Direct Operando Visualization of Metal Support Interactions Induced by Hydrogen Spillover During CO2 Hydrogenation.

The understanding of catalyst active sites is a fundamental challenge for the future rational design of optimized and bespoke catalysts. For instance, the partial reduction of Ce4+ surface sites to Ce3+ and the formation of oxygen vacancies are critical for CO2 hydrogenation, CO oxidation, and the water gas shift reaction. Furthermore, metal nanoparticles, the reducible support, and metal support interactions are prone to evolve under reaction conditions; therefore a catalyst structure must be characterized under operando conditions to identify active states and deduce structure-activity relationships. In the present work, temperature-induced morphological and chemical changes in Ni nanoparticle-decorated mesoporous CeO2 by means of in situ quantitative multimode electron tomography and in situ heating electron energy loss spectroscopy, respectively, are investigated. Moreover, operando electron energy loss spectroscopy is employed using a windowed gas cell and reveals the role of Ni-induced hydrogen spillover on active Ce3+ site formation and enhancement of the overall catalytic performance.

Overcoming Voltage Losses in Vanadium Redox Flow Batteries Using WO3 as a Positive Electrode.

Vanadium redox flow batteries (VRFBs) are appealing large-scale energy storage systems due to their unique properties of independent energy/power design. The VRFBs stack design is crucial for technology deployment in power applications. Besides the design, the stack suffers from high voltage losses caused by the electrodes. The introduction of active sites into the electrode to facilitate the reaction kinetic is crucial in boosting the power rate of the VRFBs. Here, an O-rich layer has been applied onto structured graphite felt (GF) by depositing WO3 to increase the oxygen species content. The oxygen species are the active site during the positive reaction (VO2 +/VO2+) in VRFB. The increased electrocatalytic activity is demonstrated by the monoclinic (m)-WO3/GF electrode that minimizes the voltage losses, yielding excellent performance results in terms of power density output and limiting current density (556 mWcm-2@800 mAcm-2). The results confirm that the m-WO3/GF electrode is a promising electrode for high-power in VRFBs, overcoming the performance-limiting issues in a positive half-reaction.

Insight into the Degradation Mechanisms of Atomic Layer Deposited TiO2 as Photoanode Protective Layer.

Around 100 nm thick TiO2 layers deposited by atomic layer deposition (ALD) have been investigated as anticorrosion protective films for silicon-based photoanodes decorated with 5 nm NiFe catalyst in highly alkaline electrolyte. Completely amorphous layers presented high resistivity; meanwhile, the ones synthesized at 300 °C, having a fully anatase crystalline TiO2 structure, introduced insignificant resistance, showing direct correlation between crystallization degree and electrical conductivity. The conductivity through crystalline TiO2 layers has been found not to be homogeneous, presenting preferential conduction paths attributed to grain boundaries and defects within the crystalline structure. A correlation between the conductivity atomic force microscopy measurements and grain interstitials can be seen, supported by high-resolution transmission electron microscopy cross-sectional images presenting defective regions in crystalline TiO2 grains. It was found that the conduction mechanism goes through the injection of electrons coming from water oxidation from the electrocatalyst into the TiO2 conduction band. Then, electrons are transported to the Si/SiOx/TiO2 interface where electrons recombine with holes given by the p+n-Si junction. No evidences of intra-band-gap states in TiO2 responsible of conductivity have been detected. Stability measurements of fully crystalline samples over 480 h in anodic polarization show a continuous current decay. Electrochemical impedance spectroscopy allows to identify that the main cause of deactivation is associated with the loss of TiO2 electrical conductivity, corresponding to a self-passivation mechanism. This is proposed to reflect the effect of OH- ions diffusing in the TiO2 structure in anodic conditions by the electric field. This fact proves that a modification takes place in the defective zone of the layer, blocking the ability to transfer electrical charge through the layer. According to this mechanism, a regeneration of the degradation process is demonstrated possible based on ultraviolet illumination, which contributes to change the occupancy of TiO2 electronic states and to recover the defective zone's conductivity. These findings confirm the connection between the structural properties of the ALD-deposited polycrystalline layer and the degradation mechanisms and thus highlight main concerns toward fabricating long-lasting metal-oxide protective layers for frontal illuminated photoelectrodes.

Analysis of the interfacial characteristics of BiVO4/metal oxide heterostructures and its implication on their junction properties.

