CN108311163A - A kind of bismuth oxybromide composite photo-catalyst and preparation method thereof for hydrogen manufacturing - Google Patents
A kind of bismuth oxybromide composite photo-catalyst and preparation method thereof for hydrogen manufacturing Download PDFInfo
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- CN108311163A CN108311163A CN201810159617.6A CN201810159617A CN108311163A CN 108311163 A CN108311163 A CN 108311163A CN 201810159617 A CN201810159617 A CN 201810159617A CN 108311163 A CN108311163 A CN 108311163A
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- bismuth oxybromide
- catalyst
- bismuth
- composite photo
- hydrogen manufacturing
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- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 77
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 44
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 42
- 239000001257 hydrogen Substances 0.000 title claims abstract description 42
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 33
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 44
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims abstract description 40
- 229910052750 molybdenum Inorganic materials 0.000 claims abstract description 37
- 239000011733 molybdenum Substances 0.000 claims abstract description 37
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical compound [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 claims abstract description 29
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 26
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 claims abstract description 24
- 239000011669 selenium Substances 0.000 claims abstract description 24
- 229910052711 selenium Inorganic materials 0.000 claims abstract description 24
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 23
- 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 claims abstract description 21
- 239000008367 deionised water Substances 0.000 claims abstract description 20
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 20
- 239000007788 liquid Substances 0.000 claims abstract description 17
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 17
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 17
- 238000009938 salting Methods 0.000 claims abstract description 15
- 235000010265 sodium sulphite Nutrition 0.000 claims abstract description 14
- 238000010438 heat treatment Methods 0.000 claims abstract description 9
- 238000000034 method Methods 0.000 claims abstract description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000001291 vacuum drying Methods 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 238000006243 chemical reaction Methods 0.000 claims description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 15
- 239000012153 distilled water Substances 0.000 claims description 15
- 239000003054 catalyst Substances 0.000 claims description 12
- -1 is dried in vacuo Chemical compound 0.000 claims description 10
- 150000002751 molybdenum Chemical class 0.000 claims description 9
- RVIXKDRPFPUUOO-UHFFFAOYSA-N dimethylselenide Chemical compound C[Se]C RVIXKDRPFPUUOO-UHFFFAOYSA-N 0.000 claims description 8
- 238000001556 precipitation Methods 0.000 claims description 8
- ALCDAWARCQFJBA-UHFFFAOYSA-N ethylselanylethane Chemical compound CC[Se]CC ALCDAWARCQFJBA-UHFFFAOYSA-N 0.000 claims description 4
- OZCBRUAHGPOZBQ-UHFFFAOYSA-N 2-tert-butylselanyl-2-methylpropane Chemical compound CC(C)(C)[Se]C(C)(C)C OZCBRUAHGPOZBQ-UHFFFAOYSA-N 0.000 claims description 3
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 3
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 3
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052794 bromium Inorganic materials 0.000 claims description 3
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 claims description 3
- 230000004044 response Effects 0.000 claims description 2
- 238000010025 steaming Methods 0.000 claims description 2
- 241000372132 Hydrometridae Species 0.000 claims 1
- 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 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 238000000926 separation method Methods 0.000 abstract description 4
- 230000006641 stabilisation Effects 0.000 abstract description 2
- 238000011105 stabilization Methods 0.000 abstract description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- 239000000047 product Substances 0.000 description 9
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 8
- 230000000694 effects Effects 0.000 description 8
- 239000000243 solution Substances 0.000 description 8
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 6
- QPLDLSVMHZLSFG-UHFFFAOYSA-N CuO Inorganic materials [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 6
- 229960004643 cupric oxide Drugs 0.000 description 6
- 239000002114 nanocomposite Substances 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- 239000002159 nanocrystal Substances 0.000 description 5
- 238000006303 photolysis reaction Methods 0.000 description 5
