CN109967067A - A method of bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst is prepared by raw material of HDS dead catalyst - Google Patents
A method of bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst is prepared by raw material of HDS dead catalyst Download PDFInfo
- Publication number
- CN109967067A CN109967067A CN201910227985.4A CN201910227985A CN109967067A CN 109967067 A CN109967067 A CN 109967067A CN 201910227985 A CN201910227985 A CN 201910227985A CN 109967067 A CN109967067 A CN 109967067A
- Authority
- CN
- China
- Prior art keywords
- bismuth
- solution
- molybdate
- graphene
- hds
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000003054 catalyst Substances 0.000 title claims abstract description 78
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 53
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 50
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 35
- 238000000034 method Methods 0.000 title claims abstract description 27
- 239000002994 raw material Substances 0.000 title claims abstract description 25
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 title claims description 45
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims description 43
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 28
- 239000004411 aluminium Substances 0.000 claims abstract description 28
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 28
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000000975 dye Substances 0.000 claims abstract description 3
- 230000008569 process Effects 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 82
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 77
- 235000019441 ethanol Nutrition 0.000 claims description 46
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 42
- 239000007788 liquid Substances 0.000 claims description 35
- 239000007787 solid Substances 0.000 claims description 34
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 27
- 229960004756 ethanol Drugs 0.000 claims description 26
- 230000003647 oxidation Effects 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- 239000011684 sodium molybdate Substances 0.000 claims description 20
- 239000003978 infusion fluid Substances 0.000 claims description 18
- 238000002203 pretreatment Methods 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 17
- 238000000926 separation method Methods 0.000 claims description 16
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 16
- 239000011609 ammonium molybdate Substances 0.000 claims description 15
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 15
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 15
- 229940010552 ammonium molybdate Drugs 0.000 claims description 15
- 235000015393 sodium molybdate Nutrition 0.000 claims description 14
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 13
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- 239000003795 chemical substances by application Substances 0.000 claims description 12
- 239000000706 filtrate Substances 0.000 claims description 12
- 239000011734 sodium Substances 0.000 claims description 12
- 239000002077 nanosphere Substances 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 9
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
- 229910015667 MoO4 Inorganic materials 0.000 claims description 6
- 229910004619 Na2MoO4 Inorganic materials 0.000 claims description 6
- 230000001476 alcoholic effect Effects 0.000 claims description 6
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 claims description 6
- 229910052799 carbon Inorganic materials 0.000 claims description 6
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- 229910020350 Na2WO4 Inorganic materials 0.000 claims description 5
- UNTBPXHCXVWYOI-UHFFFAOYSA-O azanium;oxido(dioxo)vanadium Chemical compound [NH4+].[O-][V](=O)=O UNTBPXHCXVWYOI-UHFFFAOYSA-O 0.000 claims description 5
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 5
- 229910020341 Na2WO4.2H2O Inorganic materials 0.000 claims description 3
- WPZFLQRLSGVIAA-UHFFFAOYSA-N sodium tungstate dihydrate Chemical compound O.O.[Na+].[Na+].[O-][W]([O-])(=O)=O WPZFLQRLSGVIAA-UHFFFAOYSA-N 0.000 claims description 3
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 claims description 2
- 230000000593 degrading effect Effects 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 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 abstract description 13
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 7
- 239000011733 molybdenum Substances 0.000 abstract description 7
- 239000000463 material Substances 0.000 abstract description 4
- 239000000284 extract Substances 0.000 abstract description 2
- 239000002904 solvent Substances 0.000 abstract 1
- 229940043267 rhodamine b Drugs 0.000 description 12
- 229910002900 Bi2MoO6 Inorganic materials 0.000 description 9
- 229910002651 NO3 Inorganic materials 0.000 description 8
- 230000015556 catabolic process Effects 0.000 description 8
- 238000006731 degradation reaction Methods 0.000 description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 5
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 5
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000001514 detection method Methods 0.000 description 4
- 229910052724 xenon Inorganic materials 0.000 description 4
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 4
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002003 electron diffraction Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 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 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000003915 air pollution Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- XDBSEZHMWGHVIL-UHFFFAOYSA-M hydroxy(dioxo)vanadium Chemical compound O[V](=O)=O XDBSEZHMWGHVIL-UHFFFAOYSA-M 0.000 description 1
- 230000001788 irregular Effects 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000003911 water pollution Methods 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
- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B01J35/23—
-
- B01J35/39—
-
- B01J35/393—
-
- B01J35/399—
-
- B01J35/51—
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- 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
- B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
-
- 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
-
- 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
-
- 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
- C02F2101/36—Organic compounds containing halogen
-
- 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
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Catalysts (AREA)
Abstract
Bismuth tungstate-bismuth molybdate-graphene heterojunction photocatalyst method is prepared by raw material of HDS dead catalyst the invention discloses a kind of, belongs to photocatalyst material preparation technical field.The present invention extracts molybdenum from aluminium base hydrodesulfurization dead catalyst (HDS) under ultrasonic wave auxiliary and passes through hydrothermal/solvent hot preparation graphene coated bismuth tungstate-bismuth molybdate self-assembled nanometer piece microballoon heterojunction photocatalyst, bismuth tungstate-bismuth molybdate-graphene heterojunction photocatalyst has the characteristics that pattern is single, surface area is big, photocatalytic activity is high, and there is bismuth tungstate-bismuth molybdate-graphene heterojunction photocatalyst preparation process simple process, proper scale to produce；Can effectively be degraded colored dyes rhodamine under visible light.
Description
Technical field
The present invention relates to one kind to prepare bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalysis by raw material of HDS dead catalyst
The method of agent belongs to photocatalyst material preparation technical field.
