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1.
Cu/TiO2 was modified by adding Rh as co-catalyst and used as a highly efficient photocatalyst for the hydrogen evolution reaction. A low amount of Rh was loaded onto Cu/TiO2 by the deposition-precipitation with urea (DPU) method to observe the effect on the hydrogen production displayed by different samples. The Rh–Cu/TiO2 oxide structure exhibited a remarkably high photocatalytic hydrogen evolution performance, which was about twofold higher than that of the Cu/TiO2 monometallic photocatalyst. This outstanding performance was due to the efficient charge carrier transfer as well as to the delayed electron-hole recombination rate caused by the addition of Rh. The influence of the different parameters of the photocatalyst synthesis and reaction conditions on the photocatalytic activity was investigated in detail. Hydrogen evolution was studied using methanol, ethanol, 2-propanol and butanol as scavengers with an alcohol:water ratio of 20:80. The methanol-water system, which showed the highest hydrogen production, was studied under 254, 365 and 450 nm irradiation; Rh–Cu/TiO2 showed high photocatalytic activity with H2 production rates of 9260, 5500, and 1940 μmol h?1 g?1, respectively. The Cu–Rh/TiO2 photocatalyst was active under visible light irritation due to its strong light absorption in the visible region, low band gap value and ability to reduce the electron (e?) and hole (h+) recombination.  相似文献   

2.
Photocatalytic Hydrogen production via water splitting is considered a sustainable ecofriendly pathway to replenish the current and future energy demands. In this study, the self-assembly synthesis of Cu nanospheres (~8 nm) surrounded by a thin conductive layer of polyaniline (Cu@PANI) was rationally engineered via in?situ polymerization. Afterward, it was successfully deposited onto the TiO2 surface to improve the photocatalytic activities for hydrogen production. The optimal Cu@PANI/TiO2 ternary photocatalyst produced a substantial hydrogen generation rate (HGR) of 17.7 mmol h?1 g?1, 207-fold higher than that of bare TiO2. The performance was considerably improved compared with (Cu–TiO2)/PANI and (PANI-TiO2)/Cu composites prepared by changing the deposition sequence of Cu and PANI. Such an improved activity was because of multiple transferring paths of photogenerated electrons in the composite. Interestingly, the as-prepared ternary photocatalyst exhibited superior hydrogen evolution compared with the binary hybrids (Cu/TiO2 and PANI/TiO2). The exceptional performance of Cu@PANI/TiO2 could be understood considering the distinctive electrical conductivity of PANI and heterojunction formed between PANI and TiO2, as well as the merits of the Schottky junction constructed between Cu and PANI. These superior features could efficiently suppress the recombination rate of the photogenerated electron–hole pairs and maximize the photocatalytic activity. This study provides new insights for understanding the effect of electron transfer pathways on photocatalytic activities.  相似文献   

3.
In this study, TiO2 coated carbon fiber (TiO2@CF) was synthesized and used for the improvement of hydrogen (H2) evolution. Obtained results from scanning electron microscopy (SEM), X-ray diffraction (XRD), gas adsorption analysis (BET), UV–vis diffuse (UV–vis), and X-ray photoelectron spectroscopy (XPS) confirmed that the surface area and light absorption of the material was significantly improved. The synthesized TiO2@CF photocatalyst exhibited improved photocatalytic performance toward hydrogen generation. The enhancement of photocatalytic H2 evolution capacity by TiO2@CF was ascribed to its narrowed bandgap energy (2.76eV) and minimized recombination of photogenerated electron-hole pairs The hydrogen production rate by the TiO2@CF reached 3.238 mmolg?1h?1, which was 4.8 times higher than unmodified TiO2 (0.674 mmolg?1h?1). The synthesized TiO2@CF was relatively stable with no distinct reduction in photocatalytic activity after five recycling runs. The photoluminescence and photocurrent were employed to support the photocatalytic H2 production mechanism proposed mechanism.Based on these results, TiO2@CF with unique properties, easy handle, and high reusability could be suggested as an efficient strategy to develop a high-performance photocatalyst for H2 production.  相似文献   

