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1.
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   

2.
In this paper, novel TiO2/CeO2 core/shell heterojunction nanorod (NR) arrays were synthesized as photoanode for photoelectrochemical (PEC) water splitting via a simple and facial two-step hydrothermal approach. This synthesis route can obtain different amount of CeO2 nanoparticles by controlling the hydrothermal time and eventually achieve uniform TiO2/CeO2 core/shell nanostructures. The uniform TiO2/CeO2 core/shell heterojunction nanoarrays exhibit a markedly enhanced photocurrent density of 5.30 mA·cm?2 compared to that of pristine TiO2 NR 1.79 mA·cm?2 at 1.23 V vs. RHE in 1 M KOH solution. The superior PEC performance of the TiO2/CeO2 core/shell heterojunction is primarily due to much enhanced visible light absorption and appropriate gradient energy gap structure. This work not only offers the synthesis route for the novel TiO2/CeO2 core/shell heterojunction, but also suggests that this new core/shell heterojunction has a great potential application for efficient PEC water splitting devices.  相似文献   

3.
The CdSe@TiO2 core‐shell nanorod arrays for photoelectrochemical (PEC) application were designed and constructed by a facile electrochemical deposition strategy. The CdSe@TiO2 photoanodes exhibit highly efficient PEC performance under visible light irradiation, among which the CdSe shell layer thickness can be precisely adjusted by different electrodeposition time. In comparison with nude TiO2 nanorods, the optimized CdSe@TiO2 photoanode (TC‐500) shows a significant saturated photocurrent density of 2.1 mA/cm2 at 0 V (vs Ag/AgCl), which is attributed to the good distribution of CdSe nanoparticles on TiO2 nanorod arrays, the favorable band alignment, and the intimate interfacial interaction between CdSe nanoparticles and TiO2 nanorods. The introduction of CdSe shell layer does not only improve light absorption ability but also enhances photogenerated charge carrier's transfer and separation. This current work systematically studies the accurate adjustment of CdSe shell layer thickness on TiO2 nanorod arrays by electrochemical deposition strategy and provides a paradigm to design and fabricate heterostructure composite for PEC application.  相似文献   

4.
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   

5.
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   

6.
Bismuth vanadate has been extensively investigated as a potential visible light photoanode for PEC water splitting. The performance of BiVO4 is restricted by fast charge recombination and slow oxygen evolution reaction kinetic. To address these issues, hierarchical SnO2 (HSN) mesoporous support is developed via a novel sol-electrophoretic approach, and BiVO4 film is decorated with silver nanorods (Ag NRs). The photocurrent density of HSN/BiVO4 photoanode is 3.98 mA/cm2 at 1.23 V vs. reversible hydrogen electrode (RHE) and onset potential (Vonset) of 0.5 V vs. RHE. The PEC performance is attributed to the appropriate band alignment between SnO2 and BiVO4, as well as the hierarchical structure of SnO2. Ag-HSN/BiVO4 photoanode shows photocurrent density of 4.30 mA/cm2 at 1.23 V vs. RHE and Vonset of 0.28 V vs. RHE. The enhanced photocurrent and negatively shifted Vonset can be attributed to radiative localized surface plasmon resonance decay and catalytic effect of Ag NRs, respectively.  相似文献   

7.
Bulk-phase doping and surface oxygen-defective engineering of TiO2-based nanostructures are identified as effective routes for enhanced photoelectrochemical (PEC) water splitting. Here, we reported a reduced Ti–Ni–O nanotubes photoanode with anatase-rutile crystalline-core and oxygen vavancies amorphous-shell for boosted PEC water splitting. The core-shell hetero-phase reduced Ti–Ni–O nanotubes were fabricated through phase-structure modulation by a thermal treatment of anodized Ti–Ni–O nanotubes on Ti–Ni alloy and with one-step electrochemical reduction. Microstructure, optical and PEC measurement results confirmed effective bulk-phase Ni-doping and surface oxygen vacancies self-doping into the reduced mixed-phase Ti–Ni–O nanotubes, which enabled high capability of optical-absorption and simultaneously favored charge separation-transfer for remarkably improved the PEC water splitting. A higher photocurrent density of 1.66 mA/cm2 at 0 V vs. Ag/AgCl and solar-to-hydrogen efficiency of 0.79% were achieved for the reduced Ti–Ni–O system, which was 5.35 and 5.27 times that of undoped TiO2, respectively. This work may shed an insight view on fabricating high-performance Ti-based nano-photoanodes with enhanced light harvesting and carrier kinetics for efficient PEC water splitting, through synergistic strategy of bulk-phase elements doping and surface oxygen vacancies self-doping.  相似文献   

