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1.
Recent advances in solar water splitting by using BiVO4 as a photoanode have greatly optimized charge carrier and reaction dynamics, but relatively wide bandgap and poor photostability are still bottlenecks. Here, an excellent photoanode of black BiVO4@amorphous TiO2?x to tackle both problems is reported. Its applied bias photon‐to‐current efficiency for solar water splitting is up to 2.5%, which is a new record for a single oxide photon absorber. This unique core–shell structure is fabricated by coating amorphous TiO2 on nanoporous BiVO4 with the aid of atomic layer deposition and further hydrogen plasma treatment at room temperature. The black BiVO4 with moderate oxygen vacancies reveals a bandgap reduction of ≈0.3 eV and significantly enhances solar utilization, charge transport and separation simultaneously, compared with conventional BiVO4. The amorphous layer of TiO2?x acts as both oxygen‐evolution catalyst and protection layer, which suppresses anodic photocorrosion to stabilize black BiVO4. This configuration of black BiVO4@amorphous TiO2?x may provide an effective strategy to prompt solar water splitting toward practical applications.  相似文献   

2.
The straightforward and inexpensive fabrication of stabilized and activated photoelectrodes for application to tandem photoelectrochemical (PEC) water splitting is reported. Semiconductors such as Si, WO3, and BiVO4 can be coated with a composite layer formed upon hydrolytic decomposition of hetero­bimetallic single source precursors (SSPs) based on Ti and Ni, or Ti and Co in a simple single‐step process under ambient conditions. The resulting 3d‐transition metal oxide composite films are multifunctional, as they protect the semiconductor electrode from corrosion with an amorphous TiO2 coating and act as bifunctional electrocatalysts for H2 and O2 evolution based on catalytic Ni or Co species. Thus, this approach enables the use of the same precursors for both photoelectrodes in tandem PEC water splitting, and SSP chemistry is thereby established as a highly versatile low‐cost approach to protect and activate photoelectrodes. In an optimized system, SSP coating of a Si photocathode and a BiVO4 photoanode resulted in a benchmark noble metal‐free dual‐photoelectrode tandem PEC cell for overall solar water splitting with an applied bias solar‐to‐hydrogen conversion efficiency of 0.59% and a half‐life photostability of 5 h.  相似文献   

3.
Developing efficient and affordable catalysts is of great significance for energy and environmental sustainability. Heterostructure photocatalysts exhibit a better performance than either of the parent phases as it changes the band bending at the interfaces and provides a driving force for carrier separation, thus mitigating the effects of carrier recombination and back‐reaction. Herein, the photo/electrochemical applications of a variety of metal sulfides (MSx) (MoS2, CdS, CuS, PbS, SnS2, ZnS, Ag2S, Bi2S3, and In2S3)/TiO2 heterojunctions are summarized, including organic degradation, water splitting, and CO2 reduction conversion. First, a general introduction on each MSx material (especially bandgap structures) will be given. Then the photo/electrochemical applications based on MSx/TiO2 heterostructures are reviewed from the perspective of light harvesting ability, charge carrier separation and transportation, and surface chemical reactions. Special focus is given to CdS/TiO2 and PbS/TiO2‐based quantum dot sensitized solar cells. Ternary composites by taking advantages of positive synergetic effects are also well summarized. Finally, conclusions are made regarding approaches for structure design, and the authors' perspective on future architectural design and electrode construction is given. This work will make up the gap for TiO2 nanocomposites and shed light on the fabrication of more efficient MSx‐metal oxide junctions in photo/electrochemical applications.  相似文献   

