Incident Photon-to-current Efficiency Research Articles

Integration of TiO2/ZnIn2S4 p‐n Heterojunction with Titanium Defects to Boost PEC Oxygen Production

AbstractTiO2 is a widely used photoelectric conversion semiconductor material. However, due to its native defects, such as the selective absorption of ultraviolet light and high recombination rate of photogenerated carriers, it exhibits poor photoelectrochemical (PEC) water splitting performance. In this study, intrinsic defect titanium vacancy and semiconductor recombination agents ZnIn2S4 were introduced into an anodization‐annealed TiO2 film (TiO2 NT) to enhance the photoanode activity. The activity‐enhanced TiO2 photoanode (ZIS@TiO2 NT‐EA) was characterized by surface analyses and photoelectrochemical measurements. Mott‐Schottky measurement indicated that the introduction of titanium vacancies into the TiO2 NT changed its semiconductor type from n to p, and significantly reduced its apparent activation energy if compared with the TiO2 NT. In addition, after the ZnIn2S4 nanoparticles were loaded on the TiO2 NT‐EA film, the carrier concentration of the ZIS@TiO2 NT‐EA was nearly 12 times higher than the pristine TiO2 NT. Due to the higher carrier separation efficiency resulting from the formation of p‐n heterojunction between TiO2 and ZnIn2S4, the photocurrent density of the ZIS@TiO2 NT‐EA reached 3.89 mA cm−2 at 1.23 V (vs. RHE), nearly 3 times higher than that of the original TiO2 NT. Amazingly, the maximum applied bias photon‐to‐current efficiency (ABPE) value of the ZIS@TiO2 NT‐EA photoanode reached 2.15 % at 0.496 V (vs. RHE), which is very competitive if compared with all the reported TiO2 film electrodes in the PEC water splitting application. The incident photon‐to current efficiency (IPCE) of the ZIS@TiO2 NT‐EA photoanode was approximately 40.9% at 300 nm, which was about 3 times higher than that of the TiO2 NT (13.6%). To understand these impressive improvements in water splitting, further analyses were conducted on the effect of the increased titanium vacancy concentration in the TiO2 lattice and the formation of p‐n junction between the TiO2 and ZnIn2S4 on the PEC behaviour, as well as on the charge transfer resistance and separation efficiency of carriers.

Enhancing Photocathodic Performances of Particulate-CuGaS2-Based Photoelectrodes via Conjugation with Conductive Organic Polymers for Efficient Solar-Driven Hydrogen Production and CO2 Reduction.

Modification with conductive organic polymers consisting of a thiophane- or pyrrole-based backbone improved the cathodic photocurrent of a particulate-CuGaS2-based photoelectrode under simulated solar light. Among these polymers, poly(3,4-ethylenedioxythiophene) (PEDOT) was the most effective in the improvements, providing a photocurrent 670 times as high as that of the bare photocathode. An incident-photon-to-current efficiency (IPCE) for water reduction to form H2 under monochromatic light irradiation (450 nm at 0 V vs RHE) was ca. 11%. The most important point is that modification of the conductive organic polymers does not involve any vacuum processes. This importance lies in the use of an electrochemically oxidative polymerization, not in a physical process such as vapor deposition of metal conductors. This is expected to be advantageous in the large-scale application of photocathodes consisting of particulate photocatalyst materials toward industrial solar-hydrogen production using photoelectrochemical-cell-based devices. Artificial photosynthesis of water splitting and CO2 reduction under simulated solar light was demonstrated by combining the PEDOT-modified CuGaS2 photocathode with a CoOx-loaded BiVO4 photoanode. Furthermore, how the cathodic photocurrent of the particulate-CuGaS2-based photocathode was drastically improved by the modification was clarified based on various characterizations and control experiments as follows: (1) selectively filling cavities between the particulate CuGaS2 photocatalysts and a conductive substrate (FTO; fluorine-doped tin oxide) with the polymers and (2) using a large driving force for carrier transportation governed by the polymers' redox potentials adjusted by functional groups.