Background technique
With economic and industry fast development, people's demands for quality of life are getting higher and higher, at the same time, environment
Deteriorate two hang-ups for becoming facing mankind with energy shortage, the air and water pollution got worse has threatened the existence of the mankind
Safety becomes human health, economy and society realize the major obstacles of sustainable development.Seek efficiently useful solution at
For the hot issue of global concern.Photocatalysis is as a green environmental protection technique, mild, the easy to operate, nothing with reaction condition
Secondary pollution can directly utilize the advantages that solar energy, have broad application prospects in environment and energy field.Simultaneously.Because of stone
Oily dead catalyst annual output is big, amount containing molybdenum is high, gradually causes the concern of people.Useless molybdenum dead catalyst is classified as molybdenum by developed country
The 4th kind of resource.Therefore, carry out the work for recycling the valuable metals such as molybdenum from molybdenum-contained waste catalyst, not only contribute to every profession and trade
Sustainable development, and the concrete embodiment for circular economy concept of turning waste into wealth, realize has significant environmental benefit, economy
Benefit and social benefit.
Summary of the invention
The technical issues of for the processing of HDS dead catalyst, the present invention provide one kind and prepare tungsten using HDS dead catalyst as raw material
The method of sour bismuth/bismuth molybdate/graphene heterojunction photocatalyst, the present invention using sodium tungstate, bismuth nitrate, graphene oxide and
Sodium molybdate is extracted from aluminium base hydrodesulfurization dead catalyst, ammonium molybdate is that raw material prepares that pattern is single, surface area with hydro-thermal method
Greatly, the high rGO-Bi of photocatalytic activity2WO6-Bi2MoO6Heterojunction photocatalysis material.
A method of bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst being prepared by raw material of HDS dead catalyst,
Specific step is as follows:
(1) aluminium scrap base Hydrobon catalyst is added in ethyl alcohol, de-oiling pre-processes 120 ~ 150min under ultrasonic conditions
Obtain oil-free aluminium scrap base Hydrobon catalyst；
(2) in air atmosphere, it is 600 ~ 900 DEG C of items that the oil-free aluminium scrap base Hydrobon catalyst of step (1), which is placed in temperature,
1 ~ 2h of roasting oxidation obtains oxidation pre-treatment dead catalyst under part；
(3) the oxidation pre-treatment dead catalyst of step (2) is added to Na2CO3In solution and ultrasonic wave auxiliary under leach 1 ~
2h obtains Na2MoO4Infusion solution；
(4) in the Na of step (3)2MoO4The pH value that hydrochloric acid adjusting infusion solution is added in infusion solution is 7 ~ 8 and reacts, solid-liquid
Isolated aluminum hydroxide solid and filtrate A；
(5) the filtrate A of step (4) is at the uniform velocity warming up to 60 ~ 80 DEG C, NH is added4Cl simultaneously reacts, and separation of solid and liquid obtains metavanadic acid
Ammonium and liquor B；Liquor B evaporative crystallization obtains sodium molybdate, ammonium molybdate；
(6) mixed alcohol of ethylene glycol and ethyl alcohol is added in graphene oxide, ultrasonic disperse handles to obtain graphene oxide/alcohol
Solution A；
(7) by the sodium molybdate, ammonium molybdate and Bi of step (5)2(NO)3·5H2O is uniformly mixed, then slow under Ultrasonic Conditions again
It is added to dissolve in graphene oxide/alcoholic solution A of step (6) and be ultrasonically treated 0.5 ~ 2h and obtains solution B；
(8) by Bi2WO6It is added in the B solution of step (7) and 1 ~ 2h of decentralized processing obtains solution C under ultrasonic conditions；
(9) by the solution C of step (8) be placed in temperature be 120 ~ 180 DEG C reaction 12 ~ for 24 hours, cooled to room temperature, be separated by solid-liquid separation,
Using dehydrated alcohol and distilled water, to solid, alternately washing more than three times, is dried in vacuo different up to bismuth tungstate/bismuth molybdate/graphene
Matter knot photochemical catalyst；
The pretreated temperature of de-oiling is 50 ~ 65 DEG C, the liquid-solid ratio mL:g of ethyl alcohol and aluminium scrap base Hydrobon catalyst be (3 ~
7):1；
The ultrasonic power is 600 ~ 800W；
Step (3) the oxidation pre-treatment dead catalyst and Na2CO3The liquid-solid ratio mL:g of solution is (8 ~ 10): 1, Na2CO3Solution
Concentration is 1.6mol/L；
NH in the step (5)4Cl's adds ammonium COEFFICIENT K to be 3 ~ 5；
The solid-to-liquid ratio g:mL of the mixed alcohol of graphene oxide and ethylene glycol and ethyl alcohol is (0.01 ~ 0.03) in the step (6):
40；
Bi in the step (8)2WO6In W and step (7) in molybdenum element molar ratio be (1:1) ~ (3:1)；Bi in solution C
Ion is excessive.
The Bi2WO6The preparation method of nanosphere is
(1) by Bi2(NO3)3·5H2O is added in acetic acid solution, and 10 ~ 30 min of ultrasonic treatment are configured to Bi2(NO3)3/ acetic acid
Solution；
(2) by Na2WO4.2H2O is added in distilled water, and 3 ~ 10min of ultrasonic treatment is configured to Na2WO4Solution；
(3) by the Na of step (2)2WO4Solution instills the Bi of step (1) dropwise2(NO3)3In/acetic acid solution ultrasonic treatment 60 ~
120min obtains reaction system, wherein Na2WO4With Bi2(NO3)3Molar ratio be 1:2, then by reaction system be placed in temperature be 120
Reaction 12 under the conditions of ~ 180 DEG C ~ for 24 hours, cooled to room temperature is separated by solid-liquid separation, and is replaced using dehydrated alcohol and distilled water to solid
Washing more than three times, is dried in vacuo up to porous autonomous dress Bi2WO6Nanosphere.
