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1.
The optimization of photoelectrode is the key issue for the efficient photoelectrochemical water splitting process. In this work, the TiO2 photoanode is synthesized and modified with ZnIn2S4 nanosheets and Co-Pi cocatalyst (TiO2/ZnIn2S4/Co-Pi) for a favorable photoelectrochemical performance. The synthesis and modification process of the TiO2 photoanode are optimized. The physical and chemical characterizations indicate that the TiO2 has a nano-cauliflower-like structure and rutile crystal form modified with a network hexagonal ZnIn2S4 nanosheets and amorphous Co-Pi groups. After optimization of the hydrothermal and annealing process, the optimized TiO2 photoanode manifests a photocurrent density of 1.82 mA cm?2, 1.73-fold of the pristine TiO2 photoanode (1.05 mA cm?2). With the surficial ZnIn2S4 and Co-Pi modification, the photocurrent density of the TiO2/ZnIn2S4/Co-Pi photoanode is raised to 5.05 mA cm?2, 5.32-fold of the optimized TiO2 photoanode (1.82 mA cm?2). The applied bias photon-to-current efficiency, the charge separation and injection efficiencies of the TiO2/ZnIn2S4/Co-Pi photoanodes are 8.79, 3.40, and 1.64-folds of the optimized TiO2 photoanode. Combined the Tauc plot, valence band XPS spectra, EIS and Mott-Schottky analysis, the PEC water splitting mechanism could be that: (i) the type II heterojunction formed by the TiO2 and ZnIn2S4 semiconductors improves the charge separation/injection efficiencies; (ii) the Co-Pi groups facilitate the oxygen evolution kinetics; (iii) the Co-Pi groups and 2D ZnIn2S4 nanosheets synergistically enhance the charge separation efficiency. This investigation could offer a prospect of practical implementation for photoelectrochemical water splitting.  相似文献   

2.
CdS has been widely used to modify TiO2-based photoanodes for photoelectrochemical (PEC) water splitting. Due to the poor interface contact between chalcogenides and oxides, however, such CdS modified TiO2 materials usually exhibit inefficient separation and transport of charges, leading to an unsatisfactory efficiency during the PEC water splitting process. Addressing this issue, we herein report a CdS/TiO2 nanotube array (CdS/TNA) photoanode that was fabricated through a successive ion layer absorption and reaction (SILAR) method with an additional subsequent annealing. This post-annealing process is essential to enhance the interface contact between the CdS and the TNAs, resulting in an accelerated transfer of photogenerated electrons from the CdS to the TNAs. In addition, the post-annealing also improves the light absorption capability of the CdS/TNA photoanode. The simultaneous enhancement of charge transport and light absorption provided by the post-annealing is essential for improving the PEC performance of the CdS/TNA photoanode. The CdS/TNA photoanode obtained by this strategy exhibits a much enhanced PEC performance in water splitting, and its photocurrent density and solar-to-hydrogen conversion efficiency could reach 4.56 mA cm−2 at 1.23 V vs. reversible hydrogen electrode and 5.61%, respectively. This simple but effective route can provide a general strategy for obtaining high-performance oxide-based photoelectrodes.  相似文献   

3.
Hydrogen treatment is a facile and efficient approach for the enhancement in the functioning of TiO2 nanoparticles for dye-sensitized solar cells (DSSC). In this work, TiO2 nanoparticles have been synthesized in the hydrogen environment followed by the deposition onto FTO glass substrates with various film thickness as photoanodes for DSSC. The synthesized hydrogen treated TiO2 nanoparticles based photoanodes have showed significantly improved photocurrent in the resulting fabricated devices. SEM and TEM analyses have confirmed the particle size and morphology of TiO2 nanoparticles at various magnifications. The crystalline structure and phase identification were studied by XRD analysis and Raman spectroscopic measurements. The UV–Vis spectroscopy analysis was carried out to find the response of samples for ultraviolet and visible light. The current-voltage measurements have confirmed the improvement of photocurrent that is principally due to improved photo-activity of hydrogen treated TiO2 nanoparticles. Moreover, hydrogen treated TiO2 nanoparticles-based photoanode with the film thickness of 11.65 μm has remarkably enhanced power conversion efficiency of 6.05% in DSSCs. The ability of highly photoactive hydrogen treated TiO2 nanoparticles will provide the new openings in different fields that include photo-electrochemical water splitting and in many other applications.  相似文献   

