Ultrasound-assisted water oxidation: unveiling the role of piezoelectric metal-oxide sonocatalysts for cancer treatment.

Ultrasound radiation has been widely used in biomedical application for both diagnosis and therapy. Metal oxides nanoparticles (NPs), like ZnO or TiO2 NPs, have been widely demonstrated to act as excellent sonocatalysts and significantly enhance cavitation at their surface, making them optimal for sonodynamic cancer therapy. These NPs often possess semiconductive and piezoelectric properties that contribute to the complex phenomena occurring at the water-oxide interface during sonostimulation. Despite the great potential in applied sonocatalysis and water splitting, the complex mechanism that governs the phenomenon is still a research subject. This work investigates the role of piezoelectric ZnO micro- and nano-particles in ultrasound-assisted water oxidation. Three metal oxides presenting fundamental electronic and mechanical differences are evaluated in terms of ultrasound-triggered reactive oxygen species generation in aqueous media: electromechanically inert SiO2 NPs, semiconducting TiO2 NPs, piezoelectric and semiconducting ZnO micro- and nanoparticles with different surface areas and sizes. The presence of silver ions in the aqueous solution was further considered to impart a potential electron scavenging effects and better evaluate the oxygen generation performances of the different structures. Following sonoirradiation, the particles are optically and chemically analyzed to study the effect of sonostimulation at their surface. The production of gaseous molecular oxygen is measured, revealing the potential of piezoelectric particles to generate oxygen under hypoxic conditions typical of some cancer environments. Finally, the best candidates, i.e. ZnO nano and micro particles, were tested on osteosarcoma and glioblastoma cell lines to demonstrate their potential for cancer treatment.

Chemically induced porosity on BiVO4 films produced by double magnetron sputtering to enhance the photo-electrochemical response.

Double magnetron sputtering (DMS) is an efficient system that is well known because of its precise control of the thin film synthesizing process over any kind of substrate. Here, DMS has been adopted to synthesize BiVO4 films over a conducting substrate (FTO), using metallic vanadium and ceramic Bi2O3 targets simultaneously. The films were characterized using different techniques, such as X-ray diffraction (XRD), UV-Vis spectroscopy, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), field emission scanning electron microscopy (FESEM) and profilometry. The photo-electrochemical analysis was performed using linear scan voltammetry, chronoamperometry and electrochemical impedance spectroscopy (EIS) under the illumination of simulated solar light at 1 Sun. The photocurrent density of the sputtered BiVO4 thin films could be improved from 0.01 mA cm(-2) to 1.19 mA cm(-2) at 1.23 V vs. RHE by chemical treatment using potassium hydroxide (KOH). The effect of KOH was the removal of impurities from the grain boundaries, leading to a more porous structure and more pure crystalline monoclinic BiVO4 particles. Such variations in the microstructure as well as the improvement of the charge transfer properties of the BiVO4 film after the KOH treatment were confirmed and studied in depth by EIS analysis.

Comparison of photocatalytic and transport properties of TiO2 and ZnO nanostructures for solar-driven water splitting.

Titanium dioxide (TiO2) and zinc oxide (ZnO) nanostructures have been widely used as photo-catalysts due to their low-cost, high surface area, robustness, abundance and non-toxicity. In this work, four TiO2 and ZnO-based nanostructures, i.e. TiO2 nanoparticles (TiO2 NPs), TiO2 nanotubes (TiO2 NTs), ZnO nanowires (ZnO NWs) and ZnO@TiO2 core-shell structures, specifically prepared with a fixed thickness of about 1.5 µm, are compared for the solar-driven water splitting reaction, under AM1.5G simulated sunlight. Complete characterization of these photo-electrodes in their structural and photo-electrochemical properties was carried out. Both TiO2 NPs and NTs showed photo-current saturation reaching 0.02 and 0.12 mA cm(-2), respectively, for potential values of about 0.3 and 0.6 V vs. RHE. In contrast, the ZnO NWs and the ZnO@TiO2 core-shell samples evidence a linear increase of the photocurrent with the applied potential, reaching 0.45 and 0.63 mA cm(-2) at 1.7 V vs. RHE, respectively. However, under concentrated light conditions, the TiO2 NTs demonstrate a higher increase of the performance with respect to the ZnO@TiO2 core-shells. Such material-dependent behaviours are discussed in relation with the different charge transport mechanisms and interfacial reaction kinetics, which were investigated through electrochemical impedance spectroscopy. The role of key parameters such as electronic properties, specific surface area and photo-catalytic activity in the performance of these materials is discussed. Moreover, proper optimization strategies are analysed in view of increasing the efficiency of the best performing TiO2 and ZnO-based nanostructures, toward their practical application in a solar water splitting device.

