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1.
Correlated electron oxides prove a diverse landscape of exotic materials' phenomena and properties. One example of such a correlated oxide material is strontium ruthenate (SrRuO3) which is known to be a metallic itinerant ferromagnet and for its widespread utility as a conducting electrode in oxide heterostructures. We observe that the complex electronic structure of SrRuO3 is also responsible for unexpected optical properties including high absorption across the visible spectrum (commensurate with a low band gap semiconductor) and remarkably low reflection compared to traditional metals. By coupling this material to a wide band gap semiconductor (TiO2) we demonstrate dramatically enhanced visible light absorption and large photocatalytic activities. The devices function by photo‐excited hot‐carrier injection from the SrRuO3 to the TiO2 and the effect is enhanced in thin films due to electronic structure changes. This observation provides an exciting new approach to the challenge of designing visible‐light photosensitive materials.  相似文献   

2.
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   

3.
The effects of nano-anatase TiO2 on light absorption, distribution, and conversion, and photoreduction activities of spinach chloroplast were studied by spectroscopy. Several effects of nano-anatase TiO2 were observed: (1) the absorption peak intensity of the chloroplast was obviously increased in red and blue region, the ratio of the Soret band and Q band was higher than that of the control; (2) the great enhancement of fluorescence quantum yield near 680 nm of the chloroplast was observed, the quantum yield under excitation wavelength of 480 nm was higher than the excitation wavelength of 440 nm; (3) the excitation peak intensity near 440 and 480 nm of the chloroplast significantly rose under emission wavelength of 680 nm, and F 480 / F 440 ratio was reduced; (4) when emission wavelength was at 720 nm, the excitation peaks near 650 and 680 nm were obviously raised, and F 650 / F 680 ratio rose; (5) the rate of whole chain electron transport, photochemical activities of PSII DCPIP photoreduction and oxygen evolution were greatly improved, but the photoreduction activities of PSI were a little changed. Together, the studies of the experiments showed that nano-anatase TiO2 could increase absorption of light on spinach chloroplast and promote excitation energy to be absorbed by LHCII and transferred to PSII and improve excitation energy from PSI to be transferred to PSII, thus, promote the conversion from light energy to electron energy and accelerate electron transport, water photolysis, and oxygen evolution.  相似文献   

4.
The spin or nonspin state of electrons in W-doped anatase TiO2 is very difficult to judge experimentally because of characterization method limitations. Hence, the effect on the microscopic mechanism underlying the visible-light effect of W-doped anatase TiO2 through the consideration of electronic spin or no-spin states is still unknown. To solve this problem, we establish supercell models of W-doped anatase TiO2 at different concentrations, followed by geometry optimization and energy calculation based on the first-principle planewave norm conserving pseudo-potential method of the density functional theory. Calculation results showed that under the condition of nonspin the doping concentration of W becomes heavier, the formation energy becomes greater, and doping becomes more difficult. Meanwhile, the total energy increases, the covalent weakens and ionic bonds strengthens, the stability of the W-doped anatase TiO2 decreases, the band gap increases, and the blue-shift becomes more significant with the increase of W doping concentration. However, under the condition of spin, after the band gap correction by the GGA+U method, it is found that the semimetal diluted magnetic semiconductors can be formed by heavy W-doped anatase TiO2. Especially, a conduction electron polarizability of as high as near 100% has been found for the first time in high concentration W-doped anatase TiO2. It will be able to be a promising new type of dilute magnetic semiconductor. And the heavy W-doped anatase TiO2 make the band gap becomes narrower and absorption spectrum red-shift.  相似文献   

5.
With a photocatalyzed characteristic, nanoanatase TiO2 under light could cause an oxidation–reduction reaction. Our studies had proved that nano-TiO2 could promote photosynthesis and greatly improve spinach growth. However, the mechanism of nano-TiO2 on promoting conversion from light energy to electron energy and from electron energy to active chemistry energy remains largely unclear. In this study, we report that the electron transfer, oxygen evolution, and photophosphorylation of chloroplast (Chl) from nanoanatase-TiO2-treated spinach were greatly increased under visible light and ultraviolet light illumination. It was demonstrated that nanoanatase TiO2 could greatly improve whole chain electron transport, photoreduction activity of photosystem II, O2-evolving and photophosphorylation activity of spinach Chl not only under visible light, but also energy-enriched electron from nanoanatase TiO2, which entered Chl under ultraviolet light and was transferred in photosynthetic electron transport chain and made NADP+ be reduced into NADPH, and coupled to photophosphorylation and made electron energy be transformed to ATP. Moreover, nanoanatase h+, which photogenerated electron holes, captured an electron from water, which accelerated water photolysis and O2 evolution.  相似文献   