4.
One key challenge in photocatalytic hydrogen production is how to construct high-performance photocatalyst. Covalent triazine framework (CTF) based polymers as photocatalysts show great application potential because of their good photocatalytic activity, high chemical stability, tunable electronic and optical properties, and easy synthesis process. In this paper, we designed the ternary Z-scheme heterojunction Au@TiO2-X%TrTh based on CTF polymer TrTh, TiO2 and Au nanoparticle, which exhibit higher photocatalytic hydrogen production rate compared with the corresponding binary heterojunction Au@TiO2 and TiO2-12%TrTh. The results of photocatalytic hydrogen production show that the optimized Au@TiO2-12%TrTh has a remarkable hydrogen production rate of 4288.54 μmol g?1 h?1, which is about 312.3 times of Au@TiO2 and 9.1 times of the TiO2-12%TrTh. The enhanced hydrogen production activity of the ternary heterojunction comes from the local surface plasmonic resonance effect of Au nanoparticle, lower recombination efficiency of photogenerated electron-holes pairs and Z-scheme electron transfer pathway of Au@TiO2-12%TrTh. The work provides a new strategy for designing efficient and practical photocatalyst.  相似文献   

5.
This study focused on the large band gap of TiO2 for its use as a photocatalyst under light emitting diode (LED) light irradiation. The photocatalytic activities of core–shell structured Au@TiO2 nanoparticles (NPs), nitrogen doped Au@TiO2 NPs, and Au@TiO2/rGO nanocomposites (NCs) were investigated under various light intensities and sacrificial reagents. All the materials showed better photocatalytic activity under white LED light irradiation than under blue LED light. The N-doped core–shell structured Au@TiO2 NPs (Au@N–TiO2) and Au@TiO2/rGO NCs showed enhanced photocatalytic activity with an average H2 evolution rate of 9205 μmol h?1g?1 and 9815 μmol h?1g?1, respectively. All these materials showed an increasing rate of hydrogen evolution with increasing light intensity and catalyst loading. In addition, methanol was more suitable as a sacrificial reagent than lactic acid. The rate of hydrogen evolution increased with increasing methanol concentration up to 25% in DI water and decreased at higher concentrations. Overall, Au@TiO2 core–shell-based nanocomposites can be used as an improved photocatalyst in photocatalytic hydrogen production.  相似文献   

6.
Solar-driven photocatalytic hydrogen generation by splitting water molecules requires an efficient visible light active photocatalyst. This work reports an improved hydrogen evolution activity of visible light active TiO2-x photocatalyst by introducing reduced graphene oxide via an eco-friendly and cost-effective hydrothermal method. This process facilitates graphene oxide reduction and incorporates intrinsic defects in TiO2 lattice at a one-pot reaction process. The characteristic studies reveal that RGO/TiO2-x nanocomposites were sufficiently durable and efficient for photocatalytic hydrogen generation under the visible light spectrum. The altered band gap of TiO2-x rationally promotes the visible light absorption, and the RGO sheets present in the composites suppresses the electron-hole recombination, which accelerates the charge transfer. Hence, the noble metal-free RGO/TiO2-x photocatalyst exhibited hydrogen production with a rate of 13.6 mmol h?1g?1cat. under solar illumination. The appreciable photocatalytic hydrogen generation activity of 947.2 μmol h?1g?1cat with 117 μAcm?2 photocurrent density was observed under visible light (>450 nm).  相似文献   

7.
In this work, amorphous cobalt sulfide with a sulfur-rich structure (sr-CoSx) is developed as the cocatalyst for photocatalytic hydrogen evolution. Through a facile hydrothermal reaction, sr-CoSx nanodots are in situ grown on TiO2 to obtain a heterojunction photocatalyst (sr-CoSx/TiO2). The as-prepared photocatalyst exhibits remarkable improved hydrogen evolution performance compared with TiO2. Under the irradiation of xenon lamp, the hydrogen evolution rate of sr-CoSx/TiO2 can reach 507 μmol h?1 g?1, which is about 121 times that of pristine TiO2, indicating that sr-CoSx is a highly efficient cocatalyst to promote hydrogen evolution on TiO2. Moreover, sr-CoSx/TiO2 exhibits better performance than crystalline CoS2 or amorphous CoS modified TiO2, suggesting the important role of sulfur-rich structure and amorphous state in promoting the cocatalytic effect. Electrochemical and photoluminescence measurements show the most efficient carrier separation between sr-CoSx and TiO2, which also contributes to its high photocatalytic hydrogen evolution performance.  相似文献   

8.
Developing appropriate photocatalyst with high efficiency is still the basic strategy for practical application of emerging technology. Herein, non-noble metal copper (Cu) nanoparticles were in situ hybrided with TiO2 by a chemical reduction method. The crystal phase and structure were characterized by XRD, SEM, and TEM measurements. Hydrogen production results showed that Cu nanoparticles significantly improved the photocatalytic hydrogen production rate. The hydrogen production rate was as high as 24160.69 μmol g?1 h?1 at 100 °C, which was 36.25 and 8.46 times higher than the hydrogen production rates of pure TiO2 and 0.13 wt% Cu/TiO2 at room temperature, respectively. PL spectra, UV–vis spectra, IR images and photoelectrochemical measurements showed that the plasma-induced photothermal effect of Cu/TiO2 nanoparticles, which raised the temperature of the reaction system and promoted photothermal catalytic performance. Briefly, this work provides a facile fabrication method of noble-metal-free photocatalysts featuring in low-cost and high efficiency. In the future, coupling the photothermal effect of plasmonic Cu to further speed up the kinetics should be another promising research direction for further improving hydrogen production.  相似文献   

