CN111790367A - TiO 22Preparation method of/ZnO heterogeneous nanofiber high-efficiency photocatalyst - Google Patents
TiO 22Preparation method of/ZnO heterogeneous nanofiber high-efficiency photocatalyst Download PDFInfo
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 85
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 53
- 238000000034 method Methods 0.000 title description 7
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 51
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 37
- 239000000463 material Substances 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 16
- 238000010041 electrostatic spinning Methods 0.000 claims abstract description 9
- 238000000231 atomic layer deposition Methods 0.000 claims abstract description 8
- 238000000151 deposition Methods 0.000 claims abstract description 8
- 230000008021 deposition Effects 0.000 claims abstract description 8
- 239000002994 raw material Substances 0.000 claims abstract description 5
- 239000000203 mixture Substances 0.000 claims abstract description 4
- HQWPLXHWEZZGKY-UHFFFAOYSA-N diethylzinc Chemical compound CC[Zn]CC HQWPLXHWEZZGKY-UHFFFAOYSA-N 0.000 claims abstract description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 14
- 229910052739 hydrogen Inorganic materials 0.000 claims description 14
- 239000001257 hydrogen Substances 0.000 claims description 14
- 238000004519 manufacturing process Methods 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 14
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 9
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 9
- 239000000835 fiber Substances 0.000 claims description 7
- 238000009987 spinning Methods 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- 238000005516 engineering process Methods 0.000 claims description 5
- APQHKWPGGHMYKJ-UHFFFAOYSA-N Tributyltin oxide Chemical compound CCCC[Sn](CCCC)(CCCC)O[Sn](CCCC)(CCCC)CCCC APQHKWPGGHMYKJ-UHFFFAOYSA-N 0.000 claims description 4
- 229960000583 acetic acid Drugs 0.000 claims description 4
- 239000013078 crystal Substances 0.000 claims description 4
- 239000007787 solid Substances 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 3
- 239000012362 glacial acetic acid Substances 0.000 claims description 3
- 238000006303 photolysis reaction Methods 0.000 claims description 3
- 230000015843 photosynthesis, light reaction Effects 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- YHWCPXVTRSHPNY-UHFFFAOYSA-N butan-1-olate;titanium(4+) Chemical compound [Ti+4].CCCC[O-].CCCC[O-].CCCC[O-].CCCC[O-] YHWCPXVTRSHPNY-UHFFFAOYSA-N 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 229910052950 sphalerite Inorganic materials 0.000 claims description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 239000004065 semiconductor Substances 0.000 abstract description 7
- 230000006798 recombination Effects 0.000 abstract description 3
- 238000005215 recombination Methods 0.000 abstract description 3
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 238000011161 development Methods 0.000 description 5
- 238000011160 research Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- NQTSTBMCCAVWOS-UHFFFAOYSA-N 1-dimethoxyphosphoryl-3-phenoxypropan-2-one Chemical compound COP(=O)(OC)CC(=O)COC1=CC=CC=C1 NQTSTBMCCAVWOS-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- FPCJKVGGYOAWIZ-UHFFFAOYSA-N butan-1-ol;titanium Chemical compound [Ti].CCCCO.CCCCO.CCCCO.CCCCO FPCJKVGGYOAWIZ-UHFFFAOYSA-N 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 238000005245 sintering Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 238000000101 transmission high energy electron diffraction Methods 0.000 description 2
- 229910052724 xenon Inorganic materials 0.000 description 2
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
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- 238000005859 coupling reaction Methods 0.000 description 1
- 238000009795 derivation Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000012153 distilled water Substances 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000002524 electron diffraction data Methods 0.000 description 1
- 238000001523 electrospinning Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052755 nonmetal Inorganic materials 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- WGPCGCOKHWGKJJ-UHFFFAOYSA-N sulfanylidenezinc Chemical compound [Zn]=S WGPCGCOKHWGKJJ-UHFFFAOYSA-N 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 1
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/06—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of zinc, cadmium or mercury
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/02—Processes for making hydrogen or synthesis gas
- C01B2203/0266—Processes for making hydrogen or synthesis gas containing a decomposition step
- C01B2203/0277—Processes for making hydrogen or synthesis gas containing a decomposition step containing a catalytic decomposition step
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- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
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Abstract
The invention belongs to the field of photocatalyst preparation, and particularly relates to TiO2A preparation method of a ZnO heterogeneous nanofiber high-efficiency photocatalyst. The preparation method comprises the following steps: 1) preparing TiO by electrostatic spinning2A nanofiber; 2) adding TiO into the mixture2The nano-fiber is placed in an atomic layer deposition system, and the ZnO grows layer by layer after deposition circulation by using diethyl zinc and water as raw materials to obtain ZnO modified TiO2Heterogeneous nanofiber high-efficiency photocatalyst materials. TiO prepared by the invention2the/ZnO heterogeneous nanofiber photocatalyst has a one-dimensional nanofiber structure with a high specific surface, and the photocatalyst compounded by two semiconductors can effectively inhibit the recombination of photo-generated electron-hole pairs and synergistically enhance the photocatalytic performance.