The present invention prepares bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst method by raw material of HDS dead catalyst
Bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst of preparation can be used for colored dyes rhodamine B of degrading under visible light.
The present invention prepares bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst method by raw material of HDS dead catalyst
Bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst of preparation can be used for reduction of hexavalent chromium under visible light.
Beneficial effects of the present invention:
(1) present invention using sodium tungstate, bismuth nitrate, graphene oxide and extracts molybdic acid from aluminium base hydrodesulfurization dead catalyst
Sodium, ammonium molybdate prepare the rGO-Bi that pattern is single, surface area is big, photocatalytic activity is high with hydro-thermal method for raw material2WO6-
Bi2MoO6Heterojunction photocatalysis material；
(2) present invention is pre-processed using aluminium base hydrodesulfurization dead catalyst as raw material using microwave outfield intensifying technology, is realized
The cleaning of pretreatment stage, low consumption, efficient Leaching Molybdenum；Simultaneously using Leaching Molybdenum prepare photochemical catalyst reached recycle, it is green
The purpose that colour circle is protected.
Detailed description of the invention
Fig. 1 is 1 bismuth tungstate of embodiment/bismuth molybdate/graphene heterojunction photocatalyst SEM figure；
Fig. 2 is 1 bismuth tungstate of embodiment/bismuth molybdate/graphene heterojunction photocatalyst TEM figure；
Fig. 3 is 1 bismuth tungstate of embodiment/bismuth molybdate/graphene heterojunction photocatalyst high magnification TEM figure；
Fig. 4 is 1 bismuth tungstate of embodiment/bismuth molybdate/graphene heterojunction photocatalyst selective electron diffraction figure；
Fig. 5 is that 1 bismuth tungstate of embodiment/bismuth molybdate/graphene heterojunction photocatalyst is degraded sieve under the visible light that xenon lamp is simulated
Red bright B degradation effect figure.
Specific embodiment
Invention is further described in detail With reference to embodiment, but protection scope of the present invention and unlimited
In the content.
Bi in all comparative examples of the present invention and embodiment2WO6The preparation method of nanosphere is
(1) by Bi2(NO3)3·5H2O is added in acetic acid solution, and ultrasonic treatment 10min is configured to Bi2(NO3)3/ acetic acid solution；
(2) by Na2WO4.2H2O is added in distilled water, and ultrasonic treatment 3min is configured to Na2WO4Solution；
(3) by the Na of step (2)2WO4Solution instills the Bi of step (1) dropwise2(NO3)360min is ultrasonically treated in/acetic acid solution
Reaction system is obtained, wherein Na2WO4With Bi2(NO3)3Molar ratio be 1:2, then by reaction system be placed in temperature be 160 DEG C of conditions
For 24 hours, cooled to room temperature is separated by solid-liquid separation for lower reaction, is alternately washed to solid more than three times using dehydrated alcohol and distilled water,
It is dried in vacuo up to porous autonomous dress Bi2WO6Nanosphere.
Comparative example: Bi2MoO6/Bi2WO6The preparation method of composite photo-catalyst, the specific steps are as follows:
(1) ethylene glycol and ethyl alcohol are uniformly mixed and are configured to mixed alcohol A；Wherein the volume ratio of ethylene glycol and ethyl alcohol is 1:3；
(2) by the sodium molybdate, ammonium molybdate and Bi of step (1)2(NO)3·5H2O is uniformly mixed, then slow under Ultrasonic Conditions again
It is added to dissolve in the mixed alcohol A of step (1) and be ultrasonically treated 0.5h and obtains solution B；
(3) by Bi2WO6It is added in the B solution of step (2) and decentralized processing 1h obtains solution C under ultrasonic conditions；Wherein
Bi2WO6In W and step (2) in molybdenum element molar ratio be 1:3；Bi ion is excessive in solution C；
(4) solution C of step (3) is placed in temperature is 140 DEG C of reaction 14h, and cooled to room temperature is separated by solid-liquid separation, using nothing
Alternately washing more than three times, is dried in vacuo up to bismuth tungstate/bismuth molybdate photochemical catalyst to solid for water-ethanol and distilled water.
