CN111905768A - MoS2/MoO3/TiO2Composite photocatalytic material and preparation method and application thereof - Google Patents
MoS2/MoO3/TiO2Composite photocatalytic material and preparation method and application thereof Download PDFInfo
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- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 title claims abstract description 145
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 53
- 229910052961 molybdenite Inorganic materials 0.000 title claims abstract description 49
- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 49
- 239000000463 material Substances 0.000 title claims abstract description 47
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000010438 heat treatment Methods 0.000 claims abstract description 76
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims abstract description 67
- 239000002131 composite material Substances 0.000 claims abstract description 63
- 239000000843 powder Substances 0.000 claims abstract description 39
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000013078 crystal Substances 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 13
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 claims abstract description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 5
- 239000010453 quartz Substances 0.000 claims description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- 239000012298 atmosphere Substances 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 3
- 239000001301 oxygen Substances 0.000 claims description 3
- 229910052760 oxygen Inorganic materials 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 239000010865 sewage Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 12
- 229940043267 rhodamine b Drugs 0.000 abstract description 10
- 239000000243 solution Substances 0.000 abstract description 9
- 230000008569 process Effects 0.000 abstract description 7
- 238000005229 chemical vapour deposition Methods 0.000 abstract description 2
- 230000007613 environmental effect Effects 0.000 abstract description 2
- 231100000956 nontoxicity Toxicity 0.000 abstract description 2
- 230000003197 catalytic effect Effects 0.000 abstract 1
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 16
- 239000011521 glass Substances 0.000 description 11
- 229910052786 argon Inorganic materials 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000001069 Raman spectroscopy Methods 0.000 description 6
- 239000008367 deionised water Substances 0.000 description 6
- 229910021641 deionized water Inorganic materials 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 4
- 229910001882 dioxygen Inorganic materials 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 230000000630 rising effect Effects 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000013505 freshwater Substances 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000003911 water pollution Methods 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000003673 groundwater Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000013535 sea water Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- -1 transition metal sulfide Chemical class 0.000 description 1
- 229910003149 α-MoO3 Inorganic materials 0.000 description 1
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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
- 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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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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Abstract
The invention discloses a MoS2/MoO3/TiO2A composite photocatalytic material and a preparation method and application thereof. The method comprises the following steps: adding MoO3Heating the powder to obtain MoO3A crystal; adding MoO3Subjecting the crystal to a first heat treatment, and simultaneously subjecting the S powder to a second heat treatment to obtain MoS2/MoO3A composite material; adding TiO into the mixture2Powder and MoS2/MoO3Adding the composite material into water, and uniformly stirring to obtain a mixed solution; drying the mixed solution to obtain powder, namely the MoS2/MoO3/TiO2Composite lightA catalytic material. The invention utilizes simple chemical vapor deposition to prepare MoS2/MoO3/TiO2The composite photocatalytic material degrades more than 90% of rhodamine B solution in 20min under visible light. The invention has simple process, environmental protection, excellent performance, no toxicity and harm, can be recycled and can be produced in batches.
Description
Technical Field
The invention belongs to the technical field of semiconductor nano material preparation, and particularly relates to a MoS2/MoO3/TiO2A composite photocatalytic material and a preparation method and application thereof.
Background
The economic development has intensified the environmental pollution, especially the water pollution, and although 70% of the earth is covered with water, seawater, deep groundwater, ice and snow solid fresh water are still difficult to use, accounting for only 2.53%, due to the difficulty of development or technical level. Since the fresh water resources on earth are not abundant, there is a need to find a method for effectively solving the problem of water pollution. Conventional photocatalytic materials such as TiO2The research has been focused and developed by researchers from the discovery, but the narrow spectral response range of the photocatalyst only absorbs the energy of ultraviolet light, and the high recombination rate of photo-generated electrons and holes leads to the reduction of the photocatalytic efficiency, which severely limits the application of the photocatalyst in practice. To TiO22The modification can effectively reduce the band gap and improve the photocatalytic performance.
