Biochar from olive tree twigs and spent malt rootlets as electrodes in Zn-air batteries.

Biochars, i.e. porous carbons obtained by pyrolysis of biomass, can act as electrocatalysts for oxygen evolution and oxygen reduction reaction. In the present work, two biochars have been prepared by using materials of completely different biomass origin: olive-tree twigs and spent malt rootlets (brewery wastes). Both biomass species were subjected to pyrolysis under limited oxygen supply and then they were activated by mixing with KOH and pyrolysis again. The obtained biochars were characterized by several techniques in order to determine their structural characteristics and the composition of their active components. Despite their different origin, the two biochars demonstrated similar structural and compositional characteristics thus highlighting the importance of the pyrolysis and activation procedure. Both biochars were used as electrocatalysts in the operation of rechargeable Zn-air batteries, where they also demonstrated similar electrocatalytic capacities with only a small advantage gained by olive-tree-twigs biochar. Compared to bare nanoparticulate carbon (carbon black), both biochars demonstrated a marked advantage towards oxygen evolution reaction.

Experimental and Theoretical Investigation of the Mechanism of the Reduction of O2 from Air to O22- by VIVO2+-N,N,N-Amidate Compounds and Their Potential Use in Fuel Cells.

The two-electron reductive activation of O2 to O22- is of particular interest to the scientific community mainly due to the use of peroxides as green oxidants and in powerful fuel cells. Despite of the great importance of vanadium(IV) species to activate the two-electron reductive activation of O2, the mechanism is still unclear. Reaction of VIVO2+ species with the tridentate-planar N,N,N-carboxamide (ΗL) ligands in solution (CH3OH:H2O) under atmospheric O2, at room temperature, resulted in the quick formation of [VV(═O)(η2-O2)(κ3-L)(H2O)] and cis-[VV(═O)2(κ3-L)] compounds. Oxidation of the VIVO2+ complexes with the sterically hindered tridentate-planar N,N,N-carboxamide ligands by atmospheric O2 gave only cis-[VV(═O)2(κ3-L)] compounds. The mechanism of formation of [VV(═O)(η2-O2)(κ3-L)(H2O)] (I) and cis-[VV(═O)2(κ3-L)] (II) complexes vs time, from the interaction of [VIV(═O)(κ3-L)(Η2Ο)2]+ with atmospheric O2, was investigated with 51V, 1H NMR, UV-vis, cw-X-band EPR, and 18O2 labeling IR and resonance Raman spectroscopies revealing the formation of a stable intermediate (Id). EPR, MS, and theoretical calculations of the mechanism of the formation of I and II revealed a pathway, through a binuclear [VIV(═O)(κ3-L)(H2O)(η1,η1-O2)VIV(═O)(κ3-L)(H2O)]2+ intermediate. The results from cw-EPR, 1H NMR spectroscopies, cyclic voltammetry, and the reactivity of the complexes [VIV(═O)(κ3-L)(Η2Ο)2]+ toward O2 reduction fit better to an intermediate with a binuclear nature. Dynamic experiments in combination with computational calculations were undertaken to fully elucidate the mechanism of the O2 reduction to O22- by [VIV(═O)(κ3-L)(Η2Ο)2]+. The galvanic cell {Zn|VIII,VII||Id, [VIVO(κ3-L)(H2O)2]+|O2|C(s)} was manufactured, demonstrating the important applicability of this new chemistry to Zn|H2O2 fuel cells technology generating H2O2 in situ from the atmospheric O2.

A brief review on solar charging of Zn-air batteries.

This brief review reveals the possibility of solar charging of Zn-air batteries. It describes the various configurations that have been adopted in order to employ solar radiation to directly charge Zn-air batteries, paying particular attention to simple constructions with a minimum number of components. Solar charging is differentiated from solar batteries, which are based on a different concept and mainly depend on the variation of the redox level of added electrolytes.

Study of the Functionalities of a Biochar Electrode Combined with a Photoelectrochemical Cell.

Biochar has been obtained by pyrolysis of spent malt rootlets under limited oxygen supply and further activated by mixing with KOH and pyrolyzed again at high temperature. The total specific surface area of such activated biochar was 1148 m2 g-1, while that of micropores was 690 m2 g-1. This biochar was used to make a functional electrode by deposition on carbon cloth and was combined with a photoelectrochemical cell. The biochar electrode functioned as a supercapacitor in combination with the electrolyte of the cell, reaching a specific capacity of 98 Fg-1, and it was capable of storing charges generated by the cell, proving current flow both under illumination and in the dark. The same electrode could be used as an air-cathode providing oxygen reduction functionality and thus demonstrating interesting electrocatalyst properties.

