Photoelectrochemical Water Oxidation Activity Research Articles

Photoanodes on titanium substrates: one-step deposited BiVO4 versus two-step nano-V2O5 films impregnated with Bi3+

One-step deposition of photoelectrochemically active BiVO4 (monoclinic) from a polyethylene glycol (PEG300) precursor paint onto titanium substrates is demonstrated to lead to more complex multioxide phase films. Photocurrents in 0.5 M Na2SO4 remain relatively low when compared to those reported on tin-doped indium oxide (ITO) substrates, possibly due to the effect of detrimental underlying titanium oxide phases or mixed phases. For comparison, the one-step deposition is demonstrated also for the direct formation of V2O5 nanocrystalline films, which also exhibited low photoelectrochemical activity. Impregnation of nanocrystalline V2O5 with aqueous Bi3+ is shown to cause substantial recrystallization with formation of much more photoactive BiVO4. In particular, on low-temperature (high surface area) nano-V2O5 (400 °C) and after further mild annealing at 400 °C much improved photoelectrochemical water oxidation activity (ca. 0.3 mA cm−2 at 1.0 V vs Ag/AgCl (KCl (3 M) at 0.1-W cm−2 xenon lamp radiation) is observed. This opens up a new mild temperature two-step route for BiVO4 photocatalysts on practical titanium substrates.

Defective ZnFe₂O₄ nanorods with oxygen vacancy for photoelectrochemical water splitting.

A one-dimensional zinc ferrite (ZnFe2O4) nanorod photoanode was prepared by a simple solution method on the F-doped tin oxide glass substrate. Thermal treatment under a hydrogen or vacuum atmosphere improved the photoelectrochemical water oxidation activity up to 20 times. The various physical characterization techniques used revealed that oxygen vacancies were created by the treatments in the near surface region, which increased the donor density and passivated the surface states. Hydrogen treatment was more effective and it was important to find optimum treatment conditions to take advantage of the positive role of oxygen vacancy as a source of electron donors and avoid its negative effect as electron trap sites.

Morphology-controlled In2O3 nanostructures enhance the performance of photoelectrochemical water oxidation.

Nanotower- and nanowall-like indium oxide structures were grown directly on fluorine-doped tin oxide (FTO)/In2O3 seeded substrates and pristine FTO substrates, respectively, by a straightforward solvothermal method. The tower-like nanostructures are proposed to form via a self-assembly process on the In2O3 seeds. The wall-like nanostructures are proposed to form via epitaxial growth from the exposed edges of SnO2 crystals of the FTO substrate. The nanotowers and nanowalls are composed of highly crystalline and ordered nanocrystals with preferred orientations in the [111] and [110] directions, respectively. The two structures display remarkably different activities when used as photoanodes in solar light-driven water splitting. X-ray photoelectron spectroscopy results suggest an increased density of hydroxyl groups in the nanowalls, which results in a decrease of the work function and a concomitant shift in the onset potential of the photocurrent in the linear sweep voltammograms, which is further confirmed by Mott-Schottky and flat-band potential measurements, indicating the importance of hydroxyl content in determining the photoelectrochemical properties of the films. Morphology-controlled, nanostructured transparent conducting oxide electrodes of the kind described in this paper are envisioned to provide valuable platforms for supporting catalysts and co-catalysts that are intentionally tailored for efficient light-assisted oxidation of water and reduction of carbon dioxide.

Comparison of photoelectrochemical water oxidation activity of a synthetic photocatalyst system with photosystem II.

This discussion describes a direct comparison of photoelectrochemical (PEC) water oxidation activity between a photosystem II (PSII)-functionalised photoanode and a synthetic nanocomposite photoanode. The semi-biological photoanode is composed of PSII from the thermophilic cyanobacterium Thermosynechococcus elongatus on a mesoporous indium tin oxide electrode (mesoITO|PSII). PSII embeds all of the required functionalities for light absorption, charge separation and water oxidation and ITO serves solely as the electron collector. The synthetic photoanode consists of a TiO(2) and NiO(x) coated nanosheet-structured WO(3) electrode (nanoWO(3)|TiO(2)|NiO(x)). The composite structure of the synthetic electrode allows mimicry of the functional key features in PSII: visible light is absorbed by WO(3), TiO(2) serves as a protection and charge separation layer and NiO(x) serves as the water oxidation electrocatalyst. MesoITO|PSII uses low energy red light, whereas nanoWO(3)|TiO(2)|NiO(x) requires high energy photons of blue-end visible and UV regions to oxidise water. The electrodes have a comparable onset potential at approximately 0.6 V vs. reversible hydrogen electrode (RHE). MesoITO|PSII reaches its saturation photocurrent at 0.84 V vs. RHE, whereas nanoWO(3)|TiO(2)NiO(x) requires more than 1.34 V vs. RHE. This suggests that mesoITO|PSII suffers from fewer limitations from charge recombination and slow water oxidation catalysis than the synthetic electrode. MesoITO|PSII displays a higher 'per active' site activity, but is less photostable and displays a much lower photocurrent per geometrical surface area and incident photon to current conversion efficiency (IPCE) than nanoWO(3)|TiO(2)|NiO(x_.

