Insights into mechanical compression and the enhancement in performance by Mg(OH)2 coating in flexible dye sensitized solar cells

The engineering of flexible dye sensitized solar cells (DSCs) by mechanical compression is one of the methods that allow low temperature processing of these devices. However, suppressing the high temperature sintering process also significantly reduces the performance of the cells. In our previous work [J. Phys. Chem. C, 116 (2012) 1211], we have attempted to improve flexible DSC performance by coating the porous TiO2 photoanode with an electrodeposited Mg(OH)2 layer. In that work, we have obtained one of the largest photovoltage reported to date in flexible DSCs (847 mV). In order to gain more insights into the reasons for both poorer performance of compressed cells and the origin of the voltage enhancement achieved by the Mg(OH)2 coating, here we present an in-depth study by means of electrochemical impedance spectroscopy, Mott-Schottky plots analysis and open-circuit voltage decays. The existence of a shunt resistance in the mechanically compressed cells is revealed, causing an additional drawback to the poor inter-particle necking. By introducing the Mg(OH)2 coating the recombination in the cell becomes significantly reduced, being the key reason which is responsible for the higher photovoltage. Additionally, the coating and the compression cause modifications in the surface states and in the nature of the interfaces with the electrolyte. This induces TiO2 conduction band displacements and shifts of the relative position of the modified states that influence the performance.This work was supported by UK EPSRC, DSTL, Johnson Matthey Plc and Department of Chemistry, Loughborough University. All members of the renewable energy r esearch group in the Department of Chemistry, Loughborough Univer sity are acknowledged for their assistance in this work. The authors would like to acknowledge previous related work conducted by S. Senthilarasu

Kinetics of oxygen evolution at alpha-Fe2O3 photoanodes: a study by photoelectrochemical impedance spectroscopy

Closed access. This article was published in the journal, Physical Chemistry Chemical Physics [© Royal Society of Chemistry] and the definitive version is available at: http://dx.doi.org/10.1039/C0CP02408BPhotoelectrochemical Impedance Spectroscopy (PEIS) has been used to characterize the kinetics of electron transfer and recombination taking place during oxygen evolution at illuminated polycrystalline α-Fe2O3 electrodes prepared by aerosol-assisted chemical vapour deposition from a ferrocene precursor. The PEIS results were analysed using a phenomenological approach since the mechanism of the oxygen evolution reaction is not known a priori. The results indicate that the photocurrent onset potential is strongly affected by Fermi level pinning since the rate constant for surface recombination is almost constant in this potential region. The phenomenological rate constant for electron transfer was found to increase with potential, suggesting that the potential drop in the Helmholtz layer influences the activation energy for the oxygen evolution process. The PEIS analysis also shows that the limiting factor determining the performance of the α-Fe2O3 photoanode is electron–hole recombination in the bulk of the oxide

Observations on the Modified Wenker Synthesis of Aziridines and the Development of a Biphasic System

This document is the Accepted Manuscript version of a Published Work that appeared in final form in Journal of Organic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher. To access the final edited and published work see http://dx.doi.org/10.1021/jo302615gA cheap and reliable process for the modified Wenker cyclization to afford aziridines has been achieved using biphasic conditions for a range of amino alcohol starting materials. A 100 mmol “one-pot” process has also been devised and enantiopurity of the starting amino alcohol is retained in the aziridine product

Water oxidation at hematite photoelectrodes: the role of surface states

Hematite (α-Fe2O3) constitutes one of the most promising semiconductor materials for the conversion of sunlight into chemical fuels by water splitting. Its inherent drawbacks related to the long penetration depth of light and poor charge carrier conductivity are being progressively overcome by employing nanostructuring strategies and improved catalysts. However, the physical–chemical mechanisms responsible for the photoelectrochemical performance of this material (J(V) response) are still poorly understood. In the present study we prepared thin film hematite electrodes by atomic layer deposition to study the photoelectrochemical properties of this material under water-splitting conditions. We employed impedance spectroscopy to determine the main steps involved in photocurrent production at different conditions of voltage, light intensity, and electrolyte pH. A general physical model is proposed, which includes the existence of a surface state at the semiconductor/liquid interface where holes accumulate. The strong correlation between the charging of this state with the charge transfer resistance and the photocurrent onset provides new evidence of the accumulation of holes in surface states at the semiconductor/electrolyte interface, which are responsible for water oxidation. The charging of this surface state under illumination is also related to the shift of the measured flat-band potential. These findings demonstrate the utility of impedance spectroscopy in investigations of hematite electrodes to provide key parameters of photoelectrodes with a relatively simple measurement