8.
Developing low-cost semiconductor photoanode toward efficient and stable oxygen evolution reaction (OER) is highly desirable for photoelectrochemical (PEC) water splitting. Herein, nanoparticulate titanium dioxide (TiO2) electrodes were prepared using Degussa P25 powders by spin-coating method. The effects of annealing conditions on the PEC performance of the nanoparticulate TiO2 photoanode was systematically investigated including temperature, annealing time and atmosphere. The results demonstrate that the TiO2/fluorine-doped tin oxide substrates (FTO/TiO2) electrode annealed at argon (Ar) atmosphere under 450 °C shows the highest PEC performance. The photocurrent density of FTO/TiO2 annealed in Ar for only 0.5 h reached to 120 μA/cm2 at 0.3 V vs. Hg/HgO which is about 10 times higher than that of the unannealed one. The X-ray photoelectron spectroscopy (XPS) results show the thermal treatment can produce oxygen vacancies on the surface of TiO2 which reduce the recombination of photogenerated electron-hole pairs and expanding the visible light absorption by introducing defective energy levels. The electrochemical impedance spectroscopy (EIS) approves that appropriate annealing treatment can effectively enhance the electron conductivity resulting in low charge transfer resistance. All these factors contribute to improving the PEC activity of TiO2 photoanode.  相似文献   

9.
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   

10.
Solar-driven water splitting of semiconductor photoelectrodes via photoelectrochemical (PEC) cell has been regarded as the most promising approach to mitigate the energy crisis and environmental issues in the future. In this work, CuS nanoparticles (NPs) are deposited on ZnO nanotube arrays (ZnO/CuS NTAs) via successive ion layer absorption and reaction method for PEC water splitting under visible light irradiation without applying bias. The excellent light harvesting capacity of CuS NPs from visible to near infrared region not only expands the light harvesting of ZnO NTAs into near infrared region, but also substantially boosts light absorption ranging from 300 to 800 nm. Moreover, CuS NPs coupled on ZnO NTAs can establish a type-II band alignment between ZnO and CuS. Consequently, the ZnO/CuS NTAs photoanode exhibits the significantly boosted PEC water splitting performance under visible light illumination (λ > 420 nm) without applying bias. The photocurrent density of the ZnO/CuS NTAs photoanode is 21.2 μA/cm2, which is increased by 9 times compared to that of the pure ZnO NTAs photoanode. The enhancement in PEC water splitting performance for ZnO/CuS NTAs is attributed to (i) the cooperative actions of ZnO and CuS; (ii) significant enhancement in light absorption from the visible to near infrared region achieved by CuS NPs and (iii) efficient charge carrier separation achieved by type-II band alignment.  相似文献   

11.
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   

12.
Decoration of semiconductors with plasmonic nanoparticles provides a new direction for efficient solar water splitting for hydrogen production. Herein, Ag nanoparticles as the plasmonic metal were electrodeposited on a TiO2 nanotube arrays (TNTA) photoelectrode by controlling deposition-charge density. The resulting Ag/TNTA electrode with 10–50 nm diameter Ag nanoparticles exhibited a higher photocurrent density and hydrogen production rate than a bare TNTA electrode under AM 1.5 irradiation. The origins of this enhancement were explored by analyzing the photoelectrochemical behaviors with the relevant optical properties. The absorption of these Ag/TNTA electrodes in the visible light region increased owing to the surface plasmon resonance (SPR) effect of the Ag nanoparticles, and only low photocurrent densities under visible light irradiation were observed. The overall enhancement is owing to the greater incident photon-to-electron conversion efficiency in the 300–400 nm range that is more dependent on the interfacial charge transfer from TNTA to Ag nanoparticles. The localized electronic field of the SPR also reduces the electron transport time in the Ag/TNTA electrodes.  相似文献   

13.
A ternary composites of MoO3/Ag/TiO2 nanotube arrays were synthesized by in-situ annealing of TiO2 nanotube arrays impregnated with AgNO3 over MoO3 powders. During the annealing process, the crystallization of the TiO2 nanotubes, the thermo-decomposition of AgNO3 to Ag nanoparticles, and the sublimation of MoO3 occur jointly. The photoelectrochemical measurements of the resultants indicate that MoO3/Ag/TiO2 nanotube arrays present better photoelectrochemical properties compared with Ag/TiO2 nanotube arrays and pristine TiO2 nanotube arrays. Especially, the highest photocurrent and open circuit voltage are up to 21.29 μA/cm2 and 0.058 V under visible light irradiation, whereas 1.77 and 3.87 times larger than those of TiO2 nanotube arrays, respectively. Superior photoelectrochemical stability and larger photo-conversion efficiency of the ternary composites are also demonstrated. The improved photoelectrochemical properties are related to the close interfacial contact among MoO3, Ag, and TiO2 as well as the surface plasma resonance of Ag in the ternary composites, which broaden the range of light response and enhance the efficiency of charge separation. This study provides a skillful solution to construct TiO2-based composite materials and demonstrates it is an unique architecture to promote the visible light driven photocatalytic application of TiO2.  相似文献   