Ca‐Doped PrFeO3 Photocathodes with Enhanced Photoelectrochemical Activity

Perovskite oxides, renowned for their adaptable structure and optoelectronic characteristics, hold significant potential for applications in catalysis and photoelectrochemical (PEC) processes. In this research, the preparation of praseodymium iron oxide (PrFeO3) by spin coating and the impact of incorporating a calcium (Ca) dopant on its PEC efficacy as photocathodes are investigated. Spin coating of a polymer containing sol–gel yields thin films with uniform morphology and porosity, facilitating effective semiconductor/electrolyte interactions, as characterized by scanning electron microscopy analyses. Evaluation of transient photocurrent responses reveals that introducing Ca at a 5 at% doping level significantly enhances the PEC activity of PrFeO3, resulting in an optimal photocurrent of −124 μA cm−2 at +0.43 V vs. a reversible hydrogen electrode (VRHE) under simulated sunlight conditions. This enhancement is accompanied by an incident photon‐to‐current efficiency (IPCE) of 3.8% at +0.43 VRHE and 350 nm, along with an onset potential of +1.1 VRHE. Ultraviolet and visible spectroscopy analyses indicate an increase in light‐absorption capabilities in the Ca‐doped films and a noticeable reduction in bandgap compared to the undoped counterparts, further supported by IPCE measurements. In the findings, the significant role of dopants in augmenting the photocurrent performance of stable perovskite oxides, highlighting their potential in advancing photon conversion technologies, is underscored.

Promoting the Photoelectrochemical Properties of BiVO4 Photoanode via Dual Modification with CdS Nanoparticles and NiFe-LDH Nanosheets.

Bismuth vanadate (BiVO4) has long been considered a promising photoanode material for photoelectrochemical (PEC) water splitting. Despite its potential, significant challenges such as slow surface water evolution reaction (OER) kinetics, poor carrier mobility, and rapid charge recombination limit its application. To address these issues, a triadic photoanode has been fabricated by sequentially depositing CdS nanoparticles and NiFe-layered double hydroxide (NiFe-LDH) nanosheets onto BiVO4, creating a NiFe-LDH/CdS/BiVO4 composite. This newly engineered photoanode demonstrates a photocurrent density of 3.1 mA cm-2 at 1.23 V vs. RHE in 0.1 M KOH under AM 1.5 G illumination, outperforming the singular BiVO4 photoanode by a factor of 5.8 and the binary CdS/BiVO4 and NiFe-LDH/BiVO4 photoanodes by factors of 4.9 and 4.3, respectively. Furthermore, it exhibits significantly higher applied bias photon-to-current efficiency (ABPE) and incident photon-to-current efficiency (ICPE) compared to pristine BiVO4 and its binary counterparts. This enhancement in PEC performance is ascribed to the formation of a CdS/BiVO4 heterojunction and the presence of a NiFe-LDH OER co-catalyst, which synergistically facilitate charge separation and transfer efficiencies. The findings suggest that dual modification of BiVO4 with CdS and NiFe-LDH is a promising approach to enhance the efficiency of photoanodes for PEC water splitting.

Mn/Fe co-doped TiO2 nanotube arrays for photoelectrochemical water splitting in neutral medium

Manganese and iron co-doped TiO2 nanotube arrays (TNTs) are grown on Ti foil by in situ electro-anodization method and employed for overall photoelectrochemical water splitting. The band gap of TiO2 is reduced from 3.3 eV to 3.1 eV with co-doping of Mn and Fe in Mn/Fe-TNT@Ti sample. Annealing Mn/Fe-TNT@Ti at 500 °C leads to the formation of trap states associated with the Fe3+ and Mn2+ ions present in the TiO2 lattice. The anatase structure of TNTs in Mn/Fe-TNT@Ti-500 sample is confirmed by XRD and Raman spectroscopy. An anodic shift in the onset potential from 0.2 VRHE to 0.08 VRHE is observed in Mn/Fe-TNT@Ti-500 sample compared to Mn/FeTNT@Ti sample. The overall photocurrent density at −0.4 VRHE is higher for Mn/Fe-TNT@Ti-500 sample (331μA/cm2) than Mn/Fe-TNT@Ti sample (251μA/cm2). The oxygen evolution activity shows similar trend with Mn/Fe-TNT@Ti-500 displaying a photocurrent density of 13.6 μA/cm2 at 1.23 VRHE. The anodic photocurrent density of Mn/Fe-TNT@Ti-500 sample is six times higher than that of the Mn/Fe-TNT@Ti at 0.8 VRHE. The incident photon to current efficiency (IPCE) measurements show that the photon absorption and conversion efficiency of the Mn/Fe-TNT@Ti-500 sample are significantly higher than that of the Mn/Fe-TNT@Ti sample. The results of this study complement the DFT calculations carried out with the generalized gradient approximation (GGA) technique. This work demonstrates possibility of designing composite materials for efficient photoreduction studies using n-type titanium nanotubes as precursors.