Embodiment 1: one kind preparing bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst by raw material of HDS dead catalyst
Method, the specific steps are as follows:
(1) aluminium scrap base Hydrobon catalyst is added in ethyl alcohol, de-oiling pretreatment 150min is obtained under ultrasonic conditions
Oil-free aluminium scrap base Hydrobon catalyst；Wherein the pretreated temperature of de-oiling is 60 DEG C, ethyl alcohol and aluminium scrap base hydrodesulfurization catalytic
The liquid-solid ratio mL:g of agent is 7:1, ultrasonic power 800W；
(2) in air atmosphere, by the oil-free aluminium scrap base Hydrobon catalyst of step (1) be placed in temperature be 600 DEG C under the conditions of
Roasting oxidation 1h obtains oxidation pre-treatment dead catalyst；
(3) the oxidation pre-treatment dead catalyst of step (2) is added to Na2CO31h is leached in solution and under ultrasonic wave auxiliary
Obtain Na2MoO4Infusion solution；Wherein ultrasonic power is 800W, oxidation pre-treatment dead catalyst and Na2CO3The liquid of solution is solid
It is 10:1, Na than mL:g2CO3Solution concentration is 1.6 mol/L；
(4) in the Na of step (3)2MoO4The pH value that hydrochloric acid adjusting infusion solution is added in infusion solution is 7 and reacts that solid-liquid divides
From obtaining aluminum hydroxide solid and filtrate A；
(5) the filtrate A of step (4) is at the uniform velocity warming up to 80 DEG C, NH is added4Cl simultaneously reacts, separation of solid and liquid obtain ammonium metavanadate and
Liquor B；Liquor B evaporative crystallization obtains sodium molybdate, ammonium molybdate；Wherein NH4Cl's adds ammonium COEFFICIENT K to be 3；
(6) mixed alcohol of ethylene glycol and ethyl alcohol is added in graphene oxide, ultrasonic disperse handles to obtain graphene oxide/alcohol
Solution A；Wherein the solid-to-liquid ratio g:mL of the mixed alcohol of graphene oxide and ethylene glycol and ethyl alcohol is 0.01:40；
(7) by the sodium molybdate, ammonium molybdate and Bi of step (5)2(NO)3·5H2O is uniformly mixed, then slow under Ultrasonic Conditions again
It is added to dissolve in graphene oxide/alcoholic solution A of step (6) and be ultrasonically treated 0.5h and obtains solution B；
(8) by Bi2WO6It is added in the B solution of step (7) and decentralized processing 1h obtains solution C under ultrasonic conditions；Wherein
Bi2WO6In W and step (7) in molybdenum element molar ratio be 1:1；Bi ion is excessive in solution C；
(9) solution C of step (8) is placed in temperature to react for 24 hours for 120 DEG C, cooled to room temperature is separated by solid-liquid separation, using nothing
Alternately washing more than three times, is dried in vacuo up to bismuth tungstate/bismuth molybdate/graphene hetero-junctions light to solid for water-ethanol and distilled water
Catalyst；
The present embodiment bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst SEM figure is as shown in Figure 1, from fig. 1, it can be seen that pass through
SEM scanning figure can be seen that obtain the Bi that product is dispersion2MoO6Nano particle is embedded in be made of irregular nanometer sheet self assembly
Bi2WO6In nanosphere gap, nanosphere average grain diameter is about 200nm, the Bi being combined into2MoO6 / Bi2WO6Nanosphere load
On the surface of graphene.The Bi of radius and the first step hydro-thermal process preparation of bismuth tungstate2WO6Granularity be basically unchanged；
The present embodiment bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst TEM figure, can as shown in Fig. 2, as can be seen from Figure 2
It is clearly seen that three-dimensional hierarchical structure Bi2WO6Microballoon edge is zigzag, is by being stacked with the three-layer laminated knot intersected to form
Structure, nanometer sheet surface is smooth, there is hole each other；Single Bi2WO6About 20 nm of the thickness of nanometer sheet, length and width be about 60 nm and
The spherical Bi of 40 nm2MoO6Nanoparticle is uniformly scattered in Bi2WO6The surface of nanometer sheet, diameter is in 10 nm or so；
The present embodiment bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst selective electron diffraction figure is as shown in figure 3, from Fig. 3
It is found that diffraction spot forms discontinuous diffraction ring, it is known that nanometer sheet is polycrystalline structure；Diffraction ring accords with orthorhombic crystal phase
Bi2WO6(113), (006), (206) and (313) crystal face；
RGO-Bi2MoO6/Bi2WO6The detection of photocatalytic degradation rhodamine B:
Using xenon long-arc lamp as catalysis light source catalytic degradation rhodamine B to RGO/ Bi2MoO6/Bi2WO6The light of composite material is urged
Change performance to be evaluated, concrete operation step are as follows:
(1) 0.1g RGO-Bi is weighed2MoO6/Bi2WO6Catalyst is added in the rhodamine B solution that 100mL concentration is 10mg/L,
Take the original liquid of 5mL；
(2) mixing is placed in photocatalysis apparatus, opens magnetic stirring apparatus, closes reaction chamber, solution 5mL is taken after half an hour；
(3) cooling circulating water is first connected, xenon long-arc lamp light source is opened, the catalysis reaction time is 90min, takes 5mL molten every 10min
Liquid；
(4) liquid is taken to complete to be centrifuged using centrifuge immediately every time, with the absorbance of spectrophotometric determination rhodamine B solution；
The present embodiment bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst rhodamine B degradation under the visible light that xenon lamp is simulated
Degradation effect figure is as shown in figure 4, as can be seen from Figure 4, select RhB as target degradation product, to Bi2WO6/Bi2MoO6Heterogeneous microballoon exists
Photocatalytic activity under visible light conditions is tested, and the present embodiment bismuth tungstate/bismuth molybdate/graphene is in radiation of visible light
It is degradable that 91.0%, 50min is reached to the degradation rate of RhB in 30min.