Description
Technical Field
The invention belongs to the field of photocatalyst preparation, and particularly relates to TiO2A preparation method of a ZnO heterogeneous nanofiber high-efficiency photocatalyst.
Background
With the rapid development of modern industry, the problems of energy crisis and environmental pollution are increasingly aggravated, and the development and utilization of clean and efficient energy become urgent. Solar energy is inexhaustible as renewable clean energy, and how to effectively utilize the solar energy becomes a hotspot of current research. The photocatalysis technology has the advantages of directly absorbing solar energy at room temperature to drive reaction and the like, and becomes an ideal production technology for directly or indirectly converting the solar energy into human available energy. The core of the application of photocatalytic technology lies in the development of photocatalysts, and hundreds of photocatalysts have been reported in the development of the past decades. However, the problems of narrow photoresponse wavelength, poor stability, low efficiency and the like of the currently reported photocatalyst generally exist, and the large-scale use of the photocatalyst is severely restricted. Therefore, the development of high-efficiency photocatalyst is hard and far.
In order to solve the problems of the photocatalyst, researchers have conducted a great deal of research and summarize the research mainly from the aspects of material structure, component optimization and the like. The optimization of the material structure mainly refers to changing the microscopic morphological characteristics of the catalyst, so that the catalyst has high specific surface area and stable geometric structure, and the capture rate of light and the adsorption capacity of reactants are improved. Research finds that the one-dimensional nanofiber structure endows high-efficiency and stable photocatalytic activity due to the unique geometric structure and high specific surface area. The component optimization reduces the forbidden band width, prolongs the service life of a photon-generated carrier and the like by changing the energy band structure. Mainly comprises non-metal element doping, semiconductor compounding, noble metal loading and the like. The coupling of different semiconductor materials can effectively retard the recombination of photon-generated carriers, and the utilization rate of solar energy is enhanced. TiO 22The semiconductor photocatalyst material is most representative of ZnO, and the literature reports that the semiconductor photocatalyst material isThey have been worked on as either a single or two of the composite semiconductor photocatalysts, but with a nanofibrous structure of TiO2No report is found on the/ZnO composite photocatalyst material.
Disclosure of Invention
The invention aims to solve the technical problems of low solar energy utilization rate, low photocatalytic efficiency and the like of the traditional photocatalyst and provides TiO2Preparation method of/ZnO heterogeneous nanofiber high-efficiency photocatalyst and prepared TiO2the/ZnO heterogeneous nanofiber visible light photocatalyst has a high specific surface area, and can efficiently decompose water to produce hydrogen under the irradiation of simulated sunlight.
The above object of the present invention is achieved by the following scheme: TiO 22The preparation method of the ZnO heterogeneous nanofiber high-efficiency photocatalyst comprises the following steps:
1) preparing TiO by electrostatic spinning2A nanofiber;
2) adding TiO into the mixture2The nano-fiber is placed in an atomic layer deposition system, and the ZnO grows layer by layer after deposition circulation by using diethyl zinc and water as raw materials to obtain ZnO modified TiO2Heterogeneous nanofiber high-efficiency photocatalyst materials.
The invention modifies TiO by ZnO2The heterogeneous nanofiber is used for preparing the nanofiber photocatalyst with a one-dimensional structure, the catalyst can simultaneously strengthen the photocatalytic performance of the catalyst from two directions, and the problems of poor stability, low efficiency and the like of the conventional photocatalyst are solved. In the above TiO2In the preparation method of the/ZnO heterogeneous nanofiber high-efficiency photocatalyst, the cycle times in the atomic layer deposition technology are 50-200. Too many cycles result in too thick ZnO being deposited, preventing absorption of light and thus reduced photocatalytic performance, whereas too little deposition results in insufficient interfacial charge transfer capability and reduced photocatalytic performance.
