Showing papers on "Water splitting published in 2012"
TL;DR: In this paper, a vision for a future sustainable hydrogen fuel community based on artificial photosynthesis is outlined and current progress towards artificial photosynthetic devices is reviewed, with particular focus on visible light active nanostructures.
Abstract: Hydrogen from solar-driven water splitting has the potential to provide clean energy. Current progress towards artificial photosynthetic devices is reviewed, with particular focus on visible light active nanostructures. A vision for a future sustainable hydrogen fuel community based on artificial photosynthesis is outlined.
1,703 citations
TL;DR: The high OER activity and simple synthesis make these Ni-based catalyst thin films useful for incorporating with semiconductor photoelectrodes for direct solar-driven water splitting or in high-surface-area electrodes for water electrolysis.
Abstract: Water oxidation is a critical step in water splitting to make hydrogen fuel. We report the solution synthesis, structural/compositional characterization, and oxygen evolution reaction (OER) electrocatalytic properties of ∼2–3 nm thick films of NiOx, CoOx, NiyCo1–yOx, Ni0.9Fe0.1Ox, IrOx, MnOx, and FeOx. The thin-film geometry enables the use of quartz crystal microgravimetry, voltammetry, and steady-state Tafel measurements to study the electrocatalytic activity and electrochemical properties of the oxides. Ni0.9Fe0.1Ox was found to be the most active water oxidation catalyst in basic media, passing 10 mA cm–2 at an overpotential of 336 mV with a Tafel slope of 30 mV dec–1 with oxygen evolution reaction (OER) activity roughly an order of magnitude higher than IrOx control films and similar to the best known OER catalysts in basic media. The high activity is attributed to the in situ formation of layered Ni0.9Fe0.1OOH oxyhydroxide species with nearly every Ni atom electrochemically active. In contrast to pr...
1,306 citations
TL;DR: Molybdenum boride and carbide are excellent catalysts for electrochemical hydrogen evolution at both pH 0 and pH 14.
Abstract: Molybdenum boride (MoB) and carbide (Mo2C) are excellent catalysts for electrochemical hydrogen evolution at both pH 0 and pH 14.
1,163 citations
TL;DR: In this article, the authors focus on catalysts made of cobalt (Co), nickel (Ni), and iron (Fe) elements for water reduction and water oxidation and discuss different series of catalysts that can be applied in electrocatalytic and photocatalytic water spitting.
Abstract: This article reviews recent significant advances in the field of water splitting. Catalysts play very important roles in two half reactions of water splitting - water reduction and water oxidation. Considering potential future applications, catalysts made of cheap and earth abundant element(s) are especially important for economically viable energy conversion. This article focuses only on catalysts made of cobalt (Co), nickel (Ni) and iron (Fe) elements for water reduction and water oxidation. Different series of catalysts that can be applied in electrocatalytic and photocatalytic water spitting are discussed in detail and their catalytic mechanisms are introduced. Finally, the future outlook and perspective of catalysts made of earth abundant elements will be discussed.
1,152 citations
TL;DR: It is shown that it is possible to close that 'two orders of magnitude' gap in the efficiency of the water oxidation with a rationally designed molecular catalyst [Ru(bda)(isoq)(2)] (H(2)bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; isoq = isoquinoline).
Abstract: Across chemical disciplines, an interest in developing artificial water splitting to O(2) and H(2), driven by sunlight, has been motivated by the need for practical and environmentally friendly power generation without the consumption of fossil fuels. The central issue in light-driven water splitting is the efficiency of the water oxidation, which in the best-known catalysts falls short of the desired level by approximately two orders of magnitude. Here, we show that it is possible to close that 'two orders of magnitude' gap with a rationally designed molecular catalyst [Ru(bda)(isoq)(2)] (H(2)bda = 2,2'-bipyridine-6,6'-dicarboxylic acid; isoq = isoquinoline). This speeds up the water oxidation to an unprecedentedly high reaction rate with a turnover frequency of >300 s(-1). This value is, for the first time, moderately comparable with the reaction rate of 100-400 s(-1) of the oxygen-evolving complex of photosystem II in vivo.
