Near-infrared CdSexTe1-x@CdS “giant” quantum dots for efficient photoelectrochemical hydrogen generation

Colloidal quantum dots (QDs) have attracted a lot of attention due to their unique optoelectronic properties. They have been widely used as building block materials for solar technologies such as solar cell, and photoelectrochemical (PEC) water splitting. Hydrogen generation by using QDs as photocatalysts has emerged a promising application in PEC devices. However, it is still very challenging to obtain high-efficiency PEC devices due to the limited absorption wavelength of QDs and the existence of surface traps which prohibit the efficient charge transfer. In this work, we synthesized ternary CdSe_xTe_1-x/CdS (CdSeTe/CdS) “giant” QDs to extend the light absorption to near infrared, matched well with Sun's spectrum. The as-synthesized CdSeTe/CdS “giant” QDs exhibit quasi-type II band alignment as confirmed by its long lifetime and red-shifted emission peak compared with bare CdSeTe QDs. The wide absorption range of “giant” core/shell QDs and their long lifetime can improve the efficient absorption of Sun's spectrum and charge transfer. As a proof-of-concept, a PEC device using QDs sensitized TiO₂ mesoporous thin film as a photoanode was used for hydrogen production. The corresponding photocurrent density was increased to 3.0 mA/cm² with the introduction of CdS shell, which is 1.5 times higher than the PEC device using CdSeTe QDs. This study indicates that ternary or polynary alloyed core/shell QDs can be used as promising optoelectronic materials for applications of PEC devices.     

CdSe quantum dots sensitized nanoporous hematite for photoelectrochemical generation of hydrogen

A novel system of CdSe quantum dots (QDs) sensitized porous hematite (α-Fe₂O₃) films has been investigated as a potential photoelectrode for hydrogen generation via photoelectrochemical (PEC) splitting of water. Before sensitization, nanoporous hematite thin films were prepared by spray pyrolysis. Characterizations for crystalline phase formation, crystallite size, absorption spectra, and flatband potential were carried out to analyze PEC data. Loading time of sensitizer to hematite thin films was found to be crucial in affecting its PEC properties. Film having sensitizer loading time as 42 h exhibited best photocurrent density of 550 μA cm⁻² at 1.0 V versus SCE. Current study, for the first time, explores the possibility of using low band gap QDs sensitization on a low band gap film, hematite in PEC splitting of water.     

Augmented photoelectrochemical response of CdS/ZnS quantum dots sensitized hematite photoelectrode

A visible light active and stable photoelectrode has been developed by depositing a passivating layer of ZnS QDs on CdS QDs sensitized hematite photoelectrode (Hematite‐CdS/ZnS) for PEC generation of hydrogen. Photoelectrochemical properties, in terms of stability and efficiency, have been investigated on the various hematite photoelectrodes sensitized with CdS QDs and CdS/ZnS QDs by varying number of SILAR cycles. I–V characteristics show that two layers of ZnS QDs deposited over three layers of CdS could enhance PEC response of hematite and efficiency by a factor of 3 and 11 respectively. Chronoamperometry measurement ensures that after adding a layer of ZnS QDs, CdS sensitized hematite film turns out to be a stable photoelectrode in the electrolyte. Prepared photoelectrodes have been characterized by XRD, SEM, HRTEM and UV–Vis spectrophotometer for various structural, morphological and optical properties to analyze PEC results. Mott–Schottky analysis and incident photon to current conversion efficiency (IPCE) measurements of sensitized hematite photoelectrode supported the improved PEC response of CdS/ZnS QDs sensitized hematite thin films. Copyright © 2016 John Wiley & Sons, Ltd.     