Doping of photoactive TiO2 films by DC plasma electrolytic oxidation: Effect of transition metals

Several beneficial features maintain TiO2 in the top list of viable materials for photocatalytic purposes. However, its relatively large band-gap (3.0–3.2 eV) still hampers practical applications under sunlight. This work explores Direct Current (DC) Plasma Electrolytic Oxidation (PEO) of titanium as a fast, easily-scalable and single-step tool to synthesise doped TiO2 photoanodes with controlled morphology, crystalline structure and thickness. Zn-, Cu- and Fe-doped crystalline TiO2 films were obtained in H2SO4 aqueous solutions containing ZnSO4, CuSO4 and FeSO4 precursors, respectively. As-prepared TiO2 films showed a porous and homogeneous sponge-like surface morphology, typical of PEO-produced oxides, and a crystalline phase structure consisting of a mixture of anatase and rutile phases. The anatase content varied in the 54–100 % range and correspondingly the band-gap energy was in the 2.85–3.07 eV range. Doped oxides prepared with a low concentration of the metal precursors showed monochromatic incident-photon-to-current-efficiency (IPCE) values exceeding those obtained with pristine TiO2 by up to 24 %, best performing in the order Zn- > Cu- > Fe-doped TiO2. Photocurrent under polychromatic UV-Vis irradiation showed an analogous trend and the estimated efficiency of solar-light harvesting was in the 0.3–4 % range, with Zn- ≈ Cu- > Fe-doped TiO2. Although the superior performance of the PEO-prepared metal-doped TiO2 could not be fully confirmed by photoelectrocatalytic oxidation tests of organics, the present investigation showed the viability of DC PEO for the synthesis of metal-doped TiO2 photoanodes.

Synthesis and characterization of new purple and green heterocyclic dyes for dye-sensitized solar cells

Due to the growing demand for energy from industrial activities, solar energy has gained increasing attention globally. In recent years, heterocyclic dyes have gained attention due to their potential use as organic photosensitizers in dye-sensitized solar cells (DSSCs). To develop new and effective synthetic dyes for DSSCs, a study was conducted to create new purple dyes 8-(4-chlorophenyl)-5-(hydroxyimino)-3H-imidazo[4′,5′:3,4]benzo[1,2-c]isoxazol-4(5H)-ylidene)-2-arylacetonitriles. These dyes were synthesized by reacting nitro derivatives of imidazo benzoxazole with arylacetonitriles in an alkaline media. Additionally, new fluorescent heterocyclic systems 3-(4-chlorophenyl)-6H-imidazo[4,5-a]isoxazolo[4,3-c]acridine-7-carbonitriles were obtained by heterocyclization of the purple dyes with SOCl2. The highest yield achieved in the synthesis of the title dyes is 74 %. The structures of the new purple and green heterocyclic dyes were confirmed through elemental analysis and spectroscopic data. The photophysical properties of the dyes were investigated using a UV–visible spectrophotometer and a fluorophotometer. The electrochemical characteristics of the purple dyes and fluorescent heterocyclic systems were also studied using cyclic voltammetry. The geometries of the dyes, as well as their highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels, were determined through theoretical calculations using density functional theory (DFT). Furthermore, the photovoltaic performance parameters of the new dyes were examined by analyzing their incident photon-to-current efficiency (IPCE) spectra and current-voltage (I-V) curves. The experimental results showed that the purple dyes exhibited remarkable photovoltaic performances, up to 6.55 %.

