Photoelectrochemical Water-splitting Performance Research Articles

Tailoring Carrier Dynamics of BiVO4 Photoanode via Dual Incorporation of Au and Co(OH)x Cooperative Modification for Photoelectrochemical Water Splitting

AbstractPhotoelectrochemical solar to hydrogen production is a promising way to achieve carbon neutrality, but severe charge recombination in photoanodes limits the conversion efficiency. Herein, Au nanoparticles and Co(OH)x co‐sensitized bismuth vanadate (BiVO4) to construct AuCo(OH)x/BiVO4 photoanode for significantly enhancing the performance of photoelectrochemical water splitting. This process significantly improves the bulk charge carrier separation efficiency, the surface kinetics of water oxidation, and the electron density of BiVO4 photoanode through Au surface plasmon resonance (SPR) and Co(OH)x oxygen evolution catalysts effect. Additionally, the enhancement of the *O and the *OOH generation accelerate the oxygen evolution reaction kinetics. Consequently, the constructed AuCo(OH)x/BiVO4 photoanode demonstrates an excellent photocurrent of 6.2 mA cm−2 at 1.23 V versus reversible hydrogen electrode and a stable continuous output within 42 h. This work contributes to developing high‐efficiency and high‐stability photoanodes for solar H2 production through SPR effect and oxygen evolution catalysts.

Aging Ni(OH)2 on 3C-SiC Photoanodes to Achieve a High Photovoltage of 1.1 V and Enhanced Stability for Solar Water Splitting in Strongly Alkaline Solutions.

Photoelectrochemical (PEC) water splitting is a promising approach to directly convert solar energy to renewable and storable hydrogen. However, the very low photovoltage and serious corrosion of semiconductor photoelectrodes in strongly acidic or alkaline electrolytes needed for water splitting severely impede the practical application of this technology. In this work, we demonstrate a facile approach to fabricate a high-photovoltage, stable photoanode by depositing Ni(OH)2 cocatalyst on cubic silicon carbide (3C-SiC), followed by aging in 1.0 M NaOH at room temperature for 40 h without applying electrochemical bias. The aged 3C-SiC/Ni(OH)2 photoanode achieves a record-high photovoltage of 1.10 V, an ultralow onset potential of 0.10 V vs the reversible hydrogen electrode, and enhanced stability for PEC water splitting in the strongly alkaline solution (pH = 13.6). This aged photoanode also exhibits excellent in-air stability, demonstrating identical PEC water-splitting performance for more than 400 days. We find that the aged Ni(OH)2 dramatically promotes the hole transport at the photoanode/electrolyte interface, thus significantly enhancing the photovoltage and overall PEC performance. Furthermore, the oxygen evolution reaction (OER) activity and the phase transitions of the Ni(OH)2 electrocatalyst before and after aging are systematically investigated. We find that the aging process is critical for the formation of the relatively stable and highly active Fe-doped β-NiOOH, which accounts for the enhanced OER activity and stability of the PEC water splitting. This work provides a simple and effective approach to fabricate high-photovoltage and stable photoanodes, bringing new premise toward solar fuel development.

Enhanced Electrochemical Performance of Tin Oxide Quantum Dots on Reduced Graphene Oxide under Light.

The study utilized a simple and cost-effective approach to improve the photoelectrochemical (PEC) water-splitting performance of various materials, including reduced graphene oxide (rGO), tin oxide nanostructures (SnO2), and rGO/SnO2 composites. The composites examined were rS15, containing 15 mg of rGO and 45 mg of SnO2, and rS5, with 5 mg of rGO and 50 mg of SnO2, tested in a sodium hydroxide (NaOH) electrolyte. Notably, the rS5 electrode showed a significant increase in PEC efficiency in 0.1 M NaOH, achieving a peak photocurrent density of 13.24 mA cm-2 under illumination, which was seven times higher than that of pristine rGO nanostructures. This enhancement was attributed to the synergistic effects of the heterostructure, which reduced resistance and minimized charge recombination, thereby maximizing the catalytic activity across the various electrochemical applications. Furthermore, the rS5 anode demonstrated improved Tafel parameters, indicating faster reaction kinetics and lower overpotential for efficient current generation. These results highlight the potential for optimizing nanostructures to significantly enhance PEC performance, paving the way for advancements in sustainable water-splitting technologies.