- 239000000725 suspension Substances 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 239000005751 Copper oxide Substances 0.000 description 3
- KVXTWIFOTZIRJQ-UHFFFAOYSA-N [S-2].[Cd+2].O(Br)Br.[Bi+3] Chemical compound [S-2].[Cd+2].O(Br)Br.[Bi+3] KVXTWIFOTZIRJQ-UHFFFAOYSA-N 0.000 description 3
- 229910052797 bismuth Inorganic materials 0.000 description 3
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910000431 copper oxide Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 235000005979 Citrus limon Nutrition 0.000 description 2
- 244000131522 Citrus pyriformis Species 0.000 description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- 230000003115 biocidal effect Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000002274 desiccant Substances 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000015843 photosynthesis, light reaction Effects 0.000 description 2
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 2
- 239000004810 polytetrafluoroethylene Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 229960005196 titanium dioxide Drugs 0.000 description 2
- 235000010215 titanium dioxide Nutrition 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- YCIHPQHVWDULOY-FMZCEJRJSA-N (4s,4as,5as,6s,12ar)-4-(dimethylamino)-1,6,10,11,12a-pentahydroxy-6-methyl-3,12-dioxo-4,4a,5,5a-tetrahydrotetracene-2-carboxamide;hydrochloride Chemical compound Cl.C1=CC=C2[C@](O)(C)[C@H]3C[C@H]4[C@H](N(C)C)C(=O)C(C(N)=O)=C(O)[C@@]4(O)C(=O)C3=C(O)C2=C1O YCIHPQHVWDULOY-FMZCEJRJSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000004065 wastewater treatment 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
- C01B3/042—Decomposition of water
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The bismuth oxybromide composite photo-catalyst and preparation method thereof that the invention discloses a kind of for hydrogen manufacturing.The bismuth oxybromide composite photo-catalyst is made by following steps：A, cetyl trimethylammonium bromide and bismuth nitrate are added in deionized water, Hybrid Heating carries out hydro-thermal reaction, and bismuth oxybromide nanometer sheet is made；B, ultrasonic disperse in molybdenum salting liquid is added in bismuth oxybromide nanometer sheet, adds selenium source, sodium sulfite and sodium borohydride, carry out microwave hydrothermal reaction to get the bismuth oxybromide for hydrogen manufacturing/selenizing molybdenum composite photo-catalyst.The method has the advantages that：Using the nanocrystalline homoepitaxial of selenizing molybdenum on the surface of bismuth oxybromide nanometer sheet, increase specific surface area, improve the utilization rate of sunlight, and be conducive to carrier separation, bismuth oxybromide and selenizing molybdenum structure stabilization and band-gap simultaneously, photocatalytic activity is good, and catalytic effect is stablized, and has excellent photocatalytic water H2-producing capacity.
Description
Technical field
The present invention relates to catalyzing manufacturing of hydrogen fields, and in particular to the preparation of photochemical catalyst being used for hydrogen manufacturing more particularly, to one kind
Bismuth oxybromide composite photo-catalyst and preparation method thereof.
Background technology
Under the dual-pressure of energy crisis and environmental problem, Hydrogen Energy because of its fuel value height, rich reserves, pollution-free form
To be most hopeful to substitute the clean energy resource of existing fossil energy, thus the exploitation of Hydrogen Energy is at the research hotspot of energy field.From
Since being found that titanium-dioxide photo electrochemical energy decomposed water generation hydrogen and oxygen in 1972 from Fujishima and Honda, section
It is to realize that solar photolysis water hydrogen is being made unremitting efforts to always to learn researcher.Over nearly ten or twenty year, other than titanium dioxide
The successive discovery of photochemical catalyst, especially can responding to visible light catalysis material appearance so that photolysis water hydrogen study into
Enter and has enlivened very much period.
BiOX is a kind of novel semi-conductor photocatalyst material developed in recent years.The study found that with phase
The band gap of increase to atomic weight, BiOX is smaller, and this provides for improved the possibilities in broad spectrum spectral absorption.However,
The microstructure of material will also directly affect its physical/chemical, studies have shown that the BiOX of nano-scale has because of it
The specific surface area of bigger and more active sites, the more conducively separation of light induced electron and hole are lived to improve its photocatalysis
Property.And current photochemical catalyst mostly uses ultraviolet light and carries out catalyzing manufacturing of hydrogen, but ultraviolet light accounted in sunlight ratio only has 2%,
Therefore it is the key content studied at present that photochemical catalyst, which makes full use of sunlight,.