Ferrocene Appended D-π-A chromophores for Dye-Sensitized Solar Cells: Synthesis, Photophysical, Effect of Co-adsorbent on Photovoltaic Efficiencies and DFT studies

A new ferrocene conjugated donor–π–acceptor type of dyes 1 and 2 were synthesized and characterized using different spectroscopic techniques (FT-IR, NMR, and ESI-mass). The intramolecular charge transfer process of both the dyes were analysed using the solvatochromic method, which reveals positive solvatochromism due to its well stabilization in the excited states than in the ground states. The electrochemical behavior of the dyes 1 and 2 were carried out by the cyclic voltammetric technique, which shows quasi-reversible in nature, and the potentials were further utilized for the band gap calculation with UV–visible data [2.99 eV (1) and 2.88 eV (2)]. The photovoltaic attainments of the dyes 1 and 2 were studied through the dye-sensitized solar cells (DSSCs) in the presence and absence of co-adsorbent like chenodeoxycholic acid (CDCA), which act as an anti-dye aggregation material. The photovoltaic parameters like short circuit current density (Jsc) = 0.067 mA cm2, open circuit voltage (Voc) = 0.444 V, fill factor (FF) = 0.447, and the cell displayed an overall conversion efficiency of 0.013 % for dye 2. In contrast, the power conversion efficiency (PCE) was found to be enhanced to 0.177 % (Jsc = 0.389 mA/cm2, Voc = 0.577 V, FF =0.790), in the presence of chenodeoxycholic acid (CDCA) co-adsorbent. This enhancement in efficiency is due to reduced dye aggregation and increased electron injection in the presence of CDCA. In addition, chromophore 2 has 1.4 times higher efficiencies than 1, attributing to the presence of an additional phenyl group making an efficient intramolecular process of 2. Furthermore, the incident photon to current efficiency (IPCE) and electrochemical impedance spectroscopy (EIS) studies reveal the dye efficiencies were directly proportional to that of the power conversion efficiency (PCE), respectively. Moreover, the electronic structure and electron density distribution analysis were analysed for both dyes 1 and 2 to confirm the intramolecular charge transfer properties using density-functional theory (DFT) and time-dependent density-functional theory (TD-DFT) calculations using the B3LYP/ 6–31+G** level of theory.

Immobilization of Prussian Blue Nanoparticles Onto Au‐Modified ZnIn2S4 Photoanode for Efficient Photoelectrochemical Water Splitting

AbstractZnIn2S4 has been regarded as a promising photoanode material for photoelectrochemical (PEC) water splitting. However, its severe charge recombination and low carrier transport efficiency limit practical applications in PEC water splitting. A novel ZnIn2S4/Au/PB photoanode was prepared by using the in‐situ photodeposition of Au nanoparticles and electrodeposition of Prussian blue (PB) nanoparticles onto ZnIn2S4 nanosheets. The photocurrent density of the prepared ternary photoanode reached 0.42 mA/cm2 at 1.23 VRHE, which is 6 times higher than pure ZnIn2S4. The introduction of Au nanoparticles remarkably improved the efficiency of carrier transport and separation. Additionally, the application of PB onto ZnIn2S4 resulted in an extended spectrum of light absorption. The incident photon‐to‐current efficiency (IPCE) value recorded was 24.6 % at 350 nm. This improvement can be attributed to the formation of a Z‐type heterojunction.

Deciphering the photoelectrochemical behaviour of MoSe2-decorated BiVO4 as a dual system for concurrent degradation of methylene blue and hydrogen generation

Green hydrogen production through photoelectrochemical (PEC) water splitting offers a sustainable energy solution, but the utilization of low-quality water is essential to conserve freshwater resources. Repurposing industrial wastewater, a substantial global issue, for PEC water splitting remains underexplored due to challenges in photoelectrode efficiency and stability. In this study, we present a MoSe2-decorated BiVO4 heterostructured photoelectrode (MoSe2/BiVO4 or BM) for green hydrogen production and efficient wastewater treatment. The optimized system yields a hydrogen production rate of 0.113 mmol from synthetic textile water (utilizing methylene blue as a model pollutant) while achieving a 94.74% degradation of pollutants. Synthesized via a hydrothermal route, BM demonstrates a high photocurrent density of 2.57 mA/cm2 at 1.23 V vs RHE, surpassing BV alone (0.14 mA/cm2). Further, BM shows incident photon to current efficiency (IPCE) of 12.24% and applied bias to photocurrent efficiency (ABPE) of 0.59%. Scavenger studies elucidate the role of holes in MB degradation. Tested in textile wastewater treatment outlets, BM exhibits a hydrogen production rate of 6.155 μmoles alongside reduced COD, BOD, TOC, and microbial load, showcasing its dual capability for hydrogen generation and simultaneous wastewater treatment. Thus, the efficiently designed type-II heterostructure formed between BV and MS behaves as a dual system with demonstrated usage in low-quality water for hydrogen generation with its simultaneous treatment.