The behaviour of an old catalyst revisited in a wet environment: Co ions in APO-5 split water under mild conditions.

Samples of the activated microporous aluminophosphate Co-APO-5, featuring ca. 20% of Co(3+) cations, when immersed in water evolve molecular oxygen at room temperature in an endothermic process, without the need for either light or a sacrificial reactant. Successive drying of the sample at temperatures around 520 K releases molecular hydrogen, with recovery of the initial conditions. Several hydration-dehydration cycles may be performed without loss of activity, i.e. water is split in a thermal cycle under relatively mild conditions.

Ultra-fast photocatalytic degradation of Rhodamine B exploiting oleate-stabilized zinc oxide nanoparticles.

Rhodamine B (RhB) is a harmful dye released by industrial wastewaters, thus necessitating its urgent removal. Advanced oxidation processes constitute promising strategies to purify polluted water. Among others, photocatalysis relies on reactive oxygen species (ROS) produced by photocatalytic particles, typically semiconductors like titania or zinc oxide (ZnO), excited by solar or UV-Vis light. However, their wide band gap limits their catalytic capabilities within the absorption of the UV spectrum and causes fast electron-hole recombination. This study presents novel strategies to overcome these limitations: (i) doping semiconductors to increase photocatalytic efficiency; (ii) sensitization-mediated photocatalysis for visible light activation using chemical moieties to trap dye molecules; (iii) nanosizing the photocatalysts to enhance the surface area. ZnO nanoparticles, doped with iron or gadolinium and capped with oleic acid are here synthesized and tested in RhB dye solutions. Remarkably, the results demonstrate an ultra-fast RhB degradation, driven by oleic acid having crucial role in dye adsorption. The degradation mechanisms, including ROS-induced N-deethylation and xanthene group cleavage, are also unraveled. These findings underscore the efficacy of the proposed semiconductor photocatalyst design, highlighting a significant advancement with extensive potential applications in wastewater remediation. This innovative approach paves the way for more efficient and practical solutions to combat industrial dye pollution.

Charge transport improvement employing TiO2 nanotube arrays as front-side illuminated dye-sensitized solar cell photoanodes.

TiO(2) nanotube (NT) arrays with different lengths were fabricated by anodic oxidation of Ti foil and free-standing NT membranes were detached by the metal substrate and bonded on the fluorine-doped tin oxide surface implementing an easy procedure. Morphology of the as-grown material and of the prepared photoanode was investigated by means of electron microscopy, deepening the investigation on the thermal treatment effect. Crystalline orientation and exposed surface area were studied by X-ray diffraction and Brunauer-Emmett-Teller measurements, showing suitable characteristics for the application in dye-sensitized solar cells (DSCs). DSCs were assembled employing a microfluidic housing system. The cell performances and the electron transport properties as a function of the tube length, before and after a TiCl(4) treatment, were characterized by I-V electrical measurements, incident photon-to-electron conversion efficiency, electrochemical impedance spectroscopy and open circuit voltage decay. Fitting the impedance spectra with an equivalent circuit, it was possible to obtain information on the electron diffusion properties into the TiO(2) nanotubes. A comparison with the charge transport properties evaluated in nanoparticle-based photoanodes witnesses a noteworthy increase of electron lifetime and diffusion length, yielding an overall power conversion efficiency up to 7.56%.

