Photoelectrochemical Applications Research Articles

Effect of arsenate and phosphate substitution on hydroxyl group in libethenite Cu2PO4OH - olivenite Cu2AsO4OH solid solution series

Libethenite and olivenite have been regarded as intriguing photocatalysts because of their singular structures. Copper hydroxy-phosphates and -arsenates exhibit distinctive properties: they incorporate bridging hydroxyl (OH) groups shared by neighboring copper atoms. In materials employed for photoelectrochemical applications, the significance of surface OH groups and OH-related defects frequently varies and is contingent upon the specific material system and the reaction under consideration. Hydroxyl groups can enhance photocatalytic performance by generating OH radicals or serving as crucial agents in catalytic reactions. Therefore, the presence of an OH group within the crystal structure of the material can give rise to potentially interesting behaviors. Seven compounds within the solid solution series of libethenite Cu2PO4OH and olivenite Cu2AsO4OH with stoichiometric ratio (Cu2(Px,As1- xO4)OH, x = 0, 0.1, 0.3, 0.5, 0.7, 0.9, 1 were synthesized at 70 °C via aqueous solutions, and their properties were examined using X-ray diffraction (XRD), Scanning electron microscopy (SEM) and energy dispersive X-ray spectroscopy (EDS), Fourier-transform infrared spectroscopy (FTIR) and Raman spectroscopy. The effect of substituting (PO4)3– ions with (AsO4)3– ions on the alteration of the lattice parameters and spectral characteristics was elucidated by analyzing the correlation between the chemical composition and X-Ray diffraction peak positions. The substitution process leads to modifications in the unit cell parameters and volume. These isomorphic substitutions can be also discerned through alterations in the infrared and Raman spectra, which exhibit variations in the position and intensity of the bands corresponding to phosphates, arsenates, and hydroxyl ions. The incorporation of As into the solid solution resulted in altered bond lengths and geometries, which is consistent with the symmetry transition from orthorhombic libethenite to monoclinic olivenite. The variations in the unit cell parameters and the shifts in the peak position exhibited non-linear trends, and a discernible step was observed between the Cu2(P0·3As0.7)O4OH and Cu2(P0·5As0.5)O4OH intermediate phases. The findings of this study will prove beneficial in evaluating the feasibility of the libethenite-olivenite isometric series as a photocatalysts.

Lewis acid catalysis of polydopamine electropolymerisation as a tool for shaping its morphology and electrochemical properties

AbstractOrganic–inorganic semiconductor interfaces are of utmost importance in many photoelectrochemical applications, including water splitting and photodegradation of pollutants. The current work focuses on the fabrication and characterisation of transition metal-loaded polydopamine (PDA) electropolymerised on the surface of titania nanotubes. The structural studies via X-ray photoelectron spectroscopy and electron microscopy confirmed the catalytic effect of d-metal salts on the formation of the PDA layer during electropolymerisation. Cu and Ni loading leads to a significant enhancement of the visible absorption compared to that of the pristine PDA, also confirmed by the density functional theory calculations. Although the boost is greater for the thickest coatings, an excess amount of polymer suppresses the charge transfer and thus photocurrent generation. Synthesis in acidic conditions—optimal for photosensitisation—provides structures with a strong increase in the photocurrent quantum efficiency in the visible range, equal to 20% at 400 nm. Graphical Abstract

Fabrication of 2D/2D InVO4/BiVO4 Heterojunction with Synergistic Effects for Enhanced Photocatalytic Degradation and Photoelectrochemical Applications

In this work, we report a novel 2D/2D InVO4/BiVO4 heterojunction nanocomposite constructed through a simple hydrothermal approach. The morphological analysis demonstrated that BiVO4 nanoflakes to be anchored on the surface of InVO4 nanosheets. The InVO4/BiVO4 heterojunction nanocomposite displayed increased light absorption promoting their visible light harvesting. The photoactivity of the prepared InVO4/BiVO4 heterojunction was explored for the degradation of tetracycline (TC) under light treatment. InVO4/BiVO4 heterojunction exhibited superior photocatalytic activity than that of bare InVO4 and BiVO4. The as-prepared InVO4/BiVO4 heterojunction photoanodes achieved a higher photocurrent density of 60 μA/cm2 under illumination in 0.5 M Na2SO4 electrolyte. The enhanced photoelectrochemical performance is attributed to the synergistic effect and interface formation between InVO4 and BiVO4 and can effectively promote the charge separation and transfer of photoinduced carriers in heterojunction.