In the above TiO2In the preparation method of the/ZnO heterogeneous nanofiber high-efficiency photocatalyst, TiO is prepared by electrostatic spinning2The nanofiber specifically comprises the following steps:
taking polyvinylpyrrolidone (PVP) and tetrabutyl titanate (TBOT) as raw materials, and absolute ethyl alcohol and glacial acetic acid as solvents to form a precursor spinning solution;
performing electrostatic spinning on the precursor spinning solution to obtain solid precursor fiber;
calcining solid precursor fiber to TiO at high temperature2And (3) nano fibers.
Preferably, the precursor dope is prepared by adding 3 to 6g of butyl titanate to 1g of PVP.
Preferably, the volume ratio of the absolute ethyl alcohol to the glacial acetic acid is 2-3:1 when the precursor spinning solution is prepared.
Preferably, the distance between the anode and the cathode in the electrostatic spinning is 12cm-18cm, and the high voltage is 15kV-20 kV.
Preferably, the drying temperature is 50-70 ℃.
Preferably, the high-temperature calcination temperature is 480-520 ℃, the heat preservation time is 1-3h, and the temperature rise speed is 0.5-3 ℃/min.
In the above TiO2TiO prepared in preparation method of/ZnO heterogeneous nanofiber high-efficiency photocatalyst2the/ZnO heterogeneous nano-fiber high-efficiency photocatalyst is of a one-dimensional nano-fiber structure and is prepared from TiO2And ZnO.
In the above TiO2TiO prepared in preparation method of/ZnO heterogeneous nanofiber high-efficiency photocatalyst2The crystal form of (A) is mainly anatase phase, and the crystal form of ZnO is sphalerite phase.
In the above TiO2In the preparation method of the ZnO heterogeneous nanofiber high-efficiency photocatalyst, the atomic percentages of Zn, O and Ti are respectively 3.05 to 7.45 at.%, 58.49 to 69.49 at.% and 23.06 to 38.46 at.%.
The invention also provides the TiO2The application of the/ZnO heterogeneous nanofiber high-efficiency photocatalyst is applied to hydrogen production by photolysis of water.
TiO2The application of the/ZnO heterogeneous nanofiber high-efficiency photocatalyst in the high-efficiency photocatalyst is to use TiO2The ZnO heterogeneous nanofiber high-efficiency photocatalyst is dispersed in a decomposed substance to perform catalytic reaction under the irradiation of light, wherein the decomposed substance is a water-containing substance (the water-containing substance can be water, salt-containing water and other substances containing water and salt)A substance having a proper amount of water, that is, the aqueous substance contains the nanofibers which exist in the form of liquid water and are capable of dispersing the catalyst in the liquid water).
The light source used for hydrogen production by water photolysis is a xenon lamp light source.
Compared with the prior art, the invention has the following effects:
1. the invention realizes TiO2Preparing a ZnO heterogeneous nanofiber high-efficiency photocatalyst;
2.TiO2the/ZnO heterogeneous nanofiber photocatalyst has a one-dimensional nanofiber structure with a high specific surface, and the photocatalyst compounded by two semiconductors can effectively inhibit the recombination of photo-generated electron-hole pairs and synergistically enhance the photocatalytic performance;
3.TiO2the/ZnO heterogeneous nanofiber photocatalyst has enhanced charge separation efficiency, high solar energy utilization rate and better application prospect in the aspects of solving the environmental problems and energy crisis.
Drawings
FIG. 1 shows TiO prepared in example 1 of the present invention2Scanning Electron Microscope (SEM) microscopic image of nanofibers;
FIG. 2 shows TiO prepared in example 1 of the present invention2High power Scanning Electron Microscope (SEM) images of nanofibers;
FIG. 3 shows TiO prepared in example 1 of the present invention2An X-ray diffraction (XRD) pattern of the nanofibers;
FIG. 4 shows TiO prepared in example 1 of the present invention2Low power Scanning Electron Microscope (SEM) image of/ZnO heterogeneous nano fiber;
FIG. 5 shows TiO prepared in example 1 of the present invention2High power Scanning Electron Microscope (SEM) image of/ZnO heterogeneous nanofiber;
FIG. 6 shows TiO prepared in example 1 of the present invention2X-ray diffraction (XRD) pattern of/ZnO heterogeneous nanofibers;
FIG. 7 shows TiO prepared in example 1 of the present invention2Transmission Electron Microscopy (TEM) image of/ZnO heterogeneous nanofibers;
FIG. 8 shows TiO prepared in example 1 of the present invention2Selective electronic derivation of/ZnO heterogeneous nano-fiberA radiographic (SAED) map;
FIG. 9 shows TiO prepared in example 1 of the present invention2High Resolution Transmission Electron Microscopy (HRTEM) images of/ZnO heterogeneous nanofibers;
FIG. 10 shows TiO prepared in example 1 of the present invention2Magnified High Resolution Transmission Electron Microscopy (HRTEM) images of/ZnO heterogeneous nanofibers;
FIG. 11 shows TiO prepared in example 1 of the present invention2Magnified High Resolution Transmission Electron Microscopy (HRTEM) images of/ZnO heterogeneous nanofibers;
FIG. 12 shows TiO prepared in example 1 of the present invention2Energy spectrum (EDS) diagram of/ZnO heterogeneous nanofiber;
FIG. 13 shows TiO prepared in example 1 of the present invention2Nano-fiber, TiO of different atomic layer deposition times2A graph comparing efficiency of a graph of the change of the photocatalytic hydrogen production amount of the ZnO heterogeneous nanofiber material along with illumination time;
FIG. 14 shows TiO prepared in example 1 of the present invention2Nano-fiber, TiO of different atomic layer deposition times2Comparison graph of photocatalytic hydrogen production efficiency of ZnO heterogeneous nanofiber material.