Cu2O/SnO2 Heterostructures: Role of the Synthesis Procedure on PEC CO2 Conversion.

Addressing the urgent need to mitigate increasing levels of CO2 in the atmosphere and combat global warming, the development of earth-abundant catalysts for selective photo-electrochemical CO2 conversion is a central and pressing challenge. Toward this purpose, two synthetic strategies for obtaining a Cu2O-SnO2 catalyst, namely co-precipitation and core-shell methods, were compared. The morphology and band gap energy of the synthesized materials were strongly different. The photoactivity of the core-shell catalyst was improved by 30% compared to the co-precipitation one, while its selectivity was shifted towards C1 products such as CO and formate. The stability of both catalysts was revealed by an easy and fast EIS analysis, indicating how the effective presence of a SnO2 shell could prevent the modification of the crystalline phase of the catalyst during PEC tests. Finally, directing the selectivity depending on the synthesis method used to produce the final Cu2O-SnO2 catalyst could possibly be implemented in syngas and formate transformation processes, such as hydroformylation or the Fischer-Tropsch process.

Understanding the role of imidazolium-based ionic liquids in the electrochemical CO2 reduction reaction.

The development of efficient CO2 capture and utilization technologies driven by renewable energy sources is mandatory to reduce the impact of climate change. Herein, seven imidazolium-based ionic liquids (ILs) with different anions and cations were tested as catholytes for the CO2 electrocatalytic reduction to CO over Ag electrode. Relevant activity and stability, but different selectivities for CO2 reduction or the side H2 evolution were observed. Density functional theory results show that depending on the IL anions the CO2 is captured or converted. Acetate anions (being strong Lewis bases) enhance CO2 capture and H2 evolution, while fluorinated anions (being weaker Lewis bases) favour the CO2 electroreduction. Differently from the hydrolytically unstable 1-butyl-3-methylimidazolium tetrafluoroborate, 1-Butyl-3-Methylimidazolium Triflate was the most promising IL, showing the highest Faradaic efficiency to CO (>95%), and up to 8 h of stable operation at high current rates (-20 mA & -60 mA), which opens the way for a prospective process scale-up.

Insights into the Electrochemical Reduction of 5-Hydroxymethylfurfural at High Current Densities.

The electrocatalytic reduction of 5-hydroxymethylfurfural (HMF) is highly selective to 2,5-bishydroxymethylfuran (BHMF) at pH=9.2, diluted HMF solutions, and low current densities. In this work, the electrochemical reduction of 0.05 m HMF solutions was investigated in the 5-50 mA cm-2 current density range over an AgCu foam electrocatalyst. The selectivity towards the formation of BHMF or the dimerization depended on the current density, likely due to differences in the electrode potential, and on the reaction time. Operating at current densities of 40-50 mA cm-2 allowed to find a trade-off between HMF and H2 O activation, achieving 85 % BHMF selectivity and fostering the productivity (0.567 mmol cm-2 h-1 ), though co-producing H2 . The electrochemical characterization by Tafel slopes and electrochemical impedance spectroscopy indicated that the HMF reduction was kinetically favored in comparison to the hydrogen evolution reaction and that the process was limited by charge transfer.

CO2 Conversion to Alcohols over Cu/ZnO Catalysts: Prospective Synergies between Electrocatalytic and Thermocatalytic Routes.