Number of patent application 201710808244.6 disclose a kind of bismuth oxybromide-cadmium sulfide nano composite photo-catalyst and its
Preparation method is related to photocatalyst material preparing technical field.It is anti-first with cetyl trimethylammonium bromide and bismuth nitrate
Bismuth oxybromide nanometer sheet should be prepared, then reaction generates CdS nanocrystal in bismuth oxybromide nanometer sheet.Prepared by the invention
Bismuth oxybromide-cadmium sulfide nano composite photo-catalyst, microstructure are：CdS nanocrystal is equably grown in bismuth oxybromide
On the surface of nanometer sheet, square structure is mainly presented in bismuth oxybromide nanometer sheet, the cadmium sulfide being grown in bismuth oxybromide nanometer sheet
Nanocrystalline is quantum dot, and particle size is between 1 ~ 5nm.This bismuth oxybromide-cadmium sulfide nano composite photo-catalyst has high
Visible light catalysis activity is remarkably improved the degradation rate of organic dyestuff, is expected to be used for sunlight degradation organic pollutants.
This preparation method process equipment is simple, easy to operate, and reproducible, raw material is cheap and easy to get, is suitble to industrialization production.
Number of patent application 201710176935.9 discloses a kind of three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst,
Including following raw material components：Bismuth nitrate, cetyl trimethylammonium bromide, ethylene glycol, cadmium sulfide；Preparation method includes following
Step：First, bismuth nitrate/ethylene glycol mixed solution is mixed with cetyl trimethylammonium bromide/ethylene glycol mixed solution, is obtained
Bismuth oxybromide precursor liquid, and sediment A is reacted to obtain, sediment A is centrifuged, drying is washed, finally bakes, that is, be prepared into again
Bismuth oxybromide microballoon；Then, cadmium sulfide and bismuth oxybromide microballoon are mixed, deionized water stirring is added, obtains three-dimensional cadmium sulfide/bromine
Bismuth oxide hetero-junctions precursor liquid, and react to obtain sediment B, sediment B is centrifuged, washing it is dry to get.The three of the present invention
The preparation method process of tieing up cadmium sulfide/bismuth oxybromide heterojunction photocatalyst is simple, morphology controllable, environmental-friendly, is urged for light
Change reduction CO2, improve photo catalytic reduction CO2Reaction rate.
Number of patent application 201710814494.0 disclose a kind of bismuth oxybromide-cupric oxide nano composite photo-catalyst and its
Preparation method is related to photocatalyst material preparing technical field.It is anti-first with cetyl trimethylammonium bromide and bismuth nitrate
Bismuth oxybromide nanometer sheet should be prepared, then reaction generates copper oxide nanocrystal in bismuth oxybromide nanometer sheet.Prepared by the invention
Bismuth oxybromide-cupric oxide nano composite photo-catalyst, microstructure are：Copper oxide nanocrystal is equably grown in bismuth oxybromide and receives
On rice piece surface, bismuth oxybromide nanometer sheet is rounded, a diameter of 0.5 ~ 2 μm, and piece thickness is 20 ~ 50nm, and copper oxide nanocrystal is amount
Sub-, particle size is between 1 ~ 5nm.Bismuth oxybromide-cupric oxide nano composite photo-catalyst has high visible light catalysis activity,
It is remarkably improved the degradation rate of organic dyestuff, is expected to be used for sunlight degradation organic pollutants.Preparation method technique is set
Standby simple, easy to operate, reproducible, raw material is cheap and easy to get, is suitble to industrialization production.
Number of patent application 201710599998.5 discloses a kind of preparation method of tungsten oxide/bismuth oxybromide composite material.
Weigh a certain amount of Bi24O31Br10Powder, is added a certain amount of deionized water thereto, and ultrasound, stirring make it be uniformly dispersed, obtain
Suspension 1；A certain amount of WO3 powders are weighed again, a certain amount of deionized water is added thereto, and ultrasound, stirring keep its dispersion equal
It is even, obtain suspension 2；Then two suspensions are mixed, stirs 8 ~ 12h, obtains suspension 3；Then by 3 turns of gained suspension
It moves on in the reaction kettle that liner is polytetrafluoroethylene (PTFE), is put into baking oven, carry out hydro-thermal reaction；After room temperature, from
The heart goes out yellow solid precipitate, wash, dry, take out, with grind be ground to it is powdered after it is spare.Prepared composite photo-catalyst
Under visible light exposure can effective catalytic degradation antibiotic quadracycline, have potential application in the wastewater treatment of antibiotic
Foreground.
It can be seen that there are specific surface areas is small for oxygen bismuth oxybromide photocatalyst in the prior art, solar energy utilization ratio is low, light
The defects of poor catalytic activity, hydrogen manufacturing low yield and poor effect, and traditional composite modification technology, there are structural instability, performance carries
Rise the problems such as limited.