InP/TiO2 heterojunction for photoelectrochemical water splitting under visible-light

Hydrogen production through photoelectrochemical (PEC) water splitting on photocatalyst is a green and clean method. In this study, we use density functional theory (DFT) calculations to find that the cage-like InP quantum dots (QDs) sensitized TiO₂ is an effective photocatalyst for PEC water splitting under visible-light. A 16-ps first-principle molecular dynamics (FPMD) simulation results indicate that the cage-like InP-12, InP-16, InP-20, InP-24, InP-28, and InP-36 QDs are stable at room temperature (300 K). Furthermore, the calculated energy gaps of InP-16, InP-20, InP-24, InP-28, and InP-36 QDs are about 2.0 eV, which are suitable for visible-light absorption. Stable InP-20/TiO₂ heterojunction structure was also obtained by FPMD simulation, and the electronic structure calculation result indicates that the InP-20/TiO₂ heterojunction has a favorable type-II band aligment, which could prevent the recombination of photoexcited carriers. Finally, the possible reaction pathways of hydrogen production on InP-20/TiO₂ heterojunction were investigated. It is found that energy barrier of hydrogen production of the InP-20/TiO₂ is 2.56 eV lower than pure TiO₂. Our calculations imply that InP QDs sensitized anatase TiO₂ is an effective photocatalyst for visible-light PEC water splitting.     

Photocatalytic properties of two-dimensional graphene and layered transition-metal dichalcogenides based photocatalyst for photoelectrochemical hydrogen generation: An overview

Hydrogen production through photoelectrochemical (PEC) water-splitting process has drawn significant research attention because it is a promising clean source of energy for improving earth climate in the future. Two-dimensional (2D) graphene and transition metal dichalcogenides (TMDCs), as the core of the system, have become versatile materials for the development of photocatalyst due to their distinct optical, electrical, thermal and mechanical properties. TMDCs have received significant consideration because of low-cost and earth-abundant catalysts that can replace noble metals, such as Pt. Therefore, comprehensive discussions on the structure and properties of 2D graphene and layered TMDCs materials are presented. We also gather and review various fabrication methods for TMDCs-based and graphene-TMDCs-based photocatalysts that can affect the PEC performance and hydrogen evolution. The inherent limitations and several future trends on 2D graphene and layered TMDCs-based photocatalyst for PEC water-splitting application are also discussed.     

Photoelectrochemical hydrogen generation with nanostructured CdS/Ti–Ni–O composite photoanode

Composite photocatalysts have aroused great interest due to combination of favorable electronic and optical properties. Herein, novel CdS/Ti–Ni–O composite photoanodes were constructed through anodic fabrication of nanostructured Ni-doped TiO₂ (Ti–Ni–O) oxide films and CdS deposition by successive ionic layer adsorption and reaction (SILAR). The morphology and composition evolution, optical properties and photoelectrochemical (PEC) performance of the photoanodes were investigated. The composite nanofilms mainly consisted of micropores and nanotubes. The CdS/Ti–Ni–O composite photoanode demonstrated remarkable PEC hydrogen generation properties with a high photocurrent density (6.72 mA·cm^?2 at 0 V vs Ag/AgCl) which was 18.2 times to that of the bare Ti–Ni–O photoanode. The synergy of Ni-doping and CdS-coupling on the enhancement of PEC performance offers useful ideas to the exploitation of effective photocatalysts and contributes to the development of solar-driven PEC hydrogen generation.     

MOFs in photoelectrochemical water splitting: New horizons and challenges

Growing energy consumption with the augmentation in universal population to more than nine billion by 2050 and exhausting fossil fuel reserves necessitates a harsh revolution from non-renewable energy reservoirs to renewable energy reservoirs with zero carbon emission. In the present scenario, solar energy prompted photoelectrochemical (PEC) water splitting or “Artificial Photosynthesis” via light gripping semiconductor material, originates out as the most promising methodology in accomplishing the global energy crisis. Recent studies have amply demonstrated the potential of metal-organic frameworks (MOF) towards PEC applications. They are porous crystalline coordination polymers assembled through an appropriate choice of metal ions and multidentate organic ligands. Owing to their structural regularity and synthetic tunability, MOFs integration with PEC is considered in terms of enhancing and broadening light absorption, providing active sites and directing charge transfer dynamics. Here, we have explored MOFs role in PEC and classified them into different categories such as photosensitizers, co-catalysts, counter electrode, template and also for imparting additional stability to the electrode system. MOFs mediated PEC water splitting is promising but is still rare and in its infancy. Therefore, it is pertinent and timely to take stock of the advancements made and develop insight on the use of MOFs, as an emerging solution for the problems encountered in PEC. This review covers the basics of MOF & mainly describes various case studies done during last 10 years and providing adequate impetus to researchers for critically assessing the recent advances and challenges that are faced by scientists and researchers at large.     