4.
A ternary Ag/TiO2/CNT photoanode was prepared by grafting Ag nanoparticles on the surface of as-synthesized TiO2/CNT nanocomposite for the photoelectrochemical (PEC) water splitting under visible light irradiance. The ternary composite photoanode was observed to generate four times higher photocurrent density compared to binary TiO2/CNT nanocomposite under visible light irradiance. The Ag nanoparticles on the surface of nanocomposite act as a surface plasmon resonance (SPR) photosensitizer under visible light. The enhanced photocurrent density of Ag/TiO2/CNT ternary photoanode is attributed to the increased light absorption in the visible region, decrease in band-bending and effective interfacial electron transfer due to the synergetic effect of Ag nanoparticles and CNTs. The enhanced charge transfer within the Ag/TiO2/CNT was also confirmed by the electrochemical impedance spectroscopy. This work demonstrates a feasible route to improve the PEC performance of TiO2 towards water splitting under sunlight irradiation.  相似文献   

5.
A photoelectrochemical (PEC) cell with an innovative design for hydrogen generation via photoelectrocatalytic water splitting is proposed and investigated. It consisted of a TiO2 nanotube photoanode, a Pt/C cathode and a commercial asbestos diaphragm. The PEC could generate hydrogen under ultraviolet (UV) light-excitation with applied bias in KOH solution. The Ti mesh was used as the substrate to synthesize the self-organized TiO2 nanotubular array layers. The effect of the morphology of the nanotubular array layers on the photovoltaic performances was investigated. When TiO2 photocatalyst was irradiated with UV-excitation, it prompted the water splitting under applied bias (0.6 V vs. Normal Hydrogen Electrode, NHE.). Photocurrent generation of 0.58 mA/cm2 under UV-light irradiation showed good performance on hydrogen production.  相似文献   

6.
Constructing heterojunction was an efficient way to promote photoelectrochemical (PEC) water splitting performance of TiO2-based nano-photoanode. In this work, we demonstrated the feasible preparation of oxygen vacancies-induced In2O3 (In2O3-x) nanorods/black Si-doped TiO2 (Ti–Si–O) nanotubes heterojunction photoanode for enhanced PEC water splitting. Black Ti–Si–O nanotubes were fabricated through Zn reduction of the as-annealed Ti–Si–O nanotubes, followed by In2O3-x nanorods coupling by a facile electrodepositing and Ar heat treatment. Solar to hydrogen conversion efficiency of the heterojunction photoanode reached as high as 1.96%, which was almost 10 times that of undoped TiO2. The improved PEC properties were mainly attributed to co-doping effects of Si and Ti3+/oxygen vacancy as well as In2O3-x decoration, which resulted in enhanced optical absorption and facilitated separation-transport process of photogenerated charge carriers. Charge transfer process in the composite system and hydrogen production mechanism were proposed. This work will facilitate designing TiO2-based nano-photoanodes for promoting water splitting by integrating with elements doping, oxygen vacancies self-doping and semiconductors coupling.  相似文献   

