Empowering Adsorption and Photocatalytic Degradation of Ciprofloxacin on BiOI Composites: A Material-by-Design Investigation.

Binary and ternary composites of BiOI with NH2-MIL-101(Fe) and a functionalized biochar were synthesized through an in situ approach, aimed at spurring the activity of the semiconductor as a photocatalyst for the removal of ciprofloxacin (CIP) from water. Experimental outcomes showed a drastic enhancement of the adsorption and the equilibrium (which increased from 39.31 mg g-1 of bare BiOI to 76.39 mg g-1 of the best ternary composite in 2 h time), while the kinetics of the process was not significantly changed. The photocatalytic performance was also significantly enhanced, and the complete removal of 10 ppm of CIP in 3 h reaction time was recorded under simulated solar light irradiation for the best catalyst of the investigated batch. Catalytic reactions supported by different materials obeyed different reaction orders, indicating the existence of different mechanisms. The use of scavengers for superoxide anion radicals, holes, and hydroxyl radicals showed that although all these species are involved in CIP photodegradation, the latter play the most crucial role, as also confirmed by carrying out the reaction at increasing pH conditions. A clear correlation between the reduction of BiOI crystallite sizes in the composites, as compared to the bare material, and the material performance as both adsorbers and photocatalyst was identified.

Tunable physics through coordination chemistry: formation on oxide surface of Ti and Al chelates with 3-hydroxyflavone capable of electron injection and light emission.

The optoelectronic features of 3-hydroxyflavone (3HF) self-assembled on the surface of an n-type semiconducting metal oxide (TiO2) and an insulator (Al2O3) are herein investigated. 3HF molecules use the coordinatively unsaturated metal ions present on the oxide surface to form metal complexes, which exhibit different behaviors upon light irradiation, depending on the nature of the metal ion. Specifically, we show that the photoluminescence of the surface species can be modulated according to the chemical properties of the complex (i.e. the binding metal ion), resulting in solid-state emitters in a high quantum yield (about 15%). Furthermore, photoinduced charge injection can be promoted or inhibited, providing a multifunctional hybrid system.

Improved thermoelectric performance of Bi-deficient BiCuSeO material doped with Nb, Y, and P.

Thermoelectric materials convert waste heat into electric energy. Oxyselenide-based material, specifically, p-type BiCuSeO, is one of the most promising materials for these applications. There are numerous approaches to improve the heat-to-electricity conversion performance. Usually, these approaches are applied individually, starting from the pure intrinsic material. Higher performance could, however, be reached by combining a few strategies simultaneously. In the current work, yttrium, niobium, and phosphorous substitutions on the bismuth sites in already bismuth-deficient Bi1-xCuSeO systems were investigated via density functional theory. The bismuth-deficient system was used as the reference system for further introduction of substitutional defects. The substitution with phosphorous showed a decrease of up to 40 meV (11%) in the energy gap between conduction and valence bands at the highest substitution concentration. Doping with niobium led to the system changing from a p-type to an n-type conductor, which provides a possible route to obtain n-type BiCuSeO systems.

miR-9 modulates and predicts the response to radiotherapy and EGFR inhibition in HNSCC.

Radiotherapy (RT) plus the anti-EGFR monoclonal antibody Cetuximab (CTX) is an effective combination therapy for a subset of head and neck squamous cell carcinoma (HNSCC) patients. However, predictive markers of efficacy are missing, resulting in many patients treated with disappointing results and unnecessary toxicities. Here, we report that activation of EGFR upregulates miR-9 expression, which sustains the aggressiveness of HNSCC cells and protects from RT-induced cell death. Mechanistically, by targeting KLF5, miR-9 regulates the expression of the transcription factor Sp1 that, in turn, stimulates tumor growth and confers resistance to RT+CTX in vitro and in vivo. Intriguingly, high miR-9 levels have no effect on the sensitivity of HNSCC cells to cisplatin. In primary HNSCC, miR-9 expression correlated with Sp1 mRNA levels and high miR-9 expression predicted poor prognosis in patients treated with RT+CTX. Overall, we have discovered a new signaling axis linking EGFR activation to Sp1 expression that dictates the response to combination treatments in HNSCC. We propose that miR-9 may represent a valuable biomarker to select which HNSCC patients might benefit from RT+CTX therapy.

