CN106964380A - A kind of three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst and preparation method and applications - Google Patents
A kind of three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst and preparation method and applications Download PDFInfo
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- CN106964380A CN106964380A CN201710176935.9A CN201710176935A CN106964380A CN 106964380 A CN106964380 A CN 106964380A CN 201710176935 A CN201710176935 A CN 201710176935A CN 106964380 A CN106964380 A CN 106964380A
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- Prior art keywords
- cadmium sulfide
- bismuth
- bismuth oxybromide
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- oxybromide
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- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical compound Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 title claims abstract description 119
- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 102
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 91
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 39
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 186
- 239000011259 mixed solution Substances 0.000 claims abstract description 43
- 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 39
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 29
- 239000002243 precursor Substances 0.000 claims abstract description 28
- 239000013049 sediment Substances 0.000 claims abstract description 28
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 12
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims abstract description 10
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000002994 raw material Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 9
- 230000035484 reaction time Effects 0.000 claims description 7
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 claims description 6
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 claims description 6
- 229910052794 bromium Inorganic materials 0.000 claims description 6
- 229910000416 bismuth oxide Inorganic materials 0.000 claims description 5
- 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 5
- 229910052797 bismuth Inorganic materials 0.000 claims description 2
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 2
- 238000002242 deionisation method Methods 0.000 claims description 2
- 229910052738 indium Inorganic materials 0.000 claims description 2
- 230000009467 reduction Effects 0.000 claims description 2
- 150000004703 alkoxides Chemical class 0.000 claims 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 claims 1
- 229910017604 nitric acid Inorganic materials 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 238000010531 catalytic reduction reaction Methods 0.000 abstract description 12
- 238000000034 method Methods 0.000 abstract description 4
- 230000008569 process Effects 0.000 abstract description 3
- 238000003756 stirring Methods 0.000 abstract 1
- JHIVVAPYMSGYDF-UHFFFAOYSA-N cyclohexanone Chemical compound O=C1CCCCC1 JHIVVAPYMSGYDF-UHFFFAOYSA-N 0.000 description 16
- 239000000047 product Substances 0.000 description 10
- 239000003054 catalyst Substances 0.000 description 9
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 description 9
- VUXKVKAHWOVIDN-UHFFFAOYSA-N Cyclohexyl formate Chemical compound O=COC1CCCCC1 VUXKVKAHWOVIDN-UHFFFAOYSA-N 0.000 description 6
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 5
- 230000009471 action Effects 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- AISMNBXOJRHCIA-UHFFFAOYSA-N trimethylazanium;bromide Chemical compound Br.CN(C)C AISMNBXOJRHCIA-UHFFFAOYSA-N 0.000 description 4
- 239000007789 gas Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- WNLRTRBMVRJNCN-UHFFFAOYSA-N adipic acid Chemical compound OC(=O)CCCCC(O)=O WNLRTRBMVRJNCN-UHFFFAOYSA-N 0.000 description 2
- 229910052793 cadmium Inorganic materials 0.000 description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 2
- JBKVHLHDHHXQEQ-UHFFFAOYSA-N epsilon-caprolactam Chemical compound O=C1CCCCCN1 JBKVHLHDHHXQEQ-UHFFFAOYSA-N 0.000 description 2
- 230000032050 esterification Effects 0.000 description 2
- 238000005886 esterification reaction Methods 0.000 description 2
- 239000000835 fiber Substances 0.000 description 2
- 235000019253 formic acid Nutrition 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000004005 microsphere Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 238000006722 reduction reaction Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- 229920002302 Nylon 6,6 Polymers 0.000 description 1
- 235000011037 adipic acid Nutrition 0.000 description 1
- 239000001361 adipic acid Substances 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 235000015173 baked goods and baking mixes Nutrition 0.000 description 1
- 229920005601 base polymer Polymers 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000003034 coal gas Substances 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000004434 industrial solvent Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000012263 liquid product Substances 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000003345 natural gas Substances 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 230000000243 photosynthetic effect Effects 0.000 description 1
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 238000005406 washing 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
- B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
- C07C45/37—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups
- C07C45/39—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of >C—O—functional groups to >C=O groups being a secondary hydroxyl group
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
Abstract
The invention particularly 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；Its preparation method comprises the following steps：First, bismuth nitrate/ethylene glycol mixed solution is mixed with cetyl trimethylammonium bromide/ethylene glycol mixed solution, obtains bismuth oxybromide precursor liquid, and sediment A is reacted to obtain, sediment A is centrifuged, drying is washed, finally bakee again, that is, be prepared into bismuth oxybromide microballoon；Then, cadmium sulfide and bismuth oxybromide microballoon are mixed, adds deionized water stirring, obtain three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions precursor liquid, and react to obtain sediment B, sediment B is centrifuged, drying is washed, produces.The preparation method process of three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst of the present invention is simple, morphology controllable, environment-friendly, for photo catalytic reduction CO2, improve photo catalytic reduction CO2Reaction rate.