7.
The design of photoanode with highly efficient light harvesting and charge collection properties is important in photoelectrochemical (PEC) cell performance for hydrogen production. Here, we report the hierarchical In2O3:Sn/TiO2/CdS heterojunction nanowire array photoanode (ITO/TiO2/CdS-nanowire array photoanode) as it provides a short travel distance for charge carrier and long light absorption pathway by scattering effect. In addition, optical properties and device performance of the ITO/TiO2/CdS-nanowire array photoanode were compared with the TiO2 nanoparticle/CdS photoanode. The photocatalytic properties for water splitting were measured in the presence of sacrificial agent such as SO32− and S2− ions. Under illumination (AM 1.5G, 100 mW/cm2), ITO/TiO2/CdS-nanowire array photoanode exhibits a photocurrent density of 8.36 mA/cm2 at 0 V versus Ag/AgCl, which is four times higher than the TiO2 nanoparticle/CdS photoanode. The maximum applied bias photon-to-current efficiency for the ITO/TiO2/CdS-nanowire array and the TiO2 nanoparticle/CdS photoanode were 3.33% and 2.09%, respectively. The improved light harvesting and the charge collection properties due to the increased light absorption pathway and reduced electron travel distance by ITO nanowire lead to enhancement of PEC performance.  相似文献   

8.
More and more metal/semiconductor nanostructures have been served as a hot-electron device with the localized surface plasmonic resonance (LSPR) effect to boost hydrogen evolution from solar water splitting. In this work, bimetallic AgCu with optimal ratio are deposited onto TiO2 nanopore/nanotube arrays to construct AgCu/TiO2 photoanode for photoelectrochemical water splitting, a novel simulation characterization to visualize the LSPR process is proposed. The near electric field enhancement and plasmon resonance energy transfer mechanisms of single Ag and Cu are inferred by time-domain characterization, illustrating the contradictory photocurrent under AM 1.5 illumination with its LSPR effect based on the particle size. The variation of local electric field over time within the interfaces of AgCu bimetals and bimetal/TiO2 models reveals the migration of hot electrons from Ag into Cu and the synergetic effect of different LSPR mechanisms. The resulting higher photoelectrochemical activities of AgCu/TiO2 also verifies the positive roles of the coexistence of AgCu on electron generation and energy transfer to interband excitation of TiO2.  相似文献   

9.
Sensitized photocatalytic production of hydrogen from water splitting is investigated under visible light irradiation over mesoporous-assembled titanium dioxide (TiO2) nanocrystal photocatalysts, without and with Pt loading. The photocatalysts are synthesized by a sol–gel process with the aid of a structure-directing surfactant and are characterized by N2 adsorption–desorption analysis, X-ray diffraction, UV–vis spectroscopy, scanning electron microscopy, transmission electron microscopy and energy-dispersive X-ray analysis. The dependence of hydrogen production on the type of TiO2 photocatalyst (synthesized mesoporous-assembled and commercial non-mesoporous-assembled TiO2 without and with Pt loading), the calcination temperature of the synthesized photocatalyst, the sensitizer (Eosin Y) concentration, the electron donor (diethanolamine) concentration, the photocatalyst dosage and the initial solution pH is systematically studied. The results show that in the presence of the Eosin Y sensitizer, the Pt-loaded mesoporous-assembled TiO2 synthesized by a single-step sol–gel process and calcined at 500 °C exhibits the highest photocatalytic activity for hydrogen production from a 30 vol.% diethanolamine aqueous solution with dissolved 2 mM Eosin Y. Moreover, the optimum photocatalyst dosage and initial solution pH for the maximum photocatalytic activity for hydrogen production are 3.33 g dm−3 and 11.5, respectively.  相似文献   

10.
Here we demonstrate that the performance of TiO2 electrodes for photoelectrochemical water oxidation can be effectively enhanced through oxygen vacancy doping. The ion irradiation is a simple method to introduce oxygen vacancies on the surface and into the interior of TiO2 for making oxygen-deficient titania (TiO2-x). The TiO2-x thin films exhibit obvious increase in the performance of photoelectrochemical water splitting under light irradiation. The photoconversion efficiency η of the TiO2-x photoanode is 0.5-fold higher than that of the pristine TiO2 photoanode, which benefits from the introducing of oxygen vacancies produced by ion irradiation. While the irradiation-induced titanium vacancies act as trapping centers for charge carriers and decrease the photoelectrochemical performance of the samples. Positron annihilation spectroscopy (PAS) was used to study the type of the formed vacancies. Combining experimental with theoretical study, this study demonstrates that ion irradiation technique combing with thermal annealing could be an effective way to enhance the performance of photoanode for water splitting.  相似文献   