The development of efficient catalysts is one of the main challenges in CO2 conversion to valuable chemicals and fuels. Herein, inspired by the knowledge of the thermocatalytic (TC) processes, Cu/ZnO and bare Cu catalysts enriched with Cu+1 were studied to convert CO2 via the electrocatalytic (EC) pathway. Integrating Cu with ZnO (a CO-generation catalyst) is a strategy explored in the EC CO2 reduction to reduce the kinetic barrier and enhance C-C coupling to obtain C2+ chemicals and energy carriers. Herein, ethanol was produced with the Cu/ZnO catalyst, reaching a productivity of about 5.27 mmol·gcat-1·h-1 in a liquid-phase configuration at ambient conditions. In contrast, bare copper preferentially produced C1 products like formate and methanol. During CO2 hydrogenation, a methanol selectivity close to 100% was achieved with the Cu/ZnO catalysts at 200 °C, a value that decreased at higher temperatures (i.e., 23% at 300 °C) because of thermodynamic limitations. The methanol productivity increased to approximately 1.4 mmol·gcat-1·h-1 at 300 °C. Ex situ characterizations after testing confirmed the potential of adding ZnO in Cu-based materials to stabilize the Cu1+/Cu0 interface at the electrocatalyst surface because of Zn and O enrichment by an amorphous zinc oxide matrix; while in the TC process, Cu0 and crystalline ZnO prevailed under CO2 hydrogenation conditions. It is envisioned that the lower *CO binding energy at the Cu0 catalyst surface in the TC process than in the Cu1+ present in the EC one leads to preferential CO and methanol production in the TC system. Instead, our EC results revealed that an optimum local CO production at the ZnO surface in tandem with a high amount of superficial Cu1+ + Cu0 species induces ethanol formation by ensuring an appropriate local amount of *CO intermediates and their further dimerization to generate C2+ products. Optimizing the ZnO loading on Cu is proposed to tune the catalyst surface properties and the formation of more reduced CO2 conversion products.

Covalent Immobilization of Dehydrogenases on Carbon Felt for Reusable Anodes with Effective Electrochemical Cofactor Regeneration.

This study presents the immobilization with aldehyde groups (glyoxyl carbon felt) of alcohol dehydrogenase (ADH) and formate dehydrogenase (FDH) on carbon-felt-based electrodes. The compatibility of the immobilization method with the electrochemical application was studied with the ADH bioelectrode. The electrochemical regeneration process of nicotinamide adenine dinucleotide in its oxidized form (NAD+ ), on a carbon felt surface, has been deeply studied with tests performed at different electrical potentials. By applying a potential of 0.4 V versus Ag/AgCl electrode, a good compromise between NAD+ regeneration and energy consumption was observed. The effectiveness of the regeneration of NAD+ was confirmed by electrochemical oxidation of ethanol catalyzed by ADH in the presence of NADH, which is the no active form of the cofactor for this reaction. Good reusability was observed by using ADH immobilized on glyoxyl functionalized carbon felt with a residual activity higher than 60 % after 3 batches.

ZnO Materials as Effective Anodes for the Photoelectrochemical Regeneration of Enzymatically Active NAD.

This work reports the study of ZnO-based anodes for the photoelectrochemical regeneration of the oxidized form of nicotinamide adenine dinucleotide (NAD+). The latter is the most important coenzyme for dehydrogenases. However, the high costs of NAD+ limit the use of such enzymes at the industrial level. The influence of the ZnO morphologies (flower-like, porous film, and nanowires), showing different surface area and crystallinity, was studied. The detection of diluted solutions (0.1 mM) of the reduced form of the coenzyme (NADH) was accomplished by the flower-like and the porous films, whereas concentrations greater than 20 mM were needed for the detection of NADH with nanowire-shaped ZnO-based electrodes. The photocatalytic activity of ZnO was reduced at increasing concentrations of NAD+ because part of the ultraviolet irradiation was absorbed by the coenzyme, reducing the photons available for the ZnO material. The higher electrochemical surface area of the flower-like film makes it suitable for the regeneration reaction. The illumination of the electrodes led to a significant increase on the NAD+ regeneration with respect to both the electrochemical oxidation in dark and the only photochemical reaction. The tests with formate dehydrogenase demonstrated that 94% of the regenerated NAD+ was enzymatically active.

CuZnAl-Oxide Nanopyramidal Mesoporous Materials for the Electrocatalytic CO2 Reduction to Syngas: Tuning of H2/CO Ratio.