Embodiment 2: one kind preparing bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst by raw material of HDS dead catalyst
Method, the specific steps are as follows:
(1) aluminium scrap base Hydrobon catalyst is added in ethyl alcohol, de-oiling pretreatment 120min is obtained under ultrasonic conditions
Oil-free aluminium scrap base Hydrobon catalyst；Wherein the pretreated temperature of de-oiling is 55 DEG C, ethyl alcohol and aluminium scrap base hydrodesulfurization catalytic
The liquid-solid ratio mL:g of agent is 3:1, ultrasonic power 600W；
(2) in air atmosphere, by the oil-free aluminium scrap base Hydrobon catalyst of step (1) be placed in temperature be 800 DEG C under the conditions of
Roasting oxidation 2h obtains oxidation pre-treatment dead catalyst；
(3) the oxidation pre-treatment dead catalyst of step (2) is added to Na2CO3It is leached in solution and under ultrasonic wave auxiliary
1.2h obtains Na2MoO4Infusion solution；Wherein ultrasonic power is 600W, oxidation pre-treatment dead catalyst and Na2CO3Solution
Liquid-solid ratio mL:g is 8:1, Na2CO3Solution concentration is 1.6 mol/L；
(4) in the Na of step (3)2MoO4The pH value that hydrochloric acid adjusting infusion solution is added in infusion solution is 7.5 and reacts, solid-liquid
Isolated aluminum hydroxide solid and filtrate A；
(5) the filtrate A of step (4) is at the uniform velocity warming up to 60 DEG C, NH is added4Cl simultaneously reacts, separation of solid and liquid obtain ammonium metavanadate and
Liquor B；Liquor B evaporative crystallization obtains sodium molybdate, ammonium molybdate；Wherein NH4Cl's adds ammonium COEFFICIENT K to be 4；
(6) mixed alcohol of ethylene glycol and ethyl alcohol is added in graphene oxide, ultrasonic disperse handles to obtain graphene oxide/alcohol
Solution A；Wherein the solid-to-liquid ratio g:mL of the mixed alcohol of graphene oxide and ethylene glycol and ethyl alcohol is 0.03:40；
(7) by the sodium molybdate, ammonium molybdate and Bi of step (5)2(NO)3·5H2O is uniformly mixed, then slow under Ultrasonic Conditions again
It is added to dissolve in graphene oxide/alcoholic solution A of step (6) and be ultrasonically treated 1.0h and obtains solution B；
(8) by Bi2WO6It is added in the B solution of step (7) and decentralized processing 1.4h obtains solution C under ultrasonic conditions；Its
Middle Bi2WO6In W and step (7) in molybdenum element molar ratio be 3:1；Bi ion is excessive in solution C；
(9) solution C of step (8) is placed in temperature is 160 DEG C of reaction 18h, and cooled to room temperature is separated by solid-liquid separation, using nothing
Alternately washing more than three times, is dried in vacuo up to bismuth tungstate/bismuth molybdate/graphene hetero-junctions light to solid for water-ethanol and distilled water
Catalyst；
RGO-Bi2MoO6/Bi2WO6The detection method of photocatalytic degradation rhodamine B is identical as embodiment 1, the present embodiment wolframic acid
Bismuth/bismuth molybdate/graphene heterojunction photocatalyst is to the photocatalytic degradation of rhodamine B, in 30min degradation rate up to 97.7%.
Embodiment 3: one kind preparing bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst by raw material of HDS dead catalyst
Method, the specific steps are as follows:
(1) aluminium scrap base Hydrobon catalyst is added in ethyl alcohol, de-oiling pretreatment 140min is obtained under ultrasonic conditions
Oil-free aluminium scrap base Hydrobon catalyst；Wherein the pretreated temperature of de-oiling is 65 DEG C, ethyl alcohol and aluminium scrap base hydrodesulfurization catalytic
The liquid-solid ratio mL:g of agent is 5:1, ultrasonic power 700W；
(2) in air atmosphere, by the oil-free aluminium scrap base Hydrobon catalyst of step (1) be placed in temperature be 900 DEG C under the conditions of
Roasting oxidation 1.2h obtains oxidation pre-treatment dead catalyst；
(3) the oxidation pre-treatment dead catalyst of step (2) is added to Na2CO32h is leached in solution and under ultrasonic wave auxiliary
Obtain Na2MoO4Infusion solution；Wherein ultrasonic power is 700W, oxidation pre-treatment dead catalyst and Na2CO3The liquid of solution is solid
It is 9:1, Na than mL:g2CO3Solution concentration is 1.6mol/L；
(4) in the Na of step (3)2MoO4The pH value that hydrochloric acid adjusting infusion solution is added in infusion solution is 8 and reacts that solid-liquid divides
From obtaining aluminum hydroxide solid and filtrate A；
(5) the filtrate A of step (4) is at the uniform velocity warming up to 70 DEG C, NH is added4Cl simultaneously reacts, separation of solid and liquid obtain ammonium metavanadate and
Liquor B；Liquor B evaporative crystallization obtains sodium molybdate, ammonium molybdate；Wherein NH4Cl's adds ammonium COEFFICIENT K to be 4；
(6) mixed alcohol of ethylene glycol and ethyl alcohol is added in graphene oxide, ultrasonic disperse handles to obtain graphene oxide/alcohol
Solution A；Wherein the solid-to-liquid ratio g:mL of the mixed alcohol of graphene oxide and ethylene glycol and ethyl alcohol is 0.02:40；
(7) by the sodium molybdate, ammonium molybdate and Bi of step (5)2(NO)3·5H2O is uniformly mixed, then slow under Ultrasonic Conditions again
It is added to dissolve in graphene oxide/alcoholic solution A of step (6) and be ultrasonically treated 1.5 h and obtains solution B；
(8) by Bi2WO6It is added in the B solution of step (7) and decentralized processing 2h obtains solution C under ultrasonic conditions；Wherein
Bi2WO6In W and step (7) in molybdenum element molar ratio be 1.5:1；Bi ion is excessive in solution C；
(9) solution C of step (8) is placed in temperature is 150 DEG C of reaction 20h, and cooled to room temperature is separated by solid-liquid separation, using nothing
Alternately washing more than three times, is dried in vacuo up to bismuth tungstate/bismuth molybdate/graphene hetero-junctions light to solid for water-ethanol and distilled water
Catalyst.