Electron spectroscopies of 3-hydroxyflavone and 7-hydroxyflavone in MCM-41 silica nanoparticles and in acetonitrile solutions. Experimental data and DFT/TD-DFT calculations.

The data presented here concern the photophysical characterization of luminescent MCM-41 nanoparticles doped with 3-hydroxyflavone and 7-hydroxyflavone, two fluorescent flavonoids. UV-Vis and fluorescence spectra obtained on freshly-prepared samples and aged (2 months exposed to air) samples are shown. The effect of light exposure is also studied. In parallel, experiments have been carried out in acetonitrile solutions of the two flavonoids as a term of comparison. Time-dependent density functional theory calculations have also been used to simulate UV-Vis and emission spectra of different species for both flavonoids (neutral molecule, tautomers, cationic and anionic forms), taking into account the effect of the surrounding medium (solvent). Density functional theory calculations of vibrational spectra (IR, Raman) of neutral and tautomeric species of 3HF and 7HF are also provided.

Nanoscale characterization of an all-oxide core-shell nanorod heterojunction using intermodulation atomic force microscopy (AFM) methods.

The electrical properties of an all-oxide core-shell ZnO-Co3O4 nanorod heterojunction were studied in the dark and under UV-vis illumination. The contact potential difference and current distribution maps were obtained utilizing new methods in dynamic multifrequency atomic force microscopy (AFM) such as electrostatic and conductive intermodulation AFM. Light irradiation modified the electrical properties of the nanorod heterojunction. The new techniques are able to follow the instantaneous local variation of the photocurrent, giving a two-dimensional (2D) map of the current-voltage curves and correlating the electrical and morphological features of the heterostructured core-shell nanorods.

Zinc phthalocyanines as light harvesters for SnO2-based solar cells: a case study.

SnO2 nanoparticles have been synthesized and used as electron transport material (ETM) in dye sensitized solar cells (DSSCs), featuring two peripherally substituted push-pull zinc phthalocyanines (ZnPcs) bearing electron donating diphenylamine substituents and carboxylic acid anchoring groups as light harvesters. These complexes were designed on the base of previous computational studies suggesting that the integration of secondary amines as donor groups in the structure of unsymmetrical ZnPcs might enhance photovoltaics performances of DSSCs. In the case of TiO2-based devices, this hypothesis has been recently questioned by experimental results. Herein we show that the same holds for SnO2, despite the optimal matching of the optoelectronic characteristics of the synthesized nanoparticles and diphenylamino-substituted ZnPcs, thus confirming that other parameters heavily affect the solar cells performances and should be carefully taken into account when designing materials for photovoltaic applications.

Self-Powered Photodetectors Based on Core-Shell ZnO-Co3O4 Nanowire Heterojunctions.

Self-powered photodetectors operating in the UV-visible-NIR window made of environmentally friendly, earth abundant, and cheap materials are appealing systems to exploit natural solar radiation without external power sources. In this study, we propose a new p-n junction nanostructure, based on a ZnO-Co3O4 core-shell nanowire (NW) system, with a suitable electronic band structure and improved light absorption, charge transport, and charge collection, to build an efficient UV-visible-NIR p-n heterojunction photodetector. Ultrathin Co3O4 films (in the range 1-15 nm) were sputter-deposited on hydrothermally grown ZnO NW arrays. The effect of a thin layer of the Al2O3 buffer layer between ZnO and Co3O4 was investigated, which may inhibit charge recombination, boosting device performance. The photoresponse of the ZnO-Al2O3-Co3O4 system at zero bias is 6 times higher compared to that of ZnO-Co3O4. The responsivity ( R) and specific detectivity ( D*) of the best device were 21.80 mA W-1 and 4.12 × 1012 Jones, respectively. These results suggest a novel p-n junction structure to develop all-oxide UV-vis photodetectors based on stable, nontoxic, low-cost materials.

Ag2S/MoS2 Nanocomposites Anchored on Reduced Graphene Oxide: Fast Interfacial Charge Transfer for Hydrogen Evolution Reaction.