Tailoring morphological characteristics of zinc oxide using a one-step hydrothermal method for photoelectrochemical water splitting application

In the present paper describe the zinc oxide (ZnO) with various morphologies have been synthesized using the one-step hydrothermal method, in which the growth of ZnO nanostructures are significantly tailored by adjusting the pH level between 9 and 12 using 0.1 M Sodium hydroxide (NaOH). Significant results reveal the morphological properties of ZnO nanostructures varied with different pH values with the formation of ZnO nanostructures have different morphological such as a baton, star, flower, and rod-like structures. The present results show the rod-like structure of ZnO nanostructures exhibits the highest photocurrent density of 746.61 μAcm⁻² (at 1.23 V vs RHE) under simulated solar AM 1.5G illumination in Potassium hydroxide (KOH) medium, also the other morphologies. The dependent of the photoelectrochemical (PEC) water splitting properties on the different morphological of ZnO nanostructures are studied. Achieving the morphological evolution mechanism has become one of the method to obtain the production of the hydrogen growth regime used for solar energy conversion and their applied storage potentials. The application of the ZnO nanostructures for PEC water splitting was proposed with the adoption of screen-printed carbon electrodes (SPCEs). These are to quantify the best degree of the highest photocurrent density with one-step tailoring with an ideal modeling system to enhance PEC water splitting performances. Thus, the screen-printed carbon electrodes (SPEs) has been used as an alternative method for fabrication and photoelectrodes testings.     

Photocorrosion-less stable heterojunction photoanode for efficient visible-light driven solar hydrogen generation

In this work, a heterostructure CdS/TiO₂ nanotubes (TNT) photoelectrode is decorated with Ni nanoparticles (NPs) to enhance hydrogen generation via the photoelectrochemical method. Herein, we report a systematic study of the effect of Ni NPs heterostructure photoelectrode to improve light absorption and photoelectrochemical (PEC) performance. The fabricated photoelectrodes were evaluated for photoelectrochemical hydrogen generation under simulated sunlight. The optimized Ni/CdS/TNT photoelectrode exhibited an improved photocurrent density of 6.5 mA cm^?2 in poly-sulfide aqueous media at a low potential of 0 V. Owing to the enhanced photocurrent density, Ni NPs also played a significant role in improving the stability of the photoelectrode. The synergistic effect with semiconductor ternary junction incites the surface plasmon resonance (SPR) for light-harvesting to enhance photoelectrochemical hydrogen generation.     

Experimental study of graded bandgap Cu(InGa)(SeS)2 thin films grown on glass/molybdenum substrates by selenization and sulphidation

High-performance Cu(InGa)(SeS)₂ (CIGSS) thin film absorbers with an intentionally graded bandgap structure grown by a two-stage method have been studied. Materials obtained from Showa Shell Sekiyu K.K., Japan have been grown using selenization and sulphidation of the Mo/Cu–Ga/In stacked precursors. Full characterizations have been carried out using X-ray diffraction, Raman, scanning electron microscopy, atomic force microscopy, X-ray photoelectron spectroscopy (XPS), X-ray fluorescence, inductively coupled plasma mass spectroscopy, glow discharge optical emission spectroscopy (GDOES) and photoelectrochemical (PEC) techniques to study various properties. The material layers were found to be polycrystalline with the (1 1 2) preferred orientation, and the largest grains were about 2 μm. Raman measurements show the presence of at least five different phases within the material. XPS confirmed the copper depletion and the richness of sulphur at the top surface region. Although the PEC studies indicate the overall electrical conductivity of the layer as p-type, GDOES profiling reveals the segregation of different phases at different depths suggesting the possibility of having buried junctions within the material itself. The results are presented together with suggestions for further improvements of CIGSS solar cell material.     