4.
Tandem photoelectrochemical water splitting cells utilizing crystalline Si and metal oxide photoabsorbers are promising for low‐cost solar hydrogen production. This study presents a device design and a scalable fabrication scheme for a tandem heterostructure photoanode: p+n black silicon (Si)/SnO2 interface/W‐doped bismuth vanadate (BiVO4)/cobalt phosphate (CoPi) catalyst. The black‐Si not only provides a substantial photovoltage of 550 mV, but it also serves as a conductive scaffold to decrease charge transport pathlengths within the W‐doped BiVO4 shell. When coupled with cobalt phosphide (CoP) nanoparticles as hydrogen evolution catalysts, the device demonstrates spontaneous water splitting without employing any precious metals, achieving an average solar‐to‐hydrogen efficiency of 0.45% over the course of an hour at pH 7. This fabrication scheme offers the modularity to optimize individual cell components, e.g., Si nanowire dimensions and metal oxide film thickness, involving steps that are compatible with fabricating monolithic devices. This design is general in nature and can be readily adapted to novel, higher performance semiconducting materials beyond BiVO4 as they become available, which will accelerate the process of device realization.  相似文献   

5.
N‐type metal oxides such as hematite (α‐Fe2O3) and bismuth vanadate (BiVO4) are promising candidate materials for efficient photoelectrochemical water splitting; however, their short minority carrier diffusion length and restricted carrier lifetime result in undesired rapid charge recombination. Herein, a 2D arranged globular Au nanosphere (NS) monolayer array with a highly ordered hexagonal hole pattern (hereafter, Au array) is introduced onto the surface of photoanodes comprised of metal oxide films via a facile drying and transfer‐printing process. Through plasmon‐induced resonance energy transfer, the Au array provides a strong electromagnetic field in the near‐surface area of the metal oxide film. The near‐field coupling interaction and amplification of the electromagnetic field suppress the charge recombination with long‐lived photogenerated holes and simultaneously enhance the light harvesting and charge transfer efficiencies. Consequently, an over 3.3‐fold higher photocurrent density at 1.23 V versus reversible hydrogen electrode (RHE) is achieved for the Au array/α‐Fe2O3. Furthermore, the high versatility of this transfer printing of Au arrays is demonstrated by introducing it on the molybdenum‐doped BiVO4 film, resulting in 1.5‐fold higher photocurrent density at 1.23 V versus RHE. The tailored metal film design can provide a potential strategy for the versatile application in various light‐mediated energy conversion and optoelectronic devices.  相似文献   

6.
State‐of‐the‐art water‐oxidation catalysts (WOCs) in acidic electrolytes usually contain expensive noble metals such as ruthenium and iridium. However, they too expensive to be implemented broadly in semiconductor photoanodes for photoelectrochemical (PEC) water splitting devices. Here, an Earth‐abundant CoFe Prussian blue analogue (CoFe‐PBA) is incorporated with core–shell Fe2O3/Fe2TiO5 type II heterojunction nanowires as composite photoanodes for PEC water splitting. Those deliver a high photocurrent of 1.25 mA cm?2 at 1.23 V versus reversible reference electrode in acidic electrolytes (pH = 1). The enhancement arises from the synergic behavior between the successive decoration of the hematite surface with nanolayers of Fe2TiO5 and then, CoFe‐PBA. The underlying physical mechanism of performance enhancement through formation of the Fe2O3/Fe2TiO5/CoFe‐PBA heterostructure reveals that the surface states’ electronic levels of hematite are modified such that an interfacial charge transfer becomes kinetically favorable. These findings open new pathways for the future design of cheap and efficient hematite‐based photoanodes in acidic electrolytes.  相似文献   