MoS2Is a layered transition metal sulfide with large specific surface area and strong absorption capacity. MoS2Has a band gap of 1.29eV to 1.8eV at MoS2The edges of the nanostructures have a large number of unsaturated bonds. Thus, the number of terminal groups per unit area can be significantly increased, resulting in MoS2Increase of active site. Preparation of MoS by Zhao et al2QDs @ TNT visible photocatalysts to prevent photoexcited electron-hole pair recombination (Nanotechnology,2018,29(10): 105403-105413); zhou et al reported a 3D TiO2@ MoS2The structure shows good performance in the aspect of photocatalytic degradation of dye molecules (Small,2013,9(1): 140-147); chen et al designed and prepared MoS2/TiO2Degradation of nano material and CO2The performance in terms of reduction, hydrogen evolution, LIBs and SIBs is improved (nanoscales, 2017,10(4): 34-68).
However, in the past work, the manufacturing method is often too complex and time-consuming, the photocatalytic performance of the molybdenum sulfide is limited, and the preparation and recycling rate of the material still have many problems.
Disclosure of Invention
In order to overcome the defects in the prior art, the invention aims to provide a MoS2/MoO3/TiO2A composite photocatalytic material and a preparation method and application thereof.
The invention aims to provide MoS2/MoO3/TiO2A preparation method of a composite photocatalytic material.
Another object of the present invention is to provide MoS prepared by the above method2/MoO3/TiO2Application of the composite photocatalytic material.
The purpose of the invention is realized by at least one of the following technical solutions.
The invention provides a MoS2/MoO3/TiO2The preparation method of the composite photocatalytic material comprises the following steps:
(1) adding MoO3Putting the powder into a quartz boat, putting the quartz boat into a double-temperature-zone tube furnace I temperature zone, heating to obtain MoO3A crystal;
(2) the MoO in the step (1) is added3Putting the crystals into a first quartz boat, putting the first quartz boat into a first temperature zone of a double-temperature-zone tube furnace, heating up for carrying out first heating treatment, putting S powder into a second quartz boat, putting the second quartz boat into a second temperature zone of the double-temperature-zone tube furnace, heating up for carrying out second heating treatment, and obtaining MoS2/MoO3A composite material;
(3) adding TiO into the mixture2Powder and MoS of step (2)2/MoO3Adding the composite material into deionized water, and magnetically stirring until the mixture is uniformly stirred to obtain a mixed solution;
(4) pouring the mixed solution obtained in the step (3) intoIn the watch glass, the watch glass is put into a drying oven for drying treatment, naturally cooled, and scraped to obtain the MoS2/MoO3/TiO2A composite photocatalytic material.
Further, the temperature rising rate of the step (1) is not higher than 10 ℃/min; the temperature of the heating treatment is 840-860 ℃, and the time of the heating treatment is 30-40 min.
Preferably, the temperature of the heat treatment in the step (1) is 850 ℃, and the time of the heat treatment is 40 min.
Further, the atmosphere of the heat treatment in the step (1) is a mixed atmosphere of nitrogen and oxygen; in the mixed atmosphere, the volume percentage concentration of oxygen is 10-15%, and the volume percentage concentration of nitrogen is 85-90%.
Preferably, in the step (1), 120sccm of argon gas with a purity of not less than 99.99% and 15sccm of oxygen gas are always introduced during the temperature rise to the heating treatment temperature.
Further, in the step (2), the temperature of the first heat treatment is 500-550 ℃, and the temperature rise rate from the room temperature to the temperature of the first heat treatment is not higher than 10 ℃/min; the temperature of the second heating treatment is 270-300 ℃, and the temperature rise rate from the room temperature to the temperature of the second heating treatment is not higher than 10 ℃/min; the first heating treatment and the second heating treatment are carried out simultaneously, and the temperature of the temperature zone I and the temperature of the temperature zone II reach the required temperature simultaneously; the time of the first heat treatment and the second heat treatment is 30-40 min.
Preferably, in the step (2), the temperature of the first heat treatment is 550 ℃; the temperature of the second heat treatment is 270 ℃; the first heating treatment and the second heating treatment are carried out simultaneously, and the temperature of the temperature zone I and the temperature of the temperature zone II reach the required temperature simultaneously; the time for the first heat treatment and the second heat treatment is 40 min.
Further, the MoO of the step (2)3The mass ratio of the crystal to the S powder is 2:1-1: 1.
Further, the first heat treatment and the second heat treatment in the step (2) are both performed under an argon atmosphere.
Preferably, in the step (2), in the process of raising the temperature to the temperature of the first heat treatment and the temperature of the second heat treatment, argon gas with the purity of not less than 99.99 percent and the flow rate of 50sccm is always introduced.