Enhancing photoelectrochemical water-splitting performance of ZnO nanostructured thin films with copper doping

A promising solution to the energy issue and environmental deterioration is to use solar energy for the generation of hydrogen fuel (H2) as a clean source of energy on a large scale. The main goal of this work includes the development of ZnO-based photoelectrodes for effective photoelectrochemical (PEC) water splitting which enables the synthesis of H2 in an environmentally acceptable manner. This study focuses on the manufacture of ZnO thin films via the utilization of cost effective Successive Ionic Layer Adsorption and Reaction (SILAR) approach. Herein, pure and Cu-doped ZnO films at different doping ratios from 2 wt% to 6 wt% were effectively prepared. The examination of the produced films’ morphological, structural, optical, and chemical composition characteristics was conducted using atomic force microscopy (AFM), x-ray diffraction (XRD), UV–vis spectroscopy and energy dispersive x-ray spectroscopy (EDX) technique. For each sample, the PEC behaviours for green H2 production and the measurements acquired from impedance spectroscopy were also examined. In the PEC test, a 6% Cu electrode proved to have the best PEC performance whereas it exhibited a maximum current density of around 3.6 mA cm−2 in 0.3 M Na2SO4 electrolyte compared with the other electrodes.

EFFECT OF SILVER DOPING ON IRON OXIDE ELECTRICAL PROPERTIES

Iron silver oxide (Agx[Formula: see text]O3; [Formula: see text]) structure for photoelectrochemical (PEC) water splitting was grown by RF–DC co-sputtering of an iron–silver target in argon/oxygen plasma mixtures at 300°C, followed by thermal annealing at 560°C. The chemical composition and structure of the deposited film can be tuned by controlling the metal doping and the annealing temperature. The thermal treatment extensively improves the PEC water-splitting performances of the films. XRD patterns of AgxFe[Formula: see text]O3 shown in the figure can be indexed to the hexagonal structure of silver oxide and the rhombohedral structure of hematite and new X-ray Diffraction (XRD) peaks of AgxFe[Formula: see text]O3 structure. The annealing and doping process seems to cause a serious change in the crystal structure of the thin film, it showed a serious change in its electrical properties. The electrical parameters of resistance for thin films were measured using the Hall measurement method at room temperature. With Hall measurements, the n-type carrier concentration of the Fe2O3 structure was calculated, and it was observed that its resistance was 1[Formula: see text]M[Formula: see text]. Likewise, it was observed that AgxFe[Formula: see text]O3 exhibited an n-type carrier concentration, and its resistance was calculated to be 0.5[Formula: see text]M[Formula: see text]. The conductivity change is based on silver doping. The doping process seems to cause a change in the bandgap of the thin film, it showed a change in its optical properties. The film’s optical absorption was measured by UV–Vis photo spectroscopy. Subsequently, the structural and topographic properties of AgxFe[Formula: see text]O3 structures were investigated by high-precision characterization devices.

Enhanced photoelectrochemical water splitting, and photocatalytic and piezo-photocatalytic pollutant removal performance over CdS/g-C3N4/ZnO ternary heterojunctions

Fromation of CdS/g-C3N4/ZnO (CdCN/Z) ternary composites for the water splitting application is reported here. Produced materials were studied for physicochemical, optical, photo-electrochemical (PEC) and photocatalytic pollutant degradation properties. The current density of CdCN/Z exhibited as 7.4 mA/cm2 which is 26.4, 21.7, 14.25, and 5.92 folds higher than g-C3N4 (CNU), ZnO (Z), CdS, and CNU/Z, respectively. Additionally, the CdCN/Z composite achieved a higher photon-to-hydrogen conversion efficiency of 0.8 %. The finale composite exhibited a effectual degradation of RhB (99 % in 45 min) in water under light and ultrasonication exposure. The coupling of CNU/Z with CdS promoted the optical absorbance in the longer wavelength. This configuration had facilitated the enhanced photogenerated charge carriers separation. The contemporary work validates that the prepared CdCN/Z heterojunction is an auspicious photocatalyst for effectual water splitting as well as photocatalytic elimination of dye pollutants.