RGO-Bi2MoO6/Bi2WO6The detection method of photocatalytic degradation rhodamine B is identical as embodiment 1, the present embodiment
Bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst is to the photocatalytic degradation of rhodamine B, and 30min degradation rate is up to 93.2%.
Embodiment 4: one kind preparing bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst by raw material of HDS dead catalyst
Method, the specific steps are as follows:
(1) aluminium scrap base Hydrobon catalyst is added in ethyl alcohol, de-oiling pretreatment 130min is obtained under ultrasonic conditions
Oil-free aluminium scrap base Hydrobon catalyst；Wherein the pretreated temperature of de-oiling is 50 DEG C, ethyl alcohol and aluminium scrap base hydrodesulfurization catalytic
The liquid-solid ratio mL:g of agent is 6:1, ultrasonic power 650W；
(2) in air atmosphere, by the oil-free aluminium scrap base Hydrobon catalyst of step (1) be placed in temperature be 800 DEG C under the conditions of
Roasting oxidation 2h obtains oxidation pre-treatment dead catalyst；
(3) the oxidation pre-treatment dead catalyst of step (2) is added to Na2CO3It is leached in solution and under ultrasonic wave auxiliary
1.5h obtains Na2MoO4Infusion solution；Wherein ultrasonic power is 600W, oxidation pre-treatment dead catalyst and Na2CO3Solution
Liquid-solid ratio mL:g is 9:1, Na2CO3Solution concentration is 1.6mol/L；
(4) in the Na of step (3)2MoO4The pH value that hydrochloric acid adjusting infusion solution is added in infusion solution is 7.5 and reacts, solid-liquid
Isolated aluminum hydroxide solid and filtrate A；
(5) the filtrate A of step (4) is at the uniform velocity warming up to 80 DEG C, NH is added4Cl simultaneously reacts, separation of solid and liquid obtain ammonium metavanadate and
Liquor B；Liquor B evaporative crystallization obtains sodium molybdate, ammonium molybdate；Wherein NH4Cl's adds ammonium COEFFICIENT K to be 5；
(6) mixed alcohol of ethylene glycol and ethyl alcohol is added in graphene oxide, ultrasonic disperse handles to obtain graphene oxide/alcohol
Solution A；Wherein the solid-to-liquid ratio g:mL of the mixed alcohol of graphene oxide and ethylene glycol and ethyl alcohol is 0.02:40；
(7) by the sodium molybdate, ammonium molybdate and Bi of step (5)2(NO)3·5H2O is uniformly mixed, then slow under Ultrasonic Conditions again
It is added to dissolve in graphene oxide/alcoholic solution A of step (6) and be ultrasonically treated 0.5h and obtains solution B；
(8) by Bi2WO6It is added in the B solution of step (7) and decentralized processing 2h obtains solution C under ultrasonic conditions；Wherein
Bi2WO6In W and step (7) in molybdenum element molar ratio be 2:1；Bi ion is excessive in solution C；
(9) solution C of step (8) is placed in temperature is 180 DEG C of reaction 12h, and cooled to room temperature is separated by solid-liquid separation, using nothing
Alternately washing more than three times, is dried in vacuo up to bismuth tungstate/bismuth molybdate/graphene hetero-junctions light to solid for water-ethanol and distilled water
Catalyst.
(10) RGO-Bi2MoO6/Bi2WO6The detection method of photocatalytic degradation rhodamine B is identical as embodiment 1, this reality
A bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst is applied to the photocatalytic degradation of rhodamine B, 30min degradation rate reaches
94.2%。
Claims (10)
1. a kind of prepare bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst method by raw material of HDS dead catalyst,
It is characterized in that, the specific steps are as follows:
(1) aluminium scrap base Hydrobon catalyst is added in ethyl alcohol, de-oiling pre-processes 120 ~ 150min under ultrasonic conditions
Obtain oil-free aluminium scrap base Hydrobon catalyst；
(2) in air atmosphere, it is 600 ~ 900 DEG C of items that the oil-free aluminium scrap base Hydrobon catalyst of step (1), which is placed in temperature,
1 ~ 2h of roasting oxidation obtains oxidation pre-treatment dead catalyst under part；
(3) the oxidation pre-treatment dead catalyst of step (2) is added to Na2CO31 ~ 2h is leached in solution and under ultrasonic wave auxiliary
Obtain Na2MoO4Infusion solution；
(4) in the Na of step (3)2MoO4The pH value that hydrochloric acid adjusting infusion solution is added in infusion solution is 7 ~ 8 and reacts, solid-liquid
Isolated aluminum hydroxide solid and filtrate A；
(5) the filtrate A of step (4) is at the uniform velocity warming up to 60 ~ 80 DEG C, NH is added4Cl simultaneously reacts, and separation of solid and liquid obtains ammonium metavanadate
And liquor B；Liquor B evaporative crystallization obtains sodium molybdate, ammonium molybdate；
(6) mixed alcohol of ethylene glycol and ethyl alcohol is added in graphene oxide, ultrasonic disperse handles to obtain graphene oxide/alcohol
Solution A；
(7) by the sodium molybdate, ammonium molybdate and Bi of step (5)2(NO)3·5H2O is uniformly mixed, then slow under Ultrasonic Conditions again
It is added to dissolve in graphene oxide/alcoholic solution A of step (6) and be ultrasonically treated 0.5 ~ 2h and obtains solution B；
(8) by Bi2WO6Nanosphere be added in the B solution of step (7) and under ultrasonic conditions 1 ~ 2h of decentralized processing obtain it is molten
Liquid C；
(9) by the solution C of step (8) be placed in temperature be 120 ~ 180 DEG C reaction 12 ~ for 24 hours, cooled to room temperature, be separated by solid-liquid separation,
Using dehydrated alcohol and distilled water, to solid, alternately washing more than three times, is dried in vacuo different up to bismuth tungstate/bismuth molybdate/graphene
Matter knot photochemical catalyst.