Further, the TiO in the step (3)2Powder and MoS2/MoO3The mass ratio of the composite material is 19:1-17: 3.
Further, the TiO in the step (3)2The mass volume ratio of the powder to the deionized water is 1:500-1:250 g/mL; the stirring speed is 1000-1200r/min, and the stirring time is 1-1.5 h.
Further, the temperature of the drying treatment in the step (4) is 40-60 ℃, and the time of the drying treatment is 4-6 h.
The invention provides MoS prepared by the preparation method2/MoO3/TiO2A composite photocatalytic material. MoS2/MoO3Composite material in MoS2/MoO3/TiO2The mass fraction of the composite photocatalytic material is 5-30%.
Compared with the prior art, the invention has the following advantages and beneficial effects:
(1) the preparation method provided by the invention is the MoS prepared by using the simple chemical vapor deposition method2/MoO3/TiO2The composite photocatalytic material has the advantages of simple process, environmental protection, excellent performance, no toxicity, harmlessness, cyclic utilization and batch production;
(2) the MoS provided by the invention2/MoO3/TiO2The composite photocatalytic material can degrade more than 90% of rhodamine B in a solution within 20min under visible light.
Drawings
FIG. 1 is a MoS prepared in example 12/MoO3/TiO2An X-ray diffraction pattern of the composite photocatalytic material;
FIG. 2 is the MoS prepared in example 12/MoO3/TiO2Scanning electron microscope images of the composite photocatalytic material;
FIG. 3 is the MoS prepared in example 12/MoO3/TiO2A transmission electron microscope image of the composite photocatalytic material;
FIG. 4 shows an embodimentMoS prepared in example 12/MoO3/TiO2A Raman spectrogram of the composite photocatalytic material;
FIG. 5 is the MoS prepared in example 12/MoO3/TiO2A photocatalytic degradation graph of the composite photocatalytic material, wherein (a) is a degradation rate curve graph, and (b) is a degradation rate curve graph;
FIG. 6 is the MoS prepared in example 12/MoO3/TiO2A cycle experimental diagram of the composite photocatalytic material.
Detailed Description
The following examples are presented to further illustrate the practice of the invention, but the practice and protection of the invention is not limited thereto. It is noted that the processes described below, if not specifically described in detail, are all realizable or understandable by those skilled in the art with reference to the prior art. The reagents or apparatus used are not indicated to the manufacturer, and are considered to be conventional products available by commercial purchase.
Example 1
MoS of the present example2/MoO3/TiO2The preparation method of the composite photocatalytic material comprises the following steps:
(1) 100mg of MoO3Putting the powder into a quartz boat, putting the quartz boat into a double-temperature-zone tube furnace I temperature zone for heating, heating from room temperature to 850 ℃ at a heating rate of not higher than 10 ℃/min, keeping the temperature at 850 ℃ for 40min, and introducing 120sccm argon gas with the purity of not less than 99.99% and 15sccm oxygen gas all the time in the whole heating process to obtain 100mg MoO3A crystal;
(2) 100mg of MoO3Putting the crystal into a quartz boat, putting the quartz boat into a double-temperature-zone tube furnace I temperature zone for heating, and heating from room temperature to 550 ℃ at a heating rate of not higher than 10 ℃/min; 200mg S powder is put into a quartz boat, the quartz boat is put into a two-temperature-zone tube furnace II temperature zone for heating, the temperature is raised from room temperature to 270 ℃ at the temperature raising rate of not higher than 10 ℃/min, the temperature of the temperature I zone and the temperature II zone are simultaneously raised to the required temperature and kept for 40min, 50sccm argon with the purity of not lower than 99.99 percent is always introduced in the whole temperature raising process, and MoS is obtained2/MoO3A composite material;
(3) 85mg of TiO2Powder and 15mg MoS2/MoO3Adding the composite material into deionized water, wherein the TiO is2The mass volume ratio of the powder to water is 1:300g/mL, and the powder and the water are magnetically stirred for 1h at the speed of 1200r/min until the powder and the water are uniformly mixed to obtain a mixed solution;
(4) pouring the mixed solution into a watch glass, putting the watch glass into a drying oven with the temperature of 60 ℃ for drying for 4h, waiting for the dried watch glass to be naturally cooled, and scraping surface powder to obtain MoS2/MoO3/TiO2(MoS2/MoO3The mass ratio is 15wt percent).