Inspired by the knowledge of the thermocatalytic CO2 reduction process, novel nanocrystalline CuZnAl-oxide based catalysts with pyramidal mesoporous structures are here proposed for the CO2 electrochemical reduction under ambient conditions. The XPS analyses revealed that the co-presence of ZnO and Al2O3 into the Cu-based catalyst stabilize the CuO crystalline structure and introduce basic sites on the ternary as-synthesized catalyst. In contrast, the as-prepared CuZn- and Cu-based materials contain a higher amount of superficial Cu0 and Cu1+ species. The CuZnAl-catalyst exhibited enhanced catalytic performance for the CO and H2 production, reaching a Faradaic efficiency (FE) towards syngas of almost 95% at -0.89 V vs. RHE and a remarkable current density of up to 90 mA cm-2 for the CO2 reduction at -2.4 V vs. RHE. The physico-chemical characterizations confirmed that the pyramidal mesoporous structure of this material, which is constituted by a high pore volume and small CuO crystals, plays a fundamental role in its low diffusional mass-transfer resistance. The CO-productivity on the CuZnAl-catalyst increased at more negative applied potentials, leading to the production of syngas with a tunable H2/CO ratio (from 2 to 7), depending on the applied potential. These results pave the way to substitute state-of-the-art noble metals (e.g., Ag, Au) with this abundant and cost-effective catalyst to produce syngas. Moreover, the post-reaction analyses demonstrated the stabilization of Cu2O species, avoiding its complete reduction to Cu0 under the CO2 electroreduction conditions.

AgCu Bimetallic Electrocatalysts for the Reduction of Biomass-Derived Compounds.

The electrochemical transformation of biomass-derived compounds (e.g., aldehyde electroreduction to alcohols) is gaining increasing interest due to the sustainability of this process that can be exploited to produce value-added products from biowastes and renewable electricity. In this framework, the electrochemical conversion of 5-hydroxymethylfurfural (HMF) to 2,5-bis(hydroxymethyl)furan (BHMF) is studied. Nanostructured Ag deposited on Cu is an active and selective electrocatalyst for the formation of BHMF in basic media. However, this catalyst deserves further research to elucidate the role of the morphology and size of the coated particles in its performance as well as the actual catalyst surface composition and its stability. Herein, Ag is coated on Cu open-cell foams by electrodeposition and galvanic displacement to generate different catalyst morphologies, deepening on the particle growth mechanism, and the samples are compared with bare Ag and Cu foams. The chemical-physical and electrochemical properties of the as-prepared and spent catalysts are correlated to the electroactivity in the HMF conversion and its selectivity toward the formation of BHMF during electroreduction. AgCu bimetallic nanoparticles or dendrites are formed on electrodeposited and displaced catalysts, respectively, whose surface is Cu-enriched along with electrochemical tests. Both types of bimetallic AgCu particles evidence a superior electroactive surface area as well as an enhanced charge and mass transfer in comparison with the bare Ag and Cu foams. These features together with a synergistic role between Ag and Cu superficial active sites could be related to the twofold enhanced selectivity of the Ag/Cu catalysts for the selective conversion of HMF to BHMF, that is, >80% selectivity and ∼ 100% conversion, and BHMF productivity values (0.206 and 0.280 mmol cm-2 h-1) ca. 1.5-3 times higher than those previously reported.

Piezo- and Photocatalytic Activity of Ferroelectric ZnO:Sb Thin Films for the Efficient Degradation of Rhodamine-ß dye Pollutant.

The discovery of novel catalytic materials showing unprecedented properties and improved functionalities represents a major challenge to design advanced oxidation processes for wastewater purification. In this work, antimony (Sb) doping is proposed as a powerful approach for enhancing the photo- and piezocatalytic performances of piezoelectric zinc oxide (ZnO) thin films. To investigate the role played by the dopant, the degradation of Rhodamine-ß (Rh-ß), a dye pollutant widely present in natural water sources, is studied when the catalyst is irradiated by ultraviolet (UV) light or ultrasound (US) waves. Depending on the doping level, the structural, optical, and ferroelectric properties of the catalyst can be properly set to maximize the dye degradation efficiency. Independently of the irradiation source, the fastest and complete dye degradation is observed in the presence of the doped catalyst and for an optimal amount of the inserted dopant. Among ZnO:Sb samples, the most doped one (5 at. %) shows improved UV light absorption and photocatalytic properties. Conversely, the piezocatalytic efficiency is maximized using the lowest Sb amount (1 at. %). The superior ferroelectric polarization observed in this case highly favors the adsorption of electrically charged species, in particular of the dye in the protonated form (Rh-ß+) and of OH-, to the catalyst surface and the production of hydroxyl radicals responsible for dye degradation.

