Incident Photon-to-current Conversion Efficiency Research Articles

Ideal Structures of Isolated BiVO4 Nanoparticles on WO3 Nanocorals to Enhance Photoelectrochemical Hydrogen Evolution

Metal oxide nanoparticles (NPs) of n-type semiconductors have recently garnered significant attention in the photoelectrochemical (PEC) field. In this study, isolated BiVO4 NPs on anodized WO3 nanocorals are investigated with respect to the formation mechanism of the NPs and the correlation between particle size and PEC efficiency. The sizes and distances of the BiVO4 NPs on the WO3 nanocorals are controlled via spin-coating and heat-treatment. The optimized BiVO4 NPs, with ideal sizes of 10 nm and distances of 100 nm between them, exhibit satisfactory electron and hole diffusion lengths, suppressing electron–hole recombination and promoting the exposure of WO3 to ultraviolet light. Furthermore, high-quality BiVO4, without the formation of by-products due to the optimized concentrations of Bi and V in the precursor solution, results in a 2.3-fold higher photocurrent density and H2 production, and a 6-fold higher incident photon-to-current conversion efficiency (IPCE) compared to those of pristine WO3 nanocorals.

Scaling-Up of Solution-Processable Tungsten Trioxide (WO3) Nanoparticles as a Hole Transport Layer in Inverted Organic Photovoltaics

We reported the comparative studies of the optimization of solution-processable tungsten trioxide (WO3) as a hole transporting layer (HTL) in inverted organic photovoltaics (OPVs) using spin coating, slot-die coating, and spray coating technologies for scaling-up applications. To facilitate the technology’s transition into commercial manufacturing, it is necessary to explore the role of scalable technologies for low-cost and efficient device fabrication. We investigated the role of diluting WO3 with isopropanol as an HTL in inverted OPVs to solve the issue of poor wettability of the hydrophobic surface of the PBDB-T: ITIC bulk heterojunction layer. The optimal dilution ratios of WO3 with isopropanol were 1:4, 1:4 and 1:8 with spin coating, slot-die coating and spray coating techniques, respectively. We evaluated the device performance by conducting a current density–voltage (J-V) analysis, incident photon-to-current conversion efficiency (IPCE) measurements, and ultraviolet–visible (UV-Vis) absorbance spectra for various WO3 concentrations. The J-V characteristics revealed that slot-die coating resulted in the highest performance, followed by the spray coating technology. We further investigated the impact of the annealing temperature on device performance for both slot-die- and spray-coated diluted WO3. The highest device performance was achieved at an annealing temperature of 120 °C for both coating technologies. This research offers valuable insights into the scalable fabrication of inverted OPV devices, paving the way for cost-effective and efficient large-scale production.

1,1'-Bis-(diphenylphosphino)ferrocene appended d8- and d10-configuration based thiosquarates: the molecular and electronic configurational insights into their sensitization and co-sensitization properties for dye sensitized solar cells.

Three new d8- and d10-configuration based 1,1'-bis-(diphenylphosphino)ferrocene (dppf) appended thiosquarates complexes with general composition [M(mtsq)2dppf] (M = Ni2+ (NiL2); Zn2+ (ZnL2) and Cd2+ (CdL2)) (mtsq = 3-ethoxycyclobutenedione-4-thiolate) have been synthesized and characterized spectroscopically as well as in case of NiL2 by single crystal X-ray diffraction technique. The single crystal X-ray analysis reveals square planar geometry around Ni(II) in NiL2, where Ni(II) coordinates with two sulfur centres of two mtsq ligands in monodentate fashion and two phosphorus of a dppf ligand in chelating mode. The supramolecular architecture of NiL2 is sustained by intermolecular C-H⋯O interactions to form one-dimensional chain. Further, the application of these newly synthesized complexes as sensitizers and co-sensitizers/co-absorbents with ruthenium based N719 sensitizer in dye-sensitized solar cells (DSSCs) have been explored. The DSSC set-up based on NiL2 offers best photovoltaic performance with photovoltaic efficiency (η) 5.12%, short-circuit current (Jsc) 11.60 mA cm-2, open circuit potential (Voc) 0.690 V and incident photon to current conversion efficiency (IPCE) 63%. In co-sensitized DSSC set-up, ZnL2 along with state-of-the-art N719 dye displays best photovoltaic performance with η 6.65%, Jsc 14.47 mA cm-2, Voc 0.729 V and IPCE 69%, thereby showing an improvement by 15.25% in photovoltaic efficiency in comparison to the photovoltaic efficiency of N719 sensitized DSSC set-up. Variation in co-sensitization behaviour have been ascribed to the differences in the excited state energy level of co-sensitizers. The ZnL2 and CdL2 have a higher energy level position than N719 dye, allowing efficient electron transfer to N719 during light irradiation, while excited state of NiL2 is lower than N719 dye, preventing photoexcited electron transfer to N719, resulting in its lowest overall efficiency among the three co-sensitized DSSC setups.