11.
Developing photoanode with proficient sunlight harvesting, stability as well as enhancing the electron injection across the interface remains a major challenge in the photoelectrochemical water splitting strategy to generate hydrogen. Herein, we design and fabricate an organic/inorganic TiO2/C3N4/CNT photoanode by a hydrothermal technique which exhibits much enhanced photoelectrochemical properties. The TiO2/C3N4/CNT photoanode exhibits a photocurrent density of 2.94 mA/cm2, which is ~6.4 time higher than pristine graphitic carbon nitride (C3N4) at an applied bias potential of 0.6 V vs. Ag/AgCl. The excellent photoelectrochemical performance benefits from the impactful migration of photo-induced electrons at the TiO2/C3N4 interface from C3N4 to TiO2 and their intimate interface contact with CNT. Kelvin probe force microscopy result shows a smaller interface barrier height (~10 meV) between TiO2 and C3N4, suggesting that electrons transport is favored through TiO2/C3N4 interfaces in a ternary photoanode. The TiO2/C3N4/CNT photoanode exhibited an onset potential of 0.25 V vs. Ag/AgCl which is much lower compared to pristine C3N4. The electrochemical impedance spectroscopy results also confirmed the enhanced electron injection across the interface in a ternary photoanode. These results demonstrate a promising approach to develop a highly proficient and visible light active photoanode with excellent stability for renewable energy applications.  相似文献   

12.
An integrated solar water splitting tandem cell without external bias was designed using a FeOOH modified TiO2/BiVO4 photoanode as a photoanode and p-Cu2O as a photocathode in this study. An apparent photocurrent (0.37 mA/cm2 at operating voltage of +0.36 VRHE) for the tandem cell without applied bias was measured, which is corresponding to a photoconversion efficiency of 0.46%. Besides, the photocurrent of FeOOH modified TiO2/BiVO4–Cu2O is much higher than the operating point given by pure BiVO4 and Cu2O photocathode (∼0.07 mA/cm2 at +0.42 VRHE). Then we established a FeOOH modified TiO2/BiVO4–Cu2O two-electrode system and measured the current density-voltage curves under AM 1.5G illumination. The unassisted photocurrent density is 0.12 mA/cm−2 and the corresponding amounts of hydrogen and oxygen evolved by the tandem PEC cell without bias are 2.36 μmol/cm2 and 1.09 μmol/cm2 after testing for 2.5 h. The photoelectrochemical (PEC) properties of the FeOOH modified TiO2/BiVO4 photoanode were further studied to demonstrate the electrons transport process of solar water splitting. This aspect provides a fundamental challenge to establish an unbiased and stabilized photoelectrochemical (PEC) solar water splitting tandem cell with higher solar-to-hydrogen efficiency.  相似文献   

13.
Photo-electrochemical (PEC) water splitting is a promising and environmentally benign approach for generation of hydrogen using solar energy with minimum greenhouse gas emissions. The development of semiconductor materials for photoanode with superior optoelectronic properties combined with excellent photoelectrochemical activity and stability is vital for the realization of viable commercial development of PEC water splitting systems. Herein, we report for the very first time, the study of nanoscale bilayer architecture of WO3 and Nb and N co-doped SnO2 nanotubes (NTs), wherein WO3 NTs are coated with (Sn0.95Nb0.05)O2:N-600 (annealed in NH3 at 600 °C) layer of different thicknesses, as a potential semiconductor photoanode material for PEC water splitting. An excellent long term photoelectrochemical stability under illumination in the acidic electrolyte solution combined with a solar-to-hydrogen efficiency (STH) of ~3.83% (under zero applied potential) is obtained for the bilayer NTs, which is the highest STH obtained thus far, to the best of our knowledge compared to the other well studied semiconductor materials, such as TiO2, ZnO and Fe2O3. These promising results demonstrate the excellent potential of bilayer NTs as a viable and promising photoanode in PEC water splitting.  相似文献   