The formation of heterostructures has proven to be a viable way to achieve high photoelectrochemical water splitting efficiencies with BiVO4 based photoanodes. Especially, cobalt and nickel based oxides are suitable low cost contact materials. However, the exact role of these contact materials is not yet completely understood because of the difficulty to individually quantify the effects of surface passivation, charge carrier separation and catalysis on the efficiency of a heterostructure. In this study, we used photoelectron spectroscopy in combination with in situ thin film deposition to obtain direct information on the interface structure between polycrystalline BiVO4 and NiO, CoOx and Sn-doped In2O3 (ITO). Strong upwards band bending was observed for the BiVO4/NiO and BiVO4/CoOx interfaces without observing chemical changes in BiVO4, while limited band bending and reduction of Bi and V was observed while forming the BiVO4/ITO interface. Thus, the tunability of the Fermi level position within BiVO4 seems to be limited to a certain range. The feasibility of high upwards band bending through junctions with high work function (WF) compounds demonstrate that nickel oxide and cobalt oxide are able to enhance the charge carrier separation in BiVO4. Similar studies could help to identify whether new photoelectrode materials and their heterostructures would be suitable for photoelectrochemical water splitting.

Multilayered Hematite Nanowires with Thin-Film Silicon Photovoltaics in an All-Earth-Abundant Hybrid Tandem Device for Solar Water Splitting.

The concept of hybrid tandem device structures that combine metal oxides with thin-film semiconducting photoabsorbers holds great promise for large-scale, robust, and cost-effective bias-free photoelectrochemical water splitting (PEC-WS). This work highlights important steps toward the efficient coupling of high-performance hematite photoanodes with multijunction thin-film silicon photocathodes providing high bias-free photocurrent density. The hybrid PEC-WS device is optimized by testing three types of multijunction silicon photocathodes with the hematite photoanode: amorphous silicon (a-Si:H) tandem: a-Si:H/a-Si:H and triple junction with microcrystalline silicon (µc-Si:H): a-Si:H/a-Si:H/µc-Si:H and a-Si:H/µc-Si:H/µc-Si:H. The results provide evidence that the multijunction structures offer high flexibility for hybrid tandem devices with regard to tunable photovoltages and spectral matching. Furthermore, both photoanode and photocathode are tested under various electrolyte and light concentration conditions, respectively, with respect to their photoelectrochemical performance and stability. A 27 % enhancement in the solar-to-hydrogen conversion efficiency is observed upon concentrating light from 100 to 300 mW cm-2 . Ultimately, bias-free water splitting is demonstrated, with a photocurrent density of 4.6 mA cm-2 (under concentrated illumination) paired with excellent operation stability for more than 24 h of the all-earth-abundant and low-cost hematite/silicon tandem PEC-WS device.

Tailoring Copper Foam with Silver Dendrite Catalysts for Highly Selective Carbon Dioxide Conversion into Carbon Monoxide.

The present study outlines the important steps to bring electrochemical conversion of carbon dioxide (CO2) closer to commercial viability by using a large-scale metallic foam electrode as a highly conductive catalyst scaffold. Because of its versatility, it was possible to specifically tailor three-dimensional copper foam through coating with silver dendrite catalysts by electrodeposition. The requirements of high-yield CO2 conversion to carbon monoxide (CO) were met by tuning the deposition parameters toward a homogeneous coverage of the copper foam with nanosized dendrites, which additionally featured crystallographic surface orientations favoring CO production. The presented results evidence that Ag dendrites, owing a high density of planes with stepped (220) surface sites, paired with the superior active surface area of the copper foam can significantly foster the CO productivity. In a continuous flow-cell reactor setup, CO Faradaic efficiencies reaching from 85 to 96% for a wide range of low applied cathode potentials (<1.0 VRHE) along with high CO current densities up to 27 mA/cm2 were achieved, far outperforming other tested scaffold materials. Overall, this research provides new strategic guidelines for the fabrication of efficient and versatile cathodes for CO2 conversion compatible with large-scale integrated prototype devices.

Turning Earth Abundant Kesterite-Based Solar Cells Into Efficient Protected Water-Splitting Photocathodes.