Invention content
Effectively to solve above-mentioned technical problem, the present invention proposes a kind of bismuth oxybromide composite photo-catalyst for hydrogen manufacturing
And preparation method thereof, the specific surface area of catalyst can be effectively improved, the utilization rate to sunlight is promoted, to significantly improve system
Hydrogen effect.
The specific technical solution of the present invention is as follows：
A kind of preparation method of bismuth oxybromide composite photo-catalyst for hydrogen manufacturing, the bismuth oxybromide composite photo-catalyst be by
Cetyl trimethylammonium bromide and bismuth nitrate carry out hydro-thermal reaction and synthesize bismuth oxybromide nanometer sheet, then using molybdenum salt, selenium source, Asia
Sodium sulphate and sodium borohydride are reacted by microwave hydrothermal by the surface homoepitaxial selenizing molybdenum of bismuth oxybromide nanometer sheet is nanocrystalline
It is made, specific preparation process is：
A, cetyl trimethylammonium bromide and bismuth nitrate are added in deionized water, 8 ~ 12min is vigorously stirred under room temperature, be added
The sodium hydroxide solution that mass concentration is 50 ~ 70% adjusts pH value to 9.5 ~ 10.5, continues 50 ~ 70min of stirring, heating carries out water
Thermal response filters after reaction, is washed repeatedly to precipitation using distilled water and absolute ethyl alcohol, is dried in vacuo, and bromine is made
Bismuth oxide nanometer sheet；
B, bismuth oxybromide nanometer sheet made from step a is added in the molybdenum salting liquid that mass concentration is 40 ~ 50%, ultrasonic disperse, then
Selenium source, sodium sulfite and sodium borohydride is added, stirs 5 ~ 10min, adjusts pH value to 3 ~ 4, microwave hydrothermal reaction is carried out, using steaming
Distilled water and absolute ethyl alcohol wash product repeatedly, and the bismuth oxybromide for hydrogen manufacturing/selenizing molybdenum complex light is made in vacuum drying
Catalyst.
Preferably, in the step a, 25 ~ 30 parts by weight of cetyl trimethylammonium bromide, 22 ~ 27 parts by weight of bismuth nitrate,
39 ~ 51 parts by weight of deionized water.
Preferably, the temperature of hydro-thermal reaction described in step a is 150 ~ 170 DEG C, and the time is 16 ~ 20h.
Preferably, vacuum drying temperature described in step a is 45 ~ 55 DEG C, and the time is 3 ~ 5h.
Preferably, the molybdenum salt is at least one in molybdenum dialkyl-dithiophosphate or molybdenum dialkyldithiocarbamacompositions
Kind.
Preferably, the selenium source is at least one of dimethyl-selenide, diethyl selenide or di-t-butyl selenium.
Preferably, in the step b, 30 ~ 34 parts by weight of bismuth oxybromide nanometer sheet, 38 ~ 48 parts by weight of molybdenum salting liquid, selenium source
17 ~ 20 parts by weight, 3 ~ 5 parts by weight of sodium sulfite, 2 ~ 3 parts by weight of sodium borohydride.
Preferably, the temperature that microwave hydrothermal described in step b reacts is 120 ~ 140 DEG C, and the time is 4 ~ 5h, and microwave frequency is
500 ~ 1000MHz, wavelength are 200 ~ 400mm.
Preferably, vacuum drying temperature described in step b is 60 ~ 70 DEG C, and the time is 2 ~ 3h.
The present invention further provides a kind of bismuth oxybromide composite photocatalysts for hydrogen manufacturing being prepared by the above method
Agent.
The present invention is used for the bismuth oxybromide composite photo-catalyst of hydrogen manufacturing, and microstructure is that the nanocrystalline homoepitaxial of selenizing molybdenum exists
On the surface of bismuth oxybromide nanometer sheet so that the composite photo-catalyst of preparation, which has, comes into contact in a large area interface, can make full use of
Sunlight is conducive to carrier separation, and bismuth oxybromide and selenizing molybdenum structure stabilization and band-gap, improves photocatalysis work
Property, catalytic effect is stablized, and with excellent photocatalytic water H2-producing capacity, application prospect is good.
Beneficial effects of the present invention are：
1. proposing a kind of bismuth oxybromide composite photo-catalyst for hydrogen manufacturing.