9.
An effective improvement of hydrogen evolution from water splitting under solar light irradiation was investigated using quantum dots (QDs) compounds loaded onto a Au/TiO2 photocatalyst. First, Au/TiO2 was prepared by the deposition-precipitation method, and then sulfide QDs were loaded onto the as-prepared Au/TiO2 by a hydrothermal method. QDs were loaded onto Au/TiO2 to enhance the energy capture of visible light and near-infrared light of the solar spectrum. The results indicated that the as-prepared heterojunction photocatalysts absorbed the energy from the range of ultraviolet light to the near-infrared light region and effectively reduced the electron-hole pair recombination during the photocatalytic reaction. Using a hydrothermal temperature of 120 °C, the as-prepared (ZnS–PbS)/Au/TiO2 photocatalyst had a PbS QDs particle size of 5 nm, exhibited an energy gap of 0.92 eV, and demonstrated the best hydrogen production rate. Additionally, after adding 20 wt % methanol as a sacrificial reagent to photocatalyze for 5 h, the hydrogen production rate reached 5011 μmol g−1 h−1.  相似文献   

10.
Direct Z-scheme Bi2WO6/TiO2 heterojunction photocatalyst was prepared by one-step solvothermal method. The catalyst was characterized by XRD, TEM, XPS, UV–Vis DRS, photoluminescence spectroscopy and photoelectrochemical studies. The photocatalytic hydrogen production experiments show that Bi2WO6 did not generate H2 and the H2-production rate of TiO2 is only 0.1 mmol⋅g−1h−1. The hydrogen production rate of the Bi2WO6/TiO2 heterojunction photocatalyst reaches 12.9 mmol⋅g−1h−1, which is 129 times that of TiO2. Compared with TiO2, the enhanced H2-production activity of the heterojunction catalyst can be attributed to the wider light absorption range and the efficient separation and migration of carriers at the close contact interface between Bi2WO6 and TiO2. Based on the work functions of Bi2WO6, TiO2 and their heterojunctions, combined with the results of electron paramagnetic resonance spectroscopy and Mott-Schottky measurements, the photocatalytic H2 production mechanism of Z-scheme heterojunction Bi2WO6/TiO2 was proposed. This work provides an easy and simple way to design a binary Z-scheme photocatalyst with efficient catalytic H2-production activity without electron mediators.  相似文献   

11.
Spent catalysts of selective catalytic reduction (SCR) contain a high content of TiO2 (>70 wt%). The effective recovery of TiO2 from spent SCR catalysts and its reuse in photocatalytic hydrogen production is of great importance for environmental protection. In this study, the recovered TiO2 from the spent SCR catalyst was recovered by the alkali washing method, and the purity of the recovered TiO2 reached 94.7%. g-C3N4 as a co-catalyst and enhanced the separation efficiency of the photogenerated electron-hole pairs of the TiO2 photocatalyst. The composite photocatalyst R–TiO2/g-C3N4 prepared by directly mixing the recovered TiO2 with g-C3N4 significantly improved the photocatalytic activity. The experimental design of the photocatalyst synthesis was optimized using the Design Expert software. The results showed that the recovered TiO2 was 0.334 g when the g-C3N4 was 0.046 g and the ultrasonic time was 163 min. Moreover, the hydrogen production rate reached 443.105 μmol g−1 h−1 within 4 h.  相似文献   

12.
The exploitation of noble-metal-free photocatalysts with high solar-to-H2 conversion efficiency is a hot topic in the photocatalysis field. Molybdenum sulfide materials, which have good physicochemical properties and excellent hydrogen evolution activity, have become an effective noble metal cocatalyst substitute and attracted widespread attention. In this work, a highly efficient photocatalyst constructed by decorating thiomolybdate [Mo2S12]2- nanoclusters on TiO2 is reported for the first time. The resultant [Mo2S12]2-/TiO2 photocatalyst shows a remarkable enhanced hydrogen evolution rate under the Xenon light irradiation. At the optimal loading amount of [Mo2S12]2-, the photocatalyst exhibits a photocatalytic hydrogen evolution rate of 213.1 μmol h?1 g?1, which is about 51 times that of the pure TiO2. Characterization results show that the intimate contact between [Mo2S12]2- and TiO2 promotes the separation of hole-electron pairs, prolongs the lifetime of carriers, and thereby increases the photocatalytic activity. Furthermore, abundant bridging S in the [Mo2S12]2- acts as active sites for hydrogen evolution, which also contributes to the enhanced hydrogen production rate. This work demonstrates an efficient way for the construction of noble-metal-free hydrogen evolution photocatalyst and provides a useful reference for the development of low cost photocatalysts in the future.  相似文献   