Development of organic co-sensitizers based on piperonal for over 10% efficient ruthenium complex dye-sensitized solar cells

In this study, two new piperonal-based organic dyes, designated D-1–2, were synthesized for use in dye-sensitized solar cells (DSSCs). The dyes studied have a D-π-A configuration and have undergone molecular engineering to fine-tune their spectral properties and energy levels. A comprehensive analysis involving both experimental and theoretical approaches was performed to investigate their optical, electrochemical, photovoltaic, geometrical, and electronic features. These newly developed dyes exhibit notably strong UV–vis absorption, with high molar extinction coefficients, making them an attractive option as co-sensitizers for ruthenium-based dye-sensitized solar cells (DSSCs). Co-sensitization at a concentration of 0.2 mM resulted in a significant increase in the PCEs of DSSCs, ranging from 7.90 % to 10.43 %, compared to the PCE of 7.31 % for DSSCs sensitized solely with N719. The improvement in PCEs can be attributed to the enhanced JCSS and Voc achieved through co-sensitization, highlighting the potential benefits of utilizing co-sensitizers to develop more efficient DSSCs. The highest PCE achieved was 10.43 %, with a Jsc of 19.05 mA.cm−2 and a VOC of 750 mV for the mixed co-sensitizers (D-1 + D-2 + N719). These findings indicate that cocktail co-sensitization is a promising strategy for constructing efficient D-π-A-type sensitizers and for evaluating the performance of DSSCs. Additionally, incident photon-to-current efficiency (IPCE) and electrochemical impedance spectroscopy (EIS) studies provide insights into the mechanisms responsible for these improvements. Based on the IPCE study, the increase in Jsc during co-sensitization is due to less photocurrent loss from the electrolyte. EIS experiments showed that making a monolayer of sensitizers that was denser and more organized probably led to less electron recombination between the injected electrons and the electrolyte. This could be because the dyes were absorbed more. The findings of this study suggest that D-1–2 co-sensitizers might be game-changers in the development of more effective DSSCs. In addition, this investigation provides crucial information regarding the underlying systems.

Understanding the Internal Conversion Efficiency of BiVO4/SnO2 Photoanodes for Solar Water Splitting: An Experimental and Computational Analysis.

This work aims to understand the spin-coating growth process of BiVO4 photoanodes from a photon absorption and conversion perspective. BiVO4 layers with thicknesses ranging from 7 to 48 nm and the role of a thin (<5 nm) SnO2 hole-blocking layer have been studied. The internal absorbed photon-to-current efficiency (APCE) is found to be nonconstant, following a specific dependence of the internal charge separation and extraction on the increasing thickness. This APCE variation with BiVO4 thickness is key for precise computational simulation of light propagation in BiVO4 based on the transfer matrix method. Results are used for accurate incident photon-to-current efficiency (IPCE) prediction and will help in computational modeling of BiVO4 and other metal oxide photoanodes. This establishes a method to obtain the sample's thickness by knowing its IPCE, accounting for the change in the internal APCE conversion. Moreover, an improvement in fill factor and photogenerated voltage is attributed to the intermediate SnO2 hole-blocking layer, which was shown to have a negligible optical effect but to enhance charge separation and extraction for the lower energetic wavelengths. A Mott-Schottky analysis was used to confirm a photovoltage shift of 90 mV of the flat-band potential.

Tungsten trioxide coatings prepared by inkjet printing of a water based formulation: structural characteristics and electrophotocatalytic properties

Thin compact layers of monoclinic tungsten trioxide (WO3) were prepared through printing of a water soluble dopamine peroxo-tungstic acid complex (DoPTA). The effect of different layer thicknesses, achieved through the sequential overlapping of layers (from one to five), on the resulting structure and photo(electrochemical) properties was investigated. After a powder XRD analysis, 450 °C was determined to be the most suitable temperature for calcination due to the formation of a crystalline phase of WO3 within a relatively short time (after 1 h) and, at the same time, this temperature does not cause any damage to the glass substrates used for the deposition of the WO3 layers. Linear scanning voltammetry as well as chronoamperometry were used, with periodic illumination, to measure the influence of the number of layers on the final electro-photocatalytic properties. The thickness of the samples prepared ranged from 0.25 µm to 1.25 µm and the three-layer sample was found to have the best performance. It had a thickness of 0.83 µm, and the incident photon to current efficiency (IPCE) was calculated to be 40.8%.