Use of Chalcogenide-Semiconductor-Sensitized Titania to Directly Charge a Vanadium Redox Battery.

Unmediated charging of a battery using solar radiation is a very attractive project of solar energy conversion and storage. In the present work, solar energy was converted into electricity using a photocatalytic fuel cell operating with a chalcogenide-semiconductor-sensitized nanoparticulate titania photoanode and an air-cathode functioning by oxygen reduction. This cell produced sufficient energy to directly charge a vanadium redox battery functioning with a VOSO4 electrolyte and carbon paper electrodes. The whole system is characterized by ease of construction and simplicity of conception; therefore, it satisfies conditions for practical applications.

Visible-Light Activated Titania and Its Application to Photoelectrocatalytic Hydrogen Peroxide Production.

Photoelectrochemical cells have been constructed with photoanodes based on mesoporous titania deposited on transparent electrodes and sensitized in the Visible by nanoparticulate CdS or CdS combined with CdSe. The cathode electrode was an air-breathing carbon cloth carrying nanoparticulate carbon. These cells functioned in the Photo Fuel Cell mode, i.e., without bias, simply by shining light on the photoanode. The cathode functionality was governed by a two-electron oxygen reduction, which led to formation of hydrogen peroxide. Thus, these devices were employed for photoelectrocatalytic hydrogen peroxide production. Two-compartment cells have been used, carrying different electrolytes in the photoanode and cathode compartments. Hydrogen peroxide production has been monitored by using various electrolytes in the cathode compartment. In the presence of NaHCO3, the Faradaic efficiency for hydrogen peroxide production exceeded 100% due to a catalytic effect induced by this electrolyte. Photocurrent has been generated by either a CdS/TiO2 or a CdSe/CdS/TiO2 combination, both functioning in the presence of sacrificial agents. Thus, in the first case ethanol was used as fuel, while in the second case a mixture of Na2S with Na2SO3 has been employed.

Study of Hole-Transporter-Free Perovskite Solar Cells based on Fully Printable Components.

Hole-transporter-free perovskite solar cells carrying a carbon back contact electrode provide the possibility of making full printable low cost and stable devices, even though their efficiency is substantially lower than those made in the standard configuration. The present work searched for simple and easy routes for constructing such devices, demonstrating that organic components do enhance device efficiency but only to a level that is not worth the trouble nor the cost. Devices based on a triple mesoporous layer of titania/zirconia/carbon with perovskite infiltration gave an efficiency of 10.7%. After 180 days of storing under ambient conditions, a small loss of efficiency has been observed for a cell made in June, in spite of the fact that in going from June to December, a large increase of the ambient humidity took place, thus verifying the protective effect that the carbon electrode is providing. The addition of spiro-OMeTAD to the hole-transporter-free device resulted in increasing the efficiency by about 10%, a change which is appreciated to be of low importance given the cost of this material. This increase mainly derived from an increase in the current. Devices of different sizes have been constructed by screen printing, using home-made pastes for all the components making the cell scaffold, i.e., for titania, zirconia, and carbon layers.

A Realistic Approach for Photoelectrochemical Hydrogen Production.

The production of hydrogen by water splitting has been a very attractive idea for several decades. However, the energy consumption that is necessary for water oxidation is too high for practical applications. On the contrary, the oxidation of organics is a much easier and less energy-demanding process. In addition, it may be used to consume organic wastes with a double environmental benefit: renewable energy production with environmental remediation. The oxidation of organics in a photoelectrochemical cell, which in that case is also referenced as a photocatalytic fuel cell, has the additional advantage of providing an alternative route for solar energy conversion. With this in mind, the present work describes a realistic choice of materials for the Pt-free photoelectrochemical production of hydrogen, by employing ethanol as a model organic fuel. The photoanode was made of a combination of titania with cadmium sulfide as the photosensitizer in order to enhance visible light absorbance. The cathode electrode was a simple carbon paper. Thus, it is shown that substantial hydrogen can be produced without electrocatalysts by simply exploiting carbon electrodes. Even though an ion transfer membrane was used in order to allow for an oxygen-free cathode environment, the electrolyte was the same in both the anode and cathode compartments. An alkaline electrolyte has been used to allow high hydroxyl concentration, thus facilitating organic fuel (photocatalytic) oxidation. Hydrogen production was then obtained by water reduction at the cathode (counter) electrode.