Description
Technical field
The present invention relates to heterojunction photocatalyst technical field, and in particular to a kind of three-dimensional cadmium sulfide/bismuth oxybromide is heterogeneous
Tie photochemical catalyst and preparation method and applications.
Background technology
The main fossil fuel based on oil, coal and natural gas of global energy consumption.Fossil fuel comes from millions of
Nian Qian, the planktonic organism for being embedded in underground develops what is formed by very long geological epoch, belongs to the Depletion energy, simultaneously because fossil
In fuel combustion process into air emission greenhouse gas particularly CO2Gas, it is unfavorable and can not that global environment is generated
The influence of reverse.CO in air2The increase of content causes global warming to turn into the environmental problem of most serious.Therefore, reduce big
CO in gas2Content and to develop renewable, clean energy resource be two large problems urgently to be resolved hurrily at present.Simulate the photosynthetic work of nature
With by CO2It is fixed or be converted into high added value hydrocarbon fuel can be while solving energy supply and environment warms problem.
CO2Itself it is a kind of carbon source, CH can be converted into4、CH3The organic compounds such as OH, but due to CO2Molecular structure is steady
It is fixed, it is difficult to be reduced under mild conditions, causes reaction rate slow, selectivity of product is poor.And photocatalysis technology is considered as
Global energy shortage and the potential solution of environmental pollution, the particularly viewpoint from natural green photosynthesis of plant, with each
Kind semiconductor photo catalytic reduction CO in water as catalyst2There are many reports, such as TiO as reducing agent2, ZnO etc., but these
Catalyst because of the greater band gap can only absorbing wavelength be less than 387nm ultraviolet light, and ultraviolet light only accounts for the 4% of solar energy total amount,
Limit utilization of such catalyst to solar energy.In addition, the factor such as active and particle diameter, pattern, surface area of catalyst is relevant,
Many studies have shown that constituting three-dimensional hierarchy photochemical catalyst by monodimension nano stick, nanotube shows good catalytic activity.
Bismuth oxybromide (BiOBr) is a kind of new ternary semiconductor oxide, with layer structure and high photochemical stability, band
Gap width is 2.9eV, conduction band positions (ECB=-0.1V vs.NHE pH=7).BiOBr is shown well under visible light action
Photocatalytic activity, but because its high photo-generate electron-hole recombination rate limits the application of the catalyst.
The content of the invention
For problems of the prior art, it is an object of the invention to provide a kind of three-dimensional cadmium sulfide/bismuth oxybromide
Heterojunction photocatalyst and preparation method and applications, the preparation method process is simple, morphology controllable, available for photo catalytic reduction
CO2, to improve photo catalytic reduction CO2Reaction rate.
In order to achieve the above object, the present invention is achieved using following technical scheme.
(1) a kind of three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst, it is characterised in that including following raw material group
Point：Bismuth nitrate, cetyl trimethylammonium bromide, ethylene glycol, cadmium sulfide.