Hydrogen evolution reaction through electrolysis holds great potential as a clean, renewable, and sustainable energy source. Platinum-based catalysts are the most efficient to catalyze and convert water into molecular hydrogen; however, their large-scale application is prevented by scarcity and cost of Pt. In this work, we propose a new ternary composite of Ag2S, MoS2, and reduced graphene oxide (RGO) flakes via a one-pot synthesis. The RGO support assists the growth of two-dimensional MoS2 nanosheets partially covered by silver sulfides as revealed by high-resolution transmission electron microscopy. Compared with the bare MoS2 and MoS2/RGO, the Ag2S/MoS2 anchored on the RGO surface (the ternary system Ag2S/MoS2/RGO) demonstrated a high catalytic activity toward hydrogen evolution reaction (HER). Its superior electrochemical activity toward HER is evidenced by the positively shifted (-190 mV vs reversible hydrogen electrode (RHE)) overpotential at a current density of -10 mA/cm2 and a small Tafel slope (56 mV/dec) compared with a bare and binary system. The Ag2S/MoS2/RGO ternary catalyst at an overpotential of -200 mV demonstrated a turnover frequency equal to 0.38 s-1. Electrochemical impedance spectroscopy was applied to understand the charge-transfer resistance; the ternary sample shows a very small charge-transfer resistance (98 Ω) at -155 mV vs RHE. Such a large improvement can be attributed to the synergistic effect resulting from the enhanced active site density of both sulfides and to the improved electrical conductivity at the interfaces between MoS2 and Ag2S. This ternary catalyst opens up further optimization strategies to design a stable and cheap catalyst for hydrogen evolution reaction, which holds great promise for the development of a clean energy landscape.

Surface modification by vanadium pentoxide turns oxide nanocrystals into powerful adsorbents of methylene blue.

HYPOTHESIS: If nanocrystals of such semiconductor as SnO2 and TiO2, which are not known as powerful adsorbents, have their surface modified by layer of V2O5, how will the adsorption properties be affected? Answering this question would provide a new set of surface properties to be designed by surface engineering of oxide nanocrystals. EXPERIMENTS: SnO2 and TiO2 colloidal nanocrystals were prepared by coupling sol-gel and solvothermal synthesis. By co-processing with V chloroalkoxide and subsequent heat-treatment at 400-500 °C, surface deposition of V2O5 layers was obtained. The methylene blue adsorption onto the prepared materials was tested and compared with the pure oxide supports. Cycling of the materials and analysis of the adsorption process was also investigated. FINDINGS: The V-modified nanocrystals extracted ∼80% methylene blue from 1.5 × 10-5 M aqueous solution after 15 min only, contrarily to pure materials, which took up only 30% of the dye even after 120 min. Comparison with pure commercial V2O5 showed that the peculiar adsorption properties were imparted by the surface deposition of the V2O5-like layers. This report demonstrates that new classes of adsorbing materials can be conceived by suitably coupling different metal oxides.

Dye-sensitized solar cells based on a push-pull zinc phthalocyanine bearing diphenylamine donor groups: computational predictions face experimental reality.

Computational studies have suggested that the integration of secondary amine as donor groups in the structure of unsymmetrical zinc phthalocyanine (ZnPc) should have positive effects on photovoltaic performance, once the molecule is integrated as light harvester in dye sensitized solar cells (DSSCs). Aiming at obtaining experimental confirmation, we synthesized a peripherally substituted push-pull ZnPc bearing three electron donating diphenylamine substituents and a carboxylic acid anchoring group and integrated it as sensitizer in TiO2-based DSSCs. Detailed functional characterization of solar energy converting devices resulted in ruling out the original hypothesis. The causes of this discrepancy have been highlighted, leading to a better understanding of the conditions for an effective design of push-pull diarylamino substituted ZnPcs for DSSCs.

Deposition of Nanostructured CdS Thin Films by Thermal Evaporation Method: Effect of Substrate Temperature.