Dinuclear uranium(VI) salen coordination compound: an efficient visible-light-active catalyst for selective reduction of CO2 to methanol.

A new dinuclear uranyl salen coordination compound, [(UO2)2(L)2]·2MeCN [L = 6,6'-((1E,1'E)-((2,2-dimethylpropane-1,3-diyl)bis(azaneylylidene))-bis(methaneylylidene))bis(2-methoxyphenol)], was synthesized using a multifunctional salen ligand to harvest visible light for the selective photocatalytic reduction of CO2 to MeOH. The assembling of the two U centers into one coordination moiety via a chelating-bridging doubly deprotonated tetradentate ligand allowed the formation of U centers with distorted pentagonal bipyramid geometry. Such construction of compounds leads to excellent activity for the photocatalytic reduction of CO2, permitting a production rate of 1.29 mmol g-1 h-1 of MeOH with an apparent quantum yield of 18%. Triethanolamine (TEOA) was used as a sacrificial electron donor to carry out the photocatalytic reduction of CO2. The selective methanol formation was purely a photocatalytic phenomenon and confirmed using isotopically labeled 13CO2 and product analysis by 13C-NMR spectroscopy. The spectroscopic studies also confirmed the interaction of CO2 with the molecule of the title complex. The results of these efforts made it possible to understand the reaction mechanism using ESI-mass spectrometry.

Sonophotocatalytic degradation mechanisms of Rhodamine B dye via radicals generation by micro- and nano-particles of ZnO.

In this work, it is proposed an environmental friendly sonophotocatalytic approach to efficiently treat polluted waters from industrial dyes exploiting ZnO micro- and nano-materials. For the first time, we deeply investigated the generation of reactive oxygen species (ROS) under ultrasound stimulation of different ZnO structures by Electron Paramagnetic Resonance Spectroscopy (EPR). Indeed, five zinc oxide (ZnO) micro- and nano-structures, i.e. Desert Roses (DRs), Multipods (MPs), Microwires (MWs), Nanoparticles (NPs) and Nanowires (NWs), were studied for the Rhodamine B (RhB) sonodegradation under ultrasonic irradiation. The DRs microparticles demonstrated the best sonocatalytic performance (100% degradation of RhB in 180 min) and the highest OH· radicals generation under ultrasonic irradiation. Strikingly, the coupling of ultrasound and sun-light irradiation in a sonophotodegradation approach led to 100% degradation efficiency, i.e. color reduction, of RhB in just 10 min, revealing a great positive synergy between the photocatalytic and sonocatalytic mechanisms. The RhB sonophotocatalytic degradation was also evaluated at different initial dye concentrations and with the presence of anions in solution. It was demonstrated a good stability over repeated cycles of dye treatment, which probe the applicability of this technique with industrial effluents. In conclusion, sonophotocatalytic degradation synergizing sunlight and ultrasound in the presence of DRs microparticles shows a great potential and a starting point to investigate further the efficient treatment of organic dyes in wastewater.

Application of Reverse Micelle Sol⁻Gel Synthesis for Bulk Doping and Heteroatoms Surface Enrichment in Mo-Doped TiO2 Nanoparticles.

