Highly Selective Tandem Photoelectrochemical C-H Activation via Bromine Evolution Reaction in Two-Phase Electrolyte.

The development of environmentally friendly and safe chemical processes using renewable energy sources is important. In this study, a photoelectrochemical (PEC) cell was used for the tandem bromination of sp3 carbon within a unique two-phase electrolyte system. By incorporation of a RuOx cocatalyst, the Ta3N5 photoelectrode demonstrated a remarkable selectivity for Br2 close to 100%. The kinetic study for charge carriers of photoelectrodes reveals that the improved charge transfer at Ta3N5/RuOx interfaces contributed to excellent photoelectrochemical Br2 evolution activity. The photoelectrochemically produced Br2 was utilized for bromination of α-sp3 carbon in toluene, 1-methylnaphthalene, ethylbenzene, or cyclohexane by the Ta3N5/RuOx photoanode with 100% regioselectivity. The coupling of the Ta3N5 photoanode and InP photocathode generated H2 and Br2 under light illumination without external bias. This study provides systematic insights into the design of photoelectrodes for solar-driven tandem bromination systems within the unique environment of a two-phase electrolyte system.

Monitoring Transformations of Catalytic Active States in Photocathodes Based on MoSx Layers on CuInS2 Using In Operando Raman Spectroscopy.

The electrochemical activation of CuInS2 /MoSx for photoelectrochemical (PEC) H2 production was revealed for the first time through in operando Raman spectroscopy. During the activation process, the initial metallic MoSx phase was transformed to semiconducting MoSx , which facilitates charge carrier transfer between CuInS2 and MoSx . Ex situ X-ray photoelectron spectroscopy and Raman spectroscopy suggest the existence of MoO3 after the activation process. However, apart from contradicting these results, in operando Raman spectroscopy revealed some of the intermediate steps of the activation process.

Photoelectrochemical CO2 Reduction with a Rhenium Organometallic Redox Mediator at Semiconductor/Aqueous Liquid Junction Interfaces.

Electrochemical and photoelectrochemical CO2 reductions were carried out with Re(bh-bipy)(CO)3 (OH2 ) cocatalysts in aqueous electrolytes. Competition between hydrogen evolution and CO2 reduction was observed under (photo)electrochemical conditions for both glassy carbon and CuInS2 electrodes. The partial current density for CO generation is limited even though the additional potential is applied. However, electrochemical hydrogen evolution was suppressed under photoelectrochemical conditions, and the selectivity and partial current density for CO were considerably increased when compared to the electrochemical reduction in an identical electrode/electrolyte system. This finding may provide insights into using semiconductor/liquid junctions for solar fuel devices to overcome the limitations of electrolysis systems with an external bias.

Charge separation properties of Ta3N5 photoanodes synthesized via a simple metal-organic-precursor decomposition process.

Here, we successfully synthesized a Ta3N5 thin film using a simple metal-organic-precursor decomposition process followed by its conversion to nitride and studied its photoelectrochemical (PEC) properties to understand charge separation on the surface. Newly synthesized Ta3N5 photoanodes showed a significant difference in the PEC activity in relation to the annealing temperature under ammonia flow, although similar light absorption properties or electronic states were obtained. Charge separation related PEC properties were analyzed using intensity modulated photocurrent density spectroscopy (IMPS) and photocurrent measurements in the absence/presence of scavengers. The charge transfer and recombination rate constants which are related to the photogenerated charge-separation dynamics on the Ta3N5 surface were found to be more sensitively influenced by the ammonia annealing temperatures, and low temperature (700 °C) treated Ta3N5 showed a fast recombination rate constant (kr). In addition, high-efficiency charge injection into the electrolyte on the surface was critically associated with the greatly enhanced photocurrent density of Ta3N5 synthesized at a higher temperature (900 °C) of ammonia annealing.

Enhanced Photocurrents with ZnS Passivated Cu(In,Ga)(Se,S)2 Photocathodes Synthesized Using a Nonvacuum Process for Solar Water Splitting.

Chalcopyrite Cu(In,Ga)(Se,S)2 (CIGS) semiconductors are potential candidates for use in photoelectrochemical (PEC) hydrogen generation due to their excellent optical absorption properties and high conduction band edge position. In the present research, CIGS thin film was successfully prepared on a transparent substrate (F:SnO2 glass) using a solution-based process and applied for a photocathode in solar water splitting, which shows control of the surface state associated with sulfurization/selenization process significantly influences on the PEC activity. A ZnS passivation surface layer was introduced, which effectively suppresses charge recombination by surface states of CIGS. The CIGS/ZnS/Pt photocathode exhibited highly enhanced PEC activity (∼24 mA·cm-2 at -0.3 V vs RHE). The performances of our CIGS photocathode on the transparent substrate were also characterized under front/back light illumination, and the incident photon to current conversion efficiency (IPCE) drastically changed depending on the illumination directions showing decreased IPCE especially under UV region with back illumination. The slow minority carrier (electron) transportation is suggested as a limiting factor for the PEC activity of the CIGS photocathode.