6.
Ag-loaded TiO2 (Ag/TiO2) nanocomposites were prepared by microwave-assisted chemical reduction method using tetrabutyl titanate as the Ti source. The prepared samples were characterized by X-ray diffraction, scanning electron microscopy, transmission electron microscopy, N2 adsorption–desorption isotherms, UV–vis absorption spectrum, X-ray photoelectron spectrum, photoluminescence spectrum, and Raman scattering spectrum, respectively. Results revealed that Ag nanoparticles (NPs) were successfully deposited on TiO2 by reduction of Ag+, and the visible light absorption and Raman scattering of TiO2 were enhanced by Ag NPs based on its surface plasmon resonance effect. Besides, Ag NPs could also effectively restrain the recombination of photogenerated electrons and holes with a longer luminescence life time. In addition, photocatalytic reduction of CO2 with H2O on the composites was conducted to obtain methanol. Experimental results indicated that Ag-loaded TiO2 had better photocatalytic activity than pure TiO2 due to the synergistic effect between UV light excitation and surface plasmon resonance enhancement, and 2.5 % Ag/TiO2 exhibited the best activity; the corresponding energy efficiency was about 0.5 % and methanol yield was 405.2 μmol/g-cat, which was 9.4 times higher than that of pure TiO2. Additionally, an excitation enhancement synergistic mechanism was proposed to explain the experimental results of photocatalytic reduction of CO2 under different reaction conditions.  相似文献   

7.
Compact TiO2 is widely used as an electron transport material in planar‐perovskite solar cells. However, TiO2‐based planar‐perovskite solar cells exhibit low efficiencies due to intrinsic problems such as the unsuitable conduction band energy and low electron extraction ability of TiO2. Herein, the planar TiO2 electron transport layer (ETL) of perovskite solar cells is modified with ionic salt CuI via a simple one‐step spin‐coating process. The p‐type nature of the CuI islands on the TiO2 surface leads to modification of the TiO2 band alignment, resulting in barrier‐free contacts and increased open‐circuit voltage. It is found that the polarity of the CuI‐modified TiO2 surface can pull electrons to the interface between the perovskite and the TiO2, which improves electron extraction and reduces nonradiative recombination. The CuI solution concentration is varied to control the electron extraction of the modified TiO2 ETL, and the optimized device shows a high efficiency of 19.0%. In addition, the optimized device shows negligible hysteresis, which is believed to be due to the removal of trap sites and effective electron extraction by CuI‐modified TiO2. These results demonstrate the hitherto unknown effect of p‐type ionic salts on electron transport material.  相似文献   

8.

The fabrication of low cost and eco-friendly transparent electronics using metal oxide semiconductors is still a challenging task. In this work, transparent nanocrystalline (Bi2O3)1−x:(TiO2)x thin films were synthesized using a pulsed laser deposition technique (PLD); XRD analysis shows the films have polycrystalline structure of monoclinic Bi2O3; morphological and topographical properties were analyzed by SEM and AFM showing the films have smooth surfaces with RMS roughness (4.26–7.37 nm) with micro-and nano-spheres (2 μm to 23 nm); the optical properties were analyzed by Uv-Vis spectrometer and revealed high transmittance in the visible range; the best results were obtained at x = 0.05 where the highest crystallinity, highest transmittance (> 82%), and highest band gap (3.769 eV) were achieved; and empirical models have been proposed to estimate the band gap and Bi–O bond lengths as a function of TiO2 concentration with excellent coincidence with the experimental data.

  相似文献   

9.
In the present work, the physical properties of alkali-earth metal and transition metal hydroxides are comprehensively investigated using the density functional theory. Here, the alkali-earth metals Ca, Mg, and transition metals Cd, Zn are considered from the II-A and II-B groups in the periodic table of elements. The first principle electronic structure calculations show that these bulk hydroxide materials are direct band gap material. Ca(OH)2 and Mg(OH)2 exhibit an insulating behavior with a very large band gap. However, Cd(OH)2 and Zn(OH)2 are found to be wide band gap semiconductors. The dielectric and optical studies reveal that these materials have a high degree of anisotropy. Hence, the light propagation in these materials behaves differently in the direction perpendicular and parallel to the optical axis, and exhibits birefringence. Therefore, these materials may be useful for optical communication. The calculated electron energy loss suggests that these materials can also be used for unwanted signal noise suppression. The wide band gap makes them useful for high-power applications. Moreover, Ca(OH)2 and Mg(OH)2 are found to be suitable for dielectric medium.  相似文献   