A comparison of the properties is made by the following characterization. MoS prepared in example 12/MoO3/TiO2The structure of the composite photocatalytic material was determined by X-ray diffraction (XRD), and the results are shown in FIG. 1, in MoS2/MoO3/TiO2MoS in XRD of2、MoO3And TiO2All the characteristic peaks exist, and the spectrogram shows that MoS exists2/MoO3/TiO2Has been successfully prepared.
MoS prepared in example 12/MoO3/TiO2The morphology characteristics of the composite photocatalytic material were determined by Scanning Electron Microscopy (SEM), and the results are shown in fig. 2. TiO22Is nanoparticle, and is covered on MoS2/MoO3And (3) surface, which shows that the composite material is mixed uniformly.
MoS prepared in example 12/MoO3/TiO2The crystal structure of the composite photocatalytic material is determined by a Transmission Electron Microscope (TEM), the result is shown in FIG. 3, and the interplanar distances of 0.62nm, 0.34nm and 0.35nm in FIG. 3 indicate MoS2、MoO3And TiO2Respectively along [002]、[040]And [101 ]]And (4) growing in a crystal direction.
MoS prepared in example 12/MoO3/TiO2The composition of the composite photocatalytic material was determined by Raman spectroscopy (Raman), and the results are shown in fig. 4. At 152.9cm-1、201cm-1、513cm-1And 637.3cm-1Can observe strong anatase type TiO2Raman vibration, corresponding to EgAnd A1gA vibration mode. Is positioned at 285cm-1、339cm-1、821cm-1And 997cm-1The peak at is alpha-MoO3The characteristic raman peak of (1). At 382cm-1And 406.6cm-1Can observe MoS2Corresponding to 2H-MoS respectively2E of (A)1 2gPeak molybdenum and sulfur in-plane vibration modes and A1gOut-of-plane vibration modes of the peaks. MoS2A of (A)1gAnd E1 2gHas a frequency difference of about 24.6cm-1Indicates MoS2Is multilayered, consistent with TEM results. The results of Raman spectroscopy confirmed that the MoS2/MoO3/TiO2The composite photocatalytic material is made of TiO2、MoS2And MoO3And (4) forming.
First 50mg of the MoS prepared in example 1 were taken2/MoO3/TiO2Placing the composite photocatalyst into 50ml of 10mg/ml rhodamine B solution, performing dark adsorption treatment for 30min, irradiating with 300w visible light lamp at a distance of 15cm from the solution, measuring the concentration of the rhodamine B solution every 10min, and collecting 50mg TiO2The powder was also subjected to the above-described operation, and the degradation effect is shown in FIG. 5. Part (a) of FIG. 5 shows TiO2And MoS2/MoO3/TiO2Composite sample (MoS)2/MoO3Mass ratio is 15%) and has photocatalytic activity under visible light. More than 90% of rhodamine B is subjected to photodegradation within 20-30 min. In general, the photocatalytic degradation reaction can use an ln (C)0/Ct) Fit by kt rule, where C0And CtThe concentrations of rhodamine B solution after equilibrium dark absorption and after irradiation time t, respectively. k is the reaction rate constant, which is the slope of the fitted line. Part (b) of FIG. 5 shows a ternary MoS2/MoO3/TiO2Degradation rate of the catalyst at irradiation time. When C is presentt/C0Without decreasing or even increasing with time, the photocatalyst is considered to have performed a sufficient function at that time. Considering 30min, the degradation rate of the composite catalyst obtained by linear fitting is 0.106min-1. In the first 20 minutes, the degradation rate is 0.134min-1(dotted line), much larger than mostSeveral reported photocatalysts. Thus, MoS could be confirmed2/MoO3/TiO2The composite photocatalytic material can be applied to degrading rhodamine B solution.
Centrifuging the rhodamine B solution subjected to the first photocatalytic experiment at 10000r/min for 3min, and collecting centrifuged MoS2/MoO3/TiO2The photocatalyst is washed in deionized water for three times, and then is dried and then is subjected to a second photocatalytic experiment in the same operation, after five times of circulation, the photocatalytic activity is not obviously reduced, and the result is shown in figure 6, which proves that MoS2/MoO3/TiO2The photocatalyst has good stability.