(2) a kind of preparation method of three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst, it is characterised in that including with
Lower step：
Step 1, bismuth oxybromide microballoon is prepared；By bismuth nitrate/ethylene glycol mixed solution and cetyl trimethylammonium bromide/
Ethylene glycol mixed solution is mixed, and obtains bismuth oxybromide precursor liquid；The bismuth oxybromide precursor liquid is transferred in reactor and reacted,
Obtain sediment A；The sediment A is centrifuged, and drying after being washed with deionized water and ethanol, desciccate is obtained, most
The desciccate is calcined afterwards, the bismuth oxybromide microballoon of three-dimensional structure is produced；
Step 2, three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions is prepared；First by prepared in cadmium sulfide and step 1 three
Bismuth oxybromide mixing is tieed up, cadmium sulfide/bismuth oxybromide mixture is made；And go the cadmium sulfide/bismuth oxybromide mixture addition
In ionized water, it is sufficiently stirred for, forms three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions precursor liquid；By the three-dimensional cadmium sulfide/bromine oxidation
Bismuth hetero-junctions precursor liquid, which is transferred in reactor, to react, and obtains sediment B；The sediment B is centrifuged, and uses deionization
Water and ethanol washing drying, produce three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst.
Preferably, in step 1, the bismuth nitrate/ethylene glycol mixed solution is mixed by bismuth nitrate and ethylene glycol,
And the concentration of bismuth nitrate is 0.05~0.06mol/L in the bismuth nitrate/ethylene glycol mixed solution.
Preferably, in step 1, the cetyl trimethylammonium bromide/ethylene glycol mixed solution is by cetyl
Trimethylammonium bromide and ethylene glycol are mixed, and 16 in the cetyl trimethylammonium bromide/ethylene glycol mixed solution
The concentration of alkyl trimethyl ammonium bromide is 0.05~0.08mol/L.
Preferably, in step 1, the bismuth nitrate/ethylene glycol mixed solution and the cetyl trimethyl bromination
The volume ratio of ammonium/ethylene glycol mixed solution is 1:1.
Preferably, in step 1, the reaction temperature reacted in the reactor is 160 DEG C, and the reaction time is 12 small
When.In step 1, the temperature of the drying is 80 DEG C, and the time of the drying is 10 hours.
Preferably, in step 1, the temperature of the roasting is 400 DEG C, and the time of the roasting is 2 hours.
Preferably, in step 2, the weight/mass percentage composition of cadmium sulfide is 1 in the cadmium sulfide/bismuth oxybromide mixture
~7%.
Preferably, in step 2, the molar concentration of the three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions precursor liquid is
0.016~0.02mol/L.
Preferably, in step 2, the reaction temperature reacted in the reactor is 140 DEG C, and the reaction time is 12 small
When.
(3) three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst is in photo catalytic reduction CO2In application.
The three-dimensional structure bismuth oxybromide (BiOBr) being made up of nanometer sheet of interlocking can obtain stronger by the multiaspect reflection of light
The absorption of light, grade microballoon is bigger than the photochemical catalyst illuminating area of two-dimensional sheet structure, can meet reduction CO at present2During light
The problem of energy utilization rate is low.The separation of photo-generated carrier can be effectively facilitated in the area load co-catalyst of catalyst, light is improved
Catalytic activity.CdS is a kind of narrow gap semiconductor, and band gap width is 2.4eV, conduction band positions (ECB=-1.0V vs.NHE pH=
7), appropriate CdS is added in BiOBr, responses of the BiOBr in visible region can be effectively widened, and photo-generated carrier can be promoted
Separation, conduction band positions more negative CdS can promote CO2Reduction.At present, CdS/BiOBr compounds use the simple precipitation method
Prepare, crystallinity is poor, catalytic activity fails good embodiment.The heterojunction photocatalyst CdS/BiOBr and use of three-dimensional structure
In photo catalytic reduction CO2Research have no report, in view of the above problems, develop a kind of high activity, with good visible light-responded
CdS/BiOBr heterojunction photocatalysts be significantly.