Detailed Description
The following are specific embodiments of the present invention and are further described with reference to the accompanying drawings, but the present invention is not limited to these embodiments.
Example 1
Dissolving 0.7g of polyvinylpyrrolidone (PVP) in a mixed solvent of 7ml of ethanol and 3ml of acetic acid, magnetically stirring for 6 hours to obtain a uniform PVP solution, slowly dropwise adding 3ml of butyl titanate (TBOT), and continuously strongly stirring for 2 hours to obtain a PVP/TBOT precursor spinning solution. Spinning under the electrospinning condition with the voltage of 18kV and the distance of 15cm to obtain precursor fiber, and drying by a constant-temperature oven at 60 ℃ to obtain the cured precursor fiber. Placing the prepared precursor fiber in a muffle sintering procedure furnace for calcination treatment, wherein the sintering temperature is 500 ℃, the heating rate is 1 ℃/min, the heat preservation time is 2h, and cooling to the room temperature along with the furnace to obtain TiO2And (5) storing the nano fibers for later use. FIGS. 1 and 2 show the preparation of TiO2The nano-fibers are arranged at different positionsSEM pictures under large times show that the prepared material is a high-purity nanofiber material. FIG. 3 is the corresponding X-ray diffraction pattern showing that the produced nanofibers are anatase TiO2A material.
0.5g of the prepared TiO was taken2The nano-fiber is placed in an atomic layer deposition system, and after 150 circulation times, the nano-fiber is placed in TiO2Wrapping ZnO with a certain thickness on the surface of the nanofiber to obtain TiO2A/ZnO heterogeneous nanofiber photocatalyst. The TiO prepared in this example2Scanning Electron Microscopy (SEM) is carried out on the/ZnO heterogeneous nano-fibers under different magnifications, and the results are shown in figures 4 and 5, which shows that the prepared material is still high-purity nano-fibers. FIG. 6 is the corresponding X-ray diffraction pattern (XRD) showing that the produced nanofibers are TiO2A/ZnO composite material. FIG. 7 shows the TiO thus prepared2TEM picture of/ZnO heterogeneous nanofiber, again illustrating the material as a typical one-dimensional nanofiber structure. FIG. 9 is a High Resolution Transmission Electron Micrograph (HRTEM) of the nanofiber, again demonstrating the ZnO and TiO interaction2And (4) forming. FIG. 10 is the corresponding selected electron diffraction pattern (SAED) demonstrating that the nanofibers are composed of ZnO and TiO2Polycrystalline structure of the composition. FIG. 10 shows the prepared TiO2TiO in/ZnO heterogeneous nano fiber2The corresponding magnified high resolution transmission electron microscope photo confirms TiO2Is anatase phase. FIG. 11 shows the TiO thus prepared2The magnified high-resolution transmission electron microscope photo corresponding to ZnO in the ZnO heterogeneous nano fiber proves that ZnO is a zinc blende phase. Fig. 12 is its corresponding Element Distribution Spectroscopy (EDS) graph, illustrating that the material consists of three elements, Ti, O and Zn, oti, in atomic percentages of 4.32 at.%, 66.84 at.% and 28.84 at.%, respectively.
0.01g of the prepared catalyst is weighed and dispersed in 40ml of distilled water, after ultrasonic dispersion is carried out for 15min, 10ml of methanol is added as a sacrificial agent, a 300W xenon lamp is used as a simulated sunlight source, the generated hydrogen is detected by an online gas chromatograph once every 30min, and the test is finished after 6 hours.