Effects of transition metals (Fe, Co) on the physical and photoelectrochemical hydrogen generation properties of copper oxide nanoparticulate films

The composites of some transition metal oxides are currently attracting interesting roles in various fields of technology and industry. The present work attempts to tune the properties of copper oxide (CuO) for hydrogen energy generation. Iron (Fe) and cobalt (Co) were intentionally doped at precise contents into CuO thin films. X-ray diffraction (XRD) indicated that the successful substitution of Fe and Co on the Cu sites created induces pressure (tensile) stress in the lattice. Fe doping deteriorated the films' crystallinity and increased the dislocation density from 1.82 × 10−3 to 4.36 × 10−3 nm−2, while Co codoping displayed unsystematic behavior. The scanning electron microscope (SEM) images showed that the films have smooth surfaces comprising a huge number of particles/unit area with a narrow size distribution. The energy-dispersive X-ray (EDX) analysis confirmed the presence of both Fe and Co with almost the pre-calculated ratios. The optical measurement showed that increasing the Fe contents increases the absorption coefficient of CuO and narrows its optical band gap from 1.7 to 1.55 eV. The photoluminescence (PL) intensity increases for Fe-doped CuO films whereas quenched when doped with Co. A series of photoelectrochemical (PEC) measurements were conducted to evaluate the performance of the prepared films in the production of solar hydrogen. The CuO–6%Fe film showed high photocatalytic performance for H2 generation from H2O splitting over a wide wavelength range of sunlight with long-term photostability. The photocurrent density of CuO–6%Fe film is about 155 times more than those obtained from pure CuO film. The incident photon-to-current efficiency (IPCE) and the solar-to-hydrogen efficiency (ηSTH) of CuO–6%Fe film were 5.98 % at 307 nm and 0.94 % under Xenon illumination, respectively. Hence, this work proposed an efficient and reasonable technique to enhance the performance of a CuO-based photoelectrode for solar hydrogen production.

Visible-Light-Active Unsymmetrical Squaraine Dyes with Pyridyl Anchoring Groups for Dye-Sensitized Solar Cells.

Visible-light-active alkyl group-wrapped unsymmetrical squaraine dyes SD1-SD3 were synthesized, featuring an indoline donor and pyridine and carboxylic acid anchoring groups. Their photophysical, electrochemical, and photovoltaic characteristics were examined by fabricating a dye-sensitized solar cell (DSSC) device. Both carboxylic acid and pyridine anchoring groups containing squaraine dyes SD3 and SD2 possess similar photophysical and electrochemical characteristics. However, their photovoltaic performances were completely different. The SD3 dye with the carboxylic acid anchoring group displayed a DSSC device efficiency of 7.20% (VOC 0.81 V; JSC 12.29 mA/cm2) using iodolyte (I-/I3-) electrolyte, compared to SD1 (VOC 0.659 V; JSC 4.97 mA/cm2; and η - 2.34%) and SD2 (VOC 0.629 V; JSC 1.68 mA/cm2; and η - 0.84%), which were featured with pyridyl anchoring groups. These results were attributed to dye loading on the Lewis and Brønsted acidic sites of TiO2 and the importance of aggregated structures for photocurrent generation. In the incident photon-to-current efficiency (IPCE) analysis, SD1 dye-sensitized devices exhibited photocurrent generation from both monomeric and aggregated dyes on the TiO2 surface. In contrast, SD2 showed photocurrent generation solely from aggregated states. Despite the introduction of long alkyl chains to reduce dye aggregation and charge recombination, the results indicated preferential charge injection from only the aggregated SD2 dye on TiO2. Fluorescence-quenching experiments indicated an efficient charge transfer from the aggregated SD2 dye to TiO2 compared to that of the monomeric dye. Cosensitization, a method to enhance the light-harvesting efficiency and photocurrent generation in DSSCs, was explored by simultaneously cosensitizing pyridyl-based dyes (SD1 and SD2) with a blue-colored carboxylic acid-based squaraine dye SD4. IPCE analysis demonstrated that both SD1 and SD4 contributed to generating a photocurrent of 9.11 mA/cm2. The sequential cosensitization of SD1 and SD4 with the coadsorbent CDCA showed the highest performance, with a VOC of 0.663 V, a JSC of 11.43 mA/cm2, and an efficiency (η) of 5.20%.