2. proposing a kind of preparation method of the bismuth oxybromide composite photo-catalyst for hydrogen manufacturing.
3. composite photo-catalyst produced by the present invention, using the nanocrystalline homoepitaxial of selenizing molybdenum in bismuth oxybromide nanometer sheet
On surface, specific surface area is increased, improves the utilization rate of sunlight, and is conducive to carrier separation.
4. in composite photo-catalyst prepared by the present invention, bismuth oxybromide is stable with selenizing molybdenum structure and band-gap, light are urged
It is good to change activity, catalytic effect is stablized, and has excellent photocatalytic water H2-producing capacity.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
A, cetyl trimethylammonium bromide and bismuth nitrate are added in deionized water, 10min is vigorously stirred under room temperature, matter is added
The sodium hydroxide solution for measuring a concentration of 60% adjusts pH value to 9.5, continues to stir 60min, heating carries out hydro-thermal reaction, reaction knot
It filters after beam, precipitation is washed repeatedly using distilled water and absolute ethyl alcohol, be dried in vacuo, bismuth oxybromide nanometer sheet is made；
B, bismuth oxybromide nanometer sheet made from step a is added in the molybdenum salting liquid that mass concentration is 45%, ultrasonic disperse, then added
Enter selenium source, sodium sulfite and sodium borohydride, stir 8min, using lemon acid for adjusting pH value to 3, carries out microwave hydrothermal reaction, adopt
Product is washed repeatedly with distilled water and absolute ethyl alcohol, is dried in vacuo, it is multiple that the bismuth oxybromide for hydrogen manufacturing/selenizing molybdenum is made
Closing light catalyst.
In step a, 28 parts by weight of cetyl trimethylammonium bromide, 25 parts by weight of bismuth nitrate, 44 parts by weight of deionized water；
In step b, 32 parts by weight of bismuth oxybromide nanometer sheet, 44 parts by weight of molybdenum salting liquid, 18 parts by weight of selenium source, 4 parts by weight of sodium sulfite,
2 parts by weight of sodium borohydride.
Molybdenum salt is molybdenum dialkyl-dithiophosphate；Selenium source is dimethyl-selenide.
The temperature of step a hydro-thermal reactions is 160 DEG C, time 18h；Vacuum drying temperature is 50 DEG C, time 4h.
The temperature of step b microwave hydrothermals reaction is 130 DEG C, time 4.5h, microwave frequency 800MHz, and wavelength is
300mm；Vacuum drying temperature is 65 DEG C, time 2.5h.
Embodiment 2
A, cetyl trimethylammonium bromide and bismuth nitrate are added in deionized water, 8min is vigorously stirred under room temperature, matter is added
The sodium hydroxide solution for measuring a concentration of 50% adjusts pH value to 10.5, continues to stir 50min, heating carries out hydro-thermal reaction, reaction knot
It filters after beam, precipitation is washed repeatedly using distilled water and absolute ethyl alcohol, be dried in vacuo, bismuth oxybromide nanometer sheet is made；
B, bismuth oxybromide nanometer sheet made from step a is added in the molybdenum salting liquid that mass concentration is 40%, ultrasonic disperse, then added
Enter selenium source, sodium sulfite and sodium borohydride, stir 5min, using lemon acid for adjusting pH value to 4, carries out microwave hydrothermal reaction, adopt
Product is washed repeatedly with distilled water and absolute ethyl alcohol, is dried in vacuo, it is multiple that the bismuth oxybromide for hydrogen manufacturing/selenizing molybdenum is made
Closing light catalyst.
In step a, 25 parts by weight of cetyl trimethylammonium bromide, 22 parts by weight of bismuth nitrate, 51 parts by weight of deionized water；
In step b, 30 ~ 3 parts by weight of bismuth oxybromide nanometer sheet, 48 parts by weight of molybdenum salting liquid, 17 parts by weight of selenium source, 3 weight of sodium sulfite
Part, 2 parts by weight of sodium borohydride.
Molybdenum salt is molybdenum dialkyldithiocarbamacompositions；Selenium source is diethyl selenide.
The temperature of step a hydro-thermal reactions is 150 DEG C, time 20h；Vacuum drying temperature is 45 DEG C, time 5h.
The temperature of step b microwave hydrothermals reaction is 120 DEG C, time 5h, microwave frequency 500MHz, wavelength 200 ~
400mm；Vacuum drying temperature is 60 DEG C, time 3h.