Improvement of the photovoltaic parameters of perovskite solar cells using a reduced-graphene-oxide-modified titania layer and soluble copper phthalocyanine as a hole transporter.

Functional perovskite solar cells can be made by using a simple, inexpensive and stable soluble tetra-n-butyl-substituted copper phthalocyanine (CuBuPc) as a hole transporter. In the present study, TiO2/reduced graphene oxide (T/RGO) hybrids were synthesized via an in situ solvothermal process and used as electron acceptor/transport mediators in mesoscopic perovskite solar cells based on soluble CuBuPc as a hole transporter and on graphene oxide (GO) as a buffer layer. The impact of the RGO content on the optoelectronic properties of T/RGO hybrids and on the solar cell performance was studied, suggesting improved electron transport characteristics and photovoltaic parameters. An enhanced electron lifetime and recombination resistance led to an increase in the short circuit current density, open circuit voltage and fill factor. The device based on a T/RGO mesoporous layer with an optimal RGO content of 0.2 wt% showed 22% higher photoconversion efficiency and higher stability compared with pristine TiO2-based devices.

Construction of Perovskite Solar Cells Using Inorganic Hole-Extracting Components.

A NiO x -graphene oxide (NiO x -GO) hybrid has been prepared by a simple solution-processed method and was used as hole-extraction material in perovskite solar cells with either gold or carbon as back contact electrode. The impact of GO content on the optoelectronic behavior of NiO x and the photovoltaic performance of the fabricated devices has been studied. Thus, GO incorporation showed a significant improvement in the performance of NiO x -based devices. The best attained efficiency was 13.3%, and it was 45% higher than that with pure NiO x . This is attributed to a significant improvement in the hole extraction, recombination resistance, and energy-level matching in comparison to pure NiO x . In addition, NiO x -GO/Au-based perovskite solar cell devices showed a negligible hysteresis effect and high reliability and repeatability. When carbon was used as back contact electrode, the obtained efficiencies were lower, but it leaves space for improvement. Devices based on inorganic hole transporters NiO x or NiO x -GO demonstrated higher stability in ambient air compared to a standard cell based on spiro-OMeTAD.

Renewable energy production by photoelectrochemical oxidation of organic wastes using WO3 photoanodes.

The present work has studied renewable hydrogen production by photoelectrocatalytic degradation of model organic substances representing biomass derived organic wastes. Its purpose was to show that renewable energy can be produced by consuming wastes. The study has been carried out by employing nanoparticulate WO3 photoanodes in the presence of ethanol, glycerol or sorbitol, i.e. three substances which are among typical biomass products. In these substances, the molecular weight and the number of hydroxyl groups increases from ethanol to sorbitol. The photocurrent produced by the cell was the highest in the presence of ethanol, smaller in the case of glycerol and further decreased in the presence of sorbitol. The photocurrent was roughly the double of that produced in the absence of an organic additive thus demonstrating current doubling phenomena. Hydrogen was produced only under illumination and was monitored at two forward bias, 0.8 and 1.6V vs Ag/AgCl. Hydrogen production rates followed the same order as the photocurrent thus indicating that hydrogen production by reduction of protons mainly depends on the current flowing through the external circuit connecting photoanode with cathode. The maximum solar-to-hydrogen efficiency reached by the present system was 2.35%.

Inverted perovskite solar cells based on lithium-functionalized graphene oxide as an electron-transporting layer.

Perovskite solar cells with an inverted p-i-n architecture were constructed under ambient conditions by employing materials of lower cost than standard cells. Thus, graphene oxide was used as a hole transporting material and Li-modified graphene oxide as an electron transporting material, while Al was used as a counter electrode. A maximum solar conversion efficiency of 10.2% was achieved by adding a Ti-based sol on the top of the Li-modified graphene oxide layer.

Photoelectrochemical cell for simultaneous electricity generation and heavy metals recovery from wastewater.