The present invention is for photo catalytic reduction CO under visible light action in the prior art2During visible light utilization efficiency is low, CO2
Conversion ratio it is low, the problems such as selectivity of product is poor, first prepare bismuth oxybromide microballoon, then cadmium sulfide nano is loaded in microsphere surface
Grain, forms three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst, photo catalytic reduction CO is carried out in cyclohexanol2Active testing
In show good catalytic performance, reduce CO under visible light action with other heterojunction photocatalysts2Compare, the life of product
Significantly improved into amount and selectivity, the preparation method of three-dimensional CdS/BiOBr heterojunction photocatalysts of the invention, which has, to be prepared
Journey is simple, morphology controllable, advantages of environment protection.
Brief description of the drawings
The present invention is described in further details with specific embodiment below in conjunction with the accompanying drawings.
Fig. 1 is the scanning electron microscope (SEM) photograph of the three-dimensional bismuth oxybromide prepared to embodiment 1；
Fig. 2 is the ESEM of the three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst prepared to embodiment 1
Figure；
Fig. 3 is that photocatalysis is also in cyclohexanol for the cadmium sulfide/bismuth oxybromide heterojunction photocatalyst for preparing of embodiment 1
Former CO2And occur the amount of esterification generation cyclohexyl formate (CF) and change with time graph of a relation；In figure, abscissa is reaction
Time, ordinate is the yield of cyclohexyl formate (CF)；
Fig. 4 is that photocatalysis is also in cyclohexanol for the cadmium sulfide/bismuth oxybromide heterojunction photocatalyst for preparing of embodiment 1
Former CO2, the amount that cyclohexanol is oxidized to cyclohexanone (CH) changes with time graph of a relation；In figure, abscissa is the reaction time, is indulged
Coordinate is the yield of cyclohexanone (CH).
Embodiment
Embodiment of the present invention is described in detail below in conjunction with embodiment, but those skilled in the art will
It will be appreciated that the following example is merely to illustrate the present invention, and it is not construed as limiting the scope of the present invention.
Embodiment 1
The present embodiment provides a kind of preparation method of three-dimensional CdS/BiOBr heterojunction photocatalysts, comprises the following steps：
Step 1, bismuth oxybromide microballoon is prepared；By bismuth nitrate/ethylene glycol mixed solution and cetyl trimethylammonium bromide/
Ethylene glycol mixed solution is mixed, and obtains bismuth oxybromide precursor liquid；The bismuth oxybromide precursor liquid is transferred in reactor, in temperature
Spend to react 12h at 160 DEG C, obtain sediment A；The sediment A is centrifuged, and washed with deionized water and ethanol
Afterwards, 10h is dried at 80 DEG C, desciccate is obtained；The desciccate is finally calcined 2h at 400 DEG C, three-dimensional structure is obtained
Bismuth oxybromide；Wherein, bismuth nitrate/ethylene glycol mixed solution is mixed by bismuth nitrate and ethylene glycol, and bismuth nitrate/ethylene glycol is mixed
The concentration for closing bismuth nitrate in solution is 0.05mol/L；Cetyl trimethylammonium bromide/ethylene glycol mixed solution is by cetyl
Trimethylammonium bromide and ethylene glycol are mixed, and cetyl in cetyl trimethylammonium bromide/ethylene glycol mixed solution
The concentration of trimethylammonium bromide is 0.05mol/L；And bismuth nitrate/ethylene glycol mixed solution and cetyl trimethylammonium bromide/
The volume ratio of ethylene glycol mixed solution is 1:1.
Step 2, three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions is prepared；By the three-dimensional bromine prepared in cadmium sulfide and step 1
Bismuth oxide is mixed, and obtains cadmium sulfide/bismuth oxybromide mixture, wherein, the quality of cadmium sulfide in cadmium sulfide/bismuth oxybromide mixture
Percentage composition is 5%；The cadmium sulfide/bismuth oxybromide mixture is added in deionized water, is sufficiently stirred for, forming concentration is
0.016mol/L three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions precursor liquid, and by the three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions
Precursor liquid is transferred in reactor, is reacted 12h at 140 DEG C, is obtained sediment B；Sediment B is centrifuged, and spend from
After sub- water and ethanol are washed and dried, three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst is produced.