1,051 citations
TL;DR: In this paper, the authors showed that the heating temperature and the presence of sulfur motifs offer a facile chemical pathway for the control of the condensation/polymerization of carbon nitride, and thus adjusting their textural and electronic properties.
Abstract: Converting solar energy into hydrogen gas by water splitting is considered as a long-term solution to address global energy and environmental problems. Great effort has been devoted to the search for abundant systems for the purpose of efficient capture, conversion, and storage of solar energy in a cost-effective manner. To further advance the recently-developed carbon nitride photocatalysis for solar hydrogen generation, thiourea, a sulfur-containing compound, was used as a cheap and easily-available starting material for the synthesis of graphitic carbon nitride semiconductors. The as-prepared photocatalysts were subjected to several characterizations, and the results showed that the heating temperature and the presence of sulfur motifs offer a facile chemical pathway for the control of the condensation/polymerization of carbon nitride, and thus adjusting their textural and electronic properties. Photocatalytic activity experiments demonstrated that the g-C3N4 synthesized from thiourea exhibited a much higher H2 production rate than that of g-C3N4 prepared from dicyanamide or urea, and this activity can be further enhanced by increasing the condensation temperature.
847 citations
TL;DR: The utility of impedance spectroscopy in investigations of hematite electrodes is demonstrated to provide key parameters of photoelectrodes with a relatively simple measurement, and new evidence of the accumulation of holes in surface states at the semiconductor/electrolyte interface, which are responsible for water oxidation.
Abstract: Hematite (α-Fe2O3) constitutes one of the most promising semiconductor materials for the conversion of sunlight into chemical fuels by water splitting. Its inherent drawbacks related to the long penetration depth of light and poor charge carrier conductivity are being progressively overcome by employing nanostructuring strategies and improved catalysts. However, the physical–chemical mechanisms responsible for the photoelectrochemical performance of this material (J(V) response) are still poorly understood. In the present study we prepared thin film hematite electrodes by atomic layer deposition to study the photoelectrochemical properties of this material under water-splitting conditions. We employed impedance spectroscopy to determine the main steps involved in photocurrent production at different conditions of voltage, light intensity, and electrolyte pH. A general physical model is proposed, which includes the existence of a surface state at the semiconductor/liquid interface where holes accumulate. T...
831 citations
TL;DR: This work creates a green and simple way for using RGO as a support to enhance the photocatalytic H(2)-production activity of Zn(x)Cd(1-x)S, and demonstrates that RGO is a promising substitute for noble metals in photocatalyst H( 2)-production.
Abstract: Design and preparation of efficient artificial photosynthetic systems for harvesting solar energy by production of hydrogen from water splitting is of great importance from both theoretical and practical viewpoints. ZnS-based solid solutions have been fully proved to be an efficient visible-light driven photocatalysts, however, the H2-production rate observed for these solid solutions is far from exciting and sometimes an expensive Pt cocatalyst is still needed in order to achieve higher quantum efficiency. Here, for the first time we report the high solar photocatalytic H2-production activity over the noble metal-free reduced graphene oxide (RGO)-ZnxCd1–xS nanocomposite prepared by a facile coprecipitation-hydrothermal reduction strategy. The optimized RGO-Zn0.8Cd0.2S photocatalyst has a high H2-production rate of 1824 μmol h–1 g–1 at the RGO content of 0.25 wt % and the apparent quantum efficiency of 23.4% at 420 nm (the energy conversion efficiency is ca. 0.36% at simulated one-sun (AM 1.5G) illuminati...
815 citations
TL;DR: Low cost and environmentally benign urea was used to synthesize the metal-free photocatalyst graphitic carbon nitride (g-C₃N₄), and a porous structure with increased BET surface area and pore volume shows a much higher hydrogen production rate under simulated sunlight irradiation.
Abstract: Energy captured directly from sunlight provides an attractive approach towards fulfilling the need for green energy resources on the terawatt scale with minimal environmental impact. Collecting and storing solar energy into fuel through photocatalyzed water splitting to generate hydrogen in a cost-effective way is desirable. To achieve this goal, low cost and environmentally benign urea was used to synthesize the metal-free photocatalyst graphitic carbon nitride (g-C3N4). A porous structure is achieved via one-step polymerization of the single precursor. The porous structure with increased BET surface area and pore volume shows a much higher hydrogen production rate under simulated sunlight irradiation than thiourea-derived and dicyanamide-derived g-C3N4. The presence of an oxygen atom is presumed to play a key role in adjusting the textural properties. Further improvement of the photocatalytic function can be expected with after-treatment due to its rich chemistry in functionalization.