Nanoscale structural disorder in manganese oxide particles embedded in Nafion

High degree of structural disorders in birnessite phase particles in Nafion are responsible for high photo-electrochemical water-oxidation activity.

Enhancement Effects of Cobalt Phosphate Modification on Activity for Photoelectrochemical Water Oxidation of TiO2 and Mechanism Insights

Cobalt phosphate-modified nanocrystalline TiO2 (nc-TiO2) films were prepared by a doctor blade method using homemade nc-TiO2 paste, followed by the post-treatments first with monometallic sodium orthophosphate solution and then with cobalt nitrate solution. The modification with an appropriate amount of cobalt phosphate could greatly enhance the activity for photoelectrochemical (PEC) water oxidation of nc-TiO2, superior to the modification only with the phosphate anions. It is clearly demonstrated that the enhanced activity after cobalt phosphate modification is attributed to the roles of cobalt(II) ions linked by phosphate groups with the surfaces of nc-TiO2 mainly by means of the surface photovoltage responses in N2 atmosphere. It is suggested that the linked cobalt(II) ions could capture photogenerated holes effectively to produce high-valence cobalt ions, further inducing oxidation reactions with water molecules to rereturn to cobalt(II) ions. This work is useful to explore feasible routes to improve the performance of oxide-based semiconductors for PEC water splitting to produce clean H2 energy.

A facile one-step synthesis of single crystalline hierarchical WO3 with enhanced activity for photoelectrochemical solar water oxidation

Hierarchical architectures consisting of one-dimensional (1D) nanostructures are of great interest for potential use in energy and environmental applications in recent years. In this work, hierarchical tungsten oxide (WO3) has been synthesized via a straightforward, template-free, hydrothermal route from ammonium metatungstate hydrate and implemented in photoanode fabrication for solar water oxidation in photoelectrochemical cells and photocatalytic oxidation of organic pollutant. The flower-like WO3 micro-patterns are constructed by self-organized nanoscale length 1D building blocks, which are single-crystalline in nature, grown along (001) direction and confirm an orthorhombic crystal phase. Time-dependent experiments have been conducted to demonstrate their morphology evolution. The hierarchical architecture based photoanodes produce higher photocurrent (2-fold high) than the nanoparticles based photoanodes from solar water oxidation. The photon to current conversion efficiency achieved with the hierarchical architectures is 45% at 400 nm. The enhanced activity can be attributed to improved charge-separation by superior charge transportation through single-crystalline 1D building blocks.

Photocatalytic and Photoelectrochemical Water Oxidation over Metal‐Doped Monoclinic BiVO4 Photoanodes