2. preparing bismuth tungstate/bismuth molybdate/graphene hetero-junctions light as raw material using HDS dead catalyst according to claim 1 to urge
The method of agent, it is characterised in that: the pretreated temperature of de-oiling is 50 ~ 65 DEG C, ethyl alcohol and aluminium scrap base Hydrobon catalyst
Liquid-solid ratio mL:g is (3 ~ 7): 1.
3. preparing bismuth tungstate/bismuth molybdate/graphene hetero-junctions light as raw material using HDS dead catalyst according to claim 1 to urge
The method of agent, it is characterised in that: ultrasonic power is 600 ~ 800W.
4. preparing bismuth tungstate/bismuth molybdate/graphene hetero-junctions light as raw material using HDS dead catalyst according to claim 1 to urge
The method of agent, it is characterised in that: step (3) oxidation pre-treatment dead catalyst and Na2CO3The liquid-solid ratio mL:g of solution be (8 ~
10): 1, Na2CO3Solution concentration is 1.6 mol/L.
5. preparing bismuth tungstate/bismuth molybdate/graphene hetero-junctions light as raw material using HDS dead catalyst according to claim 1 to urge
The method of agent, it is characterised in that: NH in step (5)4Cl's adds ammonium COEFFICIENT K to be 3 ~ 5.
6. preparing bismuth tungstate/bismuth molybdate/graphene hetero-junctions light as raw material using HDS dead catalyst according to claim 1 to urge
The method of agent, it is characterised in that: the solid-to-liquid ratio g:mL of graphene oxide and ethylene glycol and the mixed alcohol of ethyl alcohol is in step (6)
(0.01~0.03):40。
7. preparing bismuth tungstate/bismuth molybdate/graphene hetero-junctions light as raw material using HDS dead catalyst according to claim 1 to urge
The method of agent, it is characterised in that: Bi in step (8)2WO6In W and step (7) in molybdenum element molar ratio be (1:1) ~ (3:
1)；Bi ion is excessive in solution C.
8. preparing bismuth tungstate/bismuth molybdate/graphene hetero-junctions light as raw material using HDS dead catalyst according to claim 1 to urge
The method of agent, it is characterised in that: Bi2WO6The preparation method of nanosphere is
(1) by Bi2(NO3)3·5H2O is added in acetic acid solution, and 10 ~ 30min of ultrasonic treatment is configured to Bi2(NO3)3/ acetic acid is molten
Liquid；
(2) by Na2WO4.2H2O is added in distilled water, and 3 ~ 10min of ultrasonic treatment is configured to Na2WO4Solution；
(3) by the Na of step (2)2WO4Solution instills the Bi of step (1) dropwise2(NO3)3In/acetic acid solution ultrasonic treatment 60 ~
120min obtains reaction system, then reaction system is placed in reaction 12 under the conditions of temperature is 120 ~ 180 DEG C ~ for 24 hours, naturally cools to
Room temperature is separated by solid-liquid separation, and using dehydrated alcohol and distilled water, to solid, alternately washing more than three times, is dried in vacuo up to porous autonomous
Fill Bi2WO6Nanosphere.
9. preparing bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst by raw material of HDS dead catalyst described in claim 1
Method preparation bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst can be used for colored dyes sieve of degrading under visible light
Red bright B.
10. preparing bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst by raw material of HDS dead catalyst described in claim 1
Method preparation bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst can be used for reduction of hexavalent chromium under visible light.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910227985.4A CN109967067A (en) | 2019-03-25 | 2019-03-25 | A method of bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst is prepared by raw material of HDS dead catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910227985.4A CN109967067A (en) | 2019-03-25 | 2019-03-25 | A method of bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst is prepared by raw material of HDS dead catalyst |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109967067A true CN109967067A (en) | 2019-07-05 |
Family
ID=67080458
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910227985.4A Pending CN109967067A (en) | 2019-03-25 | 2019-03-25 | A method of bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst is prepared by raw material of HDS dead catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109967067A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111036193A (en) * | 2019-11-26 | 2020-04-21 | 昆明理工大学 | Preparation method and application of graphene-based hollow hierarchical structure composite photocatalyst |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1752021A (en) * | 2004-09-24 | 2006-03-29 | 刘亚光 | Method of producing ranadium pentoxide using vanadium containing waste catalyst |
| CN102050492A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for recovering metal from molybdenum-containing spent catalyst |
| JP2012091991A (en) * | 2010-09-30 | 2012-05-17 | Ohara Inc | Glass ceramic, method for producing the same, photocatalyst containing the same, slurry mixture, photocatalyst member, purifying device, filter, sintered compact and glass ceramic composite |
| CN103877971A (en) * | 2014-03-07 | 2014-06-25 | 中国科学院东北地理与农业生态研究所 | Efficient visible-light-induced photocatalyst and preparation method thereof |
| CN105727933A (en) * | 2016-03-16 | 2016-07-06 | 新乡医学院 | Bismuth tungstate-bismuth molybdate heterojunction photocatalytic material, method for preparing same and application of bismuth tungstate-bismuth molybdate heterojunction photocatalytic material |