Twisted leaf like ZnO-flake-like BiOI@CNF grown on ITO substrate as a nanostructured pioneering platform for photoelectrochemical water splitting

Despite ZnO nanostructures garnering significant attention for photoelectrochemical (PEC) water splitting, the quest for efficient ZnO-based photoelectrodes with optimal light absorption, effective electron-hole separation, and transfer remains a challenge. The formation of ZnO heterojunctions with lower bandgap nanostructures of semiconductors has emerged as a strategy to enhance charge transfer while mitigating recombination rates. Additionally, the introduction of carbon nanofibers (CNFs) to these heterojunctions serves to further suppress recombination by electron trapping and enhances catalytic active sites, thereby elevating PEC performance. In this study, twisted leaf-like ZnO, flake-like BiOI, ZnO-BiOI nanostructure heterojunctions, and ZnO-BiOI@C composites were synthesized through a solvothermal method. Notably, the ZnO-BiOI@C photoelectrode exhibited outstanding performance, achieving a photocurrent density of 5.6 mA/cm2 through linear sweep voltammetry under light illumination. Each synthesized photoelectrode demonstrated robust photocurrent responsiveness and excellent stability under chopped conditions for up to 1150 s with a 50 s interval. This remarkable stability is attributed to the unique and stable morphological characteristics and strong crystallinity of the synthesized materials. The formed heterojunction between ZnO-BiOI was found to extend light absorption capabilities, while the incorporation of CNFs effectively trapped electrons from the heterojunction's conduction band, enhancing overall water splitting performance. The results underscore the potential of the ZnO-BiOI@C composite as a high-performing photoelectrode for PEC applications, emphasizing the importance of morphological and compositional considerations in advancing PEC technologies.

Novel Phenothiazine and Coumarin based Sensitizers: Design, Synthesis and Photoelectrochemical Application by Anchoring on CdS Nanowires

Novel metal-free organic dyes (E)-2-cyano-3-(10-(prop-2-yn-1-yl)-10H-phenothiazin-3-yl)acrylic acid (PPC) and (E)-2-cyano-3-(10-((1-((7-methyl-2-oxo-2H-chromen-4-yl)methyl)-1H-1,2,3-triazol-4-yl)methyl)-4a,10a-dihydro-10H-phenothiazin-3-yl)acrylic acid (PCTC) was synthesized and then anchored to 1D cadmium sulfide nanowires (1D CdS NWs) for application in photoelectrochemical dye-sensitized solar cell (DSSC). The 1D CdS nanowires were interconnected into a nanonetwork using solution chemistry in a straightforward and efficient manner. The UV-visible spectroscopy, cyclic voltammetry and density functional theory (DFT) were effectively employed to analyze the characteristics of PPC and PCTC. The sensitizer-anchored CdS nanowires have a broader range of light absorption in the UV-visible spectrum compared to bare CdS nanowires. The complete device has the assembly FTO, compact CdS, CdS nanowires, synthesized dye and counter electrode. In photovoltaic assessment, the PCTC and PPC devices yield 3.19 and 3.04 times, respectively, more efficiency than naked CdS nanowires under conventional sunshine illumination (100 mW/cm2, AM 1.5G). The obtained results provide strong evidence supporting the presence of rising external quantum efficiency (EQE) and show a high level of consistency with the optical tests.

