functional nanostructured materials towards their implementation in high performance applications on a large scale. In this context, we demonstrate high efficiency solid‐state dye‐sensitized solar cells prepared from new porous TiO₂ photoanodes based on laser pyrolysis nanocrystals. This strategy exploits a reduced number of processing steps as well as non‐toxic chemical compounds to demonstrate highly porous TiO₂ films. The possibility to easily tune the TiO₂ nanocrystal physical properties allows us to demonstrate all solid‐state dye‐sensitized devices based on a commercial benchmark materials (organic indoline dye and molecular hole transporter) presenting state‐of‐the‐art performance comparable with reference devices based on a commercial TiO₂ paste. In particular, a drastic improvement in pore infiltration, which is found to balance a relatively lower surface area compared to the reference electrode, is evidenced using laser‐synthesized nanocrystals resulting in an improved short‐circuit current density under full sunlight. Transient photovoltage decay measurements suggest that charge recombination kinetics still limit device performance. However, the proposed strategy emphasizes the potentialities of the laser pyrolysis technique for up‐scaling nanoporous TiO₂ electrodes for various applications, especially for solar energy conversion.     

Gold nanorods-conjugated TiO<Subscript>2</Subscript> nanoclusters for the synergistic combination of phototherapeutic treatments of cancer cells

Background

Recently, a combination of photodynamic therapy (PDT) and photothermal therapy (PTT) to generate reactive oxygen species (ROS) and heat to kill cancer cells, respectively has attracted considerable attention because it gives synergistic effects on the cancer treatment by utilizing the radiation of nontoxic low-energy photons such as long wavelength visible light and near IR (NIR) penetrating into subcutaneous region. For the effective combination of the phototherapies, various organic photosensitizer-conjugated gold nanocomplexes have been developed, but they have still some disadvantages due to photobleaching and unnecessary energy transfer of the organic photosensitizers.

Results

In this study, we fabricated novel inorganic phototherapeutic nanocomplexes (Au NR–TiO₂ NCs) by conjugating gold nanorods (Au NRs) with defective TiO₂ nanoparticle clusters (d-TiO₂ NP clusters) and characterized their optical and photothermal properties. They were observed to absorb a broad range of visible light and near IR (NIR) from 500 to 1000 nm, exhibiting the generation of ROS as well as the photothermal effect for the simultaneous application of PDT and PTT. The resultant combination of PDT and PTT treatments of HeLa cells incubated with the nanocomplexes caused a synergistic increase in the cell death compared to the single treatment.

Conclusion

The higher efficacy of cell death by the combination of PDT and PTT treatments with the nanocomplexes is likely attributed to the increases of ROS generation from the TiO₂ NCs with the aid of local surface plasma resonance (LSPR)-induced hot electrons and heat generation from Au NRs, suggesting that Au NR–TiO₂ NCs are promising nanomaterials for the in vivo combinatorial phototherapy of cancer.