14.
Ag@TiO2 nanoparticle thin film was fabricated for photoelectrochemical water splitting in the visible light region. Under the irradiation of UV light, positive photocurrent was enhanced in both electrolytes of 0.1 M HNO3 and 0.1 M NaOH owing to the excitation of photoelectrons within the TiO2 shells. However, under the irradiation of visible light, the enhancement of positive photocurrent was observed only in 0.1 M HNO3 because of the formation of a Schottky barrier band bending at the Ag-TiO2 core-shell interface and the generation of photoelectrons resulted from the surface plasmon resonance of Ag cores. In 0.1 M NaOH, significant negative photocurrent was enhanced due to the influences of higher pH on the surface state and energy level of TiO2 shells. Such a visible light-induced photoresponse enhancement and photocurrent direction switching made the Ag@TiO2 nanoparticle thin film useful not only as a photoelectrode for water splitting but also as a photo-switch in a basic electrolyte.  相似文献   

15.
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   

16.
Dual co-catalysts have an essential effect on improving the photoelectrochemical (PEC) performance of semiconductor materials. In this study, Ni–Ni(OH)2 or/and Nikel phosphate (NiPi) nanocrystals co-catalysts were deposited on the surface of as-prepared TiO2 nanotube arrays (TNTAs) by a simple electrodeposition route for PEC hydrogen production. The TNTAs loading with Ni and NiPi bifunctional co-catalysts exhibited remarkably enhanced PEC performance, with about an 8.3-fold increase in the photocurrent; and an 11.7-fold improvement in H2 evolution rate in comparison to bare TNTAs. The constructed ternary TNTAs/Ni–Ni(OH)2/NiPi comprised the advantage of Ni–Ni(OH)2 and NiPi nanoparticles to enhance visible-light absorption and promote oxygen evolution reaction (OER) kinetics. The internal electric field is generated between supported p-type Ni(OH)2 and n-type TiO2 under light irradiation, which will drive holes to flow to Ni(OH)2 and oxidize it as the OER active layer. Also, the photo-generated holes remaining in the TiO2 valence band can migrate to NiPi co-catalysts to cause OER. Therefore, the photogenerated electron-hole pairs can be successfully separated under the synergetic influence of Ni–Ni(OH)2 and NiPi co-catalyst, leading to a superior PEC water splitting ability.  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.
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   

19.
BiVO4 is an ideal photoanode material for solar-driven photoelectrochemical (PEC) water splitting but it easily suffers from the recombination of photogenerated electrons and holes due to its low carrier mobility thus cause low efficiency of PEC water splitting. Herein, the BiVO4/CdS/NiCo-LDH photoanode was prepared by combining methods of metal organic decomposition, chemical and electrodeposition. The photoanode photocurrent density reaches 2.72 mA cm−2 at 1.23 V (vs. RHE), which is 3.6 folds of pure BiVO4 photoanode and onset potential shifts 450 mV toward cathodic. The incident photon-to-electron conversion efficiency (IPCE) value is 2.86 folds of BiVO4, the calculated photon–to–current efficiency (ABPE) is 1.24% at 0.62 V (vs. RHE). The obtained results are higher than that of most BiVO4 based photoanodes published so far. The enhancement benefits from increase of visible light absorption capacity, enhancement of separation efficiency of photoexcited electron-hole and fast transfer of holes accumulated on electrode/electrolyte surface for water oxidation, which has been confirmed by calculating carrier density and carrier transport rate.  相似文献   

20.
Two-dimensional heterojunction g-C3N4/BCN was constructed via thermal polymerization process. The formed two-dimensional heterostructure could enhance the interfacial contact area between BCN and porous g-C3N4 as well as shorten the photogenerated charge carriers transfer time and distance. The two-dimensional g-C3N4/BCN heterojunction photoanode shows enhanced photoelectrochemical (PEC) performance for water splitting under visible-light irradiation, which primarily originates from the improved charge transfer and separation, and prolonged lifetime of electrons. Under the visible light irradiation, the g-C3N4/BCN heterojunction sample yields a photocurrent density of ∼0.62 mA cm−2 at 1.23 V vs. RHE, which is about eight times as many as that of CN (0.08 mA cm−2) electrode at the same conditions. In addition, the possible electron transfer model and mechanism of PEC water splitting for H2 evolution have been discussed.  相似文献   

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