10.
The reduction in electronic recombination losses by the passivation of surfaces is a key factor enabling high‐efficiency solar cells. Here a strategy to passivate surface trap states of TiO2 films used as cathode interlayers in organic photovoltaics (OPVs) through applying alumina (Al2O3) or zirconia (ZrO2) insulating nanolayers by thermal atomic layer deposition (ALD) is investigated. The results suggest that the surface traps in TiO2 are oxygen vacancies, which cause undesirable recombination and high electron extraction barrier, reducing the open‐circuit voltage and the short‐circuit current of the complete OPV device. It is found that the ALD metal oxides enable excellent passivation of the TiO2 surface followed by a downward shift of the conduction band minimum. OPV devices based on different photoactive layers and using the passivated TiO2 electron extraction layers exhibit a significant enhancement of more than 30% in their power conversion efficiencies compared to their reference devices without the insulating metal oxide nanolayers. This is a result of significant suppression of charge recombination and enhanced electron extraction rates at the TiO2/ALD metal oxide/organic interface.  相似文献   

11.
TiO2 nanotube arrays (TiO2 NTs) were fabricated by anodic oxidation and then Ag nanoparticles (Ag NPs) were assembled in TiO2 NTs (Ag/TiO2 NTs) by microwave-assisted chemical reduction. The samples were characterized by X-ray diffraction (XRD), scanning electron microscope (SEM), photoluminescence spectrum (PL), UV–vis absorption spectrum (UV–vis), and Raman spectrum, respectively. The results showed that Ag NPs were well dispersed on the surface of TiO2 NTs with metallic state. The surface plasmon resonance (SPR) effect of Ag NPs could extend the visible light response and enhance the absorption capacity of TiO2. Furthermore, Ag NPs could also restrain the recombination of photo-generated electron–hole pairs of TiO2 NTs efficiently. The methylene blue photodegradation experiment proved that the SPR phenomenon had an effect on photoreaction enhancement. The results of photocatalytic water splitting indicated that Ag/TiO2 NTs samples had better photocatalytic performance than pure TiO2 NTs. The corresponding hydrogen evolution rate of Ag/TiO2 NTs prepared with 0.002 M AgNO3 solution was 3.3 times as that of pure TiO2 NTs in the test condition. Additionally, the mechanism of catalyst activity enhanced by SPR effect was proposed.  相似文献   

12.
Interfacial studies and band alignment engineering on the electron transport layer (ETL) play a key role for fabrication of high‐performance perovskite solar cells (PSCs). Here, an amorphous layer of SnO2 (a‐SnO2) between the TiO2 ETL and the perovskite absorber is inserted and the charge transport properties of the device are studied. The double‐layer structure of TiO2 compact layer (c‐TiO2) and a‐SnO2 ETL leads to modification of interface energetics, resulting in improved charge collection and decreased carrier recombination in PSCs. The optimized device based on a‐SnO2/c‐TiO2 ETL shows a maximum power conversion efficiency (PCE) of 21.4% as compared to 19.33% for c‐TiO2 based device. Moreover, the modified device demonstrates a maximum open‐circuit voltage (Voc) of 1.223 V with 387 mV loss in potential, which is among the highest reported value for PSCs with negligible hysteresis. The stability results show that the device on c‐TiO2/a‐SnO2 retains about 91% of its initial PCE value after 500 h light illumination, which is higher than pure c‐TiO2 (67%) based devices. Interestingly, using a‐SnO2/c‐TiO2 ETL the PCE loss was only 10% of initial value under continuous UV light illumination after 30 h, which is higher than that of c‐TiO2 based device (28% PCE loss).  相似文献   