Enhanced Visible Light-Driven Photocatalytic Water-Splitting Reaction of Titanate Nanotubes Sensitised with Ru(II) Bipyridyl Complex.

The ion exchange of Na+ cations was used to photosensitise titanates nanotubes (Ti-NTs) with tris(2,2'-bipyridine)ruthenium(II) cations (Ru(bpy)32+); this yielded a light-sensitised Ti-NTs composite denoted as (Ru(bpy)3)Ti-NTs, exhibiting the characteristic absorption of Ru(bpy)32+ in visible light. Incident photon-to-current efficiency (IPCE) measurements and the photocatalytic reduction of methyl viologen reaction confirmed that in the photosensitisation of the (Ru(bpy)3)Ti-NTs composite, charge transfer and charge separation occur upon excitation by ultraviolet and visible light irradiation. The photocatalytic potential of titanate nanotubes was tested in the water-splitting reaction and the H2 evolution reaction using a sacrificial agent and showed photocatalytic activity under various light sources, including xenon-mercury lamp, simulated sunlight, and visible light. Notably, in the conditions of the H2 evolution reaction when (Ru(bpy)3)Ti-NTs were submitted to simulated sunlight, they exceeded the photocatalytic activity of pristine Ti-NTs and TiO2 by a factor of 3 and 3.5 times, respectively. Also, (Ru(bpy)3)Ti-NTs achieved the photocatalytic water-splitting reaction under simulated sunlight and visible light, producing, after 4 h, 199 and 282 μmol×H2×gcat-1. These results confirm the effective electron transfer of Ru(bpy)3 to titanate nanotubes. The stability of the photocatalyst was evaluated by a reuse test of four cycles of 24 h reactions without considerable loss of catalytic activity and crystallinity.

Enhanced photoelectrochemical performance of ZnO/α-Fe2O3 heterojunction photoelectrode fabricated by facile hydrothermal and spin-coating method

The present study reports the successful fabrication of ZnO/α-Fe2O3 heterojunctions by facile and simple hydrothermal and spin-coating methods. The effect of spin-coating different FeCl3 precursor layers on the photoelectrochemical performance has been investigated. Additionally, the procedure of spin-coating FeCl3 precursors was simulated by fluent software. It is noteworthy that ZnO/α-Fe2O3 heterojunctions increase the absorption of visible light, promote the separation and transfer of photogenerated charge carriers, reduce the interfacial resistance between the photoelectrode and electrolyte, and provide a larger electrochemically active contact area in contrast to pure ZnO nanorods. The highest photocurrent density and the highest IPCE (incident photon-to-current efficiency) reach 1.82 mA cm−2 and 40 % respectively when spin-coating three layers. Moreover, the mechanism of enhanced PEC performance was further discussed via EIS (electrochemical impedance spectroscopy), Mott-Schottky curves, Energy band structure diagram, and the electrochemical active surface area (ECSA) test.

Enhancing the hydrogen photo-production using zinc oxide films doped with iron, tin, and aluminum

Hydrogen is recognized as the most promising renewable energy source and can be efficiently produced through water photo-electrolysis green process. This study investigates the performance of ZnO nanorods doped with Fe, Al, and Sn at a 2 % molar ratio for hydrogen photo-production. The films were prepared using a combination of successive ionic layer adsorption and reaction (SILAR) and chemical bath deposition (CBD) methods. X-ray diffraction (XRD) analysis confirmed the hexagonal structure of the doped ZnO films with preferential growth along the (002) orientation, while energy-dispersive X-ray spectroscopy (EDX) confirmed their high purity. The doping with Al maintains the ZnO nanorods morphology while Fe, and Sn doping induced changes to overlapped nanoflakes/nanoflowers morphology. Optical analysis revealed a clear trend in the energy band gap, with Fe-ZnO film exhibiting the lowest value (2.95 eV), followed by Al-ZnO (3.03 eV), Sn-ZnO (3.07 eV), and ZnO (3.11 eV). The Fe-ZnO film also demonstrated the best performance as a photoelectrode for hydrogen generation, achieving optimized incident photon-to-current efficiency (IPCE) and applied bias photon-to-current efficiency (ABPE) values of 1.45 % and 0.20 % respectively, under 500 nm monochromatic illumination, with high reproducibility, and durability. These findings represent one step forward to developing ZnO-doped photoanodes for efficient and sustainable hydrogen green production.