Amorphous cobalt boride exploring as the first first-row transition-metal-based metallic photocatalyst for efficient water splitting over 800 nm

Semiconductors often have limited photocatalytic water-splitting performances owing to the narrow light absorption and low effective carrier density. In response to these challenges, we report the discovery of metallic amorphous cobalt boride (Co2B) as the first first-row transition metallic photocatalyst. It was prepared via a simple chemical reduction method and performs efficient water splitting spanning the UV, visible light and near-infrared region (NIR) via interband transitions. It achieves bifunctional water splitting activities with H2 evolution rate of 202.3 μmol h−1 g−1 and O2 evolution rate of 74.8 μmol h−1 g−1, superior to the existing (semi-)metallic photocatalysts. The material shows over 1 % apparent quantum efficiency (AQE) and 20 % incident photon to current conversion efficiencies (IPCE) at the NIR region >800 nm. Theoretical and photophysical experimental studies synergistically confirm that the metallic nature with high carrier concentrations and amorphous structure with abundant active sites contribute to the good water splitting performance of Co2B. This research sets the foundation for the utilization of highly efficient transition metal-based metallic photocatalysts in photocatalysis across the entire solar spectrum.

Fabrication of ambient processed carbon-based inorganic silver bismuth iodide solar cells without any expensive hole transport materials

Recently, tremendous progress has been made in inorganic–organic hybrid lead halide perovskite solar cells (PSCs). Still, most of the reported high-efficiency PSCs were made with harmful lead (Pb), which is one of the major obstacles to large-scale adoption. Silver bismuth iodide (AgBiI4) light absorbers have been identified as promising lead-free and low-toxic metal-halide materials for solar cell applications. Here, we present hole transport material (HTM) and lead-free carbon-based inorganic Rudorffite (AgBiI4) solar cells, which can be prepared by simple spin-coating using silver iodide and bismuth iodide precursors under ambient conditions. Powder X-ray diffraction (XRD), UV–visible absorption, and field emission scanning electron microscopy (FESEM) studies were used to characterize the deposited films. The performance of the fabricated device was studied using incident photon-to-current conversion efficiency (IPCE) and current density–voltage (J-V) characteristics. Electrochemical impedance spectroscopy (EIS) was used to investigate the charge transfer process at the interface of the fabricated device. Under standard illumination test conditions, the fabricated device showed a photoelectric conversion efficiency (PCE) of 1.04%. The devices also have good stability and retained 96% of their initial PCE after 200 hrs of storage in ambient conditions. This work demonstrates the potential of HTM-free, ambient processable, and lead-free Rudorffite stable solar cells.

MoO3/BiVO4 heterojunction modified with cobalt-manganese layered double hydroxide cocatalyst for photoelectrochemical water oxidation

To improve the charge recombination and poor oxygen evolution reaction (OER) kinetics of BiVO4, in this paper, a high-performance CoMn-LDH/MoO3/BiVO4 photoanode was synthesized by a simple electrodeposition and calcination method. CoMn-LDH/MoO3/BiVO4 shows a photocurrent density of 3.78 mA cm−2 at 1.23 V vs. RHE, which is 3.78 times higher than that of pure BiVO4 with negative shift onset potentials of 330 mV. The maximum applied bias photon-to-current efficiency (ABPE) and incident photon-to-current conversion efficiency (IPCE) are 1.24 % and 55.5 %, respectively, which are 13.8 and 12.5 times higher than those of pure BiVO4. In-depth studies demonstrate that the MoO3/BiVO4 heterojunction can better drive the transfer of photogenerated carriers and suppress bulk charge recombination, CoMn-LDH improves the OER kinetics and broadens the absorption of visible light, their synergistic effect significantly enhances charge separation and light harvesting of BiVO4. This work provides a facile electrodeposition method to fabricate highly efficient photoanodes for solar-driven water splitting.

