CN109201084A - A kind of preparation method and applications of tungstic acid@molybdenum disulfide hollow tube composite catalyst - Google Patents
A kind of preparation method and applications of tungstic acid@molybdenum disulfide hollow tube composite catalyst Download PDFInfo
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- CN109201084A CN109201084A CN201811313410.6A CN201811313410A CN109201084A CN 109201084 A CN109201084 A CN 109201084A CN 201811313410 A CN201811313410 A CN 201811313410A CN 109201084 A CN109201084 A CN 109201084A
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- hollow tube
- composite catalyst
- tube composite
- preparation
- rodlike
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 65
- 239000002131 composite material Substances 0.000 title claims abstract description 55
- 239000003054 catalyst Substances 0.000 title claims abstract description 48
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 title claims abstract description 20
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 45
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 25
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000006185 dispersion Substances 0.000 claims abstract description 12
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 12
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 5
- 239000000975 dye Substances 0.000 claims abstract description 4
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 235000015393 sodium molybdate Nutrition 0.000 claims description 11
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 11
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 8
- 239000011780 sodium chloride Substances 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 4
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims 1
- 239000005864 Sulphur Substances 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 229910052750 molybdenum Inorganic materials 0.000 claims 1
- 239000011733 molybdenum Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 11
- 238000007146 photocatalysis Methods 0.000 abstract description 10
- 239000011941 photocatalyst Substances 0.000 abstract description 9
- 238000000746 purification Methods 0.000 abstract description 2
- 239000010865 sewage Substances 0.000 abstract description 2
- 230000005540 biological transmission Effects 0.000 description 13
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 2
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 239000010937 tungsten Substances 0.000 description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000005411 Van der Waals force Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- IQFVPQOLBLOTPF-HKXUKFGYSA-L congo red Chemical compound [Na+].[Na+].C1=CC=CC2=C(N)C(/N=N/C3=CC=C(C=C3)C3=CC=C(C=C3)/N=N/C3=C(C4=CC=CC=C4C(=C3)S([O-])(=O)=O)N)=CC(S([O-])(=O)=O)=C21 IQFVPQOLBLOTPF-HKXUKFGYSA-L 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000004298 light response Effects 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 229960000907 methylthioninium chloride Drugs 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 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 description 1
- 229940043267 rhodamine b Drugs 0.000 description 1
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 1
Classifications
-
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/39—
-
- 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
-
- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
A kind of preparation method and applications of tungstic acid@molybdenum disulfide hollow tube composite catalyst.The present invention relates to a kind of preparation method and applications of composite photo-catalyst.The present invention is to solve the problems, such as existing photocatalyst applications in the visible light photocatalysis low efficiency of sewage purification.Method: one, rodlike WO is prepared3；Two, by rodlike WO3Sodium molybdate and thiocarbamide are added after dispersion persistently to stir, is then transferred in polytetrafluoroethylliner liner, keeps 2 under the conditions of temperature is 160~200 DEG C~cooled to room temperature after completion of the reaction for 24 hours, washing is dry in baking oven, obtains WO3@MoS2Hollow tube composite catalyst.The present invention is used for deep purifying organic dyestuff water body.
Description
Technical field
The present invention relates to a kind of preparation method and applications of composite photo-catalyst.
Background technique
Environmental pollution restricts the sustainable development of human society, and wherein the degradation problem of Organic Pollutants In Water is still
Problem urgently to be resolved at present.And Photocatalytic Oxidation With Semiconductors technology has reaction condition mild, catalyst is easy preparation, without two
The advantages that secondary pollution is an effective way for solving problem of environmental pollution.Currently, the photocatalysis of exploitation efficient visible light response
Agent improves photo-quantum efficiency, it has also become the key issues of photocatalysis field research.