Boosted Electrochemical Activity with SnO2 Nanostructures Anchored on α-Fe2O3 for Improved Charge Transfer and Current Density

This study presents a straightforward and cost-effective method to enhance the photoelectrochemical (PEC) water-splitting performance of α-Fe2O3 (F), SnO2 (S), and α-Fe2O3 decorated with SnO2 quantum dots (FS) photoanodes in a NaOH electrolyte. The FS electrode demonstrated a notable improvement in PEC efficiency within the electrolyte. In particular, the generated charges of the FS anode in the NaOH electrolyte reached approximately 12.01 mA cm−2 under illumination, indicating that the developed heterostructures effectively enhanced kinetics, leading to improved separation of induced carrier pairs. This active carrier-pair separation mechanism contributed considerably to the increased PEC activity in the 0.1 M NaOH electrolyte. The reduction in the bandgap of FS increased its absorption capability in visible light, which further enhanced the current density. Furthermore, the reduction in electrolyte resistance (9.71 Ω), internal resistance (20.19 Ω), charge transfer resistance (3.21 kΩ), Tafel slope (45.5 mV dec-1), limiting current density (−2.09 mA cm−2), and exchange current density (−3.68 mA cm−2) under illumination at the interface enhanced the charge density of FS. Further, a strong interaction among photoanode nanostructures significantly enhances PEC activity by improving efficient charge separation and transport, reducing recombination rates, and enabling quicker movement of charge carriers to the electrode/electrolyte interface. Thus, this study provides an effective approach to increasing the PEC activity of heterostructures.

Engineering Facet‐Dependent Interface Charge Transfer in Liquid Metal‐Embraced BiVO4 Photoelectrodes for Efficient Photoelectrochemical Water Splitting

AbstractCrystal facet‐dependent photogenerated charge transfer at the semiconductor/current collector interface of photoelectrodes is equally important compared to that at the semiconductor/liquid interface for efficient photoelectrochemical (PEC) water splitting, which, however, is difficult to explore due to the rigid solid/solid interface in conventional photoelectrodes. Here, the facet‐dependent charge transfer at both semiconductor/liquid and semiconductor/collector interfaces in liquid metal‐embraced photoelectrodes is systematically investigated using faceted BiVO4 micro‐particles with different ratios of {110} and {010} facets as model materials. The results from the photo(electro)chemical and photophysical characterizations reveal that {010} facets outperform {110} facets at the semiconductor/liquid interface in triggering water oxidation due to the lower valence band maximum (VBM) of {010} facets, while {110} facets are more efficient at the semiconductor/metal interface for the collection of photogenerated electrons due to their higher conduction band minimum (CBM). Consequently, the photoelectrodes of liquid metal‐embraced BiVO4 particles exposing 53% {110} facets yield the best PEC performance for water splitting due to the well‐balanced photogenerated charge transfer at the interfaces of semiconductor/metal and semiconductor/liquid.

Solid Solution Behavior of High Performance BiOBrxI1-X Photoanodes Probed Using Solid-State NMR, XRD and Optical Spectroscopy