Photoelectrocatalytic based simultaneous removal of multiple organic micro-pollutants by using a visible light driven BiVO4 photoanode

In this research, photoelectrocatalytic (PEC) based advanced oxidation process (AOP) was studied for the removal of multiple OMPs through an oxidative mechanism. This study investigated the application of a BiVO4 photoanode in simultaneous removal of three selected OMPs: acetaminophen (ACT), benzotriazole (BTA) and propranolol (PRO). This study was carried out in demineralized water with a starting concentration of each organic micro-pollutant (OMP) at 45 μg L−1. In order to fabricate BiVO4 photoanodes, a facile and effective dip-coating method was used to deposit BiVO4 photocatalytic layers on fluorine doped tin oxide (FTO) substrate. UV–vis diffusive reflectance spectroscopy, x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS) and scanning electron microscopy (SEM) confirmed the successful fabrication of porous BiVO4 photoanode having an absorbance edge at around 526 nm. The fabricated photoanode showed incident photon to current conversion efficiency (IPCE) of 9.23% (λmax=445 nm) under 1 Sun standard illumination. Application of the fabricated photoanodes for the simultaneous removal of ACT, PRO and BTA at an applied voltage of 1 V (vs Ag/AgCl) under solar simulated light resulted in 99% removal of both ACT and PRO, and 70% removal of BTA. The first order rate coefficients and half-life times of ACT and PRO were about three times higher than those of BTA.

Heterojunction of TiO2 nanotubes arrays/Bi2Se3 quantum dots as an effective and stable photoanode for photoelectrochemical H2 generation

The use of semiconductor materials to split water through photoelectrochemical (PEC) processes is a remarkable technique that can transform solar energy into chemical energy, such as H2, in one step. For enhanced H2 generation, efficient separation of electron–hole (e−/h+) pairs and high photogenerated electron conductivity are required for photoanode substrates. In this study, an effective type II heterojunction between Bi2Se3 quantum dots (QDs) and TiO2 nanotube arrays (TNTAs) was constructed by depositing Bi2Se3 QDs on the TNTAs surface. The performance for PEC H2 generation was also investigated. The TNTAs/Bi2Se3 QDs demonstrated the highest photocurrent density of 1.75 mA cm−2, which is 3.8 times greater than bare TNTAs (0.46 mA cm−2) at 1.23 V vs. RHE. They also achieved a high hydrogen generation quantity of 355.8 μmol after 5 h, which is 3.3 times greater than bare TNTAs (105.3 μmol) at 1.23 V vs. RHE. TNTAs and TNTAs/Bi2Se3 QDs photoanodes both exhibited excellent stability for over 7 h. Compared with bare TNTAs, the TNTAs/Bi2Se3 QDs photoanode demonstrated a higher incident photon-to-current conversion efficiency (IPCE) in the UV region and expanded the light response to the visible region due to its lower charge recombination and larger visible light absorption. The exceptional performance of the TNTAs/Bi2Se3 QDs photoanode is due to its proper bandgap energy, which improves the visible light absorption, and its effective charge carrier transfer, which alleviates the recombination of e−/h+ pairs. The modification of TNTAs with Bi2Se3 QDs as a promising metal chalcogenide for improving visible light absorption and PEC water splitting performance has not yet been studied. Therefore, this work paves the way for a facile approach to construct a stable and high-performance photoanode for PEC H2 generation.

Stable metal-organic framework (MOF) integrated BCZT for improved photo-electrochemical water splitting

We report enhancement in the photo-electrochemical properties of Ba0.85Ca0.15Zr0.1Ti0.9O3 (BCZT) coupled with a copper-based metal–organic framework (Cu-MOF). The optical bandgap (Eg) of BCZT reduces to 2.2 eV from 2.8 eV after Cu-MOF coupling, leading to increased visible light absorption in the Cu-MOF/BCZT composite. The photo-current was enhanced from 20 μA/cm2 to 80 μA/cm2(∼4 times higher) in the Cu-MOF/BCZT composite under visible light illumination. The enhancement in the photo-current was well supported by enhancement in incident photon to current conversion efficiency (IPCE), electrochemical impedance spectroscopy (EIS), and Mott-Schottky measurements, respectively. The porous structure of the Cu-MOF enhances change transfer properties in the Cu-MOF/BCZT composite,which is a critical factor for the observed enhancement in the photo-electrochemical properties. This work provides a novel strategy for combining MOFs with photo-absorbing materials to design future solar-to-hydrogen conversion devices.