7.
Widespread application of solar water splitting for energy conversion is largely dependent on the progress in developing not only efficient but also cheap and scalable photoelectrodes. Metal oxides, which can be deposited with scalable techniques and are relatively cheap, are particularly interesting, but high efficiency is still hindered by the poor carrier transport properties (i.e., carrier mobility and lifetime). Here, a mild hydrogen treatment is introduced to bismuth vanadate (BiVO4), which is one of the most promising metal oxide photoelectrodes, as a method to overcome the carrier transport limitations. Time‐resolved microwave and terahertz conductivity measurements reveal more than twofold enhancement of the carrier lifetime for the hydrogen‐treated BiVO4, without significantly affecting the carrier mobility. This is in contrast to the case of tungsten‐doped BiVO4, although hydrogen is also a donor type dopant in BiVO4. The enhancement in carrier lifetime is found to be caused by significant reduction of trap‐assisted recombination, either via passivation or reduction of deep trap states related to vanadium antisite on bismuth or vanadium interstitials according to density functional theory calculations. Overall, these findings provide further insights on the interplay between defect modulation and carrier transport in metal oxides, which benefit the development of low‐cost, highly‐efficient solar energy conversion devices.  相似文献   

8.
Different mole ratios of TiO2/BiVO4 nanocomposites with effective contacts have are fabricated by putting BiVO4 nanoparticles into the TiO2 sol, followed by thermal treatment at 450 °C. Based on the transient‐state surface photovoltage responses and the atmosphere‐controlled steady‐state surface photovoltage spectra, it is concluded that the photogenerated charge carriers in the TiO2/BiVO4 nanocomposite with a proper mole ratio (5%) display much longer lifetime and higher separation than those in the BiVO4 alone. This is responsible for the unexpected activity for photoelectrochemical oxidation of water, for photocatalytic production of H2, and for photocatalytic degradation of phenol as a model pollutant under visible irradiation. Moreover, it is suggested that the prolonged lifetime and increased separation of photogenerated charges in the fabricated TiO2/BiVO4 nanocomposite is attributed to the unusual spatial transfer of visible‐excited high‐energy electrons of BiVO4 to TiO2. This work will provide feasible routes to synthesize visible‐light responsive nanomaterials for efficient solar utilization.  相似文献   

9.
The altering of electronic states of metal oxides offers a promising opportunity to realize high‐efficiency surface catalysis, which play a key role in regulating polysulfides (PS) redox in lithium–sulfur (Li–S) batteries. However, little effort has been devoted to understanding the relationship between the electronic state of metal oxides and a catalyst's properties in Li–S cells. Herein, defect‐rich heterojunction electrocatalysts composed of ultrathin TiO2‐x nanosheets and carbon nanotubes (CNTs) for Li–S batteries are reported. Theoretical simulations indicate that oxygen vacancies and heterojunction can enhance electronic conductivity and chemical adsorption. Spectroscopy and electrochemical techniques further indicate that the rich surface vacancies in TiO2‐x nanosheets result in highly activated trapping sites for LiPS and lower energy barriers for fast Li ion mobility. Meanwhile, the redistribution of electrons at the heterojunction interfaces realizes accelerated surface electron exchange. Coupled with a polyacrylate terpolymer (LA132) binder, the CNT@TiO2‐x–S electrodes exhibit a long cycle life of more than 300 cycles at 1 C and a high area capacity of 5.4 mAh cm?2. This work offers a new perspective on understanding catalyst design in energy storage devices through band engineering.  相似文献   

10.
Plasmonic metal nanostructures have been extensively investigated to improve the performance of metal oxide photoanodes for photoelectrochemical (PEC) solar water splitting cells. Most of these studies have focused on the effects of those metal nanostructures on enhancing light absorption and enabling direct energy transfer via hot electrons. However, several recent studies have shown that plasmonic metal nanostructures can improve the PEC performance of metal oxide photoanodes via another mechanism known as plasmon‐induced resonant energy transfer (PIRET). However, this PIRET effect has not yet been tested for the molybdenum‐doped bismuth vanadium oxide (Mo:BiVO4), regarded as one of the best metal oxide photoanode candidates. Here, this study constructs a hybrid Au nanosphere/Mo:BiVO4 photoanode interwoven in a hexagonal pattern to investigate the PIRET effect on the PEC performance of Mo:BiVO4. This study finds that the Au nanosphere array not only increases light absorption of the photoanode as expected, but also improves both its charge transport and charge transfer efficiencies via PIRET, as confirmed by time‐correlated single photon counting and transient absorption studies. As a result, incorporating the Au nanosphere array increases the photocurrent density of Mo:BiVO4 at 1.23 V versus RHE by ≈2.2‐fold (2.83 mA cm?2).  相似文献   