The feasibility of simultaneous recovery of heavy metals from wastewater (e.g., acid mining and electroplating) and production of electricity is demonstrated in a novel photoelectrochemical cell (PEC). The photoanode of the cell bears a nanoparticulate titania (TiO2) film capped with the block copolymer [poly(ethylene glycol)-b-poly(propylene glycol)-b-poly(ethylene glycol)] hole scavenger, which consumed photogenerated holes, while the photogenerated electrons transferred to a copper cathode reducing dissolved metal ions and produced electricity. Dissolved silver Ag+, copper Cu2+, hexavalent chromium as dichromate Cr2O72- and lead Pb2+ ions in a mixture (0.2mM each) were removed at different rates, according to their reduction potentials. Reduced Ag+, Cu2+ and Pb2+ ions produced metal deposits on the cathode electrode which were mechanically recovered, while Cr2O72- reduced to the less toxic Cr3+ in solution. The cell produced a current density Jsc of 0.23mA/cm2, an open circuit voltage Voc of 0.63V and a maximum power density of 0.084mW/cm2. A satisfactory performance of this PEC for the treatment of lead-acid battery wastewater was observed. The cathodic reduction of heavy metals was limited by the rate of electron-hole generation at the photoanode. The PEC performance decreased by 30% after 9 consecutive runs, caused by the photoanode progressive degradation.

Photocatalytic and photoelectrocatalytic degradation of the drug omeprazole on nanocrystalline titania films in alkaline media: Effect of applied electrical bias on degradation and transformation products.

Photocatalytic and photoelectrocatalytic degradation of the drug omeprazole has been studied in the presence of nanocrystalline titania films supported on glass slides or transparent FTO electrodes in alkaline environment. Its photocatalytic degradation rate was assessed by its UV absorbance and by HPLC, while its transformation products were analyzed by HR-LC-MS. Based on UV absorbance, omeprazole can be photocatalytically degraded at an average rate of 6.7×10(-4)min(-1) under low intensity UVA irradiation of 1.5mWcm(-2) in the presence of a nanoparticulate titania film. This corresponds to degradation of 1.4mg of omeprazole per gram of the photocatalyst per liter of solution per hour. The photodegradation rate can be accelerated in a photoelectrochemical cell by applying a forward bias. In this case, the maximum rate reached under the present conditions was 11.6×10(-4)min(-1) by applying a forward bias of +0.6V vs. Ag/AgCl. Four major transformation products were successfully identified and their profiles were followed by HR-LC-MS. The major degradation path includes the scission of the sulfoxide bridge into the corresponding pyridine and benzimidazole ring derivates and this is accompanied by the release of sulfate anions in the reaction mixture.

Photocatalytic and photoelectrocatalytic degradation of the antibacterial agent ciprofloxacin.

Photocatalytic and photoelectrocatalytic degradation of the antibacterial fluoroquinolone drug, ciprofloxacin, has been studied in the presence of nanocrystalline titania films supported on glass slides or transparent electrodes. The degradation has been examined either in pure water or in the presence of NaOH or NaCl. Titania films can photocatalytically or photoelectrocatalytically degrade ciprofloxacin. In the presence of NaOH, the degradation rate was lower than in pure water and this is explained by the fact that at high pH values attraction of ciprofloxacin to the titania surface is discouraged. In the presence of NaCl, the degradation rate was the highest, thanks to Cl-based radicals which can be photocatalytically created by interacting with photogenerated holes. Application of a forward (anodic) bias increased the photodegradation rate in the presence of both electrolytes while a reverse (cathodic) bias decreased the photodegradation rate. Electrocatalytic effects, i.e. degradation of ciprofloxacin in the dark or in the absence of a photocatalyst under an applied bias of up to ±1.0 V vs. Ag/AgCl, were not detected in the case of NaOH and were of limited importance in the case of NaCl.

Photocatalysis for renewable energy production using PhotoFuelCells.