CuFeO2/Cu Photoelectrode Modified with SrTiO3 Perovskite for Efficient Hydrogen Generation from Sanitation Water

We prepared a perovskite material, copper-doped strontium titanate (Cu-SrTiO3), using the chemical bath deposition method and cast it on a CuFeO2/Cu photoelectrode to generate hydrogen from sanitation water splitting. This preparation method considers a simple mass product and does not depend on complex techniques. The prepared perovskite materials had a compact nano-/microstructure. Both CuFeO2 and Cu-SrTiO3/CuFeO2 exhibited excellent optical properties, with bandgap values of 1.4 and 1.26 eV, respectively. Here, the prepared CuFeO2 and Cu-SrTiO3 thin films are used as photoelectrodes for hydrogen generation, and their current-voltage relationship is analyzed under various conditions, such as different light intensities, wavelengths, and temperatures. This approach is promising for using wastewater as a source of hydrogen gas without requiring any additional electrolyte, making it a dual-purpose approach for both hydrogen generation and wastewater treatment. Through the electrochemical study, increasing the light intensity from 25 to 100 mW.cm-2 resulted in a corresponding increase in the produced J ph values from -1.02 to -1.292 mA.cm-2. Similarly, the J ph values increased from -1.25 to -1.91 mA.cm-2 as the temperature increased from 30 to 70°C. We also calculated all thermodynamic parameters, the quantum efficiency (QE), and incident photon to current conversion efficiency (IPCE). For the Cu-SrTiO3/CuFeO2/Cu photoelectrode, the activation energy ( E a ) value was 14.14 kJ mol-1, while the Δ H ∗ and Δ S ∗ values were 11.46 kJ·mol-1 and 34.9 kJ-1·mol-1, respectively. Additionally, the IPCE value was 3.31%. The prepared photoelectrode showed high stability and low cost, making it a potential candidate for industrial applications.

Fabrication of Hematite Photoanode Consisting of (110)-Oriented Single Crystals.

In this work, α-Fe2 O3 photoanode consisted of (110)-oriented α-Fe2 O3 single crystals were synthesized by a facile hydrothermal method. By using particular additive (C4 MimBF4 ) and regulation of hydrothermal reaction time, the Fe-25 consisted of a single-layer of highly crystalline (110)-oriented crystals with fewer grain boundaries, which was vertically grown on the substrate. As a result, the charge separation efficiency and photoelectrochemical (PEC) performance of Fe-25A (Fe-25 after dehydration treatment) have been greatly improved. Fe-25A yields a photocurrent of 1.34 mA cm-2 (1.23 V vs RHE) and an incident photon-to-current conversion efficiency (IPCE) of 31.95 % (380 nm). With the assistance of cobalt-phosphate water oxidation catalyst (Co-Pi), the PEC performance could be further improved by enhancing the holes transfer at electrode/electrolyte interface and inhibiting surface recombination. Fe-25A/Co-Pi yields a photocurrent of 2.67 mA cm-2 (1.23 V vs RHE) and IPCE value of 50.8 % (380 nm), which is 3.67 times and 2.39 times as that of Fe-2A/Co-Pi. Our work provides a simple method to fabricate highly efficient Fe2 O3 photoanodes consist of characteristic (110)-oriented single crystals with high crystallinity and high quality interface contact to enhance charge separation efficiencies.

Synthesis of CuInS2 thin film photocathode with variation of sulfurization sources and Pt-In2S3 modification for photoelectrochemical water splitting

CuInS2 thin films have been successfully synthesized from the electrodeposition of copper (Cu), indium (In), and sulfurization on a molybdenum glass substrate as a water splitting photocathode. The effect of various sources of sulfurization with thiourea, sulphur, and H2S and modification with Pt-In2S3 on the character and performance of the material was observed. The success of the synthesis was confirmed by the typical peaks of 28.2, 46.8, and 55.4° on XRD, the presence of Cu, In, S elements on SEM-EDX analysis, the appearance of peaks of 298 cm−1 on Raman analysis, and the detection peaks of Cu 2p, In 3d, and S 2p with XPS analysis. Meanwhile, performance effectiveness and photoelectrochemical properties were analysed with photocurrent linear sweep voltammetry (LSV), applied bias photon-to-current efficiency (ABPE), and incident photon-to-current conversion efficiency (IPCE). Variations of sulfurization sources give different character and photocurrent results due to differences in the existing reaction mechanisms. While the modification treatment with Pt-In2S3 increased the resulting photocurrent. Sulfurization with H2S and modification of Pt-In2S3 gave the best results with a photocurrent of 18 mA cm−2, an efficiency of 3% ABPE, 47.2% IPCE, was evolved 467 μmol H2 and 230,1 μmol O2. This shows good potential as a water splitting material to produce environmentally friendly hydrogen fuel.