11.
An enormous research effort is currently being directed towards the development of efficient visible‐light‐driven photocatalysts for renewable energy applications including water splitting, CO2 reduction and alcohol photoreforming. Layered double hydroxide (LDH)‐based photocatalysts have emerged as one of the most promising candidates to replace TiO2‐based photocatalysts for these reactions, owing to their unique layered structure, compositional flexibility, controllable particle size, low manufacturing cost and ease of synthesis. By introducing defects into LDH materials through the control of their size to the nanoscale, the atomic structure, surface defect concentration, and electronic and optical characteristics of LDH materials can be strategically engineered for particular applications. Furthermore, through the use of advanced characterization techniques such as X‐ray absorption fine structure, positron annihilation spectrometry, X‐ray photoelectron spectroscopy, electron spin resonance, density‐functional theory calculations, and photocatalytic tests, structure‐activity relationships can be established and used in the rational design of high‐performance LDH‐based photocatalysts for efficient solar energy capture. LDHs thus represent a versatile platform for semiconductor photocatalyst development with application potential across the energy sector.  相似文献   

12.
Metal oxide/Si heterostructures make up an exciting design route to high‐performance electrodes for photoelectrochemical (PEC) water splitting. By monochromatic light sources, contributions of the individual layers in WO3/n‐Si heterostructures are untangled. It shows that band bending near the WO3/n‐Si interface is instrumental in charge separation and transport, and in generating a photovoltage that drives the PEC process. A thin metal layer inserted at the WO3/n‐Si interface helps in establishing the relation among the band bending depth, the photovoltage, and the PEC activity. This discovery breaks with the dominant Z‐scheme design idea, which focuses on increasing the conductivity of an interface layer to facilitate charge transport, but ignores the potential profile around the interface. Based on the analysis, a high‐work‐function metal is predicted to provide the best interface layer in WO3/n‐Si heterojunctions. Indeed, the fabricated WO3/Pt/n‐Si photoelectrodes exhibit a 2 times higher photocurrent density at 1.23 V versus reversible hydrogen electrode (RHE) and a 10 times enhancement at 1.6 V versus RHE compared to WO3/n‐Si. Here, it is essential that the native SiO2 layer at the interface between Si and the metal is kept in order to prevent Fermi level pinning in the Schottky contact between the Si and the metal.  相似文献   

13.
The most important factors dominating solar hydrogen synthesis efficiency include light absorption, charge separation and transport, and surface chemical reactions (charge utilization). In order to tackle these factors, an ordered 1D junction cascade photoelectrode for water splitting, grown via a simple low‐cost solution‐based process and consisting of nanoparticulate BiVO4 on 1D ZnO rods with cobalt phosphate (Co‐Pi) on the surface is synthesized. Flat‐band measurements reveal the feasibility of charge transfer from BiVO4 to ZnO, supported by PL measurements and photocurrent observation in the presence of an efficient hole scavenger, which demonstrate that quenching of luminescence of BiVO4 and enhanced current are caused by electron transfer from BiVO4 to ZnO. A dramatic cathodic shift in onset potential under both visible and full arc irradiation, coupled with a 12‐fold increase in photocurrent (ca. 3 mA cm‐2) are observed compared to BiVO4, resulting in ≈47% IPCE at 410 nm (4% for BiVO4) with high solar energy conversion efficiency (0.88%). The reasons for these enhancements stem from enhanced light absorption and trapping, in situ rectifying electron transfer from BiVO4 to ZnO, hole transfer to Co‐Pi for water oxidation, and facilitating electron transport along 1D ZnO.  相似文献   