Nanocrystalline CdS thin films were grown on glass substrates by a thermal evaporation method in a vacuum of about 2 × 10-5 Torr at substrate temperatures ranging between 25 °C and 250 °C. The physical properties of the layers were analyzed by transmittance spectra, XRD, SEM, and four-point probe measurements, and exhibited strong dependence on substrate temperature. The XRD patterns of the films indicated the presence of single-phase hexagonal CdS with (002) orientation. The structural parameters of CdS thin films (namely crystallite size, number of grains per unit area, dislocation density and the strain of the deposited films) were also calculated. The resistivity of the as-deposited films were found to vary in the range 3.11-2.2 × 104 Ω·cm, depending on the substrate temperature. The low resistivity with reasonable transmittance suggest that this is a reliable way to fine-tune the functional properties of CdS films according to the specific application.

Corrigendum: Inorganic Photocatalytic Enhancement: Activated RhB Photodegradation by Surface Modification of SnO2 Nanocrystals with V2O5-like species.

This corrects the article DOI: 10.1038/srep44763.

Inorganic Photocatalytic Enhancement: Activated RhB Photodegradation by Surface Modification of SnO2 Nanocrystals with V2O5-like species.

SnO2 nanocrystals were prepared by precipitation in dodecylamine at 100 °C, then they were reacted with vanadium chloromethoxide in oleic acid at 250 °C. The resulting materials were heat-treated at various temperatures up to 650 °C for thermal stabilization, chemical purification and for studying the overall structural transformations. From the crossed use of various characterization techniques, it emerged that the as-prepared materials were constituted by cassiterite SnO2 nanocrystals with a surface modified by isolated V(IV) oxide species. After heat-treatment at 400 °C, the SnO2 nanocrystals were wrapped by layers composed of vanadium oxide (IV-V mixed oxidation state) and carbon residuals. After heating at 500 °C, only SnO2 cassiterite nanocrystals were obtained, with a mean size of 2.8 nm and wrapped by only V2O5-like species. The samples heat-treated at 500 °C were tested as RhB photodegradation catalysts. At 10-7 M concentration, all RhB was degraded within 1 h of reaction, at a much faster rate than all pure SnO2 materials reported until now.

A Player Often Neglected: Electrochemical Comprehensive Analysis of Counter Electrodes for Quantum Dot Solar Cells.

The role played by the counter electrode (CE) in quantum dot sensitized solar cells (QDSSCs) is crucial: it is indeed responsible for catalyzing the regeneration of the redox electrolyte after its action to take back the oxidized light harvesters to the ground state, thus keeping the device active and stable. The activity of CE is moreover directly related to the fill factor and short circuit current through the resistance of the interface electrode-electrolyte that affects the series resistance of the cell. Despite that, too few efforts have been devoted to a comprehensive analysis of this important device component. In this work we combine an extensive electrochemical characterization of the most common materials exploited as CEs in QDSSCs (namely, Pt, Au, Cu2S obtained by brass treatment, and Cu2S deposited on conducting glass via spray) with a detailed characterization of their surface composition and morphology, aimed at systematically defining the relationship between their nature and electrocatalytic activity.

Metal-free organic dyes for TiO2 and ZnO dye-sensitized solar cells.

We report the synthesis and characterization of new metal-free organic dyes (namely B18, BTD-R, and CPTD-R) which designed with D-π-A concept to extending the light absorption region by strong conjugation group of π-linker part and applied as light harvester in dye sensitized solar cells (DSSCs). We compared the photovoltaic performance of these dyes in two different photoanodes: a standard TiO2 mesoporous photoanode and a ZnO photoanode composed of hierarchically assembled nanostructures. The results demonstrated that B18 dye has better photovoltaic properties compared to other two dyes (BTD-R and CPTD-R) and each dye has higher current density (Jsc) when applied to hierarchical ZnO nanocrystallites than the standard TiO2 mesoporous film. Transient photocurrent and photovoltage decay measurements (TCD/TVD) were applied to systematically study the charge transport and recombination kinetics in these devices, showing the electron life time (τR) of B18 dye in ZnO and TiO2 based DSSCs is higher than CPTD-R and BTD-R based DSSCs, which is consistent with the photovoltaic performances. The conversion efficiency in ZnO based DSSCs can be further boosted by 35%, when a compact ZnO blocking layer (BL) is applied to inhibit electron back reaction.