Probing the Interfacial Molecular Structure of a Co‐Prussian Blue In Situ

AbstractMolecular‐level insight into the interfacial composition of electrodes at the solid‐electrolyte and the solid‐electrode interface is essential to understanding the charge transfer processes, which are vital for electrochemical (EC) and photoelectrochemical (PEC) applications. However, spectroscopic access to both interfaces, particularly upon application of an external bias, remains a challenge. Here, in situ surface sensitive vibrational sum‐frequency generation (VSFG) spectroscopy is used for the first time to directly access the interfacial structure of a cobalt‐containing Prussian blue analog (Co‐PBA) in contact with the electrolyte and TiO2/Au surface. Structural and compositional changes of the Prussian blue layer during electrochemical oxidation are studied by monitoring the stretching vibration of the CN group. At open circuit potential, VSFG reveals a non‐homogeneous distribution of oxidation states of metal sites: FeIII–CN–CoII and FeII–CN–CoIII coordination motifs are dominantly observed at the Co‐PBA|TiO2 interface, while it is only the FeII–CN–CoII unit at the electrolyte interface. Upon increasing the potential applied to the electrode, the partial oxidation of FeII–CN–CoII to FeIII–CN–CoII is observed followed by its transformation to FeII–CN–CoIII via charge transfer and, finally, the formation of FeIII–CN–CoIII species at the interface with TiO2 and the electrolyte.

Zirconium Oxynitride Thin Films for Photoelectrochemical Water Splitting.

Transition metal oxynitrides are a promising class of functional materials for photoelectrochemical (PEC) applications. Although these compounds are most commonly synthesized via ammonolysis of oxide precursors, such synthetic routes often lead to poorly controlled oxygen-to-nitrogen anion ratios, and the harsh nitridation conditions are incompatible with many substrates, including transparent conductive oxides. Here, we report direct reactive sputter deposition of a family of zirconium oxynitride thin films and the comprehensive characterization of their tunable structural, optical, and functional PEC properties. Systematic increases of the oxygen content in the reactive sputter gas mixture enable access to different crystalline structures within the zirconium oxynitride family. Increasing oxygen contents lead to a transition from metallic to semiconducting to insulating phases. In particular, crystalline Zr2ON2-like films have band gaps in the UV-visible range and are n-type semiconductors. These properties, together with a valence band maximum position located favorably relative to the water oxidation potential, make them viable photoanode candidates. Using chopped linear sweep voltammetry, we indeed confirm that our Zr2ON2 films are PEC-active for the oxygen evolution reaction in alkaline electrolytes. We further show that high-vacuum annealing boosts their PEC performance characteristics. Although the observed photocurrents are low compared to state-of-the-art photoanodes, these dense and planar thin films can offer a valuable platform for studying oxynitride photoelectrodes, as well as for future nanostructuring, band gap engineering, and defect engineering efforts.

A facile route for decoration of hematite photoanodes by transition metal hydroxide co‐catalysts

AbstractEarth‐abundant α‐Fe2O3 (hematite) is a convincing photoanode for photoelectrochemical (PEC) water splitting; however, its intrinsic properties of inferior charge transfer and sluggish water oxidation kinetics limit its performance. Here, we report a straightforward decoration method for transition metal hydroxides to accelerate the oxygen evolution reaction (OER) of hematite photoanodes grown by electric field‐assisted liquid phase deposition (EA‐LPD). The investigations revealed that Co(OH)2 acts as a superior co‐catalyst compared with hydroxides of Mn, Fe, Co, Ni, and Zn. EA‐LPD‐grown hematite photoanode loaded with cobalt hydroxide exhibited an excellent PEC performance. A photocurrent density of 0.93 mA.cm−2 at 1.23 V versus reversible hydrogen electrode was achieved for the modified hematite, ∼3 times more than that of pristine hematite, and a cathodic shift of 100 mV for the onset potential was observed. The proposed simple and cost‐effective co‐catalyst loading strategy provides a high degree of freedom in the design of co‐catalysts with a complex chemical composition comprising transition metal oxyhydroxides and hydroxides on different photoanodes for more efficient charge carrier separation for the PEC applications.

Elucidating Solvatochromic Shifts in Two-Dimensional Photocatalysts by Solving the Bethe-Salpeter Equation Coupled with Implicit Solvation Method.

Many studies have focused on tailoring the photophysical properties of two-dimensional (2D) materials for photocatalytic (PC) or photoelectrochemical (PEC) applications. To understand the optical properties of 2D materials in solution, we established a computational method that combined the Bethe-Salpeter equation (BSE) calculations with our GW-GPE method, allowing for GW/BSE-level calculations with implicit solvation described using the generalized Poisson equation (GPE). We applied this method to MoS2, phosphorene (PP), and g-C3N4 and found that when the solvent dielectric increased, it reduced the exciton binding energy and quasiparticle bandgap, resulting in almost no solvatochromic shift in the excitonic peaks of MoS2 and PP, which is consistent with previous experiments. However, our calculations predicted that the solvent dielectric had a significant impact on the excitonic properties of g-C3N4, exhibiting a large solvatochromic shift. We expect that our GW/BSE-GPE method will offer insights into the design of 2D materials for PC and PEC applications.