CZTS/Se kesterite-based solar cells have been protected by conformal atomic layer deposition (ALD)-deposited TiO2 demonstrating its feasibility as powerful photocathodes for water splitting in highly acidic conditions (pH < 1), achieving stability with no detected degradation and with current density levels similar to photovoltaic productivities. The ALD has allowed low deposition temperatures of 200 °C for TiO2, preventing significant variations to the kesterite structure and CdS heterojunction, except for the pure-sulfide stoichiometry, which was studied by Raman spectroscopy. The measured photocurrent at 0 V vs reversible hydrogen electrode, 37 mA·cm-2, is the highest reported to date, and the associated half-cell solar-to-hydrogen efficiency reached 7%, being amongst the largest presented for kesterite-based photocathodes, corroborating the possibility of using them as abundant low-cost alternative photoabsorbers as their efficiencies are improved toward those of chalcopyrites. An electrical circuit has been proposed to model the photocathode, which comprises the photon absorption, charge transfer through the protective layer, and catalytic performance, which paves the way to the design of highly efficient photoelectrodes.

Role of Bismuth in the Electrokinetics of Silicon Photocathodes for Solar Rechargeable Vanadium Redox Flow Batteries.

The ability of crystalline silicon to photoassist the V3+ /V2+ cathodic reaction under simulated solar irradiation, combined with the effect of bismuth have led to important electrochemical improvements. Besides the photovoltage supplied by the photovoltaics, additional decrease in the onset potentials, high reversibility of the V3+ /V2+ redox pair, and improvement in the electrokinetics were attained thanks to the addition of bismuth. In fact, Bi0 deposition has shown to slightly decrease the photocurrent, but the significant enhancement in the charge transfer, reflected in the overall electrochemical performance clearly justifies its use as additive in a photoassisted system for maximizing the efficiency of solar charge to battery.

Insights into the Performance of CoxNi1-xTiO3 Solid Solutions as Photocatalysts for Sun-Driven Water Oxidation.

CoxNi1-xTiO3 systems evaluated as photo- and electrocatalytic materials for oxygen evolution reaction (OER) from water have been studied. These materials have shown promising properties for this half-reaction both under (unbiased) visible-light photocatalytic approach in the presence of an electron scavenger and as electrocatalysts in dark conditions in basic media. In both situations, Co0.8Ni0.2TiO3 exhibits the best performance and is proved to display high faradaic efficiency. A synergetic effect between Co and Ni is established, improving the physicochemical properties such as surface area and pore size distribution, besides affecting the donor density and the charge carrier separation. At higher Ni content, the materials exhibit behavior more similar to that of NiTiO3, which is a less suitable material for OER than CoTiO3.

Charge Transfer Characterization of ALD-Grown TiO2 Protective Layers in Silicon Photocathodes.

A critical parameter for the implementation of standard high-efficiency photovoltaic absorber materials for photoelectrochemical water splitting is its proper protection from chemical corrosion while remaining transparent and highly conductive. Atomic layer deposited (ALD) TiO2 layers fulfill material requirements while conformally protecting the underlying photoabsorber. Nanoscale conductivity of ALD TiO2 protective layers on silicon-based photocathodes has been analyzed, proving that the conduction path is through the columnar crystalline structure of TiO2. Deposition temperature has been explored from 100 to 300 °C, and a temperature threshold is found to be mandatory for an efficient charge transfer, as a consequence of layer crystallization between 100 and 200 °C. Completely crystallized TiO2 is demonstrated to be mandatory for long-term stability, as seen in the 300 h continuous operation test.

Hydrogen-Treated Rutile TiO2 Shell in Graphite-Core Structure as a Negative Electrode for High-Performance Vanadium Redox Flow Batteries.

Hydrogen-treated TiO2 as an electrocatalyst has shown to boost the capacity of high-performance all-vanadium redox flow batteries (VRFBs) as a simple and eco-friendly strategy. The graphite felt-based GF@TiO2 :H electrode is able to inhibit the hydrogen evolution reaction (HER), which is a critical barrier for operating at high rate for long-term cycling in VRFBs. Significant improvements in charge/discharge and electron-transfer processes for the V3+ /V2+ reaction on the surface of reduced TiO2 were achieved as a consequence of the formation of oxygen functional groups and oxygen vacancies in the lattice structure. Key performance indicators of VRFB have been improved, such as high capability rates and electrolyte-utilization ratios (82 % at 200 mA cm-2 ). Additionally, high coulombic efficiencies (ca. 100 % up to the 96th cycle, afterwards >97 %) were obtained, demonstrating the feasibility of achieving long-term stability.

Mn3O4@CoMn2O4-CoxOy Nanoparticles: Partial Cation Exchange Synthesis and Electrocatalytic Properties toward the Oxygen Reduction and Evolution Reactions.