Modulating Exciton Dynamics in Composite Nanocrystals for Excitonic Solar Cells.

Quantum dots (QDs) represent one of the most promising materials for third-generation solar cells due to their potential to boost the photoconversion efficiency beyond the Shockley-Queisser limit. Composite nanocrystals can challenge the current scenario by combining broad spectral response and tailored energy levels to favor charge extraction and reduce energy and charge recombination. We synthesized PbS/CdS QDs with different compositions at the surface of TiO2 nanoparticles assembled in a mesoporous film. The ultrafast photoinduced dynamics and the charge injection processes were investigated by pump-probe spectroscopy. We demonstrated good injection of photogenerated electrons from QDs to TiO2 in the PbS/CdS blend and used the QDs to fabricate solar cells. The fine-tuning of chemical composition and size of lead and cadmium chalcogenide QDs led to highly efficient PV devices (3% maximum photoconversion efficiency). This combined study paves the way to the full exploitation of QDs in next-generation photovoltaic (PV) devices.

Metal oxide semiconductors for dye- and quantum-dot-sensitized solar cells.

This Review provides a brief summary of the most recent research developments in the synthesis and application of nanostructured metal oxide semiconductors for dye sensitized and quantum dot sensitized solar cells. In these devices, the wide bandgap semiconducting oxide acts as the photoanode, which provides the scaffold for light harvesters (either dye molecules or quantum dots) and electron collection. For this reason, proper tailoring of the optical and electronic properties of the photoanode can significantly boost the functionalities of the operating device. Optimization of the functional properties relies with modulation of the shape and structure of the photoanode, as well as on application of different materials (TiO2, ZnO, SnO2) and/or composite systems, which allow fine tuning of electronic band structure. This aspect is critical because it determines exciton and charge dynamics in the photoelectrochemical system and is strictly connected to the photoconversion efficiency of the solar cell. The different strategies for increasing light harvesting and charge collection, inhibiting charge losses due to recombination phenomena, are reviewed thoroughly, highlighting the benefits of proper photoanode preparation, and its crucial role in the development of high efficiency dye sensitized and quantum dot sensitized solar cells.

Effect of blocking layer to boost photoconversion efficiency in ZnO dye-sensitized solar cells.

The effect of a ZnO compact blocking layer (BL) in dye-sensitized solar cells (DSSCs) based on ZnO photoanodes is investigated. BL is generated through spray deposition onto fluorine-doped tin oxide (FTO) conducting glass before the deposition of a ZnO active layer. The functional properties of dye-sensitized solar cells (DSSCs) are then investigated as a function of the thickness of the BL for two different kinds of ZnO active layer, i.e., hierarchically self-assembled nanoparticles and microcubes composed of closely packed ZnO sheets. Presence of BL leads to the improvement of photoconversion efficiency (PCE), by physically insulating the electrolyte and the FTO. This effect increases at increasing BL thickness up to around 800 nm, while thicker BL results in reduced cell performance. Remarkable increase in Jsc is recorded, which doubles as compared to cells without blocking layer, leading to PCE as high as 5.6% in the best cell under one sun irradiation (AM 1.5 G, 100 mW cm(-2)). Electrochemical impedance spectroscopy (EIS) elucidates the mechanism boosting the functional features of the cells with BL, which relies with enhanced chemical capacitance together with an almost unchanged recombination resistance, which are reflected in an increased electron lifetime. The results foresee a straightforward way to significantly improve the performance of ZnO-based DSSCs.

Nanostructured metal oxide gas sensors, a survey of applications carried out at SENSOR lab, Brescia (Italy) in the security and food quality fields.

In this work we report on metal oxide (MOX) based gas sensors, presenting the work done at the SENSOR laboratory of the CNR-IDASC and University of Brescia, Italy since the 80s up to the latest results achieved in recent times. In particular we report the strategies followed at SENSOR during these 30 years to increase the performance of MOX sensors through the development of different preparation techniques, from Rheotaxial Growth Thermal Oxidation (RGTO) to nanowire technology to address sensitivity and stability, and the development of electronic nose systems and pattern recognition techniques to address selectivity. We will show the obtained achievement in the context of selected applications such as safety and security and food quality control.