Improved photoelectrochemical water oxidation kinetics using a TiO2 nanorod array photoanode decorated with graphene oxide in a neutral pH solution.

We prepared TiO2 nanorod (NR) arrays on a fluorine-doped tin oxide substrate and decorated with graphene oxide (GO) to study their photoelectrochemical (PEC) water oxidation activities in two different electrolytes. The PEC performances of GO-decorated TiO2 NR photoanodes were characterized by optical and electrochemical impedance spectroscopy measurements. In 1 M KOH, the photocurrent density of the TiO2 NR film decreased after deposition of GO, while in the neutral pH electrolyte (phosphate buffered 0.5 M Na2SO4), the TiO2 NR photoanode showed enhanced performance after deposition with the 2 wt% GO solution. This was a consequence of the decrease in charge transfer resistance between the electrode surface and the electrolyte. The improvement of photocurrents by GO decoration was obvious near the onset potential of the photocurrents in the neutral pH electrolyte. These opposite contributions of GO on the TiO2 NR photoanodes suggest that GO can promote water oxidation effectively in a neutral electrolyte because depending on the pH of the electrolyte, different chemical species interact with the surface of the photoanode in the water oxidation reaction.

Recent Advances in CuInS2-Based Photocathodes for Photoelectrochemical H2 Evolution.

Photoelectrochemical (PEC) H2 production from water using solar energy is an ideal and environmentally friendly process. CuInS2 is a p-type semiconductor that offers many advantages for PEC H2 production. Therefore, this review summarizes studies on CuInS2-based PEC cells designed for H2 production. The theoretical background of PEC H2 evolution and properties of the CuInS2 semiconductor are initially explored. Subsequently, certain important strategies that have been executed to improve the activity and charge-separation characteristics of CuInS2 photoelectrodes are examined; these include CuInS2 synthesis methods, nanostructure development, heterojunction construction, and cocatalyst design. This review helps enhance the understanding of state-of-the-art CuInS2-based photocathodes to enable the development of superior equivalents for efficient PEC H2 production.

CuInS2 Photocathodes with Atomic Gradation-Controlled (Ta,Mo)x(O,S)y Passivation Layers for Efficient Photoelectrochemical H2 Production.

An atomic gradient passivation layer, (Ta,Mo)x(O,S)y, is designed to improve the charge transportation and photoelectrochemical activity of CuInS2-based photoelectrodes. We found that Mo spontaneously diffused to the a-TaOx layer during e-beam evaporation. This result indicates that the gradient profile of MoOx/TaOx is formed in the sublayer of (Ta,Mo)x(O,S)y. To understand the atomic-gradation effects of the (Ta,Mo)x(O,S)y passive layer, the composition and (photo)electrochemical properties have been characterized in detail. When this atomic gradient-passive layer is applied to CuInS2-based photocathodes, promising photocurrent and onset potential are seen without using Pt cocatalysts. This is one of the highest activities among reported CuInS2 photocathodes, which are not combined with noble metal cocatalysts. Excellent photoelectrochemical activity of the photoelectrode can be mainly achieved by (1) the electron transient time improved due to the conductive Mo-incorporated TaOx layer and (2) the boosted electrocatalytic activity by Mox(O,S)y formation.

p-CuInS2 /n-Polymer Semiconductor Heterojunction for Photoelectrochemical Hydrogen Evolution.

An inorganic p-type CuInS2 semiconductor was combined with the semiconducting polymer of PNDI3OT-Se1 and PNDI3OT-Se2 with different HOMO/LUMO levels for photoelectrochemical hydrogen production. Charge transfer behaviors at polymer/CuInS2 junctions were investigated by electrochemical impedance spectroscopy. The heterojunction of p-CuInS2 and n-type polymer (both PNDI3OT-Se1 and Se2) successfully made p-n junctions and showed improved charge transfer. However, we found that higher HOMO levels of polymer than valence band maximum (VBM) of CuInS2 spurred charge recombination at interfaces. As a result, CuInS2 /PNDI3OT-Se1/TiO2 /Pt, which has suitable energy levels matched between PNDI3OT-Se1 and CuInS2 , shows photocurrent (-15.67 mA cm-2 ) improved concretely when compared to a CuInS2 /TiO2 /Pt photoelectrode (-7.11 mA cm-2 ) at 0.0 V vs. RHE applied potential. Additionally, the photoelectrochemical stability of CuInS2 /PNDI3OT-Se1/TiO2 /Pt photoelectrode was also investigated.

Recent Advances in TiO2-Based Photocatalysts for Reduction of CO2 to Fuels.

Titanium dioxide (TiO2) has attracted increasing attention as a candidate for the photocatalytic reduction of carbon dioxide (CO2) to convert anthropogenic CO2 gas into fuels combined with storage of intermittent and renewable solar energy in forms of chemical bonds for closing the carbon cycle. However, pristine TiO2 possesses a large band gap (3.2 eV), fast recombination of electrons and holes, and low selectivity for the photoreduction of CO2. Recently, considerable progress has been made in the improvement of the performance of TiO2 photocatalysts for CO2 reduction. In this review, we first discuss the fundamentals of and challenges in CO2 photoreduction on TiO2-based catalysts. Next, the recently emerging progress and advances in TiO2 nanostructured and hybrid materials for overcoming the mentioned obstacles to achieve high light-harvesting capability, improved adsorption and activation of CO2, excellent photocatalytic activity, the ability to impede the recombination of electrons-holes pairs, and efficient suppression of hydrogen evolution are discussed. In addition, approaches and strategies for improvements in TiO2-based photocatalysts and their working mechanisms are thoroughly summarized and analyzed. Lastly, the current challenges and prospects of CO2 photocatalytic reactions on TiO2-based catalysts are also presented.