With the rise of the two-dimensional materials research boom such as graphene, MoS2Research also result in extensive concern.MoS2Layer
It is maintained between layer by relatively weak Van der Waals force, therefore shows many excellent properties.MoS2Material in lubricant, urge
The fields such as agent and transistor are all widely used.Nanometer MoS2Forbidden bandwidth in 1.20-1.9eV, have in visible light
Under photocatalytic activity, while MoS2Lamella edge has more active sites, and then can improve its catalytic activity, therefore
MoS2It is widely used in the catalysis such as hydrodesulfurization, photolysis water hydrogen and photocatalysis degradation organic contaminant reaction.But MoS2Quilt
After excited by visible light, photo-generate electron-hole is compound to easily occurring, and causes individual MoS2Photocatalysis efficiency is low.
Summary of the invention
The present invention be in order to solve the problems, such as existing photocatalyst applications in the visible light photocatalysis low efficiency of sewage purification,
And provide a kind of preparation method and applications of tungstic acid@molybdenum disulfide hollow tube composite catalyst.
A kind of preparation method of tungstic acid@molybdenum disulfide hollow tube composite catalyst specifically carries out according to the following steps
:
One, sodium tungstate and sodium chloride are dissolved into 10~20min of magnetic agitation in deionized water, uses concentration for 3mol/L
HCl solution adjust pH to 1~3, be then transferred in polytetrafluoroethylliner liner, temperature be 160~200 DEG C under the conditions of keep
18~26h, cooled to room temperature, first adopts and is washed with deionized 3~5 times again using dehydrated alcohol washing 3 after completion of the reaction
It is placed on dry 10~14h in the baking oven that temperature is 50~80 DEG C for~5 times, obtaining faint yellow solid is rodlike WO3；The tungsten
The quality of sour sodium and the volume ratio of deionized water are 1g:(20~25) mL；The quality of the sodium chloride and the volume of deionized water
Than for 1g:(40~50) mL；
Two, by rodlike WO3In deionized water, 8~12min of ultrasonic disperse obtains WO for dispersion3Dispersion liquid, to WO3Dispersion
Sodium molybdate is added in liquid and thiocarbamide persistently stirs 1~3h, is then transferred in polytetrafluoroethylliner liner, is 160~200 in temperature
Keep 2 under the conditions of DEG C~for 24 hours, cooled to room temperature after completion of the reaction first adopts and is washed with deionized 3~5 times again using nothing
Water-ethanol washs 3~5 times and is placed on dry 10~14h in the baking oven that temperature is 50~80 DEG C, and obtaining black solid is WO3@
MoS2Hollow tube composite catalyst；The rodlike WO3Quality and deionized water volume ratio be 1g:(300~500) mL；It is described
Rodlike WO3Mass ratio with sodium molybdate is 1:(1~8)；The rodlike WO3Mass ratio with thiocarbamide is 1:(3~15).
The tungstic acid@molybdenum disulfide hollow tube composite catalyst of above method preparation is used for deep purifying organic dyestuff water
Body.
Beneficial effects of the present invention:
The present invention prepares hollow tubular WO by simple hydro-thermal method3@MoS2Composite photo-catalyst, this method are simple, high
Effect, composite catalyst pattern is unique, at present it is not yet found that closing report.The composite material has the advantage that 1, one-dimensional tubulose
Material can effectively improve the transmission rate of light induced electron；2,MoS2With large specific surface area, more active sites can be provided；
3, optical response range, WO are widened3For wide bandgap semiconductor, ultraviolet light can only be absorbed and utilized, with MoS2After compound, hetero-junctions is formed
Structure can greatly improve visible light utilization efficiency.
Detailed description of the invention
Fig. 1 is the WO of differential responses time3@MoS2The XRD diagram of hollow tube composite catalyst；Wherein 1 is WO3, 2 be HW@M-
02,3 is HW@M-04, and 4 be HW@M-06, and 5 be HW@M-10, and 6 be HW@M-12, and 7 be HW@M-24, and 8 be MoS2；
Fig. 2 is the rodlike WO that one step 1 of embodiment obtains3Transmission electron microscope TEM figure；
Fig. 3 is the WO that embodiment two obtains3@MoS2The transmission electron microscope TEM of hollow tube composite catalyst schemes；
Fig. 4 is the WO that embodiment three obtains3@MoS2The transmission electron microscope TEM of hollow tube composite catalyst schemes；
Fig. 5 is the WO that example IV obtains3@MoS2The transmission electron microscope TEM of hollow tube composite catalyst schemes；
Fig. 6 is the WO that embodiment one obtains3@MoS2The transmission electron microscope TEM of hollow tube composite catalyst schemes；
Fig. 7 is the WO that embodiment five obtains3@MoS2The transmission electron microscope TEM of hollow tube composite catalyst schemes；
Fig. 8 is the WO that embodiment six obtains3@MoS2The transmission electron microscope TEM of hollow tube composite catalyst schemes.