13.
Constructing core/shell nanostructures with optimal structure and composition could maximize the solar light utilization. Here, using an Al nanocone array as a substrate, a well‐defined regular array of AZO/TiO2 core/shell nanocones with uniformly dispersed Au nanoparticles (AZO/TiO2/Au NCA) is successfully realized through three sequential steps of atomic layer deposition, physical vapor deposition, and annealing processes. By tuning the structural and compositional parameters, the advantages of light trapping and short carrier diffusion from the core/shell nanocone array, as well as the surface plasmon resonance and catalytic effects from the Au nanoparticles can be maximally utilized. Accordingly, a remarkable photoelectrochemical (PEC) performance can be acquired and the photocurrent density of the AZO/TiO2/Au NCA electrode reaches up to 1.1 mA cm?2 at 1.23 V, versus reversible hydrogen electrode (RHE) under simulated sunlight illumination, which is five times that of a flat AZO/TiO2 electrode (0.22 mA cm?2). Moreover, the photoconversion of the AZO/TiO2/Au NCA electrode approaches 0.73% at 0.21 V versus RHE, which is one of the highest values with the lowest applied bias ever reported in Au/TiO2 PEC composites. These results demonstrate a feasible route toward the scalable fabrication of well‐modulated core/shell nanostructures and can be easily applied to other metal/semiconductor composites for high‐performance PEC.  相似文献   

14.

Background

Titania dioxide (TiO2) photocatalyst is primarily induced by ultraviolet light irradiation. Visible-light responsive anion-doped TiO2 photocatalysts contain higher quantum efficiency under sunlight and can be used safely in indoor settings without exposing to biohazardous ultraviolet light. The antibacterial efficiency, however, remains to be further improved.

Methodology/Principal Findings

Using thermal reduction method, here we synthesized silver-nanostructures coated TiO2 thin films that contain a high visible-light responsive antibacterial property. Among our tested titania substrates including TiO2, carbon-doped TiO2 [TiO2 (C)] and nitrogen-doped TiO2 [TiO2 (N)], TiO2 (N) showed the best performance after silver coating. The synergistic antibacterial effect results approximately 5 log reductions of surviving bacteria of Escherichia coli, Streptococcus pyogenes, Staphylococcus aureus and Acinetobacter baumannii. Scanning electron microscope analysis indicated that crystalline silver formed unique wire-like nanostructures on TiO2 (N) substrates, while formed relatively straight and thicker rod-shaped precipitates on the other two titania materials.

Conclusion/Significance

Our results suggested that proper forms of silver on various titania materials could further influence the bactericidal property.  相似文献   

15.
Inverted organic solar cells generally exhibit a strong s‐shaped kink in the current–voltage characteristics (JV curve) that may be removed by exposure to UV light (light‐soaking) leading to a drastically improved performance. Using in‐device characterization methods the origin of the light‐soaking issue in inverted solar cells employing titanium dioxide (TiO2) as an electron selective layer is clarified. An injected hole reservoir accumulated at the TiO2/organic interface of the pristine device is observed from extraction current transients; the hole reservoir increases the recombination and results in an s‐shape in the JV curve of pristine devices. The hole reservoir and the s‐shape is a result of the energetics at the selective contact in the pristine device; the effect of UV exposure is to decrease the work function of the indium tin oxide/TiO2‐contact, increasing the built‐in potential. This hinders the build‐up of the hole reservoir and the s‐shape is removed. The proposed model is in excellent agreement with drift‐diffusion simulations.  相似文献   

16.
Here we report a simple, inexpensive, energy benign, yet novel pH-driven chemical precipitation technique to achieve microstructural and band gap engineering of calcium hydroxide nanoparticles (CHNPs). The chemical precipitation route involved the use of 0.4–1.6 M Ca(NO3)2.4H2O solutions as the precursor and 1 M NaOH solution as the precipitator. The simple variation in precursor molarity induces a pH change from about 12.4 to 11.3 in the reactant solution. The CHNPs characterized by X-ray diffraction (XRD), field emission scanning electron microscopy (FESEM), Fourier transform infrared spectroscopy (FTIR), dynamic light scattering (DLS), and ultraviolet–visible (UV–Vis) spectroscopy techniques confirm a jump of nanocrystallite size from ~50–70 nm with a concomitant reduction of direct optical band gap energy from ~5.38–5.26 eV. The possible mechanisms that could be operative behind obtaining microstructurally tuned (MT)-CHNPS and band gap engineering (BGE) are discussed from both theoretical and physical process perspectives. Furthermore, the implications of these novel results for possible futuristic applications are briefly hinted upon.  相似文献   