Embodiment 2
The present embodiment provides a kind of preparation method of three-dimensional CdS/BiOBr heterojunction photocatalysts, comprises the following steps：
Step 1, bismuth oxybromide microballoon is prepared；By bismuth nitrate/ethylene glycol mixed solution and cetyl trimethylammonium bromide/
Ethylene glycol mixed solution is mixed, and obtains bismuth oxybromide precursor liquid；The bismuth oxybromide precursor liquid is transferred in reactor, in temperature
Spend to react 12h at 160 DEG C, obtain sediment A；The sediment A is centrifuged, and washed with deionized water and ethanol
Afterwards, 10h is dried at 80 DEG C, desciccate is obtained；The desciccate is finally calcined 2h at 400 DEG C, three-dimensional structure is obtained
Bismuth oxybromide；Wherein, bismuth nitrate/ethylene glycol mixed solution is mixed by bismuth nitrate and ethylene glycol, and bismuth nitrate/ethylene glycol is mixed
The concentration for closing bismuth nitrate in solution is 0.06mol/L；Cetyl trimethylammonium bromide/ethylene glycol mixed solution is by cetyl
Trimethylammonium bromide and ethylene glycol are mixed, and cetyl in cetyl trimethylammonium bromide/ethylene glycol mixed solution
The concentration of trimethylammonium bromide is 0.06mol/L；And bismuth nitrate/ethylene glycol mixed solution and cetyl trimethylammonium bromide/
The volume ratio of ethylene glycol mixed solution is 1:1.
Step 2, three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions is prepared；By the three-dimensional bromine prepared in cadmium sulfide and step 1
Bismuth oxide is mixed, and obtains cadmium sulfide/bismuth oxybromide mixture, wherein, the quality of cadmium sulfide in cadmium sulfide/bismuth oxybromide mixture
Percentage composition is 1%；The cadmium sulfide/bismuth oxybromide mixture is added in deionized water, is sufficiently stirred for, forming concentration is
0.018mol/L three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions precursor liquid, and by the three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions
Precursor liquid is transferred in reactor, is reacted 12h at 140 DEG C, is obtained sediment B；Sediment B is centrifuged, and spend from
After sub- water and ethanol are washed and dried, three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst is produced.
Embodiment 3
The present embodiment provides a kind of preparation method of three-dimensional CdS/BiOBr heterojunction photocatalysts, comprises the following steps：
Step 1, bismuth oxybromide microballoon is prepared；By bismuth nitrate/ethylene glycol mixed solution and cetyl trimethylammonium bromide/
Ethylene glycol mixed solution is mixed, and obtains bismuth oxybromide precursor liquid；The bismuth oxybromide precursor liquid is transferred in reactor, in temperature
Spend to react 12h at 160 DEG C, obtain sediment A；The sediment A is centrifuged, and washed with deionized water and ethanol
Afterwards, 10h is dried at 80 DEG C, desciccate is obtained；The desciccate is finally calcined 2h at 400 DEG C, three-dimensional structure is obtained
Bismuth oxybromide；Wherein, bismuth nitrate/ethylene glycol mixed solution is mixed by bismuth nitrate and ethylene glycol, and bismuth nitrate/ethylene glycol is mixed
The concentration for closing bismuth nitrate in solution is 0.06mol/L；Cetyl trimethylammonium bromide/ethylene glycol mixed solution is by cetyl
Trimethylammonium bromide and ethylene glycol are mixed, and cetyl in cetyl trimethylammonium bromide/ethylene glycol mixed solution
The concentration of trimethylammonium bromide is 0.08mol/L；And bismuth nitrate/ethylene glycol mixed solution and cetyl trimethylammonium bromide/
The volume ratio of ethylene glycol mixed solution is 1:1.