799 citations
TL;DR: In this article, localized surface plasmons and their effects on semiconductors, particularly in terms of energy transfer, scattering, and hot electron transfer, are reviewed, and the relevant physics, device geometries, and research progress in this area are discussed.
Abstract: The study of the optoelectronic effects of plasmonic metal nanoparticles on semiconductors has led to compelling evidence for plasmon-enhanced water splitting. We review the relevant physics, device geometries, and research progress in this area. We focus on localized surface plasmons and their effects on semiconductors, particularly in terms of energy transfer, scattering, and hot electron transfer.
758 citations
TL;DR: It is found that a robust nanoparticulate electrocatalytic material, H(2-CoCat, can be electrochemically prepared from cobalt salts in a phosphate buffer and can be converted on anodic equilibration into the previously described amorphous cobalt oxide film (O(2)-CoCat or CoPi) catalysing O(2) evolution.
Abstract: The future of energy supply depends on innovative breakthroughs regarding the design of cheap, sustainable and efficient systems for the conversion and storage of renewable energy sources. The production of hydrogen through water splitting seems a promising and appealing solution. We found that a robust nanoparticulate electrocatalytic material, H(2)-CoCat, can be electrochemically prepared from cobalt salts in a phosphate buffer. This material consists of metallic cobalt coated with a cobalt-oxo/hydroxo-phosphate layer in contact with the electrolyte and mediates H(2) evolution from neutral aqueous buffer at modest overpotentials. Remarkably, it can be converted on anodic equilibration into the previously described amorphous cobalt oxide film (O(2)-CoCat or CoPi) catalysing O(2) evolution. The switch between the two catalytic forms is fully reversible and corresponds to a local interconversion between two morphologies and compositions at the surface of the electrode. After deposition, the noble-metal-free coating thus functions as a robust, bifunctional and switchable catalyst.
TL;DR: The BiVO(4)/FeOOH photoanode exhibitied significantly improved photocurrent and stability for photo-oxidation of water, which is one of the best among all oxide-based phoatoanode systems reported to date, and shows an outstanding performance in the low bias region.
Abstract: BiVO(4) films were prepared by a simple electrodeposition and annealing procedure and studied as oxygen evolving photoanodes for application in a water splitting photoelectrochemical cell. The resulting BiVO(4) electrodes maintained considerable photocurrent for photo-oxidation of sulfite, but generated significantly reduced photocurrent for photo-oxidation of water to oxygen, also decaying over time, suggesting that the photoelectrochemical performance of BiVO(4) for water oxidation is mainly limited by its poor catalytic ablity to oxidize water. In order to improve the water oxidation kinetics of the BiVO(4) electrode, a layer of FeOOH was placed on the BiVO(4) surface as an oxygen evolution catalyst using a new photodeposition route. The resulting BiVO(4)/FeOOH photoanode exhibitied significantly improved photocurrent and stability for photo-oxidation of water, which is one of the best among all oxide-based phoatoanode systems reported to date. In particular, the BiVO(4)/FeOOH photoanode showed an outstanding performance in the low bias region (i.e., E < 0.8 V vs RHE), which is critical in determining the overall operating current density when assembling a complete p-n photoelectrochemical diode cell. The photocurrent-to-O(2) conversion efficiency of the BiVO(4)/FeOOH photoanode is ca. 96%, confirming that the photogenerated holes in the BiVO(4)/FeOOH photoanode are indeed excusively used for O(2) evolution.
TL;DR: A tuneable α-β surface phase junction on Ga(2)O(3) can significantly improve photocatalytic overall water splitting into H( 2) and O(2), mainly attributed to the efficient charge separation and transfer across the α- β phase junction.
Abstract: When Alpha met Beta: a tuneable α-β surface phase junction on Ga(2)O(3) can significantly improve photocatalytic overall water splitting into H(2) and O(2) over individual α-Ga(2)O(3) or β-Ga(2)O(3) surface phases. This enhanced photocatalytic performance is mainly attributed to the efficient charge separation and transfer across the α-β phase junction.