Titanium dioxide (TiO2) and gel-polymer solar cells

This research focuses on the study of semiconductor-based solar cells utilizing titanium dioxide (TiO2) and gel-polymer electrolytes. The technology for preparing the electrolytes used in these solar cells has been developed, encompassing both liquid and gel polymer electrolyte compositions. The electrochemical impedance method is employed to determine important parameters such as diffusion coefficient, mobility, and charge carrier concentration in both liquid and gel-polymer electrolytes. Experimental results are compared with theoretical calculations utilizing the electrochemical impedance spectroscopy graph. Moreover, the photon-to-current conversion efficiency of the semiconductor-based solar cells is determined using the Incident Photon to Current Conversion Efficiency (IPCE) method, covering a wavelength range of 300 nm to 900 nm.

Enhanced Photoelectrochemical Properties of ZnO-CdS Composite Nanofiber Electrodes for Water Splitting

Well distributed and uniform nanofibers (NFs) of Zinc Oxide (ZnO) decorated with Cadmium sulfide (CdS) nanoparticles (NPs) were successfully fabricated using the Electrospinning method (ES). A ZnO-CdS junction electrode was created by loading the CdS NPs onto the ZnO NFs using the deposition process. X-ray diffraction of both ZnO NFs and CdS NPs revealed a mixed phase with a hexagonal wurtzite structure. SEM images confirm that the surface of the 33–71[Formula: see text]nm diameter and several microns long pure ZnO nanofibers was smooth and became granular when CdS nanoparticles were added. The photo-response to visible light at the ZnO-CdS CNFs junction electrode was very strong, which increased the photoelectrochemical activity. Considering this, it was determined that ZnO-CdS CNFs had an incident photon-to-current conversion efficiency (IPCE) of about 60% as opposed to pure ZnO NFs, which had an IPCE of 33%. In conclusion, ZnO-CdS CNFs generated by a simple, inexpensive, and applicable cell are a promising clean renewable source for usage such as water splitting.

Two-dimensional lateral anatase-rutile TiO2 phase junctions with oxygen vacancies for robust photoelectrochemical water splitting

Exploiting the photoelectrode materials with broad solar light response, high-efficient separation of photogenerated charges and abundant active sites is extremely vital yet enormously challenging. Herein, an innovative two-dimensional (2D) lateral anatase-rutile TiO2 phase junctions with controllable oxygen vacancies perpendicularly aligned on Ti mesh is presented. Our experimental observations and theoretical calculations corroborate explicitly that the 2D lateral phase junctions together with three-dimensional arrays not only exhibit the high-efficient photogenerated charges separation guaranteed by the build-in electric field at the side-to-side interface, but also furnish enriching active sites. Moreover, the interfacial oxygen vacancies generate new defect energy levels and serve as electron donors, hence extending visible light response and further accelerating the separation and transfer of photogenerated charges. Profiting from these merits, the optimized photoelectrode yield a pronounced photocurrent density of 1.2 mA/cm2 at 1.23 V vs. RHE with Faradic efficiency of 100%, which is approximately 2.4 times larger than that of pristine 2D TiO2 nanosheets. Furthermore, the incident photon to current conversion efficiency (IPCE) of the optimized photoelectrode is also boosted within both ultraviolet and visible light regions. This research is envisioned deliver the new insight in developing the novel 2D lateral phase junctions for PEC applications.