The visible-light-induced water oxidation ability of metal-ion-doped BiVO(4) was investigated and of 12 metal ion dopants tested, only W and Mo dramatically enhanced the water photo-oxidation activity of bare BiVO(4); Mo had the highest improvement by a factor of about six. Thus, BiVO(4) and W- or Mo-doped (2 atom %) BiVO(4) photoanodes about 1 μm thick were fabricated onto transparent conducting substrate by a metal-organic decomposition/spin-coating method. Under simulated one sun (air mass 1.5G, 100 mW cm(-2)) and at 1.23 V versus a reversible hydrogen electrode, the highest photocurrent density (J(PH)) of about 2.38 mA cm(-2) was achieved for Mo doping followed by W doping (J(PH) ≈ 1.98 mA cm(-2)), whereas undoped BiVO(4) gave a J(PH) value of about 0.42 mA cm(-2). The photoelectrochemical water oxidation activity of W- and Mo-doped BiVO(4) photoanodes corresponded to the incident photon to current conversion efficiency of about 35 and 40 % respectively. Electrochemical impedance spectroscopy and Mott-Schottky analysis indicated a positive flat band shift of about 30 mV, a carrier concentration 1.6-2 times higher, and a charge-transfer resistance reduced by 3-4-fold for W- or Mo-doped BiVO(4) relative to undoped BiVO(4). Electronic structure calculations revealed that both W and Mo were shallow donors and Mo doping generated superior conductivity to W doping. The photo-oxidation activity of water on BiVO(4) photoanodes (undoped<W doped<Mo doped) was in accordance with the results from electrochemical impedance spectroscopy, Mott-Schottky analysis, and theoretical electronic structural calculations. Thus, Mo or W doping enhanced the photocatalytic and photoelectrochemical water oxidation activity of monoclinic BiVO(4) by drastically reducing its charge-transfer resistance and thereby minimizing photoexcited electron-hole pair recombination.

Phosphate Doping into Monoclinic BiVO4 for Enhanced Photoelectrochemical Water Oxidation Activity

Ein monoklines BiVO4-Gitter wurde mit Phosphat dotiert, was die Aktivität in der photoelektrochemischen und photokatalytischen Wasseroxidation mit sichtbarem Licht gegenüber reinem BiVO4 ungefähr um den Faktor 30 steigerte. Elektrochemische Impedanzspektroskopie und Dichtefunktionalrechnungen identifizieren einen deutlich verbesserten Ladungstransfer des BiVO4 als den Hauptgrund für die verstärkte photoelektrochemische Aktivität. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents are peer-reviewed, but not copy-edited or typeset. They are made available as submitted by the authors. Please note: The publisher is not responsible for the content or functionality of any supporting information supplied by the authors. Any queries (other than missing content) should be directed to the corresponding author for the article.

Phosphate Doping into Monoclinic BiVO4 for Enhanced Photoelectrochemical Water Oxidation Activity

Phos-phorus is a typical dopant for silicon or germanium to make itan n-type semiconductor. However, it has been rarely used asdopant for semiconductor photocatalysts. This is rathersurprising because other non-metallic elements, such as N,C, and S, have been widely used as anionic dopants forphotocatalysts to reduce their band-gap energies.

Graphene–carbon nanotube composite as an effective conducting scaffold to enhance the photoelectrochemical water oxidation activity of a hematite film

The iron oxide photoanode was modified with a graphene–carbon nanotube (CNT) composite conducting scaffold for efficient charge transfer from Fe2O3 particles to transparent conducting oxide substrate in photoelectrochemical water splitting cells. The Fe2O3–composite photoanode showed a photocurrent increase of 530% compared with to the bare Fe2O3 photoanode at 1.23 V vs. RHE, while the increase was only 200 and 240% for Fe2O3–CNT and Fe2O3–graphene photoanodes, respectively. This remarkable performance enhancement by the composite scaffold was attributed to synergistic effects induced by the formation of a 3D-like architecture from 1D CNT and 2D graphene. They become a spacer for each other forming a more open and highly exposed structure, in which both 2D graphene and 1D CNT can exist in the forms with much less self-agglomeration, thus not only enlarging the contact area between the conducting scaffold and Fe2O3 particles but also recovering in part the intrinsic conducting ability of graphene and CNT.

Photoelectrochemical Oxidation of Water Using Nanostructured BiVO4 Films

Nanostructured BiVO4 films were synthesized by coevaporation of bismuth and vanadium in an oxygen ambient, a process referred to as reactive ballistic deposition (RBD). The films were tested in various electrolyte solutions to assess their activity for photoelectrochemical water oxidation. Deposition parameters, including the V/Bi atomic flux ratio and the incident angle of deposition, were adjusted. Films deposited with excess vanadium (V/Bi = 2) and incident angles of deposition at 65° showed the highest initial photocurrents with IPCE values above 21% for light wavelengths of 340−460 nm (in 0.5 M Na2SO4 at 1.0 V vs Ag/AgCl). With continued illumination the excess vanadium in these films dissolved into the electrolyte and the photocurrents dropped by 60−75% before reaching steady state. The steady-state photocurrent and IPCE values (above 14% for 340−460 nm light) were higher than the initial values for films synthesized with stoichiometric amounts of vanadium and bismuth (V/Bi = 1) and incident angles ...