A highly efficient Cu(In,Ga)(S,Se)2 photocathode without a hetero-materials overlayer for solar-hydrogen production.

Surface modification of a Cu(In,Ga)(S,Se)2 (CIGSSe) absorber layer is commonly required to obtain high performance CIGSSe photocathodes. However, surface modifications can cause disadvantages such as optical loss, low stability, the use of toxic substances and an increase in complexity. In this work, we demonstrate that a double-graded bandgap structure (top-high, middle-low and bottom-high bandgaps) can achieve high performance in bare CIGSSe photocathodes without any surface modifications via a hetero-materials overlayer that have been fabricated in a cost-effective solution process. We used two kinds of CIGSSe film produced by different precursor solutions consisting of different solvents and binder materials, and both revealed a double-graded bandgap structure composed of an S-rich top layer, Ga- and S-poor middle layer and S- and Ga-rich bottom layer. The bare CIGSSe photocathode without surface modification exhibited a high photoelectrochemical activity of ~6 mA·cm-2 at 0 V vs. RHE and ~22 mA·cm-2 at -0.27 V vs. RHE, depending on the solution properties used in the CIGSSe film preparation. The incorporation of a Pt catalyst was found to further increase their PEC activity to ~26 mA·cm-2 at -0.16 V vs. RHE.

Insight into Charge Separation in WO3/BiVO4 Heterojunction for Solar Water Splitting.

Recently, the WO3/BiVO4 heterojunction has shown promising photoelectrochemical (PEC) water splitting activity based on its charge transfer and light absorption capability, and notable enhancement of the photocurrent has been achieved via morphological modification of WO3. We developed a graft copolymer-assisted protocol for the synthesis of WO3 mesoporous thin films on a transparent conducting electrode, wherein the particle size, particle shape, and thickness of the WO3 layer were controlled by tuning the interactions in the polymer/sol-gel hybrid. The PEC performance of the WO3 mesoporous photoanodes with various morphologies and the individual heterojunctions with BiVO4 (WO3/BiVO4) were characterized by measuring the photocurrents in the absence/presence of hole scavengers using light absorption spectroscopy and intensity-modulated photocurrent spectroscopy. The morphology of the WO3 photoanode directly influenced the charge separation efficiency within the WO3 layer and concomitant charge collection efficiency in the WO3/BiVO4 heterojunction, showing the smaller sized nanosphere WO3 layer showed higher values than did the plate-like or rod-like one. Notably, we observed that photocurrent density of WO3/BiVO4 was not dependent on the thickness of WO3 film or its charge collection time, implying slow charge flow from BiVO4 to WO3 can be a crucial issue in determining the photocurrent, rather than the charge separation within the nanosphere WO3 layer.

Highly stable tandem solar cell monolithically integrating dye-sensitized and CIGS solar cells.

UNLABELLED: A highly stable monolithic tandem solar cell was developed by combining the heterogeneous photovoltaic technologies of dye-sensitized solar cell (DSSC) and solution-processed CuInxGa1-xSeyS1-y (CIGS) thin film solar cells. The durability of the tandem cell was dramatically enhanced by replacing the redox couple from to [Co(bpy)3](2+) /[Co(bpy)3](3+)), accompanied by a well-matched counter electrode ( PEDOT: PSS) and sensitizer (Y123). A 1000 h durability test of the DSSC/CIGS tandem solar cell in ambient conditions resulted in only a 5% decrease in solar cell efficiency. Based on electrochemical impedance spectroscopy and photoelectrochemical cell measurement, the enhanced stability of the tandem cell is attributed to minimal corrosion by the cobalt-based polypyridine complex redox couple.

Effect of the Si/TiO2/BiVO4 heterojunction on the onset potential of photocurrents for solar water oxidation.

BiVO4 has been formed into heterojunctions with other metal oxide semiconductors to increase the efficiency for solar water oxidation. Here, we suggest that heterojunction photoanodes of Si and BiVO4 can also increase the efficiency of charge separation and reduce the onset potential of the photocurrent by utilizing the high conduction band edge potential of Si in a dual-absorber system. We found that a thin TiO2 interlayer is required in this structure to realize the suggested photocurrent density enhancement and shifts in onset potential. Si/TiO2/BiVO4 photoanodes showed 1.0 mA/cm(2) at 1.23 V versus the reversible hydrogen electrode (RHE) with 0.11 V (vs RHE) of onset potential, which were a 3.3-fold photocurrent density enhancement and a negative shift in onset potential of 300 mV compared to the performance of FTO/BiVO4 photoanodes.