Step 2, three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions is prepared；By the three-dimensional bromine prepared in cadmium sulfide and step 1
Bismuth oxide is mixed, and obtains cadmium sulfide/bismuth oxybromide mixture, wherein, the quality of cadmium sulfide in cadmium sulfide/bismuth oxybromide mixture
Percentage composition is 3%；The cadmium sulfide/bismuth oxybromide mixture is added in deionized water, is sufficiently stirred for, forming concentration is
0.02mol/L three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions precursor liquid, and by the three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions
Precursor liquid is transferred in reactor, is reacted 12h at 140 DEG C, is obtained sediment B；Sediment B is centrifuged, and spend from
After sub- water and ethanol are washed and dried, three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst is produced.
Embodiment 4
The present embodiment provides a kind of preparation method of three-dimensional CdS/BiOBr heterojunction photocatalysts, comprises the following steps：
Step 1, bismuth oxybromide microballoon is prepared；By bismuth nitrate/ethylene glycol mixed solution and cetyl trimethylammonium bromide/
Ethylene glycol mixed solution is mixed, and obtains bismuth oxybromide precursor liquid；The bismuth oxybromide precursor liquid is transferred in reactor, in temperature
Spend to react 12h at 160 DEG C, obtain sediment A；The sediment A is centrifuged, and washed with deionized water and ethanol
Afterwards, 10h is dried at 80 DEG C, desciccate is obtained；The desciccate is finally calcined 2h at 400 DEG C, three-dimensional structure is obtained
Bismuth oxybromide；Wherein, bismuth nitrate/ethylene glycol mixed solution is mixed by bismuth nitrate and ethylene glycol, and bismuth nitrate/ethylene glycol is mixed
The concentration for closing bismuth nitrate in solution is 0.06mol/L；Cetyl trimethylammonium bromide/ethylene glycol mixed solution is by cetyl
Trimethylammonium bromide and ethylene glycol are mixed, and cetyl in cetyl trimethylammonium bromide/ethylene glycol mixed solution
The concentration of trimethylammonium bromide is 0.08mol/L；And bismuth nitrate/ethylene glycol mixed solution and cetyl trimethylammonium bromide/
The volume ratio of ethylene glycol mixed solution is 1:1.
Step 2, three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions is prepared；By the three-dimensional bromine prepared in cadmium sulfide and step 1
Bismuth oxide is mixed, and obtains cadmium sulfide/bismuth oxybromide mixture, wherein, the quality of cadmium sulfide in cadmium sulfide/bismuth oxybromide mixture
Percentage composition is 7%；The cadmium sulfide/bismuth oxybromide mixture is added in deionized water, is sufficiently stirred for, forming concentration is
0.02mol/L three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions precursor liquid, and by the three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions
Precursor liquid is transferred in reactor, is reacted 12h at 140 DEG C, is obtained sediment B；Sediment B is centrifuged, and spend from
After sub- water and ethanol are washed and dried, three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst is produced.
The three-dimensional bismuth oxybromide prepared to embodiment 1 and three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst point
Not carry out SEM tests, test result as depicted in figs. 1 and 2, as seen from Figure 1, prepared using the hydro-thermal method that provides of the present invention
The stereoscan photograph of bismuth oxybromide show the interlaced three-dimensional microballoon of nanometer sheet；As seen from Figure 2, three-dimensional vulcanization
The three-dimensional microsphere surface of ESEM display of cadmium/bismuth oxybromide hetero-junctions is loaded with high-visible cadmium sulfide nanoparticles.
Three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst that embodiment 1 is prepared is applied in photo catalytic reduction
CO2In, at normal temperatures and pressures, photocatalysis experiment is carried out in paste state bed reactor, using 500W halogen lamps as light source, coordinate 400nm's
Optical filter is used；Specific operation process is as follows：The cadmium sulfide that 10mg embodiments 1 are prepared/bismuth oxybromide hetero-junctions light is urged
Agent is added in 10mL cyclohexanol, and before reaction starts, high-purity CO is passed through into solution2(99.99%) 30min is molten to remove
Dissolved oxygen in liquid；Reactor is sealed, light source is opened, starts magnetic stirring apparatus and starts reaction；React after the specific time, will
After liquid product is centrifuged, detected by gas chromatograph.
