Wireless photoelectrochemical (PEC) devices promise easy device fabrication as well as reduced losses. Here, the design and fabrication of a stand-alone ion exchange material-embedded, Si membrane-based, photoelectrochemical cell architecture with micron-sized pores is shown, to overcome the i) pH gradient formation due to long-distance ion transport, ii) product crossover, and iii) parasitic light absorption by application of a patterned catalyst. The membrane-embedded PEC cell with micropores utilizes a triple Si junction cell as the light absorber, and Pt and IrO _x as electrocatalysts for the hydrogen evolution reactions and oxygen evolution reactions, respectively. The solar-to-hydrogen efficiency of 7% at steady-state operation, as compared to an unpatterned η _PV of 10.8%, is mainly attributed to absorption losses by the incorporation of the micropores and catalyst microdots. The introduction of the Nafion ion exchange material ensures an intrinsically safe PEC cell, by reducing the total gas crossover to <0.1%, while without a cation exchange membrane, a crossover of >6% is observed. Only in a pure electrolyte of 1 m H ₂ SO ₄ , a pH gradient-free system is observed thus completely avoiding the build-up of a counteracting potential.

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Solar fuels are a promising way to store solar energy seasonally. This paper proposes an earth-abundant heterostructure to split water using a photovoltaic-electrochemical device (PV-EC). The heterostructure is based on a hybrid architecture of a thin-film (TF) silicon tandem on top of a c-Si wafer (W) heterojunction solar cell (a-Si:H (TF)/nc-Si:H (TF)/c-Si(W)) The multijunction approach allows to reach enough photovoltage for water splitting, while maximizing the spectrum utilization. However, this unique approach also poses challenges, including the design of effective tunneling recombination junctions (TRJ) and the light management of the cell. Regarding the TRJs, the solar cell performance is improved by increasing the n-layer doping of the middle cell. The light management can be improved by using hydrogenated indium oxide (IOH) as transparent conductive oxide (TCO). Finally, other light management techniques such as substrate texturing or absorber bandgap engineering were applied to enhance the current density. A correlation was observed between improvements in light management by conventional surface texturing and a reduced nc-Si:H absorber material quality. The final cell developed in this work is a flat structure, using a top absorber layer consisting of a high bandgap a-Si:H. This triple junction cell achieved a PV efficiency of 10.57%, with a fill factor of 0.60, an open-circuit voltage of 2.03 V and a short-circuit current density of 8.65 mA/cm ² . When this cell was connected to an IrO _x /Pt electrolyser, a stable solar-to-hydrogen (STH) efficiency of 8.3% was achieved and maintained for 10 hours.

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One of the main problems of renewable energies is storage of the energy carrier. For long-term storage, solar fuels seem to be a good option. Direct solar water splitting could play an important role in the production of these solar fuels. One of the main challenges of this process is the charge separation and collection at the interfaces. The knowledge on photovoltaic (PV) junctions can be used to tackle this challenge. In this work, the use of doped layers to enhance the electric field in an a-SiC:H photocathode, and the use of thin-film silicon multijunction devices to achieve a stand-alone solar water splitting device are discussed. Using a p-i-n structure as a-SiC:H photocathode, a current density of 10mA/cm² is achievable. The p-i-n structure proposed also indicates the suitability of traditional PV structures for solar water splitting. In addition, hybrid devices, including a silicon heterojunction PV device, are proposed. A combination of the a-SiC:H photocathode with a nc-Si:H/c-Si is demonstrated and potential STH efficiencies of 7.9% have been achieved. Furthermore, a purely PV approach such as a triple junction a-Si:H/nc-Si:H/nc-Si:H solar cell is demonstrated, with solar-to-hydrogen (STH) efficiencies of 9.8%

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Currently available (photo-)electrochemical technologies for water treatment establish a trade-off between low-pollutant concentration and costs. This paper aims at decoupling these two variables by designing a photo-oxidation device using earth abundant materials and an electronic-free approach. The proposed device combines a graphite/graphite electrochemical system with a silicon-based solar cell that provides the necessary electrical power. First, the optimum operational voltage for the graphite/graphite electrochemical system was found to be around 1.6 V. That corresponded closely to the voltage produced by an a-Si:H/a-Si:H tandem solar cell of approximately 1.35 V. This configuration was shown to provide the best pollutant degradation in relation to the device area, removing 70% of the initial concentration of phenol and 90% of the methylene blue after 4 h of treatment. The chemical oxygen demand (COD) removal of these two contaminants after 4 h of treatment was also promising, 55 and 30%, respectively. Moreover, connecting several solar cells in series led to higher pollutant degradation but lower COD removal, suggesting that the degradation of the intermediate components is a limiting factor. This is expected to be due to the higher currents achieved by the series-connected configuration, which would favor other reactions such as polymerization over the degradation of intermediate species.