The present work is a short review of our recent studies on PhotoFuelCells, that is, photoelectrochemical cells which consume a fuel to produce electricity or hydrogen, and presents some unpublished data concerning both electricity and hydrogen production. PhotoFuelCells have been constructed using nanoparticulate titania photoanodes and various cathode electrodes bearing a few different types of electrocatalyst. In the case where the cell functioned with an aerated cathode, the cathode electrode was made of carbon cloth carrying a carbon paste made of carbon black and dispersed Pt nanoparticles. When the cell was operated in the absence of oxygen, the electrocatalyst was deposited on an FTO slide using a special commercial carbon paste, which was again enriched with Pt nanoparticles. Mixing of Pt with carbon paste decreased the quantity of Pt necessary to act as electrocatalyst. PhotoFuelCells can produce electricity without bias and with relatively high open-circuit voltage when they function in the presence of fuel and with an aerated cathode. In that case, titania can be sensitized in the visible region by CdS quantum dots. In the present work, CdS was deposited by the SILAR method. Other metal chalcogenides are not functional as sensitizers because the combined photoanode in their presence does not have enough oxidative power to oxidize the fuel. Concerning hydrogen production, it was found that it is difficult to produce hydrogen in an alkaline environment even under bias, however, this is still possible if losses are minimized. One way to limit losses is to short-circuit anode and cathode electrode and put them close together. This is achieved in the "photoelectrocatalytic leaf", which was presently demonstrated capable of producing hydrogen even in a strongly alkaline environment.

A photoactivated fuel cell used as an apparatus that consumes organic wastes to produce electricity.

A two-compartment photoelectrochemical cell has been constructed and employed as a photoactivated fuel cell that can consume organic material to produce electricity. The cell comprises of a fluorine-doped tin oxide transparent anode electrode supporting a nanocrystalline titania photocatalyst, a Pt/carbon-black electrocatalyst deposited on a carbon cloth as the cathode and a porous membrane (glass frit) separating the two compartments. Both the anode and cathode compartments contain 1.0 M NaOH, but the anode compartment also contains the photodegradable organic substance. The cell runs without any external bias, only by UVA (black light) irradiation or by natural solar light. Glycerol and two higher polyols, xylitol and sorbitol, were tested as fuels. Both the open-circuit voltage and the short-circuit current depended on the polyol concentration up to a saturation value. The maximum current density was around 0.8 mA cm(-2), calculated over the anode active geometrical area, and maximum open-circuit voltage was around 1.3 V. For quasi-monochromatic incident radiation (363 nm wavelength), the above maximum current density corresponded to an external quantum efficiency (IPCE%) of 77%. The fill factor of the cell was relatively small but improved when a thin cell design was applied. All three studied polyols gave similar data for the same molar concentration, suggesting that photodegradation possibly proceeds by steps affecting a single hydroxyl group at a time.

Production of electricity and hydrogen by photocatalytic degradation of organic wastes in a photoelectrochemical cell: the concept of the Photofuelcell: a review of a re-emerging research field.

The present review aims to give to a researcher who has no experience with Photofuelcells all necessary basic knowledge to join the field without much trouble and to give to an experienced researcher a handy manual of reference. The author has dealt with the principal matters related with the design of a photoelectrochemical cell and the factors that affect efficient production of electricity by photocatalytic degradation of (principally) organic and (secondarily) inorganic waste materials. A large portion of the paper is devoted to the review of materials used for making a photoanode since most of the accomplished research is on this exact matter. The paper also briefly reviews the materials used to make the rest of the components of the cell as well as the models of cell efficiency and photodegradation procedures during cell operation.

A new precursor for the preparation of nanocrystalline TiO2 films and their photocatalytic properties.

In this work, we present a new precursor for the preparation of thin and transparent nanocrystalline TiO2 films, which involves the use of Titanium(IV) bis(ammonium lactato) dihydroxide as Ti(IV) source and Triton X-100 as surfactant template. The films were heated at various temperatures in order to optimize their nanostructure and their photocatalytic activity. The morphology and the nanostructure of the films were characterized by SEM and AFM. Crystallinity of the films was examined by XRD and their light absorption with UV-Vis spectroscopy. The photocatalytic activity of the films was investigated by using an azo dye: Basic Blue 41. Excitation of the samples was made by low intensity black light tubes emitting in the Near-UV. The photodegradation of the dye was studied as a function of the quality of the deposited TiO2 films and the calcination temperature in comparison with similar films made by standard procedures.

Photoelectrochemical oxidation of organic substances and electricity generation in the presence of nanocrystalline titania photocatalyst.

A chemically biased, two compartment cell has been used to photoelectrochemically degrade several substances and produce electricity. The photoanode of the cell was made of nanocrystalline Titania deposited on a conductive transparent fluorine-doped tin oxide electrode. The dark cathode was made of an identical electrode as the photoanode with Pt nanoparticles deposited on the nanocrystalline Titania film. The photoanode was activated by UVA radiation emitted by Black-light tubes or directly by natural (Solar) light. Photo-oxidation of several substances produced electricity. Efficiency calculations have been made in all studied cases.