Reduced band gap & charge recombination rate in Se doped α-Bi2O3 leads to enhanced photoelectrochemical and photocatalytic performance: Theoretical & experimental insight

For better utilization of solar spectrum and complete redox of water for water splitting applications, it is required to have a semiconductor which is photoactive in visible region. In this study, we report theoretical and experimental investigations on morphological and opto-electronic modifications induced in α-Bi₂O₃ due to Selenium (Se) doping tested for photoelectrochemical (PEC) & photocatalytic properties. Density Functional Theory (DFT) calculations revealed band gap reduction and direct to indirect transitions in Se-doped α-Bi₂O_3. This reduction in band gap is attributed to hybridization of Se p & Bi s in valence band and Se d & Bi p orbital in conduction band. To support this finding experimentally, we synthesized Se-doped α-Bi₂O₃ using simple chemical precipitation method and measured its band gap using photoluminescence and UV–Vis spectroscopy. Experimental results also confirmed the reduction in band gap energy and recombination rate of charge carriers as compared to pristine α-Bi₂O₃ sample. PEC study of Se-doped α-Bi₂O₃ showed an increased photocurrent density, charge carrier density and lowered impedance, which indicates its efficient solar spectrum utilization and better hydrogen generation efficiency. Photocatalytic measurement also revealed higher rate of dye degradation with Se doped α-Bi₂O₃.     

Recent trends in development of hematite (α-Fe2O3) as an efficient photoanode for enhancement of photoelectrochemical hydrogen production by solar water splitting

Solar-assisted water splitting using photoelectrochemical (PEC) cell is an environmentally benign technology for the generation of hydrogen fuel. However, several limitations of the materials used in fabrication of PEC cell have considerably hindered its efficiency. Extensive efforts have been made to enhance the efficiency and reduce the hydrogen generation cost using PEC cells. Photoelectrodes that are stable, efficient and made of cost-effective materials with simple synthesizing methods are essential for commercially viable solar water splitting through PEC technology. To this end, hematite (α-Fe₂O₃) has been explored as an excellent photoanode material to be used in the application of PEC water oxidation owing to its suitable bandgap of 2.1 eV that can utilize almost 40% of the visible light. In this study, we have summarized the recent progress of α-Fe₂O₃ nanostructured thin films for improving the water oxidation. Strategic modifications of α-Fe₂O₃ photoanodes comprising nanostructuring, heterojunctions, surface treatment, elemental doping, and nanocomposites are highlighted and discussed. Some prospects related to the challenges and research in this innovative research area are also provided as a guiding layout in building design principles for the improvement of α-Fe₂O₃ photoanodes in photoelectrochemical water oxidation to solve the increasing environmental issues and energy crises.     

Enhanced photoelectrochemical response of reduced-graphene oxide/Zn1−xAgxO nanocomposite in visible-light region

Graphene based nanocomposites have the potential to work as efficiently, multifunctional materials for energy conversion & storage. These composites may exhibit better photocatalytic properties by the improvement of their electronic and structural properties than pure photocatalysts. In the present work, reduced graphene oxide (rGO) & ZnO nanocomposite with 0–5 atom% Ag doping was prepared by electrodeposition method and characterized by XRD, Raman spectroscopy, FE-SEM, EDX, UV–Vis spectroscopy and final photoelectrochemical activity was assessed under 1.5 AM solar simulator in 1 M NaOH as electrolyte. Significant changes in the Raman spectrum for the nanocomposite suggest the possible electronic interaction between rGO and ZnO nanocomposite and its successful fabrication, which improves the charge separation and enhanced photoelectrochemical activity in the nanocomposite. We find a red-shift of 0.35 eV in the UV–vis spectrum and therefore an enhanced photoelectrochemical activity in the visible range on Ag doping in rGO/ZnO nanocomposite. Nanocomposite with 1 atom% Ag doping showed the highest photocurrent density of 2.48 mA/cm² at 0.8 V vs Ag/AgCl over other samples, which was almost five times higher than that for undoped rGO/ZnO composite. Calculated Flat-band potential and donor densities using Mott–Schottky data also supported the better photoelectrochemical response for Ag doping in nanocomposite.     