Specific embodiment
Specific embodiment 1: a kind of system of tungstic acid@molybdenum disulfide hollow tube composite catalyst of present embodiment
What Preparation Method specifically carried out according to the following steps:
One, sodium tungstate and sodium chloride are dissolved into 10~20min of magnetic agitation in deionized water, uses concentration for 3mol/L
HCl solution adjust pH to 1~3, be then transferred in polytetrafluoroethylliner liner, temperature be 160~200 DEG C under the conditions of keep
18~26h, cooled to room temperature, first adopts and is washed with deionized 3~5 times again using dehydrated alcohol washing 3 after completion of the reaction
It is placed on dry 10~14h in the baking oven that temperature is 50~80 DEG C for~5 times, obtaining faint yellow solid is rodlike WO3；The tungsten
The quality of sour sodium and the volume ratio of deionized water are 1g:(20~25) mL；The quality of the sodium chloride and the volume of deionized water
Than for 1g:(40~50) mL；
Two, by rodlike WO3In deionized water, 8~12min of ultrasonic disperse obtains WO for dispersion3Dispersion liquid, to WO3Dispersion
Sodium molybdate is added in liquid and thiocarbamide persistently stirs 1~3h, is then transferred in polytetrafluoroethylliner liner, is 160~200 in temperature
Keep 2 under the conditions of DEG C~for 24 hours, cooled to room temperature after completion of the reaction first adopts and is washed with deionized 3~5 times again using nothing
Water-ethanol washs 3~5 times and is placed on dry 10~14h in the baking oven that temperature is 50~80 DEG C, and obtaining black solid is WO3@
MoS2Hollow tube composite catalyst；The rodlike WO3Quality and deionized water volume ratio be 1g:(300~500) mL；It is described
Rodlike WO3Mass ratio with sodium molybdate is 1:(1~8)；The rodlike WO3Mass ratio with thiocarbamide is 1:(3~15).
Specific embodiment 2: the present embodiment is different from the first embodiment in that: used in step 1 concentration for
The HCl solution of 3mol/L adjusts pH to 2.Other steps and parameter are same as the specific embodiment one.
Specific embodiment 3: the present embodiment is different from the first and the second embodiment in that: in temperature in step 2
4h is kept under the conditions of being 200 DEG C, after completion of the reaction cooled to room temperature.Other steps and parameter and specific embodiment one or
Two is identical.
Specific embodiment 4: unlike one of present embodiment and specific embodiment one to three: in step 2
Temperature keeps 6h under the conditions of being 200 DEG C, after completion of the reaction cooled to room temperature.Other steps and parameter and specific embodiment
One of one to three is identical.
Specific embodiment 5: unlike one of present embodiment and specific embodiment one to four: in step 2
Temperature keeps 10h under the conditions of being 200 DEG C, after completion of the reaction cooled to room temperature.Other steps and parameter and specific embodiment party
One of formula one to four is identical.
Specific embodiment 6: unlike one of present embodiment and specific embodiment one to five: in step 2
Temperature keeps 12h under the conditions of being 200 DEG C, after completion of the reaction cooled to room temperature.Other steps and parameter and specific embodiment party
One of formula one to five is identical.
Specific embodiment 7: unlike one of present embodiment and specific embodiment one to six: institute in step 2
State rodlike WO3Quality and deionized water volume ratio be 1g:400mL.Other steps and parameter and specific embodiment one to
One of six is identical.
Specific embodiment 8: unlike one of present embodiment and specific embodiment one to seven: institute in step 2
State rodlike WO3Mass ratio with sodium molybdate is 1:2；The rodlike WO3Mass ratio with thiocarbamide is 1:4.Other steps and parameter with
One of specific embodiment one to seven is identical.