13.
Constructing heterostructures with efficient charge separation is a promising route to improve photocatalytic hydrogen production. In this paper, MoSx/CdS/KTaO3 ternary heterojunction photocatalysts were successfully prepared by a two-step method (hydrothermal method and photo deposition method), which improved the photocatalytic hydrogen evolution activity. The results show that the rate of hydrogen evolution for the optimized photocatalyst is 2.697 mmol g?1·h?1under visible light, which is 17 times and 2.6 times of the original CdS (0.159 mmol g?1 h?1) and the optimal CdS/KTaO3(1.033 mmol g?1 h?1), respectively, and the ternary photocatalyst also shows good stability. The improvement on photocatalytic hydrogen evolution performance can be attributed to the formation of heterojunction between the prepared composite materials, which effectively promotes the separation and migration of photo-generated carriers. Amorphous MoSx acts as an electron trap to capture photogenerated electrons, providing active sites for proton reduction. This provides beneficial enlightenment for hydrogen production by efficiently utilizing sunlight to decompose water.  相似文献   

14.
In this study, we developed a polystyrene-platinum/nitrogen-doped titanium dioxide/strontium titanate composite-polyvinylpyrrolidone (PS-PNS-PVP) photocatalyst film, which is applied in the process of photocatalytic hydrolysis under simulated sunlight to produce hydrogen, is developed. PS, which is cheap, non-toxic, with high UV resistance, and chemical inertness, is used as a carrier, and a highly effective hydrogen production of Pt/N–TiO2/SrTiO3 as a photocatalyst. The influence of the PS concentration on the stability, optical, and electrical properties of the photocatalyst film is discussed. In addition, the influence of the photocatalyst dispersion in the film on the activity under various photocatalyst concentrations was investigated. A polyvinylpyrrolidone pore-forming agent was then used to examine the effect on the photocatalyst film structure and optical properties, and the subsequent influence on photocatalytic hydrogen energy activity. Adjusting the PS concentration to 20 wt% produced good film-forming stability, and the photocatalyst dispersibility in the film under different photocatalyst concentrations. A photocatalyst concentration of 2.5 wt% resulted in good film dispersibility and the realization of added pore-forming agent. The modified photocatalyst film changed the film from a blind pore structure to a connecting void structure, increasing the film's porosity and hydrophilicity. This increased the number of photocatalytic sites, and the optimal hydrogen production of the photocatalyst film reached 21,333 μmol h?1 g?1.  相似文献   

15.
Photocatalytic hydrogen production under the visible spectrum of solar light is an important topic of research. To achieve the targeted visible light hydrogen production and improve the charge carrier utilization, bandgap engineering and surface modification of the photocatalyst plays a vital role. Present work reports the one-pot synthesis of Cu–TiO2/CuO nanocomposite photocatalyst using green surfactant -aided -ultrasonication method. The materials characterization data reveals the TiO2 particle size of 20–25 nm and the existence of copper in the lattice as well as in the surface of anatase TiO2. This is expected to facilitate better optical and surface properties. The optimized photocatalyst shows enhanced H2 production rate of 10,453 μmol h−1 g−1 of the catalyst which is 21 fold higher than pure TiO2 nanoparticles. The photocatalyst was tested for degradation of methylene blue dye (90% in 4 h) in aqueous solution and photocatalytic reduction of toxic Cr6+ ions (55% in 4 h) in aqueous solution. A plausible mechanistic pathway is also proposed.  相似文献   

16.
A series of Au/TiO2 photocatalysts was synthesized via the light assistance through the photo-deposition for H2 production by photocatalytic water splitting using ethanol as the hole scavenger. Effect of solution pH in the range of 3.2–10.0 on the morphology and photocatalytic activity for H2 production of the obtained Au/TiO2 photocatalysts was explored. It was found that all Au/TiO2 photocatalysts prepared in different solution pH exhibited comparable anatase fraction (~0.84–0.85) and crystallite size of TiO2 (21–22 nm), but showed different quantity of deposited Au nanoparticles (NPs) and other properties, particularly the particle size of the Au NPs. Among all prepared Au/TiO2 photocatalysts, the Au/TiO2 (10.0) photocatalyst exhibited the highest photocatalytic activity for H2 production, owning to its high metallic state and small size of Au NPs. Via this photocatalyst, the maximum H2 production of 296 μmol (~360 μmol/g?h) was gained at 240 min using the 30 vol% ethanol as the hole scavenger at the photocatalyst loading of 1.33 g/L under the UV light intensity of 0.24 mW/cm2 with the quantum efficiency of 61.2% at 254 nm. The loss of the photocatalytic activity of around 20% was observed after the 5th use.  相似文献   