Electrochemical reduction induced self-doping of oxygen vacancies into Ti–Si–O nanotubes as efficient photoanode for boosted photoelectrochemical water splitting

Self-doping of oxygen vacancies (V_O) states into TiO₂-based nanotubes was an efficient way for improving photoelectrochemical (PEC) water splitting properties. Here we induced oxygen vacancies into Si-doped TiO₂ (Ti–Si–O) nanotubes on Ti–Si alloy via a facile electrochemical surface reduction, and applied it for PEC water splitting. Systematic studies revealed that the self-doped oxygen vacancies not only promoted optical absorption of the doped nanotubes but also enhanced separation-transport processes of the photo-generated charge carriers, and thus resulted in improved PEC water splitting properties. The V_O/Ti–Si–O co-doping system exhibited a higher photocurrent density of 1.63 mA/cm² at 0 V vs. Ag/AgCl. Corresponding solar-to-hydrogen efficiency could reach 0.81%, which was about 5.4 times that of undoped TiO₂. It's believed that elements doping and oxygen vacancies self-doping synergistic strategy employed in this work, may provide theoretical and practical significance for designing and fabricating efficient TiO₂-based nanostructures photoanodes in PEC water splitting for boosted solar-to-hydrogen conversion.     

Growth of n- and p-type ZnTe semiconductors by intrinsic doping

Using intrinsic doping, n- and p-type ZnTe thin films have been electrodeposited (ED) on glass/fluorine-doped tin oxide (FTO) conducting substrate in aqueous solutions of ZnSO₄·7H₂O and TeO₂. The intrinsic doping was achieved by simply varying the deposition potential. The films have been characterised for their structural, optical, electrical, morphological and compositional properties using X-ray diffraction (XRD), optical absorption, photoelectrochemical (PEC) cell measurements, scanning electron microscopy and energy-dispersive X-ray analysis techniques, respectively. The XRD results reveal that the electroplated films are polycrystalline and have hexagonal crystal structures. Optical absorption measurements have been used for the bandgap determination of as-deposited and heat-treated ZnTe layers. The bandgap of the as-deposited ZnTe films are in the range (1.70–2.60) eV depending on the deposition potential. PEC cell measurements reveal that the ED-ZnTe films have both n- and p-type electrical conductivity. Using the n- and p-type ZnTe layers, a p-n homo-junction diode with device structure of glass/FTO/n-ZnTe/p-ZnTe/Au was fabricated. The fabricated diode showed rectification factor of 10², ideality factor of 2.58 and threshold voltage of ~0.25 V.     

Fabrication of large area nanorod like structured CdS photoanode for solar H2 generation using spray pyrolysis technique

Large area nanorod like structured CdS films (9 × 9 cm²) were deposited on the FTO glass substrate using simple and economic spray pyrolysis deposition technique for photoelectrochemical (PEC) hydrogen production. With an intention of electrode scaling-up, the deposition area of photoanode was varied to evaluate its effect on the PEC hydrogen generation capability. High photocurrent of 5 mA has been achieved from the PEC active area of 37.5 cm². Its unit area (1 cm²) counterpart yielded Solar-to-Hydrogen (STH) conversion efficiency of 0.20% at a bias of 0.2 V vs Ag/AgCl using sacrificial reagents under solar simulator (AM1.5) with 80 mW/cm² irradiance. The 500 nm thick film exhibiting uniformly distributed nano-rod features yielded 3-times more photocurrent, as well as hydrogen evolution than other films. It exhibited an enhanced photo-activity as indicated by the higher IPCE values (5–9%) in the wavelength range of 450–550 nm. It exhibited superior optical properties (E_g ∼2.4 eV), and formation of high crystallinity hexagonal CdS phase with space group P63MC. The superior performance of the photoanode is attributed to the nanostructured morphology acquired under optimized spray pyrolysis conditions. Large area photoanodes showed unaltered photo-activity indicating the homogeneity in the film properties even in scaled-up version.     