Bismuth oxyhalides (BIOX) are a family of solution-synthesizable 2D layered semiconductors constituted of earth-abundant elements namely bismuth, oxygen and the halogens. BIOX based thin films and heterojunctions are the subject of immense scientific interest due to their impressive performance in photocatalytic and photoelectrochemical devices. Solid solutions of Br/I bismuth oxyhalides exhibit continuously tunable absorption and emission spectra similar to that observed in mixed halide MAPbClxBryI3-x-y perovskites and mixed anion III-V GaAsxP1-x semiconductors. The excited state decay showed two components for all the mixed halide BiOX semiconductors with a dominant short-lived component in the nanosecond range and a weaker longer-lived component of ~100 ns. The average photoluminescence (PL) lifetime varied from 5.4 ns in bare BiOI to 1.49 ns in bare BiOBr with intermediate compositions exhibiting monotonically increasing average PL lifetimes with increasing iodine content. Using a combination of characterization techniques such as solid-state nuclear magnetic resonance (ssNMR), x-ray diffraction (XRD), x-ray photoelectron spectroscopy (XPS) and optical spectroscopy, we demonstrate the formation of atomic level solid solutions in Br/I bismuth oxyhalides. Through refinement of the lattice parameters using powder XRD and complementary atomic-level 209Bi SSNMR spectroscopy, we found that Vegard's law was obeyed by the BIOBrxI1-x solid solutions. By varying the Br:I ratio, it is also possible to tune the electronic band gap as well as the energy levels corresponding to the conduction band minimum (ECB, min) and the valence band maximum (EVB, max), thus allowing control over the thermodynamic driving force available to drive chemical reactions using photogenerated or electrically injected charge carriers. Suppression of the longitudinal optical phonon in solid solutions of Br/I bismuth oxyhalides is suggestive of lower phonon scattering of charge carriers and improved electronic transport. A synergistic enhancement of more than 1 order of magnitude in the photoelectrochemical water-splitting performance was obtained for the optimized solid solution (BiOBr0.67I0.33) under AM 1.5G 1 sun illumination. Our results pave the way for a one pot synthesis protocol to form BiOX thin films, powders and colloidal suspensions with deterministic control over the stoichiometry.

Electrolyte and interfacial engineering for self-formation of In₂S₃/In₂O₃ heterojunction with an enhanced photoelectrochemical activity

Electrolyte and interfacial engineering of photoanodes has become a crucial approach to enhance photoelectrochemical water-splitting performance. By optimizing both the electrolyte and the interfacial properties of the photoanode, the synergistic effects of the heterojunction and electrolyte can be leveraged to improve efficiency. In this work, we explore the crucial role of electrolyte and interfacial engineering in optimizing photoanode performance. By engineering an In2O3 film in a polysulfide electrolyte to form an in-situ In₂S₃/In₂O₃ heterojunction interface, we demonstrate a significant increase in anodic photocurrent compared to traditional aqueous Na2SO4 or NaOH electrolytes. This enhancement is attributed to both the thermodynamically favorable oxidation of sulfide and sulfite, and the unique electronic structure developed at the In₂S₃/In₂O₃ junction, which significantly improves charge separation and overall performance. Based on this finding, an efficient In₂S₃/In₂O3 heterojunction interface through optimal anion exchange with sulfur was developed, leading to a maximum photocurrent density of 5.57 mA cm−2 in the polysulfide electrolyte. In addition, detailed structural, optical, and photoelectrochemical properties of the In₂S₃/In₂O₃ interface providing insights into the mechanisms underlying the enhanced water-splitting performance have also been discussed.

Enhanced photoelectrochemical water splitting and photocatalytic decomposition performance of visible light active MgMnO3 perovskite nanostructure

Clean energy production and environmental remediation are imperative for sustainable future. Specially, exploration of multifunctional catalyst, for production of low-cost and eco-friendly hydrogen (H2) fuel as well as efficient decomposition of emerging pollutants are certainly needed. This study investigates magnesium manganese oxide (MgMnO3), a perovskite oxide, synthesized by simple citrate sol–gel technique, and its structural, morphological, optical, and photoelectrochemical properties were analyzed for the photodegradation of ciprofloxacin (CIP) antibiotic, methylene blue (MB) dye, and photoelectrochemical (PEC) water splitting. The cubic spinel crystal structure of MgMnO3 was confirmed through powder X-ray diffraction (XRD) analysis. FE-SEM images of the MgMnO3 material revealed a cauliflower-like morphology, consisting of an assembly of microspherical grains of varying sizes. UV–Vis spectroscopy exhibited broad absorption in the UV–Visible region, and the Tauc plot estimated a band gap of 1.54 eV. The MgMnO3 catalyst showed 88% and 96% for photodecomposition of CIP (10 mg/L) and MB (10 mg/L), respectively, using 35 mg and 30 mg of catalyst quantity over 90 min. In addition, MgMnO3 photoelectrode showcases superior photoelectrochemical behavior, exhibiting maximal photocurrent density of 13.21 mA cm−2 measured at 1.2 V vs. RHE and achieving a solar-to-hydrogen conversion efficiency of 2.45% compared to MgO and MnO2 photoelectrode. EIS measurements of MgMnO3 show enhanced charge transfer and recombination kinetics. Notably, the MgMnO3 electrode reveals outstanding photoelectrochemical durability, maintaining its stability even after continuous illumination for 9 h. Improved PEC properties could be attributed to wider light absorption, enhanced photo-induced charge-separations, and electron mobility. Thus, present study established an efficient and enduring multifunctional catalyst, catering photocatalytic degradation and PEC H2 generation.