Electrochemical and Photoelectrochemical Investigation of Water Oxidation with Hematite Electrodes

Atomic layer deposition (ALD) was utilized to deposit uniform thin films of hematite (α-Fe2O3) on transparent conductive substrates for photocatalytic water oxidation studies. Comparison of the oxidation of water to the oxidation of a fast redox shuttle allowed for new insight in determining the rate limiting processes of water oxidation at hematite electrodes. It was found that an additional overpotential is needed to initiate water oxidation compared to the fast redox shuttle. A combination of electrochemical impedance spectroscopy, photoelectrochemical and electrochemical measurements were employed to determine the cause of the additional overpotential. It was found that photogenerated holes initially oxidize the electrode surface under water oxidation conditions, which is attributed to the first step in water oxidation. A critical number of these surface intermediates need to be generated in order for the subsequent hole-transfer steps to proceed. At higher applied potentials, the behavior of the electrode is virtually identical while oxidizing either water or the fast redox shuttle; the slight discrepancy is attributed to a shift in potential associated with Fermi level pinning by the surface states in the absence of a redox shuttle. A water oxidation mechanism is proposed to interpret these results

Preparation of nanocrystalline TiO2 electrodes for flexible dye-sensitized solar cells: influence of mechanical compression

Nanocrystalline TiO2 electrodes were prepared using binder-free TiO2 paste on conductive ITO-PEN substrates by the doctor-blade method at significantly low temperature (140 °C), and the electrodes were further processed under different compressions (10−60 MPa) in order to improve interparticle connections and adhesion between the nanoparticles and the ITOPEN substrate. TiO2 electrodes compressed at 30 and 40 MPa had relatively less cracks with low crack width. Electrode compressed at 30 MPa showed the highest internal surface area. Electrode prepared at this compression showed the best dyesensitized solar cell (DSC) performance with Voc of 805 mV, Jsc of 9.24 mA cm−2 , and an overall efficiency of 4.39%. Electrochemical impedance spectroscopy (EIS) studies of the sandwiched cells employing bare nanocrystalline TiO2 electrode and Pt counter electrode in I−/I3 − electrolyte showed that electrode compression significantly influences the stability of the cells. EIS data suggested that degradation/corrosion processes may take place on ITO-PEN for sandwiched cells made by TiO2 electrodes compressed at all pressures. Thirty and 40 MPa compressions showed a minor degradation of ITO. The recombination dynamics at the TiO2/electrolyte interface were influenced by the changes in the nanostructured electrode internal surface area, changes in electron transport properties (due to improved sintering), and possible degradation/corrosion of ITO-PEN. Open-circuit voltage decay (OCVD) measurements showed that the DSC made by the 30 MPa compressed TiO2 electrode had the highest decay time, indicating low recombination properties, which is in a good agreement with other data

Hydrogen for Cooking: A Review of Cooking Technologies, Renewable Hydrogen Systems and Techno-Economics

About 3 billion people use conventional carbon-based fuels such as wood, charcoal, and animal dung for their daily cooking needs. Cooking with biomass causes deforestation and habitat loss, emissions of greenhouse gases, and smoke pollution that affects people’s health and well-being. Hydrogen can play a role in enabling clean and safe cooking by reducing household air pollution and reducing greenhouse gas emissions. This first-of-a-kind review study on cooking with hydrogen assessed existing cooking technologies and hydrogen systems in developing country contexts. Our critical assessment also included the modelling and experimental studies on hydrogen. Renewable hydrogen systems and their adoptability in developing countries were analysed. Finally, we presented a scenario for hydrogen production pathways in developing countries. Our findings indicated that hydrogen is attractive and can be safely used as a cooking fuel. However, radical and disruptive models are necessary to transform the traditional cooking landscape. There is a need to develop global south-based hydrogen models that emphasize adoptability and capture the challenges in developing countries. In addition, the techno-economic assumptions of the models vary significantly, leading to a wide-ranging levelized cost of electricity. This finding underscored the necessity to use comprehensive techno-economic assumptions that can accurately predict hydrogen costs