Fabrication of single-step novel synthesis of ZnCd(S0.5Se0.5)2 thin films for photoelectrochemical (PEC) cell application

In our study, we use a new method called the arrested precipitation technique (APT) to create CdZn(SSe)2 (CZSS) thin films. We obtain samples at different deposition times, ranging from 2.5 to 4 h, and analyze the effects of deposition time on the opto-structural, morphological, compositional, and photoelectrochemical (PEC) solar cell properties. As a result, we find that the band gap energy increases from 2.366 to 2.60 eV with prolonged growth time, as shown by UV–Vis spectra. X-ray diffraction (XRD) analysis confirms that the crystal structure is hexagonal, with the crystallite size increasing from 76 to 93 nm. The dislocation density and microstrain, determined by the Scherrer formula, decrease from 1.72 to 1.14 lines m−2 and from 4.75 × 10−3 to 3.87 × 10−3 (lines m−2), respectively. These results are validated using the Williamson-Hall (WH) plot and size-strain plot. The average grain size, evaluated using the standard scale bar method in scanning electron microscopy (SEM), ranges from 80 to 150 nm across CZ1 to CZ4 samples. Transmission electron microscopy (TEM) images of CZ4 and CZ2 reveal particle sizes of 101 nm and 87 nm, respectively, while selected area electron diffraction (SAED) patterns confirm the polycrystalline nature of the material. Energy dispersive X-ray spectroscopy (EDS) and X-ray photoelectron spectroscopy (XPS) analyses confirm the presence of Cd, Zn, S, and Se elements in their intended stoichiometry. Notably, CZSS photoelectrodes deposited over 4 h show better performance in Photoelectrochemical cells (PEC), achieving the highest photoconversion efficiency (ɳ) at 2.33 %, as evidenced by J-V measurements.

Sensitize BiVO4 with rhodamine B using BiOCl as a bridge to yield more photoelectrons for photoelectrochemical application

Sensitize BiVO4 with rhodamine B using BiOCl as a bridge to yield more photoelectrons for photoelectrochemical application

Lotus pollen-derived nitrogen and phosphorus self-doped TiO2/carbon materials for photoelectrochemical application

The wide band gap and low conductivity of TiO2 limit its application for photocatalytic H2 production. In this work, a nitrogen (N) and phosphorus (P) self-doped TiO2/Carbon (TiO2/C) composite with an egg yolk-shell structure was successfully synthesized using a lotus pollen template synthesis approach. The microstructure and photoelectrochemical performance of the composite materials were investigated. The introduction of hetero elements decreased the band gap of the TiO2/C composite, extending light absorption to the visible light region. Additionally, the enhanced conductivity facilitated fast charge transfer and prolonged the lifespan of electron/hole pairs. Consequently, the N, P self-doped TiO2/C composite exhibited higher H2 production (656.18 μmol·g−1·h−1) than commercial TiO2 (418.12 μmol·g−1·h−1) under simulated sunlight irradiation.

Optimization of Electrolyte Composition for Enhanced Photocatalytic Performance of the Ceramic Coating Produced on Brass by Plasma Electrolytic Oxidation

PEO coatings are formed by subjecting a metal substrate to an electrolytic plasma discharge, resulting in the formation of a porous and rough oxide layer. Herein, the significant role of the chemical composition of the electrolyte system and additives in the formation of an oxide coating on brass alloy in the PEO process was investigated. It was observed that the coating created with 8 g/l aluminate, 1 g/l NaOH, and 1 g/l KF electrolyte had higher homogeneity than other coatings. This is because a composite oxide coating of Cu2O, ZnO, and AlCuO2 was formed. Methylene Blue (MB), a widely used dye in various industries, is known to be persistent and environmentally harmful. The photocatalytic activity of the PEO coating on brass for the removal of MB was investigated under visible light exposure. According to the results, the presence of the sample produced in an electrolyte containing 8 g/l Aluminate, 1 g/l NaOH, and 1 g/l KF resulted in a degradation rate of approximately 65% for MB photodegradation after 6 h of irradiation. The PEO-coated brass shows promising photocatalytic efficiency compared to our research group's PEO-coated TiO2 coatings, indicating its potential as a photocatalyst. The results highlight that PEO coating on brass could be a potential candidate for photocatalytic and photoelectrochemical applications.