A novel in situ synthesis of TiO2/CdS heterojunction for improving photoelectrochemical water splitting

We report a novel hydrothermal in situ synthesis route for the CdS-sensitized TiO₂ nanorod array films and their photoelectrochemical (PEC) performance are investigated in this paper. Although heterojunctions have been well recognized for enhancing the PEC performance of TiO₂ nanostructures, the specific synthesis methodology of high production quality, low preparation cost, and high controllability over the heterojunction structures is still a hot and open topic. In this work, controllable nanoscale TiO₂/CdS heterojunctions have been successfully realized through hydrothermal synthesis. The absorption spectrum is shown to be broadened from ~350 nm to ~570 nm, and the photocurrent density increases from 0.35 to 2.03 mA/cm², corresponding to photo-conversion efficiency of ~0.88%. The method is considered as an efficient and facile choice in the fabrication of TiO₂-based PEC hydrogen production functional materials.     

Enhanced photoelectrocatalytic hydrogen production performance of porous MoS2/PPy/ZnO film under visible light irradiation

Photoelectrochemical (PEC) water splitting provides a “green” approach for hydrogen production. However, the design and fabrication of high-efficient catalysts are the bottleneck for PEC water splitting owing to the involved thermodynamic and kinetic challenges. Herein, we report a new strategy for constructing a porous MoS₂/PPy/ZnO thin film photocatalyst with large specific surface area and excellent conductivity to achieve photoelectrochemical water splitting under visible light irradiation. Porous PPy/ZnO was synthesized via template-assisted electrodeposition, and MoS₂ was further electrodeposited to construct porous MoS₂/PPy/ZnO thin film photocatalyst. The hydrogen evolution rate of MoS₂/PPy/ZnO exhibits about 3.5-fold increase to 40.22 μmol cm⁻² h⁻¹ under visible light irradiation. The enhancement for photoelectrochemical hydrogen production is not only ascribed to enlarged specific surface area of the porous structure, but also attributed to the synergistic effects of MoS₂ and porous PPy/ZnO, which could dramatically improve its visible light absorption capacity and enhance the separation and transfer of photogenerated charges. Thus, more abundant photogenerated electrons and holes participate in photoelectrochemical process, which significantly enhances its photoelectrochemical hydrogen production performance.     

Photocurrent enhancement of interlocked LB film dye layers in a p-CuSCN sensitised photoelectrochemical cell

Dye sensitised photoelectrochemical (PEC) cells based on Cu/p-CuSCN/LB films have been studied with mixed Langmuir Blodgett (LB) films as the dye layer. The effects of mixed layers were investigated in detail by observing the changes of optical absorption and photocurrent in a PEC cell configuration. Enhancements in both optical absorption and photocurrent were found when a mixture of octadecyl methylviolet–C₁₈ (M–C₁₈) and dioctadecyl rhodamine (C₁₈–R–C₁₈) were deposited using the LB technique on p-CuSCN wide band gap semiconductor. The maximum photocurrent quantum efficiency of the PEC cell reached ≈36% in KI (10⁻² M)+I₂ (10⁻⁴ M) electrolyte solution when mixed LB films were used as the dye layer. Photocurrent enhancement is believed to be the enhancement of light absorption of the dye layers due to the interlocking of M–C₁₈ between the double C₁₈ chains of rhodamine.     

Nanostructured hematite photoelectrochemical electrodes prepared by the low temperature thermal oxidation of iron

We report on a facile low temperature method for the preparation of high surface area, nanostructured α-Fe₂O₃ (hematite) thin films and their application as photoelectrochemical (PEC) water splitting electrodes. The hematite films are fabricated by thermal oxidation in air of DC sputter deposited iron films at temperatures as low as 255 °C. This method results in films with a higher surface area than typically obtained by directly sputtering α-Fe₂O₃. It is shown that beyond a minimum iron thickness, α-Fe₂O₃ nanowires result upon thermal treatment in atmospheric conditions. Structural and optical characteristics of the resulting films are analyzed. The oxidation process is studied in detail and correlated to the photoelectrical properties. The Fe films oxidize in stages via Fe-oxide layers of increasing oxidation states. Resulting photoelectrochemical performance of fully oxidized films is a balance between optical absorption and charge collection, which varies with film thickness. The optimum film achieved a net photocurrent density of 0.18 mA/cm² in 1 M NaOH at 1.23 V vs. RHE under simulated AM1.5 sunlight, amongst the highest values reported for undoped hematite films produced at low temperature.