Mn3O4@CoMn2O4 nanoparticles (NPs) were produced at low temperature and ambient atmosphere using a one-pot two-step synthesis protocol involving the cation exchange of Mn by Co in preformed Mn3O4 NPs. Selecting the proper cobalt precursor, the nucleation of CoxOy crystallites at the Mn3O4@CoMn2O4 surface could be simultaneously promoted to form Mn3O4@CoMn2O4-CoxOy NPs. Such heterostructured NPs were investigated for oxygen reduction and evolution reactions (ORR, OER) in alkaline solution. Mn3O4@CoMn2O4-CoxOy NPs with [Co]/[Mn] = 1 showed low overpotentials of 0.31 V at -3 mA·cm(-2) and a small Tafel slope of 52 mV·dec(-1) for ORR, and overpotentials of 0.31 V at 10 mA·cm(-2) and a Tafel slope of 81 mV·dec(-1) for OER, thus outperforming commercial Pt-, IrO2-based and previously reported transition metal oxides. This cation-exchange-based synthesis protocol opens up a new approach to design novel heterostructured NPs as efficient nonprecious metal bifunctional oxygen catalysts.

Tailoring Multilayered BiVO4 Photoanodes by Pulsed Laser Deposition for Water Splitting.

Pulsed laser deposition (PLD) is proposed as promising technique for the fabrication of multilayered BiVO4-based photoanodes. For this purpose, bare BiVO4 films and two heterojunctions, BiVO4/SnO2 and BiVO4/WO3/SnO2, have been prepared using consecutive ablation of assorted targets in a single batch. The ease, high versatility and usefulness of this technique in engineering the internal configuration of the photoanode with stoichiometric target-to-substrate transfer are demonstrated. The obtained photocurrent densities are among the highest reported values for undoped BiVO4 without oxygen evolution catalysts (OEC). A detailed analysis of the influence of SnO2 and WO3 layers on the charge transport properties because of the changes at the internal FTO/semiconductor interface is performed through transient photocurrent measurements (TPC), showing that the BiVO4/WO3/SnO2 heterostructure attains a significant decrease in the internal losses and reaches high photocurrent values. This study is expected to open the door to the fabrication of other systems based on ternary (or even more complex) metal oxides as photoanodes for water splitting, which is a promising alternative for obtaining materials able to fulfill the different requierements in the development of more efficient systems for this process.

Surface modification of TiO2 nanocrystals by WO(x) coating or wrapping: solvothermal synthesis and enhanced surface chemistry.

TiO2 anatase nanocrystals were prepared by solvothermal processing of Ti chloroalkoxide in oleic acid, in the presence of W chloroalkoxide, with W/Ti nominal atomic concentration (R(w)) ranging from 0.16 to 0.64. The as-prepared materials were heat-treated up to 500 °C for thermal stabilization and sensing device processing. For R(0.16), the as-prepared materials were constituted by an anatase core surface-modified by WO(x) monolayers. This structure persisted up to 500 °C, without any WO3 phase segregation. For R(w) up to R(0.64), the anatase core was initially wrapped by an amorphous WO(x) gel. Upon heat treatment, the WO(x) phase underwent structural reorganization, remaining amorphous up to 400 °C and forming tiny WO3 nanocrystals dispersed into the TiO2 host after heating at 500 °C, when part of tungsten also migrated into the TiO2 structure, resulting in structural and electrical modification of the anatase host. The ethanol sensing properties of the various materials were tested and compared with pure TiO2 and WO3 analogously prepared. They showed that even the simple surface modification of the TiO2 host resulted in a 3 orders of magnitude response improvement with respect to pure TiO2.

Solvothermal, chloroalkoxide-based synthesis of monoclinic WO(3) quantum dots and gas-sensing enhancement by surface oxygen vacancies.

We report for the first time the synthesis of monoclinic WO3 quantum dots. A solvothermal processing at 250 °C in oleic acid of W chloroalkoxide solutions was employed. It was shown that the bulk monoclinic crystallographic phase is the stable one even for the nanosized regime (mean size 4 nm). The nanocrystals were characterized by X-ray diffraction, High resolution transmission electron microscopy, X-ray photoelectron spectroscopy, UV-vis, Fourier transform infrared and Raman spectroscopy. It was concluded that they were constituted by a core of monoclinic WO3, surface covered by unstable W(V) species, slowly oxidized upon standing in room conditions. The WO3 nanocrystals could be easily processed to prepare gas-sensing devices, without any phase transition up to at least 500 °C. The devices displayed remarkable response to both oxidizing (nitrogen dioxide) and reducing (ethanol) gases in concentrations ranging from 1 to 5 ppm and from 100 to 500 ppm, at low operating temperatures of 100 and 200 °C, respectively. The analysis of the electrical data showed that the nanocrystals were characterized by reduced surfaces, which enhanced both nitrogen dioxide adsorption and oxygen ionosorption, the latter resulting in enhanced ethanol decomposition kinetics.