01 Jan 2012
TL;DR: In this article, the basic principles of photoelectrochemical cells and their properties and properties are discussed. And a discussion of emerging trends in Water Photoelectrolysis is presented.
Abstract: Part I: Basic Principles: Introduction.- Principles of Photoelectrochemical Cells.- Photoelectrochemical Measurements.- Part II: Materials Properties and Synthesis: Nanostructured alpha-Fe2O3 Photoanodes.- Mixed Metal Oxide Photoelectrodes and Photocatalysts.- Combinatorial Identification and Optimization of New Oxide Semiconductors.- Part III: Devices and Device Characterization.- Multijunction Approaches to Photo-electrochemical Water Splitting.- Part IV: Future Perspectives.- Economic and Business Perspectives.- Emerging Trends in Water Photoelectrolysis.
TL;DR: A Plasmonic water splitting cell in which 95% of the effective charge carriers derive from surface plasmon decay to hot electrons is reported, as evidenced by fuel production efficiencies up to 20-fold higher at visible, as compared to UV, wavelengths.
Abstract: We report a plasmonic water splitting cell in which 95% of the effective charge carriers derive from surface plasmon decay to hot electrons, as evidenced by fuel production efficiencies up to 20-fold higher at visible, as compared to UV, wavelengths. The cell functions by illuminating a dense array of aligned gold nanorods capped with TiO2, forming a Schottky metal/semiconductor interface which collects and conducts the hot electrons to an unilluminated platinum counter-electrode where hydrogen gas evolves. The resultant positive charges in the Au nanorods function as holes and are extracted by an oxidation catalyst which electrocatalytically oxidizes water to oxygen gas.
TL;DR: This work performs periodic density functional theory + U calculations for the water oxidation reaction on the fully hydroxylated hematite (0001) surface and shows that moderately charged O anions give rise to smaller overpotentials.
Abstract: In photoelectrochemical cells, sunlight may be converted into chemical energy by splitting water into hydrogen and oxygen molecules. Hematite (α-Fe(2)O(3)) is a promising photoanode material for the water oxidation component of this process. Numerous research groups have attempted to improve hematite's photocatalytic efficiency despite a lack of foundational knowledge regarding its surface reaction kinetics. To elucidate detailed reaction mechanisms and energetics, we performed periodic density functional theory + U calculations for the water oxidation reaction on the fully hydroxylated hematite (0001) surface. We investigate two different concentrations of surface reactive sites. Our best model involves calculating water oxidation mechanisms on a pure (1×1) hydroxylated hematite slab (corresponding to 1/3 ML of reactive sites) with an additional overlayer of water molecules to model solvation effects. This yields an overpotential of 0.77 V, a value only slightly above the 0.5-0.6 V experimental range. To explore whether doped hematite can exhibit an even lower overpotential, we consider cation doping by substitution of Fe by Ti, Mn, Co, Ni, or Si and F anion doping by replacing O on the fully hydroxylated surface. The reaction energetics on pure or doped hematite surfaces are described using a volcano plot. The relative stabilities of holes on the active O anions are identified as the underlying cause for trends in energetics predicted for different dopants. We show that moderately charged O anions give rise to smaller overpotentials. Co- or Ni-doped hematite surfaces give the most thermodynamically favored reaction pathway (lowest minimum overpotential) among all dopants considered. Very recent measurements (Electrochim. Acta 2012, 59, 121-127) reported improved reactivity with Ni doping, further validating our predictions.
TL;DR: This review concerns the efficient conversion of sunlight into chemical fuels through the photoelectrochemical splitting of water, which has the potential to generate sustainable hydrogen fuel through variousphotoelectrode materials and relative design strategies with their associated fabrication for solar water splitting.
Abstract: This review concerns the efficient conversion of sunlight into chemical fuels through the photoelectrochemical splitting of water, which has the potential to generate sustainable hydrogen fuel. In this review, we discuss various photoelectrode materials and relative design strategies with their associated fabrication for solar water splitting. Factors affecting photoelectrochemical performance of these materials and designs are also described. The most recent progress in the research and development of new materials as well as their corresponding photoelectrodes is also summarized in this review. Finally, the research strategies and future directions for water splitting are discussed with recommendations to facilitate the further exploration of new photoelectrode materials and their associated technologies.