Specific embodiment 9: unlike one of present embodiment and specific embodiment one to eight: institute in step 2
State rodlike WO3Mass ratio with sodium molybdate is 1:6；The rodlike WO3Mass ratio with thiocarbamide is 1:12.Other steps and parameter
It is identical as one of specific embodiment one to eight.
Specific embodiment 10: present embodiment tungstic acid@molybdenum disulfide hollow tube composite catalyst is net for depth
Change organic dyestuff water body.
Beneficial effects of the present invention are verified by following embodiment:
Embodiment one: a kind of preparation method of tungstic acid@molybdenum disulfide hollow tube composite catalyst be specifically press it is following
What step carried out:
One, that 0.825g sodium tungstate and 0.4g sodium chloride are dissolved in magnetic agitation 10min, use in 19mL deionized water is dense
The HCl solution that degree is 3mol/L adjusts pH to 2, is then transferred in polytetrafluoroethylliner liner, protects under the conditions of temperature is 180 DEG C
It holds for 24 hours, after completion of the reaction cooled to room temperature, first adopts and be washed with deionized 3~5 times again using dehydrated alcohol washing 3~5
Dry 12h in the secondary baking oven for being placed on temperature and being 50 DEG C, obtaining faint yellow solid is rodlike WO3；
Two, by the rodlike WO of 0.1g3It is dispersed in 40mL deionized water, ultrasonic disperse 10min obtains WO3Dispersion liquid, to WO3
0.4g sodium molybdate is added in dispersion liquid and 0.8g thiocarbamide persistently stirs 1h, is then transferred in polytetrafluoroethylliner liner, in temperature
10h is kept under the conditions of being 200 DEG C, after completion of the reaction cooled to room temperature, first adopts and be washed with deionized 3~5 times and use again
Dehydrated alcohol washs 3~5 times and is placed on dry 12h in the baking oven that temperature is 50 DEG C, and obtaining black solid is WO3@MoS2It is hollow
Pipe composite catalyst；Labeled as HW@M-10.
Embodiment two: the present embodiment and embodiment one the difference is that: step 2 is kept under the conditions of temperature is 200 DEG C
2h, cooled to room temperature, first adopts and is washed with deionized 3~5 times again using dehydrated alcohol washing 3~5 times after completion of the reaction
It is placed on dry 12h in the baking oven that temperature is 50 DEG C, obtaining black solid is WO3@MoS2Hollow tube composite catalyst；Label
For HW@M-02.
Embodiment three: the present embodiment and embodiment one the difference is that: step 2 is kept under the conditions of temperature is 200 DEG C
4h, cooled to room temperature, first adopts and is washed with deionized 3~5 times again using dehydrated alcohol washing 3~5 times after completion of the reaction
It is placed on dry 12h in the baking oven that temperature is 50 DEG C, obtaining black solid is WO3@MoS2Hollow tube composite catalyst；Label
For HW@M-04.
Example IV: the present embodiment and embodiment one the difference is that: step 2 is kept under the conditions of temperature is 200 DEG C
6h, cooled to room temperature, first adopts and is washed with deionized 3~5 times again using dehydrated alcohol washing 3~5 times after completion of the reaction
It is placed on dry 12h in the baking oven that temperature is 50 DEG C, obtaining black solid is WO3@MoS2Hollow tube composite catalyst；Label
For HW@M-06.
Embodiment five: the present embodiment and embodiment one the difference is that: step 2 is kept under the conditions of temperature is 200 DEG C
12h, cooled to room temperature, first adopts and is washed with deionized 3~5 times again using dehydrated alcohol washing 3~5 times after completion of the reaction
It is placed on dry 12h in the baking oven that temperature is 50 DEG C, obtaining black solid is WO3@MoS2Hollow tube composite catalyst；Label
For HW@M-12.