14.
A novel photoelectrochemical cell (PEC) for generation of hydrogen via photocatalytic water splitting is proposed and investigated. At the heart of the PEC is a membrane electrode assembly (MEA) integrated with Degussa P25 TiO2 powder as a model photocatalyst for the photoanode and Pt catalyst powder for the dark cathode, respectively. It serves as a compact photocatalytic reactor for water splitting as well as an effective separator for the generated hydrogen and oxygen. The unique characteristic of the MEA-based PEC is that the use of co-catalyst, sacrificial reagent and supporting electrolyte in the cell is totally not required. The novel PEC can be operated without addition of water in the cathode compartment resulting in improved photo conversion efficiency. In addition, the application of a Degussa P25/BiVO4 mixed photocatalyst was found to significantly enhance the hydrogen generation. Further improvements for the MEA-based PEC utilizing solar energy are also proposed.  相似文献   

15.
Photoelectrochemical (PEC) hydrogen generation gives an opportunity to acquire energy by means of clean and renewable resources such as water and solar light. A major problem in the PEC system is the stability of the photoanode material for long-term applications. Recently, self-assembled titanium dioxide (TiO2) semiconductors (and their hybrids) have shown potential to generate hydrogen in the PEC system. In the present investigation, stability of the nanotubular TiO2 in 1 M KOH solution under illumination conditions is investigated. The photoanode is found to be stable (in terms of activity and morphologically) for one month (8 h/day) without much change in the hydrogen generation rate. Possible photoelectrochemical reactions that can be responsible for degradation of performance of nanotubular TiO2 material are identified. Various spectroscopic and electrochemical measurements, viz., SEM, XRD, DRUV-Vis and Mott–Schottky are employed to confirm that the nanotubular TiO2 photoanode can be used for long-term applications.  相似文献   

16.
The electronic and optical properties are studied using the density functional theory in (Si,Fe)-codoped anatase TiO2. The calculated results suggest that the synergistic effects of (Si,Fe) codoping can effectively induce the redshift of optical absorption edge, which leads to higher visible-light photocatalytic activity for hydrogen production by water splitting than pure anatase TiO2. To verify the reliability of our calculated results, nanocrystalline (Si,Fe)-codoped TiO2 is synthesized by a sol-gel-solvothermal method, and excellent absorption performance and photocatalytic activity for hydrogen production by water splitting are observed in our experiments.  相似文献   

17.
The hydrogen generation from photoelectrochemical (PEC) water splitting under visible light was investigated using large area tungsten oxide (WO3) photoanodes. The photoanodes for PEC hydrogen generation were prepared by screen printing WO3 films having typical active areas of 0.36, 4.8 and 130 cm2 onto the conducting fluorine-doped tin oxide (FTO) substrates with and without embedded inter-connected Ag grid lines. TiO2 based dye-sensitized solar cell was also fabricated to provide the required external bias to the photoanodes for water splitting. The structural and morphological properties of the WO3 films were studied before scaling up the area of photoanodes. The screen printed WO3 film sintered at 500 °C for 30 min crystallized in a monoclinic crystal structure, which is the most useful phase for water splitting. Such WO3 film revealed nanocrystalline and porous morphology with grain size of ∼70-90 nm. WO3 photoanode coated on Ag grid embedded FTO substrate exhibited almost two-fold degree of photocurrent density enhancement than that on bare FTO substrate under 1 SUN illumination in 0.5 M H2SO4 electrolyte. With such enhancement, the calculated solar-to-hydrogen conversion efficiencies under 1 SUN were 3.24% and ∼2% at 1.23 V for small (0.36 cm2) and large (4.8 cm2) area WO3 photoanodes, respectively. The rate of hydrogen generation for large area photoanode (130.56 cm2) was 3 mL/min.  相似文献   