Embodiment 3
A, cetyl trimethylammonium bromide and bismuth nitrate are added in deionized water, 12min is vigorously stirred under room temperature, matter is added
The sodium hydroxide solution for measuring a concentration of 70% adjusts pH value to 9.5, continues to stir 70min, heating carries out hydro-thermal reaction, reaction knot
It filters after beam, precipitation is washed repeatedly using distilled water and absolute ethyl alcohol, be dried in vacuo, bismuth oxybromide nanometer sheet is made；
B, bismuth oxybromide nanometer sheet made from step a is added in the molybdenum salting liquid that mass concentration is 50%, ultrasonic disperse, then added
Enter selenium source, sodium sulfite and sodium borohydride, stir 10min, using vinegar acid for adjusting pH value to 3, carries out microwave hydrothermal reaction, use
Distilled water and absolute ethyl alcohol wash product repeatedly, and it is compound that the bismuth oxybromide for hydrogen manufacturing/selenizing molybdenum is made in vacuum drying
Photochemical catalyst.
In step a, 30 parts by weight of cetyl trimethylammonium bromide, 27 parts by weight of bismuth nitrate, 39 parts by weight of deionized water；
In step b, 34 parts by weight of bismuth oxybromide nanometer sheet, 38 parts by weight of molybdenum salting liquid, 20 parts by weight of selenium source, 5 parts by weight of sodium sulfite,
3 parts by weight of sodium borohydride.
Molybdenum salt is molybdenum dialkyl-dithiophosphate；Selenium source is di-t-butyl selenium.
The temperature of step a hydro-thermal reactions is 170 DEG C, time 16h；Vacuum drying temperature is 55 DEG C, time 3h.
The temperature of step b microwave hydrothermals reaction is 140 DEG C, time 4h, microwave frequency 1000MHz, and wavelength is
200mm；Vacuum drying temperature is 70 DEG C, time 2h.
Embodiment 4
A, cetyl trimethylammonium bromide and bismuth nitrate are added in deionized water, 9min is vigorously stirred under room temperature, matter is added
The sodium hydroxide solution for measuring a concentration of 55% adjusts pH value to 10, continues to stir 55min, heating carries out hydro-thermal reaction, and reaction terminates
After filter, precipitation is washed repeatedly using distilled water and absolute ethyl alcohol, is dried in vacuo, obtained bismuth oxybromide nanometer sheet；
B, bismuth oxybromide nanometer sheet made from step a is added in the molybdenum salting liquid that mass concentration is 42%, ultrasonic disperse, then added
Enter selenium source, sodium sulfite and sodium borohydride, stir 9min, adjust pH value to 4, carry out microwave hydrothermal reaction, using distilled water and
Absolute ethyl alcohol washs product repeatedly, and the bismuth oxybromide for hydrogen manufacturing/selenizing molybdenum composite photocatalyst is made in vacuum drying
Agent.
In step a, 26 parts by weight of cetyl trimethylammonium bromide, 24 parts by weight of bismuth nitrate, 48 parts by weight of deionized water；
In step b, 31 parts by weight of bismuth oxybromide nanometer sheet, 46 parts by weight of molybdenum salting liquid, 18 parts by weight of selenium source, 3 parts by weight of sodium sulfite,
2 parts by weight of sodium borohydride.
Molybdenum salt is molybdenum dialkyldithiocarbamacompositions；Selenium source is dimethyl-selenide.
The temperature of step a hydro-thermal reactions is 155 DEG C, time 19h；Vacuum drying temperature is 50 DEG C, time 5h.
The temperature of step b microwave hydrothermals reaction is 125 DEG C, time 5h, microwave frequency 700MHz, wavelength 350mm；
Vacuum drying temperature is 62 DEG C, time 3h.
Embodiment 5
A, cetyl trimethylammonium bromide and bismuth nitrate are added in deionized water, 11min is vigorously stirred under room temperature, matter is added
The sodium hydroxide solution for measuring a concentration of 65% adjusts pH value to 9.5, continues to stir 60min, heating carries out hydro-thermal reaction, reaction knot
It filters after beam, precipitation is washed repeatedly using distilled water and absolute ethyl alcohol, be dried in vacuo, bismuth oxybromide nanometer sheet is made；
B, bismuth oxybromide nanometer sheet made from step a is added in the molybdenum salting liquid that mass concentration is 48%, ultrasonic disperse, then added
Enter selenium source, sodium sulfite and sodium borohydride, stir 8min, adjust pH value to 3, carry out microwave hydrothermal reaction, using distilled water and
Absolute ethyl alcohol washs product repeatedly, and the bismuth oxybromide for hydrogen manufacturing/selenizing molybdenum composite photocatalyst is made in vacuum drying
Agent.