Embodiment six: the present embodiment and embodiment one the difference is that: step 2 is kept under the conditions of temperature is 200 DEG C
For 24 hours, cooled to room temperature after completion of the reaction is first adopted and is washed with deionized 3~5 times and is washed 3~5 times using dehydrated alcohol again
It is placed on dry 12h in the baking oven that temperature is 50 DEG C, obtaining black solid is WO3@MoS2Hollow tube composite catalyst；Label
For HW@M-24.
Embodiment seven: hollow tubular WO obtained in 5mg above-mentioned steps two is weighed3@MoS2Composite photo-catalyst is added to
Congo red solution (the C of 50mL0=30mg/L), stir 60min in the dark first, then 35min carries out photocatalysis under visible light
Degradation, calculates its degradation efficiency and reaches 98.8%.
Embodiment eight: hollow tubular WO obtained in 5mg above-mentioned steps two is weighed3@MoS2Composite photo-catalyst is added to
50mL rhodamine B solution (C0=20mg/L), stir 60min in the dark first, then 35min carries out photocatalysis under visible light
Degradation, calculates its degradation efficiency and reaches 85.2%.
Embodiment nine: hollow tubular WO obtained in 5mg above-mentioned steps two is weighed3@MoS2Composite photo-catalyst is added to
50m methylene blue solution (C0=10mg/L), stir 60min in the dark first, then 35min carries out photocatalysis under visible light
Degradation, calculates its degradation efficiency and reaches 89.3%.
Embodiment ten: hollow tubular WO obtained in 5mg above-mentioned steps two is weighed3@MoS2Composite photo-catalyst is added to
50m methyl orange solution (C0=5mg/L), stir 60min in the dark first, then 35min carries out photocatalysis drop under visible light
Solution, calculates its degradation efficiency and reaches 57.6%.
Fig. 1 is the WO of differential responses time3@MoS2The XRD diagram of hollow tube composite catalyst；Wherein 1 is WO3, 2 be HW@M-
02,3 is HW@M-04, and 4 be HW@M-06, and 5 be HW@M-10, and 6 be HW@M-12, and 7 be HW@M-24, and 8 be MoS2；From the XRD of Fig. 1
Figure is it can be seen that WO3Diffraction maximum fade away with the extension in reaction time, until reaction 4 hours when, WO3Diffraction maximum it is unknown
It is aobvious, illustrate at this moment WO3It is etched to tubulose, and content is less.Meanwhile MoS2Diffraction maximum gradually increase, illustrate reaction to 4
Hour starts MoS2It has been formed that, until being reacted to 24 hours, impurity generation is found no in composite material.
Fig. 2 is the rodlike WO that one step 1 of embodiment obtains3Transmission electron microscope TEM figure；Fig. 3 is what embodiment two obtained
WO3@MoS2The transmission electron microscope TEM of hollow tube composite catalyst schemes；Fig. 4 is the WO that embodiment three obtains3@MoS2Hollow tube is compound
The transmission electron microscope TEM of catalyst schemes；Fig. 5 is the WO that example IV obtains3@MoS2The transmission electron microscope TEM of hollow tube composite catalyst
Figure；Fig. 6 is the WO that embodiment one obtains3@MoS2The transmission electron microscope TEM of hollow tube composite catalyst schemes；Fig. 7 obtains for embodiment five
The WO arrived3@MoS2The transmission electron microscope TEM of hollow tube composite catalyst schemes；Fig. 8 is the WO that embodiment six obtains3@MoS2Hollow tube
The transmission electron microscope TEM of composite catalyst schemes；Fig. 2 is rodlike WO3Transmission electron microscope picture, average length is in 1-2um.Fig. 3-8 points
Not Wei reaction time 2-24 hour when HW M composite catalyst TEM figure.With the extension in reaction time, WO3Stick is rapid
It is etched into tubulose, while MoS2Also it is grown in WO3The outside of pipe, until when reaction reaches 24 hours, WO3Pipe is etched completely away,
MoS2Also reunite together, form ball.