17.
Yolk‐like TiO2 are prepared through an asymmetric Ostwald ripening, which is simultaneously doped by nitrogen and wrapped by carbon from core to shell. It presents a high specific surface area (144.9 m2 g?1), well‐defined yolk‐like structure (600–700 nm), covered with interweaved nanosheets (3–5 nm) and tailored porosity (5–10 nm) configuration. When first utilized as anode material for sodium‐ion batteries (SIBs), it delivers a high reversible specific capacity of 242.7 mA h g?1 at 0.5 C and maintains a considerable capacity of 115.9 mA h g?1 especially at rate 20 C. Moreover, the reversible capacity can still reach 200.7 mA h g?1 after 550 cycles with full capacity retention at 1 C. Even cycled at extremely high rate 25 C, the capacity retention of 95.5% after 3000 cycles is acquired. Notably, an ultrahigh initial coulombic efficiency of 59.1% is achieved. The incorporation of nitrogen with narrowing the band gap accompanied with carbon uniformly coating from core to shell make the NC TiO2‐Y favor a bulk type conductor, resulting in fast electron transfer, which is beneficial to long‐term cycling stability and remarkable rate capability. It is of great significance to improve the energy‐storage properties through development of the bulk type conductor as anode materials in SIBs.  相似文献   

18.
Titanium dioxide (TiO2) has been extensively studied and demonstrated to be suitable to enhance the efficiency of solar cell. In this work, TiO2 is doped with silver nanoparticles (AgNP’s) on glass and the Si substrate by using Pulsed Laser Deposition (PLD) technique. UV–vis spectroscopy, X-ray diffraction (XRD), X-ray fluorescence (XRF), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Atomic Force Microscope (AFM), electrical conductivity (σ dc), Hall coefficient (RH), current–voltage (I–V), and capacity–voltage (C–V) characterizations have been used to examine the optical, the morphological, and the electrical properties of the films. It has been found that 5 wt.% (Ag) doped TiO2 thin film has the most effect on efficiency of TiO2:Ag /Si solar cell. The (I–V) characteristics showed that the (TiO2) thin film enhances the efficiency of the (p–n) junction solar cell from 1.26 % pure TiO2 to 7.19 % with doping of noble metal (Ag) representing improvement in the efficiency of solar cell leading to estimate empirical equations between efficiency, extinction coefficient, and energy band gap which have a total fit with the experimental data.  相似文献   

19.
Controversial and inconsistent results on the eco-toxicity of TiO2 nanoparticles (NPs) are commonly found in recorded studies and more experimental works are therefore warranted to elucidate the nanotoxicity and its underlying precise mechanisms. Toxicities of five types of TiO2 NPs with different particle sizes (10∼50 nm) and crystal phases were investigated using Escherichia coli as a test organism. The effect of water chemistry on the nanotoxicity was also examined. The antibacterial effects of TiO2 NPs as revealed by dose-effect experiments decreased with increasing particle size and rutile content of the TiO2 NPs. More bacteria could survive at higher solution pH (5.0–10.0) and ionic strength (50–200 mg L−1 NaCl) as affected by the anatase TiO2 NPs. The TiO2 NPs with anatase crystal structure and smaller particle size produced higher content of intracellular reactive oxygen species and malondialdehyde, in line with their greater antibacterial effect. Transmission electron microscopic observations showed the concentration buildup of the anatase TiO2 NPs especially those with smaller particle sizes on the cell surfaces, leading to membrane damage and internalization. These research results will shed new light on the understanding of ecological effects of TiO2 NPs.  相似文献   

20.
A 3D transparent conducting oxide (3D‐TCO) has been fabricated by growing Sn‐doped indium oxide (ITO) nanowire arrays on glass substrates via a vapor transport method. The 3D TCO charge‐collection properties have been compared to those of conventional two‐dimensional TCO (2D‐TCO) thin films. For use as a photoelectrode in dye‐sensitized solar cells, ITO‐TiO2 core‐shell nanowire arrays were prepared by depositing a 45 nm‐thick mesoporous TiO2 shell layer consisting of ~6 nm anatase nanoparticles using TiCl4 treatments. Dye‐sensitized solar cells fabricated using these ITO‐TiO2 core‐shell nanowire arrays show extremely fast charge collection owing to the shorter electron paths across the 45 nm‐thick TiO2 shell compared to the 2D TCO. Interestingly, the charge‐collection time does not increase with the overall electrode thickness, which is counterintuitive to conventional diffusion models. This result implies that, in principle, maximum light harvesting can be achieved without hindering the charge collection. The proposed new 3D TCO should also be attractive for other photovoltaic applications where the active layer thickness is limited by poor charge collection.  相似文献   

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