Promoting active sites of Fe3+ ions in SrTiO3 nanosphere: A superior candidate for high performances of Dye-sensitized solar cell and Photocatalytic dye degradation

In the present exploration, the impurity like Fe is doped in the SrTiO3 (STO) in order to enhance the physical properties which in turn used to engineer the material for the specific applications like photoanode in Dye-sensitized solar cell (DSSC) along with the visible-light driven photocatalyst. X-ray diffraction (XRD) confirms the formation of cubic perovskite structured SrTiO3 nanoparticles. The UV-Vis studies reveal that the impurity energy level of the Fe3+ electron could be excited to the conduction band of the SrTiO3, resulting in light absorption in the visible region. The DSSC based on Fe doped STO photoanode shows a lower recombination rate of photogenerated carriers and a longer lifetime, as evidenced by Photoluminescence spectroscopy (PL), Incident Photon to Current Conversion Efficiency (IPCE) and Electrochemical Impedance Spectroscopy (EIS). Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) images show the spherical-like morphology. Energy-dispersive X-ray spectroscopy (EDX) and X-ray photoelectron spectroscopy (XPS) revealed the elements present in the material and chemical compositions. When compared with the bare STO photoanode, STF5 photoanode showed two fold increase in the highest power conversion efficiency (PCE) of 3.23 % with an open-circuit voltage (Voc) of 0.72 V, short circuit current (Jsc) of 7.32 mA cm-2, fill factor (FF) of 0.61 and four fold enhancement in IPCE of 41.18 %. Additionally, profit from the merits of STF5 photocatalyst showed a significantly enhanced photocatalytic efficiency (82 %) of methylene blue (MB) degradation under Visible light irradiation. The detailed results are presented and discussed.

The fingerprint of charge transport mechanisms on the incident photon-to-current conversion efficiency spectra of perovskite solar cells

Perovskite solar cells (PSCs), the most promising nanostructured solar cells for large-scale production, have been fabricated with different types of electron and hole collectors to improve efficiency and stability. Incident photon-to-current conversion efficiency (IPCE) is an important measurement to evaluate the optical/electrical behavior of the structure to modify the device structure. In this research, we have investigated how different mechanisms affect the IPCE spectra and the difference between short-circuit current density (Jsc) recorded from the current density-voltage (J-V) and the IPCE curves of n-i-p PSCs. Results show that by removing the electron-transport layer (ETL) in a device with a compact PSK layer, the IPCE spectrum does not change and only a slight shift of interference peak position is observable. By removing the hole-transport layer (HTL), not only IPCE value drops substantially for all wavelengths, its shape (including interference peaks) deforms significantly in the 500–800 nm wavelength range. In the case of cells with imperfect HTLs, only a slight change in this range (not the blue range) is observable. Utilizing different charge-transport and PSK materials, we have shown how significant the nonlinearity of the device's characteristics (such as charge-transfer resistance) with light intensity increases in the difference between Jsc value from J-V and integrated Jsc from IPCE curves. Selecting charge-collecting layers also directly affect interference peaks in IPCE spectra, for instance using TiO2 nanograss as ETL or CuIn0.75Ga0.25S2/carbon hole-collector instead of Spiro OMeTAD/Au hole-collector results in disappearing interference peaks.

Temperature-Controlled Transformation of WO3 Nanowires into Active Facets-Exposed Hexagonal Prisms toward Efficient Visible-Light-Driven Water Oxidation.

A unique transformation of WO3 nanowires (NW-WO3) into hexagonal prisms (HP-WO3) was demonstrated by tuning the temperature of the (N2H4)WO3 precursor suspension prepared from tungstic acid and hydrazine as a structure-directing agent. The precursor preparation at 20 °C followed by calcination at 550 °C produced NW-WO3 nanocrystals (ca. <100 nm width, 3-5 μm length) with anisotropic growth of monoclinic WO3 crystals to (002) and (200) planes and a polycrystalline character with randomly oriented crystallites in the lateral face of nanowires. The precursor preparation at 45 °C followed by calcination at 550 °C produced HP-WO3 nanocrystals (ca. 500-1000 nm diameter) with preferentially exposed (002) and (020) facets on the top-flat and side-rectangle surfaces, respectively, of hexagonal prismatic WO3 nanocrystals with a single-crystalline character. The HP-WO3 electrode exhibited the superior photoelectrochemical (PEC) performance for visible-light-driven water oxidation to that for the NW-WO3 electrode; the incident photon-to-current conversion efficiency (IPCE) of 47% at 420 nm and 1.23 V vs RHE for HP-WO3 was 3.1-fold higher than 15% for the NW-WO3 electrode. PEC impedance data revealed that the bulk electron transport through the NW-WO3 layer with the unidirectional nanowire structure is more efficient than that through the HP-WO3 layer with the hexagonal prismatic structure. However, the water oxidation reaction at the surface for the HP-WO3 electrode is more efficient than the NW-WO3 electrode, contributing significantly to the superior PEC water oxidation performance observed for the HP-WO3 electrode. The efficient water oxidation reaction at the surface for the HP-WO3 electrode was explained by the high surface fraction of the active (002) facet with fewer grain boundaries and defects on the surface of HP-WO3 to suppress the electron-hole recombination at the surface.