18.
In this work, we report for the first time a plasmonic photoanode by decorating Au nanoparticles (NPs) onto two-dimensional (2D) Co3O4 nanosheets (NSs)/one-dimensional (1D) TiO2 nanorod arrays (NRAs) (Au/Co3O4/TiO2-NRAs) for enhanced visible-light photoelectrochemical (PEC) water splitting. In this plasmonic photoanode, TiO2 NRAs act as an electron acceptor, plasmonic Au NPs and hierarchical Co3O4 NSs serve as visible-light harvesters. Light absorption shows that Au/Co3O4/TiO2-NRAs heterojunction architectures exhibit greatly improved ability to harvest visible light due to the surface plasmon resonance (SPR) absorption of Au NPs and visible light harvesting ability of Co3O4 NSs. Spectroscopic measurements demonstrate that a type II band alignment is formed between Co3O4 and TiO2. Benefiting from the SPR effect, type II band alignment and novel hierarchical architecture, plasmonic Au/Co3O4/TiO2-NRAs photoanode shows remarkably enhanced visible-light PEC water splitting activity compared with Co3O4/TiO2-NRAs and pristine TiO2-NRAs photoanodes. Photocurrent density achieved by plasmonic photoanode is 37 and 1.2 times higher than those of TiO2-NRAs and Co3O4/TiO2-NRAs photoanodes, respectively. This work provides a promising strategy to highly enhance visible-light PEC water splitting activity of wide band-gap semiconductor-based photoelectrode materials.  相似文献   

19.
Hydrogen production by solar energy is an efficient and clean approach to fulfill the future energy demand. Herein, a novel multi-shelled porous heterostructure CoOx/CdS/TiO2 photoanode was fabricated by the hydrothermal and chemical method. There were more active sites, suitable surface defects and heterojunction structures in the homogeneous-porous-multi-shelled CoOx/CdS/TiO2 photoanode. It showed a photocurrent density of 2.89 mA/cm2 at 1.23V vs. RHE, which is 2.22 fold of the original TiO2 photoanode. The heterostructure fabrication of the CdS/TiO2 could broaden the visible light absorption and enhance the charge separation efficiency. The multi-shelled homogeneous porous structure of the CoOx/CdS/TiO2 further enhanced the charge separation efficiency and accelerated the interfacial oxygen evolution kinetics. The mechanism for the enhanced photoelectrochemical water splitting of favorable CoOx/CdS/TiO2 photoanode is proposed.  相似文献   

20.
In this work, 1D core-shell Si/metal oxide nanopillar (NP) photoanodes were synthesized for enhanced solar-driven water splitting processes. The core-shell structures were fabricated by atomic layer deposition of different metal oxides (TiO2 and ZnO) onto Si NP, which were synthesized by metal-assisted chemical etching and nanosphere lithography. In order to characterize produced photoanodes various experimental techniques (SEM/TEM, XRD, Transmittance, Reflectance, Raman spectroscopy) were applied. Photoelectrochemical (PEC) water oxidation of produced photoanodes was studied. It was shown that composition of n-Si/TiO2/ZnO NP exhibited enhanced photocurrents due to barrier effects. The enhanced PEC properties of core-shell Si/TiO2/ZnO NP are caused by efficient charge separation of photogenerated electron-hole pairs in the TiO2/ZnO shell and effective holes transfer to the shell-electrolyte interface. The superior photoelectrochemical performance of a photoanode based on core-shell Si/TiO2/ZnO NP has been confirmed through electrochemical impedance spectroscopy and voltamperometric measurements under electrode irradiation. 1D core-shell Si/TiO2/ZnO NP offer a new approach for preparing stable and highly efficient photoanodes for PEC water-splitting process.  相似文献   

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