La implanted band engineering of ZnO nanorods for enhanced photoelectrochemical water splitting performance

In the quest to improve photoelectrochemical water-splitting performance, we have doped lanthanum (La) in highly crystalline zinc oxide (ZnO) nanorods (NRs) using a facile and low-temperature hydrothermal route and successful substitution of La3+ at the Zn2+ site is confirmed from structural and chemical analysis. The tapered NRs morphology gained after La doping resulted in lower optical bandgap of 3.17 eV, enhanced visible light trapping, and multiphoton absorption, which assist in achieving good PEC activity. The La doping also offered higher Urbach energy (EU), subsidizing the number of oxygen vacancies. The UPS spectra show that La doping reduces conduction band energy level and endorses smooth charge transportation. The La-doped ZnO exhibits two times enhancement in photocurrent (1.54 mA·cm−2) compared to pristine ZnO (0.81 mA·cm−2). The higher applied bias to the photon conversion efficiency of ∼1.14% for La-doped ZnO confirms the efficient utilization of solar energy. The EIS measurements demonstrated reduction in charge transfer resistance with La-doping. Mott-Schottky analysis shows that La doping lowers the flat-band potential and enhances charge transportation, making it a potential photoanode for PEC water-splitting applications.

In-Sb Covalent Bonds over Sb2Se3/In2Se3 Heterojunction for Enhanced Photoelectrochemical Water Splitting.

Antimony selenide is a promising P-type photocatalyst, but it has a large number of deep energy level defects, leading to severe carrier recombination. The construction of a heterojunction is a common way to resolve this problem. However, the conventional heterojunction system inevitably introduces interface defects. Herein, we employ in situ synthesis to epitaxially grow In2Se3 nanosheets on Sb2Se3 nanorods and form In-Sb covalent interfacial bonds. This petal-shaped heterostructure reduced interface defects and enhanced the efficiency of carrier separation and transport. In this work, the photocurrent density in the proposed Sb2Se3/In2Se3 photocathode is 0.485 mA cm-2 at 0 VRHE, which is 30 times higher than that of pristine Sb2Se3 and it has prominent long-term stability for 24 h without obvious decay. The results reveal that the synergy of the bidirectional built-in electric field constructed between In2Se3 and Sb2Se3 and the solid In-Sb interfacial bonds together build a high-efficiency transport channel for the photogenerated carriers that display enhanced photoelectrochemical (PEC) water-splitting performance. This work provides efficient guidance for reducing interface defects via the in situ synthesis and construction of interfacial bonds.

Transition‐Metal‐Doped TiO2 Nanorods with High‐Visible‐Light Response via a Simple Hydrothermal Method

Transition‐metal‐ion doping is an effective method to shorten bandgap and enhance visible‐light absorption of TiO2, but there are still some serious challenges for most doping technologies, such as nonuniform doping, severe lattice damages, metal atoms agglomeration, and inactivated impurities. Herein, a simple and universal hydrothermal method is developed to realize the effective transition‐metal ions doping of TiO2 (including Fe, Co, Mn, Cu, V, and Cr). The photoelectrochemical water splitting performances of Cr‐doped TiO2 nanorods with multifarious Cr ion valence states (Cr3+ or Cr6+ ions), various Cr‐ion concentrations, with or without oxygen vacancy activation are emphatically and systematically studied. Experiments and theoretical calculations demonstrate that the remarkably enhanced carrier separation and injection efficiencies are the key factors to improve the visible‐light photoactivity, benefiting from the homogeneous distribution of impurity atoms and the incorporation of oxygen vacancies. The Cr3+‐ion‐doped TiO2 nanorod arrays with oxygen vacancy activation (Cr3+/Ov–TiO2) displays an impressive incident photon‐to‐electron conversion efficiency of 5.4% at 450 nm visible light, far superior to the pure TiO2 of 0.03%. Furthermore, no obvious photocurrent decay is observed in the Cr3+/Ov–TiO2 photoanode after 12 h continuous light illumination.