TL;DR: In this paper, a photoelectrochemical cell made from combining a dye-sensitized solar cell with a semiconductor-oxide photoanode is demonstrated to perform water splitting with an efficiency of up to 3.1%.
Abstract: Photoelectrochemical water-splitting devices, which use solar energy to convert water into hydrogen and oxygen, have been investigated for decades. Multijunction designs are most efficient, as they can absorb enough solar energy and provide sufficient free energy for water cleavage. However, a balance exists between device complexity, cost and efficiency. Water splitters fabricated using triple-junction amorphous silicon1,2 or III–V3 semiconductors have demonstrated reasonable efficiencies, but at high cost and high device complexity. Simpler approaches using oxide-based semiconductors in a dual-absorber tandem approach4,5 have reported solar-to-hydrogen (STH) conversion efficiencies only up to 0.3% (ref. 4). Here, we present a device based on an oxide photoanode and a dye-sensitized solar cell, which performs unassisted water splitting with an efficiency of up to 3.1% STH. The design relies on carefully selected redox mediators for the dye-sensitized solar cell6,7 and surface passivation techniques8 and catalysts9 for the oxide-based photoanodes. A photoelectrochemical cell made from combining a dye sensitized solar cell with a semiconductor-oxide photoanode is demonstrated to perform water splitting with an efficiency of up to 3.1%. As the scheme uses relatively inexpensive materials and fabrication techniques it could provide a cost effective approach to hydrogen production.
TL;DR: In this paper, the authors proposed a two-step electrochemical strategy for the synthesis of the Cu2O/CuO composite, which is composed of a thin layer of Cu 2 O with a thin film of Cu O on its top as a protecting coating.
Abstract: Hydrogen generation through photoelectrochemical (PEC) water splitting using solar light as an energy resource is believed to be a clean and efficient way to overcome the global energy and environmental problems. Extensive research effort has been focused on n-type metal oxide semiconductors as photoanodes, whereas studies of p-type metal oxide semiconductors as photocathodes where hydrogen is generated are scarce. In this paper, highly efficient and stable copper oxide composite photocathode materials were successfully fabricated by a facile two-step electrochemical strategy, which consists of electrodeposition of a Cu film on an ITO glass substrate followed by anodization of the Cu film under a suitable current density and then calcination to form a Cu2O/CuO composite. The synthesized Cu2O/CuO composite was composed of a thin layer of Cu2O with a thin film of CuO on its top as a protecting coating. The rational control of chemical composition and crystalline orientation of the composite materials was easily achieved by varying the electrochemical parameters, including electrodeposition potential and anodization current density, to achieve an enhanced PEC performance. The best photocathode material among all materials prepared was the Cu2O/CuO composite with Cu2O in (220) orientation, which showed a highly stable photocurrent of −1.54 mA cm−2 at a potential of 0 V vs reversible hydrogen electrode at a mild pH under illumination of AM 1.5G. This photocurrent density was more than 2 times that generated by the bare Cu2O electrode (−0.65 mAcm−2) and the stability was considerably enhanced to 74.4% from 30.1% on the bare Cu2O electrode. The results of this study showed that the top layer of CuO in the Cu2O/CuO composite not only minimized the Cu2O photocorrosion but also served as a recombination inhibitor for the photogenerated electrons and holes from Cu2O, which collectively explained much enhanced stability and PEC activity of the Cu2O/CuO composite. Thus, the electrochemical strategy proposed in this study for the synthesis of the Cu2O/CuO composite opens a new way to use copper oxides as photocathode materials in PEC cells for a highly stable and effective water splitting.
TL;DR: In the early 1970s, the works by Fujishima and Honda (1) and Honda et al. (2) reported on the results of a now famous experiment that showed that band gap excitation of anatase TiO2 in a photoelectrochemical cell with a Pt counter electrode and an applied bias resulted in water splitting into hydrogen and oxygen.