| CN106040310A (en) * | 2016-06-06 | 2016-10-26 | 东华大学 | Preparation method for textile fiber/graphene/Bi2MoO6/Bi2WO6 composite environmental catalytic material |
-
2019
- 2019-03-25 CN CN201910227985.4A patent/CN109967067A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1752021A (en) * | 2004-09-24 | 2006-03-29 | 刘亚光 | Method of producing ranadium pentoxide using vanadium containing waste catalyst |
| CN102050492A (en) * | 2009-10-27 | 2011-05-11 | 中国石油化工股份有限公司 | Method for recovering metal from molybdenum-containing spent catalyst |
| JP2012091991A (en) * | 2010-09-30 | 2012-05-17 | Ohara Inc | Glass ceramic, method for producing the same, photocatalyst containing the same, slurry mixture, photocatalyst member, purifying device, filter, sintered compact and glass ceramic composite |
| CN103877971A (en) * | 2014-03-07 | 2014-06-25 | 中国科学院东北地理与农业生态研究所 | Efficient visible-light-induced photocatalyst and preparation method thereof |
| CN105727933A (en) * | 2016-03-16 | 2016-07-06 | 新乡医学院 | Bismuth tungstate-bismuth molybdate heterojunction photocatalytic material, method for preparing same and application of bismuth tungstate-bismuth molybdate heterojunction photocatalytic material |
| CN106040310A (en) * | 2016-06-06 | 2016-10-26 | 东华大学 | Preparation method for textile fiber/graphene/Bi2MoO6/Bi2WO6 composite environmental catalytic material |
Non-Patent Citations (4)
| Title |
|---|
| 中国冶金百科全书总编辑委员会: "《中国冶金百科全书：有色金属冶金》", 31 January 1999, 冶金工业出版社 * |
| 姜宇晴等: "钨酸铋-石墨烯复合光催化剂的制备及其光催化性能", 《大连工业大学学报》 * |
| 王璐: "超声波辅助石油炼制废催化剂除油实验研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
| 贺格平等: "《半导体材料》", 31 August 2018, 北京：冶金工业出版社 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111036193A (en) * | 2019-11-26 | 2020-04-21 | 昆明理工大学 | Preparation method and application of graphene-based hollow hierarchical structure composite photocatalyst |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106076421B (en) | A kind of MIL-53 (Fe)/g-C3N4The preparation method of nanometer sheet composite photocatalyst material | |
| Mohapatra et al. | Photocatalytic reduction of hexavalent chromium in aqueous solution over sulphate modified titania | |
| Xiao et al. | Fabrication of ultrafine ZnFe2O4 nanoparticles for efficient photocatalytic reduction CO2 under visible light illumination | |
| Issarapanacheewin et al. | A novel CeO2/Bi2WO6 composite with highly enhanced photocatalytic activity | |
| CN109772355A (en) | Amorphous FeOOH/alum acid bismuth composite photocatalyst material preparation method | |
| CN104117367B (en) | A kind of BiOBr/RGO composite aerogel and its preparation method and application | |
| CN107715906B (en) | A kind of preparation method of the direct Z-type heterojunction composite photocatalyst of carbonitride/zinc titanate/titanium oxide sandwich-like | |
| CN105797753A (en) | MoS2/TiO2 two-dimensional composite nanometer photocatalyst and preparation method and application thereof | |
| CN110064394A (en) | A kind of Ag@Ag with high catalytic degradation activity2O/BiOCl composite material and preparation method | |
| CN103831093A (en) | Zinc oxide based composite photocatalytic nano-material and preparation method thereof | |
| CN102172540A (en) | Polyoxometallate-based industrial dye decoloring photocatalyst and preparation method thereof | |
| CN105056973B (en) | Efficient Bi2S3-BiFeO3 composite visible-light-driven photocatalyst prepared through in-situ growth with chemical corrosion method and application of Bi2S3-BiFeO3 composite visible-light-driven photocatalyst | |
| CN106512987A (en) | Ismuth tungstate/graphene aerogel compound visible-light-induced photocatalyst and preparation method thereof | |
| CN104667950A (en) | Method for preparing graphene-SnIn4S8 nano composite photocatalyst at low temperature by adopting coprecipitation method | |
| CN106582812A (en) | Composite photocatalyst with titanium dioxide axially functionalized by metallic zinc porphyrin and preparation method thereof | |
| CN109201100A (en) | A kind of Z-type hetero-junctions g-C of load silver3N4@Bi4O7Nanocomposite and preparation method thereof | |
| Feng et al. | Facile synthesis of Cu2O nanoparticle-loaded carbon nanotubes composite catalysts for reduction of 4-nitrophenol | |
| Yang et al. | Investigation of electron beam irradiation on In2S3-MxInySz (M= Bi or La) Z-scheme heterojunctions for efficient and stable degradation of water pollutants | |
| CN105668649A (en) | Preparation method and application of nano Co3O4 catalyst with cubic morphology | |
| Song et al. | Template assisted synthesis of Ag/AgBr/AgCl hollow microspheres with heterojunction structure as highly activity and stability photocatalyst | |
| CN109967067A (en) | A method of bismuth tungstate/bismuth molybdate/graphene heterojunction photocatalyst is prepared by raw material of HDS dead catalyst | |
| Al-Mhyawi et al. | Enhancement of photocatalytic activity of Gd (OH) 3 nanoparticles by Pd deposition for reduction of CO2 to methanol | |
| CN102806078B (en) | Method for preparing one-dimensional hollow superstructure photocatalytic material of Bi system composite oxide | |
| CN107159218A (en) | The preparation method of nanometer copper sheet/Zinc oxide nano sheet composite and application | |
| CN107570159A (en) | One kind prepares high-performance black TiO2The method of photochemical catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190705 |