Example 2
Only the deposition cycle of the ZnO layer is 50 times different from that of example 1, and other processes are the same as those of example 1 and are not described herein again.
Example 3
Only the deposition cycle of the ZnO layer is 100 times different from that of embodiment 1, and other processes are the same as those of embodiment 1 and are not described herein again.
Example 4
Only the deposition cycle of the ZnO layer is 200 times different from that of embodiment 1, and other processes are the same as those of embodiment 1 and are not described herein again.
Comparative example
The nanofibers produced according to the method of example 1 were anatase TiO2A material. I.e. the comparative example does not deposit ZnO.
The hydrogen production test results of the catalysts prepared in examples 1 to 4 and in the comparative example are shown in fig. 13, and fig. 13 is a graph showing the hydrogen production as a function of the light irradiation time, with the surface hydrogen production increasing linearly with the increase in time. FIG. 14 is a graph comparing hydrogen production efficiencies of different photocatalysts, illustrating TiO prepared2The ZnO heterogeneous nano fiber has obviously improved photocatalytic performance, and the hydrogen production efficiency can reach 1190.9 mu mol g-1h-1Phase contrast pure phase TiO2The hydrogen production efficiency is improved by more than 6.5 times. As can be seen from fig. 13 and 14, the catalyst produced when the deposition cycle was 150 times had the best hydrogen production efficiency.
The technical scope of the invention claimed by the embodiments herein is not exhaustive and new solutions formed by equivalent replacement of single or multiple technical features in the embodiments are also within the scope of the invention, and all parameters involved in the solutions of the invention do not have mutually exclusive combinations if not specifically stated.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
While the invention has been described in detail and with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (9)
1. TiO 22The preparation method of the/ZnO heterogeneous nanofiber high-efficiency photocatalyst is characterized by comprising the following steps:
1) preparing TiO by electrostatic spinning2A nanofiber;
2) adding TiO into the mixture2The nano-fiber is placed in an atomic layer deposition system, and the ZnO grows layer by layer after deposition circulation by using diethyl zinc and water as raw materials to obtain ZnO modified TiO2Heterogeneous nanofiber high-efficiency photocatalyst materials.
2. The TiO of claim 12The preparation method of the/ZnO heterogeneous nanofiber high-efficiency photocatalyst is characterized in that the cycle times in the atomic layer deposition technology are 50-200.
3. The TiO of claim 12The preparation method of the/ZnO heterogeneous nanofiber high-efficiency photocatalyst is characterized in that TiO is prepared by electrostatic spinning2The nanofiber specifically comprises the following steps:
taking polyvinylpyrrolidone (PVP) and tetrabutyl titanate (TBOT) as raw materials, and absolute ethyl alcohol and glacial acetic acid as solvents to form a precursor spinning solution;
performing electrostatic spinning on the precursor spinning solution to obtain solid precursor fiber;
calcining solid precursor fiber to TiO at high temperature2And (3) nano fibers.
4. The TiO of claim 32The preparation method of the/ZnO heterogeneous nanofiber high-efficiency photocatalyst is characterized in that the distance between an anode and a cathode in electrostatic spinning is 12cm-18cm, and the high voltage is 15kV-20 kV.
5. According to the claimsThe TiO described in claim 32The preparation method of the/ZnO heterogeneous nanofiber high-efficiency photocatalyst is characterized in that the high-temperature calcination temperature is 480-520 ℃, the heat preservation time is 1-3h, and the temperature rise speed is 0.5-3 ℃/min.
6. TiO produced by the production method according to claim 12the/ZnO heterogeneous nano-fiber high-efficiency photocatalyst is characterized in that the TiO is2the/ZnO heterogeneous nano-fiber high-efficiency photocatalyst is of a one-dimensional nano-fiber structure and is prepared from TiO2And ZnO.
7. The TiO of claim 62the/ZnO heterogeneous nano-fiber high-efficiency photocatalyst is characterized in that TiO is2The crystal form of (A) is mainly anatase phase, and the crystal form of ZnO is sphalerite phase.
8. TiO according to claim 6 or 72The ZnO heterogeneous nanofiber high-efficiency photocatalyst is characterized in that the atomic percentages of Zn, O and Ti in the catalyst are respectively 3.05-7.45 at.%, 58.49-69.49 at.% and 23.06-38.46 at.%.
9. The TiO of claim 62The application of the/ZnO heterogeneous nanofiber high-efficiency photocatalyst is characterized by being applied to hydrogen production through water photolysis.
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