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The current energy scenario requires not only the conversion of renewable energy sources into electrical energy, but also a way to store it to match the demand and supply. In particular, solar energy can be used to stabilize energy conversion and energy supply by converting the energy in other diverse ways. And important possibility are photo electrochemical (PEC) reactions for water splitting and water treatment. To be able to directly drive these kind of reactions using solar energy, the interactions between the different elements must be studied in detail. In particular, the semiconductor/electrolyte interface seems to play a very important role in these kinds of devices. Moreover, each of these reactions needs specific conditions in terms of current and voltage, and thus specific semiconductor device architectures would be needed. In these two cases, both a study of the reaction, focusing on the semiconductor/ electrolyte interface, and a device optimization was performed. @en

Amorphous silicon carbide (a-SiC:H) is a promising material for photoelectrochemical water splitting owing to its relatively small band-gap energy and high chemical and optoelectrical stability. This work studies the interplay between charge-carrier separation and collection, and their injection into the electrolyte, when modifying the semiconductor/electrolyte interface. By introducing an n-doped nanocrystaline silicon oxide layer into a p-doped/intrinsic a-SiC:H photocathode, the photovoltage and photocurrent of the device can be significantly improved, reaching values higher than 0.8V. This results from enhancing the internal electric field of the photocathode, reducing the Shockley-Read-Hall recombination at the crucial interfaces because of better charge-carrier separation. In addition, the charge-carrier injection into the electrolyte is enhanced by introducing a TiO₂ protective layer owing to better band alignment at the interface. Finally, the photocurrent was further enhanced by tuning the absorber layer thickness, arriving at a thickness of 150nm, after which the current saturates to 10mAcm^-2 at 0V vs. the reversible hydrogen electrode in a 0.2m aqueous potassium hydrogen phthalate (KPH) electrolyte at pH4.

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The removal of organics by photoelectrocatalytic oxidation offers a viable option to remove the contaminants at low concentrations. In this paper, we propose a BiVO4 thin films synthesized via spray pyrolysis for photoelectrocatalyic oxidation of phenol with solar light. We compare the properties of BiVO4 with those of the commonly used photocatalyst TiO2. In addition, BiVO4 films with W gradient doping were fabricated and tested for improving the photocatalytic performance of BiVO4. X-ray diffraction, atomic force microscopy, incident photon to current efficiency and spectrophotometry have been conducted for BiVO4 films of different thicknesses, as well as for TiO2. The electrochemical impedance spectroscopy and dark conductivity measurements were conducted. Phenol removal has been measured for both the TiO2 and BiVO4 samples. The best performance was found to be for a 300 nm undoped BiVO4 film, being able to reduce the phenol concentration up to 30.0% of the initial concentration in four hours.

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One of the main problems of renewable energies is storage of the energy carrier. For long-term storage, solar fuels seem to be a good option. Direct solar water splitting could play an important role in the production of these solar fuels. One of the main challenges of this process is the charge separation and collection at the interfaces. The knowledge on photovoltaic (PV) junctions can be used to tackle this challenge. In this work, the use of doped layers to enhance the electric field in an a-SiC:H photocathode, and the use of thin-film silicon multijunction devices to achieve a stand-alone solar water splitting device are discussed. Using a p-i-n structure as a-SiC:H photocathode, a current density of 10mA/cm2 is achievable. The p-i-n structure proposed also indicates the suitability of traditional PV structures for solar water splitting. In addition, hybrid devices, including a silicon heterojunction PV device, are proposed. A combination of the a-SiC:H photocathode with a nc-Si:H/c-Si is demonstrated and potential STH efficiencies of 7.9% have been achieved. Furthermore, a purely PV approach such as a triple junction a-Si:H/nc-Si:H/nc-Si:H solar cell is demonstrated, with solar-to-hydrogen (STH) efficiencies of 9.8%.@en

A hybrid tandem solar cell consisting of a thin-film, nanocrystalline silicon top junction and a siliconheterojunction bottom junction is proposed as a supporting solar cell for photoelectrochemical applications.Tunneling recombination junction engineering is shown to be an important consideration indesigning this type of solar cell. The best hybrid cell produced has a spectral utilization of 30.6 mA cm2a JSC of 14 mA cm2, a VOC of 1.1 V, a fill factor of 0.67 and thus an efficiency of 10.3%. A high solar-tohydrogenefficiency of 7.9% can be predicted when using the hybrid cell in conjunction with current a-SiCphotocathode technology.@en

Photoelectrochemical (PEC) water splitting is a sustainable approach to produce a renewable fuel by harvesting the energy of the Sun to split water to form hydrogen and oxygen. In order to drive the water splitting reaction efficiently, substantial ohmic losses due to poor ionic conductivity of the electrolyte should be avoided, and therefore the reaction should be carried out at an extreme electrolyte pH. Herein we demonstrate the photoelectrochemical activity of an amorphous silicon carbide (a-SiC) photocathode for solar hydrogen evolution using an ultrathin nickel (Ni) film coupled with a nickel molybdenum catalyst (Ni-Mo) in a highly alkaline solution (pH 14). The incorporation of the Ni film coupled with Ni-Mo nanoparticles increases the number of active sites and therefore improves the kinetics of the hydrogen evolution reaction. Additionally, we report the influence of the catalyst configurations on the ohmic and solid liquid junction behavior on semiconducting interfacial layers. The a-SiC photocathode coated with the Ni/Ni-Mo dual-catalyst produces a photocurrent density of -14 mA cm^-2 at 0 V vs. RHE using only cheap and abundant materials. This photocurrent is the highest recorded value from an amorphous-Si-based photocathode, and is achieved with a total film thickness of less than 150 nm.

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