17.
Nano TiO2 prepared by a hydrothermal method and silver-loaded nano TiO2 prepared by impregnation were studied for the photocatalytic production of hydrogen from glycerol:water mixtures. The structural characteristics were revealed using XRD, EDAX, DRS, TEM, XPS, BET surface area and Raman techniques. The photocatalytic hydrogen production has been investigated under solar light irradiation. Effects of nano TiO2 calcination temperature, silver loading, photocatalyst content, light source and Ag oxidation state on hydrogen production have been systematically studied. Maximum hydrogen production of 200 μmol h?1 g?1 is observed on 4wt% silver-loaded nano TiO2 catalyst in pure water and the maximum hydrogen production of 7030 μmol h?1 g?1 is observed on 3wt% silver-loaded nano TiO2 catalyst in glycerol: water mixtures. Silver-loaded nano TiO2 reduced and photodeposited catalysts show similar hydrogen production activities in glycerol: water mixtures under solar irradiation. The optimum catalyst modified with conducting carbon materials (graphene oxide, graphene, carbon nanotubes) by a solid-state dispersion method were also studied for hydrogen production under solar light irradiation. Compared with pure nano TiO2, a 3wt% silver-loaded nano TiO2/graphene composite exhibited an approximately 17-fold enhancement of hydrogen production leading to hydrogen production rates of 12,100 μmol h?1 g?1. Based on the characterization results and hydrogen production activity on these catalysts, a structure–activity correlation has been proposed wherein the interacting Ag2OAg phases on the surface of nano TiO2 play an important role in maintaining a high hydrogen production activity under solar irradiation.  相似文献   

18.
Photocatalysis is an effective way to utilize solar energy to produce hydrogen from water. Au/TiO2 nanoparticles (NPs) have a better performance in photocatalytic hydrogen generation because of the localized surface plasmon resonance (LSPR) effect of Au/TiO2 NPs. In the photocatalytic hydrogen generation experiments, it was found that light intensity plays a key role in the photocatalytic reaction rate of Au/TiO2 NPs. At a light intensity of 0–7 kW/m2, the reaction rate has a super-linear law dependence on the light intensity (Rate ∝ Intensityn, with n > 1). However, at a light intensity of 7–9 kW/m2, the dependency becomes sub-linear (n < 1). This means that the increase rate of photocatalytic rate is smaller than that of light intensity when the light intensity exceeds 7 kW/m2. In addition, the finite element method (FEM) was utilized to further elucidate the role of light intensity by calculating the absorption power and nearfield intensity mapping of a Au/TiO2 nanoparticle. The variation trend of the calculated total absorption power agrees with the photocatalytic experimental results for different light intensities. These results shed light on the utilization of concentrated solar photocatalysis to increase the solar-to-hydrogen performance of Au/TiO2 NPs.  相似文献   

19.
A TiO2 nanotube-based nanoreactor was designed and fabricated by facile two steps synthesis: firstly, hydrothermal synthesized SrTiO3 was deposited on TiO2 nanotubes (TiO2NTs). Secondly, the Au nanoparticles (NPs) were encapsulated inside the TiO2NTs followed by vacuum-assisted impregnation. The as-synthesized composites were characterized using Transmission electron microscopy (TEM), X-ray powder diffraction (XRD), X-ray photoelectron spectroscopy (XPS), Photoluminescence spectra (PL) and Ultraviolet–visible absorption spectroscopy (UV–vis). The photocatalytic performance was evaluated by the hydrogen evolution reaction. The results revealed that the SrTiO3 modified TiO2NTs confined Au NPs (STO-TiO2NTs@Au) achieved an enhanced hydrogen evolution rate at 7200 μmol h−1 g−1, which was 2.2 times higher than that of bald TiO2NTs@Au at 3300 μmol h−1 g−1. The improved photocatalytic activity could be attributed to the synergistic effect of the electron-donating of SrTiO3 and TiO2NTs confinement. The as-designed nanoreactor structure provides an example of efficient carriers' separation photocatalyst.  相似文献   

20.
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   

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