Abstract: In the early 1970s, the works by Fujishima and Honda (1) and Honda et al. (2) reported on the results of a now famous experiment. They showed that band gap excitation of anatase TiO2 in a photoelectrochemical cell with a Pt counter electrode and an applied bias resulted in water splitting into hydrogen and oxygen. The timing of the result was impeccable. In 1973, the Organization of the Petroleum Exporting Countries (OPEC) declared an embargo on oil imports to the West, resulting in gasoline shortages and long lines at gas pumps. Suddenly, there was a pressing need for energy independence and new ways of providing for the energy-hungry economies of Western Europe, Japan, and the United States. The international research community responded. There was a short lived explosion of interest in converting sunlight into high-energy molecules by what we now call artificial photosynthesis to make solar fuels. Target reactions were water splitting into hydrogen and oxygen (1) and light-driven reduction of CO2 by water to give CO, other oxygenates, or hydrocarbons. Methane is shown as the product in equation 2, but the ultimate target is liquid hydrocarbons to power our existing energy infrastructure (1 and 2):
TL;DR: In this paper, the authors examined the factors that determine the photocurrent performance as well as the stability of these photoelectrodes and demonstrated that 62% stability over 10 hours of testing has been demonstrated without re-platinization.
Abstract: The utilisation of Cu2O photocathodes for photoelectrochemical water splitting requires their stabilisation due to photocorrosion in aqueous electrolytes. Ultrathin films of wide band gap semiconducting oxides deposited by atomic layer deposition (ALD) on top of cuprous oxide can perform the dual function of both facilitating charge extraction (through the creation of a p–n junction) and protecting the absorber material from the aqueous electrolyte, thereby suppressing corrosion in favor of hydrogen generation. The factors that determine the photocurrent performance as well as the stability of these photoelectrodes are examined. Specifically, the influence of ALD deposition temperature, electrolyte pH, electrolyte composition as well as post-deposition annealing treatments was studied. The successful development of protective overlayers must fulfil the dual requirements of favourable band alignments as well as chemical stability. At long time scales, the deactivation of the photocathodes proceeds through etching of the amorphous overlayer, accompanied by the loss of the platinum catalyst particles. Through the deposition of a semi-crystalline TiO2 overlayer, 62% stability over 10 hours of testing has been demonstrated without re-platinization.
TL;DR: The facile synthesis of nickel cobalt layered double hydroxides (LDHs) on conducting Zn(2)SnO(4) (ZTO) and the application of this material to a supercapacitor is reported and the first report of an enhancement of the active faradic reaction sites (electroactive sites) resulting from the heterostructure is presented.
Abstract: Conducting nanowires are of particular interest in energy-related research on devices such as supercapacitors, batteries, water splitting electrodes and solar cells. Their direct electrode/current collector contact and highly conductive 1D structure enable conducting nanowires to provide ultrafast charge transportation. In this paper, we report the facile synthesis of nickel cobalt layered double hydroxides (LDHs) on conducting Zn2SnO4 (ZTO) and the application of this material to a supercapacitor. This study also presents the first report of an enhancement of the active faradic reaction sites (electroactive sites) resulting from the heterostructure. This novel material demonstrates outstanding electrochemical performance with a high specific capacitance of 1805 F g−1 at 0.5 A g−1, and an excellent rate performance of 1275 F g−1 can be achieved at 100 A g−1. Furthermore, an asymmetric supercapacitor was successfully fabricated using active carbon as a negative electrode. This asymmetric device exhibits a high energy density of 23.7 W h kg−1 at a power density of 284.2 W kg−1. Meanwhile, a high power density of 5817.2 W kg−1 can be achieved at an energy density of 9.7 W h kg−1. More importantly, this device exhibits long-term cycling stability, with 92.7% capacity retention after 5000 cycles.
TL;DR: In this review, the fabrication, photocatalytic performance and operating principles of photoelectrochemical cells for water splitting based on WO(3) photoanodes, with an emphasis on the last decade, are discussed.
Abstract: Nanostructured WO3 has been developed as a promising water-splitting material due to its ability of capturing parts of the visible light and high stability in aqueous solutions under acidic conditions. In this review, the fabrication, photocatalytic performance and operating principles of photoelectrochemical cells (PECs) for water splitting based on WO3 photoanodes, with an emphasis on the last decade, are discussed. The morphology, dimension, crystallinity, grain boundaries, defect and separation, transport of photogenerated charges will also be mentioned as the impact factors on photocatalytic performance.