Claims (10)
1. a kind of preparation method of tungstic acid@molybdenum disulfide hollow tube composite catalyst, it is characterised in that bis- sulphur of tungstic acid@
What the preparation method of change molybdenum hollow tube composite catalyst specifically carried out according to the following steps:
One, sodium tungstate and sodium chloride are dissolved into 10~20min of magnetic agitation in deionized water, uses concentration for 3mol/L's
HCl solution adjusts pH to 1~3, is then transferred in polytetrafluoroethylliner liner, keeps 18 under the conditions of temperature is 160~200 DEG C
~26h, cooled to room temperature, first adopts and is washed with deionized 3~5 times again using dehydrated alcohol washing 3~5 after completion of the reaction
Dry 10~14h in the secondary baking oven for being placed on temperature and being 50~80 DEG C, obtaining faint yellow solid is rodlike WO3；The wolframic acid
The quality of sodium and the volume ratio of deionized water are 1g:(20~25) mL；The quality of the sodium chloride and the volume ratio of deionized water
For 1g:(40~50) mL；
Two, by rodlike WO3In deionized water, 8~12min of ultrasonic disperse obtains WO for dispersion3Dispersion liquid, to WO3In dispersion liquid
Sodium molybdate is added and thiocarbamide persistently stirs 1~3h, is then transferred in polytetrafluoroethylliner liner, is 160~200 DEG C of items in temperature
Keep 2 under part~for 24 hours, cooled to room temperature after completion of the reaction first adopts and is washed with deionized 3~5 times again using anhydrous second
Alcohol washs 3~5 times and is placed on dry 10~14h in the baking oven that temperature is 50~80 DEG C, and obtaining black solid is WO3@MoS2In
Blank pipe composite catalyst；The rodlike WO3Quality and deionized water volume ratio be 1g:(300~500) mL；It is described rodlike
WO3Mass ratio with sodium molybdate is 1:(1~8)；The rodlike WO3Mass ratio with thiocarbamide is 1:(3~15).
2. a kind of preparation method of tungstic acid@molybdenum disulfide hollow tube composite catalyst according to claim 1, special
Sign is that concentration is used to adjust pH to 2 for the HCl solution of 3mol/L in step 1.
3. a kind of preparation method of tungstic acid@molybdenum disulfide hollow tube composite catalyst according to claim 1, special
It levies and is in step 2 to keep 4h under the conditions of temperature is 200 DEG C, after completion of the reaction cooled to room temperature.
4. a kind of preparation method of tungstic acid@molybdenum disulfide hollow tube composite catalyst according to claim 1, special
It levies and is in step 2 to keep 6h under the conditions of temperature is 200 DEG C, after completion of the reaction cooled to room temperature.
5. a kind of preparation method of tungstic acid@molybdenum disulfide hollow tube composite catalyst according to claim 1, special
It levies and is in step 2 to keep 10h under the conditions of temperature is 200 DEG C, after completion of the reaction cooled to room temperature.
6. a kind of preparation method of tungstic acid@molybdenum disulfide hollow tube composite catalyst according to claim 1, special
It levies and is in step 2 to keep 12h under the conditions of temperature is 200 DEG C, after completion of the reaction cooled to room temperature.
7. a kind of preparation method of tungstic acid@molybdenum disulfide hollow tube composite catalyst according to claim 1, special
Sign is rodlike WO described in step 23Quality and deionized water volume ratio be 1g:400mL.
8. a kind of preparation method of tungstic acid@molybdenum disulfide hollow tube composite catalyst according to claim 1, special
Sign is rodlike WO described in step 23Mass ratio with sodium molybdate is 1:2；The rodlike WO3Mass ratio with thiocarbamide is 1:4.
9. a kind of preparation method of tungstic acid@molybdenum disulfide hollow tube composite catalyst according to claim 1, special
Sign is rodlike WO described in step 23Mass ratio with sodium molybdate is 1:6；The rodlike WO3Mass ratio with thiocarbamide is 1:
12。
10. the application of the tungstic acid@molybdenum disulfide hollow tube composite catalyst of method preparation as described in claim 1, special
Sign is tungstic acid@molybdenum disulfide hollow tube composite catalyst for deep purifying organic dyestuff water body.
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| CN111974418A (en) * | 2020-07-13 | 2020-11-24 | 重庆大学 | Preparation of ternary composite magnetic photocatalytic material MoS2/WO3/SrFe12O19Method (2) |
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