New insights into enhancement of bio-hydrogen production through encapsulated microalgae with alginate under visible light irradiation

The production of green hydrogen is a promising alternative to fossil fuels. The current study focuses on the design of microalgae as a catalyst in bioelectrochemical systems for the generation of biohydrogen. Furthermore, the abovementioned target could be achieved by optimizing different parameters, including strains of microalgae, different optical filters, and their shapes. Synechocystis sp. PAK13 (Ba9), Micractinium sp. YACCYB33 (R4), and Desmodesmus intermedius (Sh42) were used and designed as free cells and immobilized microalgae for evaluating their performance for hydrogen production. Alginate was applied for immobilization not only for protecting the immobilized microalgae from stress but also for inhibiting the agglomeration of microalgae and improving stability. The amount of studied immobilized microalgae was 0.01 g/5 ml algae-dissolved in 10 ml alginate gel at 28 °C, 12 h of light (light intensity 30.4 μmol m−2 s−1), and 12 h of darkness with continual aeration (air bump in every strain flask) at pH = 7.2 ± 0.2 in 0.05 %wuxal buffer which has 3.7 ionic strength. Different modalities, including FTIR, UV, and SEM, were performed for the description of selected microalgae. The surface morphology of Ba9 with alginate composite (immobilized Ba9) appeared as a stacked layer with high homogeneity, which facilitates hydrogen production from water. The conversion efficiencies of the immobilized microalgae were evaluated by incident photon-to-current efficiency (IPCE). Under optical filters, the optimum IPCE value was ∼ 7 % at 460 nm for immobilized Ba9. Also, its number of hydrogen moles was calculated to be 16.03 mmol h−1 cm−2 under optical filters. The electrochemical stability of immobilized Ba9 was evaluated through repetitive 100 cycles as a short-term stability test, and the curve of chrono-amperometry after 30 min in 0.05 %wuxal at a constant potential of 0.9 V for 30 min of all studied samples confirmed the high stability of all sample and the immobilized Ba9 has superior activity than others.

In-Situ-Grown Cu Dendrites Plasmonically Enhance Electrocatalytic Hydrogen Evolution on Facet-Engineered Cu2 O.

Herein, facet-engineered Cu2 O nanostructures are synthesized by wet chemical methods for electrocatalytic HER, and it is found that the octahedral Cu2 O nanostructures with exposed crystal planes of (111) (O-Cu2 O) has the best hydrogen evolution performance. Operando Raman spectroscopy and ex-situ characterization techniques showed that Cu2 O is reduced during HER, in which Cu dendrites are grown on the surface of the Cu2 O nanostructures, resulting in the better HER performance of O-Cu2 O after HER (O-Cu2 O-A) compared with that of the as-prepared O-Cu2 O. Under illumination, the onset potential of O-Cu2 O-A is ca. 52 mV positive than that of O-Cu2 O, which is induced by the plasmon-activated electrochemical system consisting of Cu2 O and the in-situ generated Cu dendrites. Incident photon-to-current efficiency (IPCE) measurements and the simulated UV-Vis spectrum demonstrate the hot electron injection (HEI) from Cu dendrites to Cu2 O. Ab initio nonadiabatic molecular dynamics (NAMD) simulations revealed the transfer of photogenerated electrons (27 fs) from Cu dendrites to Cu2 O nanostructures is faster than electron relaxation (170 fs), enhancing its surface plasmons activity, and the HEI of Cu dendrites increases the charge density of Cu2 O. These make the energy level of the catalyst be closer to that of H+ /H2 , evidenced by the plasmon-enhanced HER electrocatalytic activity.