Advancements in Transparent Conductive Oxides for Photoelectrochemical Applications.

Photoelectrochemical cells (PECs) are an important technology for converting solar energy, which has experienced rapid development in recent decades. Transparent conductive oxides (TCOs) are also gaining increasing attention due to their crucial role in PEC reactions. This review comprehensively delves into the significance of TCO materials in PEC devices. Starting from an in-depth analysis of various TCO materials, this review discusses the properties, fabrication techniques, and challenges associated with these TCO materials. Next, we highlight several cost-effective, simple, and environmentally friendly methods, such as element doping, plasma treatment, hot isostatic pressing, and carbon nanotube modification, to enhance the transparency and conductivity of TCO materials. Despite significant progress in the development of TCO materials for PEC applications, we at last point out that the future research should focus on enhancing transparency and conductivity, formulating advanced theories to understand structure-property relationships, and integrating multiple modification strategies to further improve the performance of TCO materials in PEC devices.

First-Principles Studies of the Electronic and Optical Properties of Zinc Titanium Nitride: The Role of Cation Disorder.

Cation disorder is an established feature of heterovalent ternary nitrides, a promising class of semiconductor materials. A recently synthesized wurtzite-family ternary nitride, ZnTiN2, shows potential for durable photoelectrochemical applications with a measured optical absorption onset of 2 eV, which is 1.4 eV lower than previously predicted, a large difference attributed to cation disorder. Here, we use first-principles calculations based on density functional theory to establish the role of cation disorder in the electronic and optical properties of ZnTiN2. We compute antisite defect arrangement formation energies for one hundred 128-atom supercells and analyze their trends and their effect on electronic structures, rationalizing experimental results. We demonstrate that charge imbalance created by antisite defects in Ti and N local environments, respectively, broadens the conduction and valence bands near the band edges, reducing the band gap relative to the cation-ordered limit, a general mechanism relevant to other multivalent ternary nitrides. Charge-imbalanced antisite defect arrangements that lead to N-centered tetrahedral motifs fully coordinated by Zn are the most energetically costly and introduce localized in-gap states; cation arrangements that better preserve local charge balance have smaller formation energies and have less impact on the electronic structure. Our work provides insights into the nature of cation disorder in the newly synthesized semiconductor ZnTiN2, with implications for its performance in energy applications, and provides a baseline for the future study of controlling cation order in ZnTiN2 and other ternary nitrides.

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.

CdS/CdSe/PbS quantum dots sensitized TiO2 eggshell hollow microspheres photoanode to boost photocurrent and power conversion efficiency of QDSSC

Light harvesting plays crucial role for high photovoltaic performance of quantum dots sensitized solar cell (QDSSC). However, there are still issues need to be tackled, such as enlarging light response range and enhancing light scattering capability. In this work, TiO2 eggshell hollow microspheres (EHMS) were synthesized by carbonaceous microspheres (CMS) template method and co-sensitized by CdS/CdSe/PbS quantum dots (QDs) for application in QDSSC. Compared with QDSSC based on TiO2 nanoparticles (NP) and TiO2 hollow microspheres (HMS), the TiO2 EHMS based QDSSC showed a remarkable increase of short-circuit current density (Jsc) to 24.81 mA cm−2 with a power conversion efficiency (PCE) of 4.07 %. Photoelectrochemical analysis of QDSSC indicate that CdS/CdSe/PbS QDs can enlarge the light response range, and the TiO2 EHMS improve the light scattering, leading to the improvement of light harvesting efficiency. Charges dynamics tests results proved that a larger charges recombination resistance at photoanode/electrolyte interface and longer electron lifetime can be achieved with TiO2 EHMS, contributing to the boost of Jsc. The presented study introduces a simple strategy for researchers interested in designing photoanode for various photoelectrochemical applications.