Example 2
(1) 100mg of MoO3Putting the powder into a quartz boat, putting the quartz boat into a double-temperature-zone tube furnace I temperature zone for heating, heating from room temperature to 840 ℃ at a heating rate of not higher than 10 ℃/min, keeping the temperature at 840 ℃ for 35min, and introducing 120sccm argon gas with the purity of not less than 99.99% and 15sccm oxygen gas all the time in the whole heating process to obtain 100mg MoO3A crystal;
(2) 100mg of MoO3Putting the crystal into a quartz boat, putting the quartz boat into a double-temperature-zone tube furnace I temperature zone for heating, and heating from room temperature to 520 ℃ at a heating rate of not higher than 10 ℃/min; 200mg S powder is put into a quartz boat, the quartz boat is put into a two-temperature-zone tube furnace II temperature zone for heating, the temperature is raised from room temperature to 280 ℃ at the temperature raising rate of not higher than 10 ℃/min, the temperature of the temperature I zone and the temperature II zone are simultaneously kept for 35min, 50sccm argon gas with the purity of not lower than 99.99 percent is always introduced in the whole temperature raising process, and MoS is obtained2/MoO3A composite material;
(3) 90mg of TiO2Powder and 10mg MoS2/MoO3Adding the composite material into deionized water, wherein the TiO is2The mass volume ratio of the powder to water is 1:250g/mL, and the powder and the water are magnetically stirred for 1h at the speed of 1200r/min until the powder and the water are uniformly mixed to obtain a mixed solution;
(4) pouring the mixed solution into a watch glass, putting the watch glass into a drying oven at 50 ℃ for drying for 5h, waiting for the dried watch glass to be naturally cooled, and then pouring the mixed solution into the watch glassSurface powder scraping to obtain MoS2/MoO3/TiO2(MoS2/MoO 310 percent of composite photocatalytic material by mass).
MoS obtained in example 22/MoO3/TiO2The composite photocatalytic material can degrade rhodamine B under visible light, has good cycle stability, and can be shown in figures 5 and 6.
Example 3
(1) 100mg of MoO3Putting the powder into a quartz boat, putting the quartz boat into a double-temperature-zone tube furnace I temperature zone for heating, heating from room temperature to 860 ℃ at a heating rate of not higher than 10 ℃/min, keeping the temperature at 860 ℃ for 30min, and introducing 120sccm argon gas with the purity of not less than 99.99% and 15sccm oxygen gas all the time in the whole heating process to obtain 100mg MoO3A crystal;
(2) 100mg of MoO3Putting the crystal into a quartz boat, putting the quartz boat into a double-temperature-zone tube furnace I temperature zone for heating, and heating from room temperature to 500 ℃ at a heating rate of not higher than 10 ℃/min; 200mg S powder is put into a quartz boat, the quartz boat is put into a two-temperature-zone tube furnace II temperature zone for heating, the temperature is increased from room temperature to 300 ℃ at the temperature rising rate of not higher than 10 ℃/min, the temperature of the temperature I zone and the temperature II zone are simultaneously kept for 30min, 50sccm argon gas with the purity of not lower than 99.99 percent is always introduced in the whole temperature rising process, and MoS is obtained2/MoO3A composite material;
(3) 95mg of TiO2Powder and 5mg MoS2/MoO3Adding the composite material into deionized water, wherein the TiO is2The mass volume ratio of the powder to water is 1:500g/mL, and the powder and the water are magnetically stirred for 1.5 hours at the speed of 1000r/min until the powder and the water are uniformly mixed to obtain a mixed solution;
(4) pouring the mixed solution into a watch glass, putting the watch glass into a drying oven with the temperature of 40 ℃ for drying for 6h, waiting for the dried watch glass to be naturally cooled, and scraping surface powder to obtain MoS2/MoO3/TiO2(MoS2/MoO 35 percent of composite photocatalytic material by mass).
MoS obtained in example 32/MoO3/TiO2The composite photocatalytic material can degrade rhodamine B under visible light, has good cycle stability, and can be shown in figures 5 and 6.
The invention provides a method for preparing MoS with excellent photocatalytic performance2/MoO3/TiO2A composite photocatalytic material. It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. MoS2/MoO3/TiO2The preparation method of the composite photocatalytic material is characterized by comprising the following steps:
(1) adding MoO3Putting the powder into a quartz boat, putting the quartz boat into a double-temperature-zone tube furnace I temperature zone, heating to obtain MoO3A crystal;
(2) the MoO in the step (1) is added3Putting the crystals into a first temperature zone of a double-temperature-zone tube furnace for heating up for first heating treatment, and putting S powder into a second temperature zone of the double-temperature-zone tube furnace for heating up for second heating treatment to obtain MoS2/MoO3A composite material;
(3) adding TiO into the mixture2Powder and MoS of step (2)2/MoO3Adding the composite material into water, and uniformly stirring to obtain a mixed solution;
(4) drying the mixed solution obtained in the step (3) to obtain powder, namely the MoS2/MoO3/TiO2A composite photocatalytic material.