In step a, 29 parts by weight of cetyl trimethylammonium bromide, 25 parts by weight of bismuth nitrate, 42 parts by weight of deionized water；
In step b, 33 parts by weight of bismuth oxybromide nanometer sheet, 41 parts by weight of molybdenum salting liquid, 19 parts by weight of selenium source, 5 parts by weight of sodium sulfite,
2 parts by weight of sodium borohydride.
Molybdenum salt is molybdenum dialkyl-dithiophosphate；Selenium source is diethyl selenide.
The temperature of step a hydro-thermal reactions is 165 DEG C, time 17h；Vacuum drying temperature is 55 DEG C, time 4h.
The temperature of step b microwave hydrothermals reaction is 135 DEG C, time 4.5h, microwave frequency 900MHz, and wavelength is
250mm；Vacuum drying temperature is 65 DEG C, time 2h.
Comparative example 1
Cetyl trimethylammonium bromide and bismuth nitrate are added in deionized water, 10min is vigorously stirred under room temperature, quality is added
A concentration of 60% sodium hydroxide solution adjusts pH value to 9.5, continues to stir 60min, heating carries out hydro-thermal reaction, and reaction terminates
After filter, precipitation is washed repeatedly using distilled water and absolute ethyl alcohol, is dried in vacuo, obtained bismuth oxybromide nanometer sheet light is urged
Agent.
Each component mass parts are：28 parts by weight of cetyl trimethylammonium bromide, 25 parts by weight of bismuth nitrate, deionized water 44
Parts by weight.
The temperature of hydro-thermal reaction is 160 DEG C, time 18h；Vacuum drying temperature is 50 DEG C, time 4h.
Bismuth oxybromide photocatalyst made from above-described embodiment 1 ~ 5 and comparative example 1 tests its specific surface area, solar energy profit
With rate and photodissociation aquatic products hydrogen activity, method or the condition for testing characterization are as follows：
Specific surface area：The ratio of composite photo-catalyst is measured using MicromeriticsASP2010 specific surfaces and lacunarity analysis instrument
Surface area.
Solar energy utilization ratio：Using sunlight as light source, the luminous energy absorbed by catalyst is measured using photovoltaic tester, with quilt
Absorb the percentage characterization sun light utilization efficiency that luminous energy accounts for irradiation luminous energy.
Photodissociation aquatic products hydrogen activity：1g composite photo-catalysts are put into 300mL water, are irradiated using sunlight, 3h is reacted, are surveyed
Determine hydrogen yield, calculate photodissociation aquatic products hydrogen activity, characterizes hydrogen capacity.
The results are shown in Table 1.
Table 1：
Claims (10)
1. a kind of preparation method of bismuth oxybromide composite photo-catalyst for hydrogen manufacturing, it is characterised in that：The bismuth oxybromide is multiple
Closing light catalyst is to carry out hydro-thermal reaction by cetyl trimethylammonium bromide and bismuth nitrate to synthesize bismuth oxybromide nanometer sheet, then adopt
With molybdenum salt, selenium source, sodium sulfite and sodium borohydride by microwave hydrothermal react bismuth oxybromide nanometer sheet surface homoepitaxial
Selenizing molybdenum is nanocrystalline and obtained, and specific preparation process is：
A, cetyl trimethylammonium bromide and bismuth nitrate are added in deionized water, 8 ~ 12min is vigorously stirred under room temperature, be added
The sodium hydroxide solution that mass concentration is 50 ~ 70% adjusts pH value to 9.5 ~ 10.5, continues 50 ~ 70min of stirring, heating carries out water
Thermal response filters after reaction, is washed repeatedly to precipitation using distilled water and absolute ethyl alcohol, is dried in vacuo, and bromine is made
Bismuth oxide nanometer sheet；
B, bismuth oxybromide nanometer sheet made from step a is added in the molybdenum salting liquid that mass concentration is 40 ~ 50%, ultrasonic disperse, then
Selenium source, sodium sulfite and sodium borohydride is added, stirs 5 ~ 10min, adjusts pH value to 3 ~ 4, microwave hydrothermal reaction is carried out, using steaming
Distilled water and absolute ethyl alcohol wash product repeatedly, and the bismuth oxybromide for hydrogen manufacturing/selenizing molybdenum complex light is made in vacuum drying
Catalyst.