Enhanced photovoltaic performance of nanowire dye-sensitized solar cells based on coaxial TiO2@TiO heterostructures with a cobalt(II/III) redox electrolyte.

The growth of a TiO shell at the surface of TiO2 nanowires (NWs) allowed us to improve the power conversion efficiency of NW-based dye-sensitized solar cells (DSCs) by a factor 2.5. TiO2@TiO core-shell NWs were obtained by a two-step process: First, rutile-phase TiO2 NWs were hydrothermally grown. Second, a hongquiite-phase TiO shell was electrochemically deposited at the surface of the TiO2 NWs. Bare TiO2 and heterojunction TiO2@TiO NW-based DSCs were obtained using a cobalt(II/III) redox electrolyte and LEG4 as the dye. With this electrolyte/dye combination, DSCs with outstanding Voc values above 900 mV were systematically obtained. While TiO2@TiO NW-based DSCs had slightly lower Voc values than bare TiO2 NW-based DSCs, they provided 3-fold higher photocurrents, overall reaching 2.5-fold higher power conversion efficiencies. The higher photocurrents were associated with the larger surface roughness and an enhanced charge-carrier separation/transfer at the NW/dye interface.

Effectiveness of nitrogen incorporation to enhance the photoelectrochemical activity of nanostructured TiO2:NH3 versus H2-N2 annealing.

Highly ordered TiO(2) nanohole layers were synthesized by anodic oxidation of titanium foils using ethylene glycol and ammonium fluoride as the electrolyte. The effectiveness of different methods, namely annealing at 500 °C in NH(3) and in H(2) diluted in N(2), to incorporate nitrogen into TiO(2) and thus extend its photoelectrochemical (PEC) activity to the visible range was studied. The intra-gap levels introduced by both processes were identified by means of XPS and PL measurements. Water splitting experiments demonstrated that annealing in H(2) improved the photocatalytic activity of pure TiO(2), while annealing in ammonia led to a decrease in the PEC performance.

On the photoconduction properties of low resistivity TiO2 nanotubes.

TiO(2) nanotubes were synthesized by anodic oxidation of titanium foils using dimethyl sulfoxide and hydrofluoric acid as the electrolyte. The electrical properties of individual nanotube-based devices were evaluated and modeled after exposing some of them to different gas and illumination conditions. Resistivity values fully comparable to those of TiO(2) single crystal anatase (ρ(SA) = 1.09 ± 0.01Ω cm) were found, and their photoconductive characteristics, explained in terms of the Shockley-Read-Hall model for non-radiative recombination in semiconductors, were found to be strongly influenced by the applied experimental conditions such as the surrounding atmosphere. These devices may have potential applications in photocatalytic processes, such as CO(2) reduction or H(2)O splitting, avoiding the interfering effects typical of nanotube arrays.

Algunos parámetros bioquímicos en trabajadores expuestos al mercurio / Some biochemical parameters in workers exposed to mercury

Se estudiaron 140 trabajadores expuestos al mercurio de las clínicas estomatológicas de la provincia La habana, se agruparon por el tiempo de exposición al mismo y se compararon con 30 controles. Se determinaron simultáneamente concentraciones de mercurio en orina, colinesterasa en sangre total y en suero, creatinina, fosfatasa alcalina, ácido delta aminolevolínico (ALA) dehidrasa, urea y electroforesis de seroproteínas, se les realizó además, examen médico. fueron observadas alteraciones de la colinesterasa en sangre total en casi todos los trabajadores, se detectaron también, diferencias significativas en las creatininas

Algunos parámetros bioquímicos en trabajadores expuestos al mercurio / Soe biochemical parameters in workers exposed to mercury

Se estudiaron 140 trabajadores expuestos al mercurio de las clínicas estomatológicas de la provincia La habana, se agruparon por el tiempo de exposición al mismo y se compararon con 30 controles. Se determinaron simultáneamente concentraciones de mercurio en orina, colinesterasa en sangre total y en suero, creatinina, fosfatasa alcalina, ácido delta aminolevolínico (ALA) dehidrasa, urea y electroforesis de seroproteínas, se les realizó además, examen médico. fueron observadas alteraciones de la colinesterasa en sangre total en casi todos los trabajadores, se detectaron también, diferencias significativas en las creatininas (AU)