14.
Direct photo‐electrochemical (PEC) water splitting is of great practical interest for developing a sustainable energy systems, but remains a big challenge owing to sluggish charge separation, low efficiency, and poor stability. Herein, a 3D porous In2O3/In2S3 pyramid heterostructure array on a fluorine‐doped tin oxide substrate is fabricated by an ion exchange–induced synthesis strategy. Based on the synergistic structural and electronic modulations from density functional theory calculations and experimental observations, 3D porous In2O3/In2S3 photoanode by the protective layer delivers a low onset potential of ≈0.02 V versus reversible hydrogen electrode (RHE), the highest photocurrent density of 8.2 mA cm?2 at 1.23 V versus RHE among all the In2S3 photoanodes reported to date, an incident photon‐to‐current efficiency of 76% at 400 nm, and high stability over 20 h for PEC water splitting are reported. This work provides an alternative promising prototype for the design and construction of novel heterostructures in robust PEC water splitting applications.  相似文献   

15.
Atomically thin 2D heterostructures have opened new realms in electronic and optoelectronic devices. Herein, 2D lateral heterostructures of mesoporous In2O3–x/In2S3 atomic layers are synthesized through the in situ oxidation of In2S3 atomic layers by an oxygen plasma‐induced strategy. Based on experimental observations and theoretical calculations, the prolonged charge carrier lifetime and increased electron density reveal the efficient photoexcited carrier transport and separation in the In2O3–x/In2S3 layers by interfacial bonding at the atomic level. As expected, the synergistic structural and electronic modulations of the In2O3–x/In2S3 layers generate a photocurrent of 1.28 mA cm?2 at 1.23 V versus a reversible hydrogen electrode, nearly 21 and 79 times higher than those of the In2S3 atomic layers and bulk counterpart, respectively. Due to the large surface area, abundant active sites, broadband‐light harvesting ability, and effective charge transport pathways, the In2O3–x/In2S3 layers build efficient pathways for photoexcited charge in the 2D semiconductive channels, expediting charge transport and kinetic processes and enhancing the robust broadband‐light photo‐electrochemical water splitting performance. This work paves new avenues for the exploration and design of atomically thin 2D lateral heterostructures toward robust photo‐electrochemical applications and solar energy utilization.  相似文献   

16.
Two main requirements must be fulfilled in order to construct an efficient TiO2‐based photo‐electrochemical water splitting cell. One is the expansion of the cell's spectral response, usually by the attachment of a sensitizing dye monolayer on the surface of the TiO2. The second involves the incorporation of a water oxidation catalyst that reduces the overpotential for the oxygen evolution reaction. These requirements are often achieved by the co‐adsorption of both the dye and the catalyst on the TiO2, or by a covalent attachment of the catalyst to the dye molecule. Here, the possibility to use a single material that acts as a sensitizer and a catalyst is presented. The use of a catechol molecule to form a type II charge transfer complex with TiO2 widens the absorption of the system into the visible region. The TiO2‐catechol complex is highly catalytic toward the oxidation of water to oxygen, reducing the electrocatalytic reaction overpotential by 500 mV compared to bare TiO2. A suggested catalytic mechanism for the water oxidation reaction is described. This methodology opens a new path for type II charge transfer complexes to be utilized as catalysts/light absorbers in water splitting systems based on TiO2 or other metal oxides.  相似文献   

17.
A major limit for planar perovskite solar cells is the trap‐mediated hysteresis and instability, due to the defective metal oxide interface with the perovskite layer. Passivation engineering with fullerenes has been identified as an effective approach to modify this interface. The rational design of fullerene molecules with exceptional electrical properties and versatile chemical moieties for targeted defect passivation is therefore highly demanded. In this work, novel fulleropyrrolidine (NMBF‐X, X?H or Cl) monomers and dimers are synthesized and incorporated between metal oxides (i.e. TiO2, SnO2) and perovskites (i.e. MAPbI3 and (FAPbI3)x(MAPbBr3)1‐x). The fullerene dimers provide superior stability and efficiency improvements compared to the corresponding monomers, with chlorinated fullerene dimers being most effective at coordinating with both metal oxides and perovskite via the chlorine terminals. The non‐encapsulated planar device delivers a maximum power conversion efficiency of 22.3% without any hysteresis, while maintaining over 98% of initial efficiency after ambient storage for 1000 h, and exhibiting an order of magnitude improvement of the T80 lifetime.  相似文献   