2. The MoS of claim 12/MoO3/TiO2The preparation method of the composite photocatalytic material is characterized in that the heating rate in the step (1) is not higher than 10 ℃/min; the temperature of the heating treatment is 840-860 ℃, and the time of the heating treatment is 30-40 min; the heating treatment atmosphere is a mixed atmosphere of nitrogen and oxygen; in a mixed atmosphere, oxygenThe volume percentage concentration of the nitrogen is 10-15%, and the volume percentage concentration of the nitrogen is 85-90%.
3. The MoS of claim 12/MoO3/TiO2The preparation method of the composite photocatalytic material is characterized in that in the step (2), the temperature of the first heating treatment is 500-550 ℃, and the heating rate from the room temperature to the temperature of the first heating treatment is not higher than 10 ℃/min; the temperature of the second heating treatment is 270-300 ℃, and the temperature rise rate from the room temperature to the temperature of the second heating treatment is not higher than 10 ℃/min; the first heating treatment and the second heating treatment are carried out simultaneously, and the temperature of the temperature zone I and the temperature of the temperature zone II reach the required temperature simultaneously; the time of the first heat treatment and the second heat treatment is 30-40 min.
4. The MoS of claim 12/MoO3/TiO2The preparation method of the composite photocatalytic material is characterized in that the MoO in the step (2)3The mass ratio of the crystal to the S powder is 2:1-1: 1.
5. The MoS of claim 12/MoO3/TiO2The preparation method of the composite photocatalytic material is characterized in that the first heating treatment and the second heating treatment in the step (2) are both carried out in an argon atmosphere.
6. The MoS of claim 12/MoO3/TiO2The preparation method of the composite photocatalytic material is characterized in that the TiO in the step (3)2Powder and MoS2/MoO3The mass ratio of the composite material is 19:1-17: 3.
7. The MoS of claim 12/MoO3/TiO2The preparation method of the composite photocatalytic material is characterized in that the TiO in the step (3)2The mass-volume ratio of the powder to the water is 1:500-1:250 g/mL; the stirring speed is 1000-1200r/min, and the stirring time is 1-1.5 h.
8. The MoS of claim 12/MoO3/TiO2The preparation method of the composite photocatalytic material is characterized in that the drying temperature in the step (4) is 40-60 ℃, and the drying time is 4-6 h.
9. MoS prepared by the preparation method of any one of claims 1 to 82/MoO3/TiO2The composite photocatalytic material is characterized in that MoS2/MoO3Composite material in MoS2/MoO3/TiO2The mass fraction of the composite photocatalytic material is 5-30%.
10. The MoS of claim 92/MoO3/TiO2The composite photocatalytic material is applied to degrading rhodamine in sewage.
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Citations (2)
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|---|---|---|---|---|
| CN105148947A (en) * | 2015-08-27 | 2015-12-16 | 江南大学 | Preparation and application of TiO2@MoS2 composite |
| CN109675596A (en) * | 2019-01-24 | 2019-04-26 | 山东科技大学 | Titanium carbide/titanium dioxide/molybdenum sulfide composite material and preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105148947A (en) * | 2015-08-27 | 2015-12-16 | 江南大学 | Preparation and application of TiO2@MoS2 composite |
| CN109675596A (en) * | 2019-01-24 | 2019-04-26 | 山东科技大学 | Titanium carbide/titanium dioxide/molybdenum sulfide composite material and preparation method and application |
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| Title |
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| LEI WANG ET AL.: ""Novel Red Emission from MoO3/MoS2−MoO2−MoO3 Core−Shell Belt Surface"", 《ACS APPLIED MATERIALS & INTERFACES》 * |
| MOON-JIN HWANG ET AL.: ""Preparation of MoO3/MoS2/TiO2 Composites for Catalytic Degradation of Methylene Blue"", 《JOURNAL OF NANOSCIENCE AND NANOTECHNOLOGY》 * |
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