Double oxygen evolution co-catalysts modified BiVO4 to boost photoelectrochemical water oxidation performance

Improving the kinetics of oxygen evolution is crucial for enhancing the performance of photoelectrochemical (PEC) water splitting. Herein, this study utilizes a chemical self-growth method to grow NiFe tannic acid complex (NFTA) and Co(OH)2 on the surface of BiVO4 photoanode (BiVO4/NFTA/Co). As a result, the synergistic effects of NFTA and Co(OH)2 layers promote the efficiency and stability of BiVO4 photoanode towards PEC water oxidation. The photocurrent density of the obtained BiVO4/NFTA/Co photoanode reaches 4.97 mA cm−2, which is significantly greater than those of BiVO4/NFTA (4.36 mA cm−2), BiVO4/Co (2.51 mA cm−2), BiVO4 (1.34 mA cm−2), respectively. Detailed analysis confirms that NFTA could provide an efficient way to hasten the transfer of photo-generated holes on the photoanode surface and diminish the surface charge transfer resistance. In other hand, Co(OH)2 could be served as a cocatalyst to accelerate charge transfer for efficient oxygen evolution reaction as well as a protective layer to maintain the long-term stability of NFTA on the surface of BiVO4 during water oxidation. Such double oxygen evolution co-catalysts decoration strategy paves an effective pathway to enhance the PEC water oxidation performance of BiVO4 photoanode.

Facile synthesis of TiO2 nanothorn-coated Cu2O nanowires with improved stability and performance for photoelectrochemical water splitting

Copper(I) oxide (Cu2O) based photocathodes are promising in photoelectrochemical (PEC) water splitting due to their bandgap, natural abundance, and low cost. However, the stability issues have impeded their practical application. This study presents a solution through a novel photocathode, TiO2 nanothorns-coated Cu2O nanowires (TCNW), synthesized using simple wet chemical methods. TCNW outperformed pristine Cu2O nanowires (CNW), achieving a stable PEC current density of ∼3.8 mA∙cm−2 at 0 V vs RHE, compared to ∼1.9 mA∙cm−2 of CNW. TCNW also displayed an H2 evolution rate of ∼64.2 μmol∙cm−2∙h−1 with a 93.9% faradaic efficiency, whilst CNW reached only ∼6.8 μmol∙cm−2∙h−1 and 37.3%. These improvements stem from the protective TiO2 nanothorn layer, which enhances light absorption (300–500 nm) and improves charge separation and transfer by forming a p-n junction with Cu2O. This work underscores the importance of well-crafted surface p-n junctions and conformal protective layers in optimizing the efficiency and stability.

Improvement of photoelectrochemical water splitting performance using photoanodes based on reduced graphene oxide and ZnO nanotubes

Increasing the visible light efficiency, effective charge separation, and reducing the rate of charge recombination are essential factors in improving the performance of photoelectrochemical (PEC) water splitting. To enforce these, herein zinc oxide nanotube arrays hybridized with reduced graphene oxide (rGO/ZnO NTs) are synthesized on the fluorine-doped tin oxide substrates by using an electrodeposition technique for surveying PEC water splitting efficiency under visible light. The synthesized photoanodes were characterized by field emission scanning electron microscope, energy-dispersive X-ray spectroscopy, X-ray diffraction, and UV–visible absorption spectroscopy. The linear sweep voltammetry, electrochemical impedance spectroscopy, and Mott-Schottky analysis were used to evaluate the PEC performance. The rGO/ZnO NT photoanode shows a high photocurrent density of 0.441 mA/cm2 at 1.8 V vs. RHE compared to other samples. The improved PEC performance of rGO/ZnO NTs is attributed to the prominent role of rGO in more efficient charge separation, band gap reduction, and charge recombination.

Gamma-irradiated stibnite thin films set a remarkable benchmark performance for photoelectrochemical water splitting.