TL;DR: A photoanode based on ZnO nanotetrapods, which feature good vectorial electron transport and network forming ability, has been developed for efficient photoelectrochemical water splitting andNitrogen-doping represents the second strategy, which yielded a photocurrent density higher than those of the corresponding nanowire devices reported so far.
Abstract: A photoanode based on ZnO nanotetrapods, which feature good vectorial electron transport and network forming ability, has been developed for efficient photoelectrochemical water splitting. Two strategies have been validated in significantly enhancing light harvesting. The first was demonstrated through a newly developed branch-growth method to achieve secondary and even higher generation branching of the nanotetrapods. Nitrogen-doping represents the second strategy. The pristine ZnO nanotetrapod anode yielded a photocurrent density higher than those of the corresponding nanowire devices reported so far. This photocurrent density was significantly increased for the new photoanode architecture based on the secondary branched ZnO nanotetrapods. After N-doping, the photocurrent density enjoyed an even more dramatic enhancement to 0.99 mA/cm2 at +0.31 V vs Ag/AgCl. The photocurrent enhancement is attributed to the greatly increased roughness factor for boosting light harvesting associated with the ZnO nanotetr...
TL;DR: In black and white: The hydrogenation of TiO(2) can extend its optical absorption into the visible and infrared region and change its color from white to black.
Abstract: In black and white: The hydrogenation of TiO(2) can extend its optical absorption into the visible and infrared region and change its color from white to black. Furthermore, the hydrogenated black TiO(2) exhibits excellent photocatalytic activity for the splitting of water to yield H(2).
TL;DR: In this article, a comprehensive review of the development of photocatalytic water splitting for generating hydrogen, particularly under visible-light irradiation, is given, which includes an introduction of hydrogen production technologies.
Abstract: Hydrogen is the ideal fuel for the future because it is clean, energy efficient, and abundant in nature. While various technologies can be used to generate hydrogen, only some of them can be considered environmentally friendly. Recently, solar hydrogen generated via photocatalytic water splitting has attracted tremendous attention and has been extensively studied because of its great potential for low-cost and clean hydrogen production. This paper gives a comprehensive review of the development of photocatalytic water splitting for generating hydrogen, particularly under visible-light irradiation. The topics covered include an introduction of hydrogen production technologies, a review of photocatalytic water splitting over titania and non-titania based photocatalysts, a discussion of the types of photocatalytic water-splitting approaches, and a conclusion for the current challenges and future prospects of photocatalytic water splitting. Based on the literatures reported here, the development of highly stable visible–light-active photocatalytic materials, and the design of efficient, low-cost photoreactor systems are the key for the advancement of solar-hydrogen production via photocatalytic water splitting in the future.
TL;DR: In this article, the authors reported a red anatase TiO2 microsphere with a bandgap gradient varying from 1.94 eV on its surface to 3.22 eV in its core by a conceptually different doping approach.
Abstract: Narrowing the bandgap of wide-bandgap semiconductor photocatalysts (for instance, anatase TiO2) by introducing suitable heteroatoms has been actively pursued for increasing solar absorption, but usually suffers from a limited thermodynamic/kinetic solubility of substitutional dopants in bulk and/or dopant-induced recombination centres. Here we report a red anatase TiO2 microsphere with a bandgap gradient varying from 1.94 eV on its surface to 3.22 eV in its core by a conceptually different doping approach for harvesting the full spectrum of visible light. This approach uses a pre-doped interstitial boron gradient to weaken nearby Ti-O bonds for the easy substitution of oxygen by nitrogen, and consequently it substantially improves the nitrogen solubility. Furthermore, no nitrogen-related Ti3+ was formed in the red TiO2 due to a charge compensation effect by boron, which inevitably occurs in common nitrogen doped TiO2. The red anatase TiO2 exhibits photoelectrochemical water splitting activity under visible light irradiation. The results obtained may shed light on how to increase high visible light absorbance of wide-bandgap photocatalysts.