Unraveling Electron Dynamics in p-type Indium Phosphide (100): A Time-Resolved Two-Photon Photoemission Study.

Renewable ("green") hydrogen production through direct photoelectrochemical (PEC) water splitting is a potential key contributor to the sustainable energy mix of the future. We investigate the potential of indium phosphide (InP) as a reference material among III-V semiconductors for PEC and photovoltaic (PV) applications. The p(2 × 2)/c(4 × 2)-reconstructed phosphorus-terminated p-doped InP(100) (P-rich p-InP) surface is the focus of our investigation. We employ time-resolved two-photon photoemission (tr-2PPE) spectroscopy to study electronic states near the band gap with an emphasis on normally unoccupied conduction band states that are inaccessible through conventional single-photon emission methods. The study shows the complexity of the p-InP electronic band structure and reveals the presence of at least nine distinct states between the valence band edge and vacuum energy, including a valence band state, a surface defect state pinning the Fermi level, six unoccupied surface resonances within the conduction band, as well as a cluster of states about 1.6 eV above the CBM, identified as a bulk-to-surface transition. Furthermore, we determined the decay constants of five of the conduction band states, enabling us to track electron relaxation through the bulk and surface conduction bands. This comprehensive understanding of the electron dynamics in p-InP(100) lays the foundation for further exploration and surface engineering to enhance the properties and applications of p-InP-based III-V-compounds for, e.g., efficient and cost-effective PEC hydrogen production and highly efficient PV cells.

BODIPY Chemisorbed on SnO2 and TiO2 Surfaces for Photoelectrochemical Applications.

Advancement toward dye-sensitized photoelectrochemical cells to produce solar fuels by solar-driven water splitting requires a photosensitizer that is firmly attached to the semiconducting photoelectrodes. Covalent binding enhances the efficiency of electron injection from the photoexcited dye into the metal oxide. Optimization of charge transfer, efficient electron injection, and minimal electron-hole recombination are mandatory for achieving high efficiencies. Here, a BODIPY-based dye exploiting a novel surface-anchoring mode via boron is compared to a similar dye bound by a traditional carboxylic acid anchoring group. Through terahertz and transient absorption spectroscopic studies, along with interfacial electron transfer simulations, we find that, when compared to the traditional carboxylic acid anchoring group, electron injection of boron-bound BODIPY is faster into both TiO2 and SnO2. Although the surface coverage is low compared with carboxylic acids, the binding stability is improved over a wide range of pH. Subsequent photoelectrochemical studies using a sacrificial electron donor showed that this combined dye and anchoring group maintained photocurrent with good stability over long-time irradiation. This recently discovered binding mode of BODIPY shows excellent electron injection and good stability over time, making it promising for future investigations.

Anodizing Tungsten Foil with Ionic Liquids for Enhanced Photoelectrochemical Applications.

This research examines the influence of adding a commercial ionic liquid to the electrolyte during the electrochemical anodization of tungsten for the fabrication of WO3 nanostructures for photoelectrochemical applications. An aqueous electrolyte composed of 1.5 M methanesulfonic acid and 5% v/v [BMIM][BF4] or [EMIM][BF4] was used. A nanostructure synthesized in an ionic-liquid-free electrolyte was taken as a reference. Morphological and structural studies of the nanostructures were performed via field emission scanning electron microscopy and X-ray diffraction analyses. Electrochemical characterization was carried out using electrochemical impedance spectroscopy and a Mott-Schottky analysis. From the results, it is highlighted that, by adding either of the two ionic liquids to the electrolyte, well-defined WO3 nanoplates with improved morphological, structural, and electrochemical properties are obtained compared to samples synthesized without ionic liquid. In order to evaluate their photoelectrocatalytic performance, the samples were used as photocatalysts to generate hydrogen by splitting water molecules and in the photoelectrochemical degradation of methyl red dye. In both applications, the nanostructures synthesized with the addition of either of the ionic liquids showed a better performance. These findings confirm the suitability of ionic liquids, such as [BMIM][BF4] and [EMIM][BF4], for the synthesis of highly efficient photoelectrocatalysts via electrochemical anodization.