2. a kind of preparation method of bismuth oxybromide composite photo-catalyst for hydrogen manufacturing, feature exist according to claim 1
In：In step a, 25 ~ 30 parts by weight of cetyl trimethylammonium bromide, 22 ~ 27 parts by weight of bismuth nitrate, 39 ~ 51 weight of deionized water
Measure part.
3. a kind of preparation method of bismuth oxybromide composite photo-catalyst for hydrogen manufacturing, feature exist according to claim 1
In：The temperature of hydro-thermal reaction described in step a is 150 ~ 170 DEG C, and the time is 16 ~ 20h.
4. a kind of preparation method of bismuth oxybromide composite photo-catalyst for hydrogen manufacturing, feature exist according to claim 1
In：Vacuum drying temperature described in step a is 45 ~ 55 DEG C, and the time is 3 ~ 5h.
5. a kind of preparation method of bismuth oxybromide composite photo-catalyst for hydrogen manufacturing, feature exist according to claim 1
In：The molybdenum salt is at least one of molybdenum dialkyl-dithiophosphate or molybdenum dialkyldithiocarbamacompositions.
6. a kind of preparation method of bismuth oxybromide composite photo-catalyst for hydrogen manufacturing, feature exist according to claim 1
In：The selenium source is at least one of dimethyl-selenide, diethyl selenide or di-t-butyl selenium.
7. a kind of preparation method of bismuth oxybromide composite photo-catalyst for hydrogen manufacturing, feature exist according to claim 1
In：In step b, 30 ~ 34 parts by weight of bismuth oxybromide nanometer sheet, 38 ~ 48 parts by weight of molybdenum salting liquid, 17 ~ 20 parts by weight of selenium source, sulfurous
3 ~ 5 parts by weight of sour sodium, 2 ~ 3 parts by weight of sodium borohydride.
8. a kind of preparation method of bismuth oxybromide composite photo-catalyst for hydrogen manufacturing, feature exist according to claim 1
In：The temperature that microwave hydrothermal described in step b reacts is 120 ~ 140 DEG C, and the time is 4 ~ 5h, and microwave frequency is 500 ~ 1000MHz, wave
A length of 200 ~ 400mm.
9. a kind of preparation method of bismuth oxybromide composite photo-catalyst for hydrogen manufacturing, feature exist according to claim 1
In：Vacuum drying temperature described in step b is 60 ~ 70 DEG C, and the time is 2 ~ 3h.
10. a kind of bismuth oxybromide composite photo-catalyst for hydrogen manufacturing that any one of claim 1-9 the methods are prepared.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111254461A (en) * | 2020-01-19 | 2020-06-09 | 安徽大学 | Tungsten oxide/bismuth oxyiodide heterojunction material for photo-reduction of carbon dioxide and preparation method and application thereof |
| CN111617783A (en) * | 2020-06-05 | 2020-09-04 | 吉林大学 | Dark red BiOI submicron sphere catalyst containing oxygen vacancies, preparation method and application thereof in hydrogen production by photocatalytic water decomposition |
| CN113501504A (en) * | 2021-07-21 | 2021-10-15 | 苏州普轮电子科技有限公司 | Novel semiconductor material with micro-nano structure and preparation method thereof |
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2018
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111254461A (en) * | 2020-01-19 | 2020-06-09 | 安徽大学 | Tungsten oxide/bismuth oxyiodide heterojunction material for photo-reduction of carbon dioxide and preparation method and application thereof |
| CN111254461B (en) * | 2020-01-19 | 2021-08-27 | 安徽大学 | Tungsten oxide/bismuth oxyiodide heterojunction material for photo-reduction of carbon dioxide and preparation method and application thereof |
| CN111617783A (en) * | 2020-06-05 | 2020-09-04 | 吉林大学 | Dark red BiOI submicron sphere catalyst containing oxygen vacancies, preparation method and application thereof in hydrogen production by photocatalytic water decomposition |
| CN113501504A (en) * | 2021-07-21 | 2021-10-15 | 苏州普轮电子科技有限公司 | Novel semiconductor material with micro-nano structure and preparation method thereof |
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