Ti-doped Fe2O3 photoanodes on three-dimensional titanium microfiber felt substrate for photoelectrochemical oxygen evolution reaction

The macroporous structure of conductive substrates with large surface areas is crucial for fabricating semiconductor electrodes that offer better photoelectrochemical (PEC) performance in the water-splitting reaction. In this study, three-dimensional (3D) titanium microfiber felt (Ti felt) was used as a conductive substrate to prepare a Ti-doped Fe2O3 photoanode via a hydrothermal method with a two-step annealing treatment in air and argon atmospheres. Compared to conventional two-dimensional (2D) substrates, such as fluorine-doped tin oxide (FTO)-coated glass and Ti sheets, the loading amount of Fe2O3 on Ti felt was 2–5 times higher for a similar substrate geometric area. The thickness of Fe2O3 on the Ti felt (∼0.6 µm) was less than that on the 2D substrates. Ti-doped Fe2O3 on Ti felt (Ti-felt/Ti-Fe2O3) exhibits a higher photocurrent density than FTO/Ti-Fe2O3 and Ti-sheet/Ti-Fe2O3. Mott–Schottky analysis shows that the donor density of Ti-felt/Ti-Fe2O3 (8.58 × 1021 cm−3) was more than 10 times higher than that of FTO/Ti-Fe2O3 and Ti-sheet/Ti-Fe2O3. Analyses of the incident photon-to-current conversion efficiency (IPCE) and Faradaic efficiency indicated that Ti-felt/Ti-Fe2O3 showed higher PEC activity for the oxygen evolution reaction (OER) than FTO/Ti-Fe2O3. The enhanced PEC activity is ascribed to the higher donor density and moderate thickness of the Ti-doped Fe2O3 layer, which contribute to a short electron transport distance. Furthermore, the high loading of Fe2O3 on the Ti-felt substrate increased the photoabsorption in the UV and visible light regions and the photocurrent response at wavelengths near the band edge, even at low light intensities. This study provides new insights for preparing hematite photoanodes with higher PEC activity for the OER using a 3D porous substrate, rather than conventional 2D substrates.

Controllable Synthesis of N2-Intercalated WO3 Nanorod Photoanode Harvesting a Wide Range of Visible Light for Photoelectrochemical Water Oxidation.

A highly efficient visible-light-driven photoanode, N2-intercalated tungsten trioxide (WO3) nanorod, has been controllably synthesized by using the dual role of hydrazine (N2H4), which functioned simultaneously as a structure directing agent and as a nitrogen source for N2 intercalation. The SEM results indicated that the controllable formation of WO3 nanorod by changing the amount of N2H4. The β values of lattice parameters of the monoclinic phase and the lattice volume changed significantly with the nW: nN2H4 ratio. This is consistent with the addition of N2H4 dependence of the N content, clarifying the intercalation of N2 in the WO3 lattice. The UV-visible diffuse reflectance spectra (DRS) of N2-intercalated exhibited a significant redshift in the absorption edge with new shoulders appearing at 470-600 nm, which became more intense as the nW:nN2H4 ratio increased from 1:1.2 and then decreased up to 1:5 through the maximum at 1:2.5. This addition of N2H4 dependence is consistent with the case of the N contents. This suggests that N2 intercalating into the WO3 lattice is responsible for the considerable red shift in the absorption edge, with a new shoulder appearing at 470-600 nm owing to formation of an intra-bandgap above the VB edges and a dopant energy level below the CB of WO3. The N2 intercalated WO3 photoanode generated a photoanodic current under visible light irradiation below 530 nm due to the photoelectrochemical (PEC) water oxidation, compared with pure WO3 doing so below 470 nm. The high incident photon-to-current conversion efficiency (IPCE) of the WO3-2.5 photoanode is due to efficient electron transport through the WO3 nanorod film.