18.
Using a novel statistical approach that efficiently explores the space of possible defect configurations, the present study investigates the chemomechanical coupling between interfacial structural defects and phase boundary alignments within phase‐separating electrode particles. Applied to the battery cathode material LiXFePO4 as an example, the theoretical analysis reveals that small, defect‐induced deviations from an ideal interface can lead to dramatic shifts in the orientations of phase boundaries between Li‐rich and Li‐lean phases, stabilizing otherwise unfavorable orientations. Significantly, this stabilization arises predominantly from configurational entropic factors associated with the presence of the interfacial defects rather than from absolute energetic considerations. The specific entropic factors pertain to the diversity of defect configurations and their contributions to rotational/orientational rigidity of phase boundaries. Comparison of the predictions with experimental observations indicates that the additional entropy contributions indeed play a dominant role under actual cycling conditions, leading to the conclusion that interfacial defects must be considered when analyzing the stability and evolution kinetics of the internal phase microstructure of strongly phase‐separating systems. Possible implications for tuning the kinetics of (de)lithiation based on selective defect incorporation are discussed. This understanding can be generalized to the chemomechanics of other defective solid phase boundaries.  相似文献   

19.
With high theoretical energy density, rechargeable metal–gas batteries (e.g., Li–CO2 battery) are considered as one of the most promising energy storage devices. However, their practical applications are hindered by the sluggish reaction kinetics and discharge product accumulation during battery cycling. Currently, the solutions focus on exploration of new catalysts while the thorough understanding of their underlying mechanisms is often ignored. Herein, the interfacial electronic interaction within rationally designed catalysts, ZnS quantum dots/nitrogen‐doped reduced graphene oxide (ZnS QDs/N‐rGO) heterostructures, and their effects on transformation and deposition of discharge products in the Li–CO2 battery are revealed. In this work, the interfacial interaction can both enhance the catalytic activities of ZnS QDs/N‐rGO heterostructures and induce the nucleation of discharge products to form a homogeneous Li2CO3/C film with excellent electronic transmission and high electrochemical activities. When the batteries cycle within a cutoff specific capacity of 1000 mAh g?1 at a current density of 400 mA g?1, the cycling performance of the Li–CO2 battery using a ZnS QDs/N‐rGO cathode is over 3 and 9 times than those coupled with a ZnS nanosheets (NST)/N‐rGO cathode and a N‐rGO cathode, respectively. This work provides comprehensive understandings on designing catalysts for Li–CO2 batteries as well as other rechargeable metal–gas batteries.  相似文献   

20.

In this paper, we have inspected the optical characteristics of one-dimensional periodic structure (1DPS) of TiO2 and MgF2 dielectric materials with defect layer of liquid crystal (LC) sandwiched with two silver layers, i.e., (TiO2|MgF2)3|Ag|LC|Ag|(TiO2/MgF2)3 using transfer matrix method (TMM). The optical tunable properties of considered periodic structures investigated at different incident angles and temperatures for TE and TM modes. Our study shows that absorption peak of 1DPS varies with incident angle and temperature. The defect layer (Ag-LC-Ag), sandwiched LC within two metallic (Ag) layers, exhibits the surface plasmon waves at the metal LC interfaces. The effect of surface plasmon waves can be better understand through the optical sensing property of such defect periodic structure. The detailed study concludes that such a type of one-dimensional periodic structure (1DPS) may be useful to design a tunable sensor and monochromatic filter.

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