TiO2 nanoparticles containing 0.0, 1.0, 5.0, and 10.0 wt.% Mo were prepared by a reverse micelle template assisted sol⁻gel method allowing the dispersion of Mo atoms in the TiO2 matrix. Their textural and surface properties were characterized by means of X-ray powder diffraction, micro-Raman spectroscopy, N2 adsorption/desorption isotherms at -196 °C, energy dispersive X-ray analysis coupled to field emission scanning electron microscopy, X-ray photoelectron spectroscopy, diffuse reflectance UV⁻Vis spectroscopy, and ζ-potential measurement. The photocatalytic degradation of Rhodamine B (under visible light and low irradiance) in water was used as a test reaction as well. The ensemble of the obtained experimental results was analyzed in order to discover the actual state of Mo in the final materials, showing the occurrence of both bulk doping and Mo surface species, with progressive segregation of MoOx species occurring only at a higher Mo content.

Insights Into the Sunlight-Driven Water Oxidation by Ce and Er-Doped ZrO 2.

In the present work, the activity of Ce and Er-doped ZrO2 nanopowders for sun-driven photocatalytic water oxidation has been investigated. ZrO2 powders with tunable amounts of tetragonal, monoclinic and cubic polymorphs have been synthesized by introducing Ce and Er (from 0.5 to 10 mol % on an oxide basis) through hydrothermal method. The aim of this work is to investigate the role of rare earth (RE) ions rich of electrons (Er3+) and with entirely empty levels (Ce4+) in the ZrO2 matrix for the sun-driven photocatalytic water oxidation reaction. The samples have been characterized by means of UV-Vis spectroscopy, X-Ray diffraction (XRD), N2 adsorption, X-ray photoelectron spectrophotometry (XPS) and transmission electronic microscopy (TEM) with energy dispersive spectroscopy (EDS). With respect to the bare ZrO2 mainly containing monoclinic (m-) phase, an increasing amount of rare-earth (RE) dopant was found to improve the specific BET surface area and to stabilize the tetragonal (t-) or cubic (c-) polymorphs of ZrO2 at room temperature. XRD data confirmed that dopants were mainly inserted in the t-ZrO2 phase. The photocatalytic O2 evolution from water under AM 1.5 G simulated sunlight illumination of the prepared samples have been correlated with their optical, structural and chemical properties. The effect of the dopant concentration on the chemical-physical and photocatalytic properties of the Er- and Ce-doped ZrO2 materials was elucidated. The samples with 5% of RE oxide were the most active, i.e., three times more than pure zirconia. Their superior photocatalytic activity was found to be mainly correlated to two factors: (i) an optimal surface concentration of RE ions of about 3.7%, which increased charge carriers separation in the photocatalysts surface due more superficial defects of the t-ZrO2 and a higher surface area, thus enhancing the reaction kinetics, (ii) a controlled amount of monoclinic vs. tetragonal (or cubic) polymorphs of zirconia with an optimum ratio of about 70/30 of t-ZrO2/m-ZrO2. Instead, the increased ability of the RE-doped ZrO2 to harvest visible light was found to have a secondary role on the photocatalytic activity of the Ce-doped ZrO2 material.

Highly Uniform Anodically Deposited Film of MnO2 Nanoflakes on Carbon Fibers for Flexible and Wearable Fiber-Shaped Supercapacitors.

A highly uniform porous film of MnO2 was deposited on carbon fiber by anodic electrodeposition for the fabrication of high-performance electrodes in wearable supercapacitors (SCs) application. The effects of potentiostatic and galvanostatic electrodeposition and the deposition time were investigated. The morphology, crystalline structure, and chemical composition of the obtained fiber-shaped samples were analyzed by field-emission scanning electron microscopy (FESEM), X-ray diffraction (XRD), Raman spectroscopy, and X-ray photoelectron spectroscopy (XPS). The charge storage performance of the carbon fibers@MnO2 composite electrode coupled to a gel-like polymeric electrolyte was investigated by cyclic voltammetry and galvanostatic charge-discharge measurements. The specific capacitance of the optimized carbon fiber@MnO2 composite electrodes could reach up to 62 F g-1 corresponding to 23 mF cm-1 in PVA/NaCl gel-polymer electrolyte, i.e., the highest capacitance value ever reported for fiber-shaped SCs. Finally, the stability and the flexibility of the device were studied, and the results indicate exceptional capacitance retention and superior stability of the device subjected to bending even at high angles up to 150°.