The study sets out to show the positive impact of sulfur vacancy engineering on the structural, morphological, optical, electrical, and photoelectrochemical (PEC) properties of Sb2S3 films synthesized using the spin coating technique. The produced films were exposed to γ-irradiation with different doses from 0 to 20 kGy. We have demonstrated the formation of sulfur vacancies and loss of oxygen content in the irradiated samples. XRD measurements revealed that all films exhibit a polycrystalline structure, and the crystallite size increases with the rising radiation dose, reaching the highest value of 87.4 nm measured for the Sb2S3 film irradiated with 15 kGy. The surface roughness of the irradiated samples increases with increasing γ-irradiation dose. The increase in surface roughness not only raises the active sites but enhances the conductivity of the Sb2S3 material as well. The wettability properties of the irradiated films were affected by γ-irradiation doses and the sample irradiated with 15 kGy exhibited the lowest hydrophobicity compared to others. The Hall measurements reveal that irradiated samples exhibit p-type semiconductor behavior. The optical band gap decreased progressively from 1.78 eV to 1.60 eV up to the irradiation dose of 15 kGy and slightly increased thereafter. The irradiated sample with 15 kGy showed a maximum photocurrent density of ca. 1.62 mA cm-2 at 0 V vs. reverse hydrogen electrode (RHE) under AM 1.5 G illumination with applied bias photon-to-current efficiency (ABPE) of 0.82% at 0.47 V vs. RHE, suggesting superior PEC water splitting performance compared to other samples. At 0 V vs. RHE and 648 nm, the incident photon current efficiency (IPCE) and absorbed photon current efficiency (APCE) of the photocathode irradiated with 15 kGy are significantly higher than those of the other photocathodes with values of 9.35% and 14.47%, respectively. Finally, Mott-Schottky measurement was also performed on all photocathodes to estimate their acceptor density and flat band potential.

Melamine Cyanaurate Microrods Decorated with SnO2 Quantum Dots for Photoelectrochemical Applications

This study employs a simple and cost-effective technique to enhance the photoelectrochemical (PEC) water-splitting performance of melamine cyanaurate microrods (M), SnO2 nanostructures (S), and melamine cyanaurate microrods decorated with SnO2 quantum dots (MS) by optimizing NaOH and Na2SO3 electrolytes. Notably, the MS electrode demonstrates a remarkable improvement in PEC efficiency in Na2SO3 solution associated with NaOH solution. Specifically, the induced currents of the MS anode in the Na2SO3 electrolyte are approximately 6.28 mAcm−2 more than those observed in the NaOH electrolyte solution. It is revealed that SO32− anions effectively consume the holes, leading to improved separation of the generated charge pairs. This effective charge separation mechanism significantly contributes to the enhanced PEC performance observed in Na2SO3 electrolytes. The findings of this study suggest a capable approach for improving the PEC activity of the materials through the careful optimization of the supported electrolytes.

Improvement in Photoelectrochemical Water Splitting Performance of GaN-nanowire Photoanode Using MXene.

The photoelectrochemical water splitting (PEC-WS) performance of a photoanode consisting of GaN nanowires (NWs) is significantly improved using a Ti3C2-MXene coating as an intermediate layer to promote carrier transfer toward the electrolyte. The maximum current density and applied-bias photon-to-current efficiency of the photoanode comprising GaN NWs coated with Ti3C2-MXene (MGNWs) are measured to be 34.24 mA/cm2 and 14.47% at 1.2 and 0.4 V versus a reversible hydrogen electrode (RHE), respectively. These values are much higher than those of the GaN-NW photoanode without Ti3C2-MXene (4.04 mA/cm2 and 1.95%) and also markedly exceed those of previously reported photoanodes. After 8 days of PEC-WS, the current density was measured to be 31.07 mA/cm2, which corresponds to 97.58% of that measured immediately after the reaction started. Based on the time dependence of the current density, the hydrogen evolution rate over the reaction time is calculated to be 0.58 mmol/cm2·h. The results confirm that the PEC-WS performance of the optimized MGNW photoanode is superior to and more stable than those of previously reported photoanodes.