Fig. 3 and Fig. 4 are respectively photo catalytic reduction CO in cyclohexanol2Generation product changes with time graph of a relation, can by figure
To find out, under normal temperature and pressure and visible light action, photo catalytic reduction CO in cyclohexanol2, cyclohexanol is oxidized to cyclohexanone simultaneously
Produce Hydrogen Proton, CO2It is reduced to formic acid and esterification generation cyclohexyl formate occurs for cyclohexanol.Target product cyclohexanone and
The growing amount of cyclohexyl formate increases with the extension in reaction time, with the increase of vulcanization cadmium content, and the growing amount of product increases
Greatly, when the percentage composition of cadmium sulfide reaches 5%, the growing amount of product reaches maximum, continues to increase cadmium sulfide in bismuth oxybromide
Content the growing amount of product can be caused to decline.
Product formic acid cyclohexyl is a kind of spices, is mainly used in ices, baked goods；Cyclohexanone is that one kind organises
Work raw material, is monomer caprolactam, the main intermediate of adipic acid for producing nylon66 fiber, can also be used to contain nitre as industrial solvent
Chemical fibre dimension, vinyl chloride-base polymer and copolymer paint；Both products all have good application value.
Although the present invention is described in detail with a general description of the specific embodiments in this specification,
But on the basis of the present invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.
Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to claimed model
Enclose.
Claims (10)
1. a kind of three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst, it is characterised in that including following raw material components：Nitric acid
Bismuth, cetyl trimethylammonium bromide, ethylene glycol, cadmium sulfide.
2. a kind of preparation method of three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst, it is characterised in that including following step
Suddenly：
Step 1, bismuth oxybromide microballoon is prepared；By bismuth nitrate/ethylene glycol mixed solution and cetyl trimethylammonium bromide/second two
Mixed alkoxide solution is mixed, and obtains bismuth oxybromide precursor liquid；The bismuth oxybromide precursor liquid is transferred in reactor and reacted, is obtained
Sediment A；The sediment A is centrifuged, and drying after wash with deionized water and ethanol, desciccate is obtained, finally general
The desciccate roasting, produces the bismuth oxybromide microballoon of three-dimensional structure；
Step 2, three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions is prepared；First by the three-dimensional bromine prepared in cadmium sulfide and step 1
Bismuth oxide is mixed, and cadmium sulfide/bismuth oxybromide mixture is made；And the cadmium sulfide/bismuth oxybromide mixture is added into deionization
In water, it is sufficiently stirred for, forms three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions precursor liquid；Three-dimensional cadmium sulfide/the bismuth oxybromide is different
Matter knot precursor liquid, which is transferred in reactor, to react, and obtains sediment B；The sediment B is centrifuged, and with deionized water and
Ethanol washs drying, produces three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst.
3. the preparation method of three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst according to claim 2, its feature exists
In in step 1, the bismuth nitrate/ethylene glycol mixed solution is mixed by bismuth nitrate and ethylene glycol, and the bismuth nitrate/second
The concentration of bismuth nitrate is 0.05~0.06mol/L in two mixed alkoxide solutions；Cetyl trimethylammonium bromide/the ethylene glycol is mixed
Solution is closed to be mixed by cetyl trimethylammonium bromide and ethylene glycol, and the cetyl trimethylammonium bromide/second two
The concentration of cetyl trimethylammonium bromide is 0.05~0.08mol/L in mixed alkoxide solution.
4. the preparation method of three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst according to claim 2, its feature exists
In, in step 1, the bismuth nitrate/ethylene glycol mixed solution and the cetyl trimethylammonium bromide/ethylene glycol mixed solution
Volume ratio be 1:1.
5. the preparation method of three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst according to claim 2, its feature exists
In in step 1, the reaction temperature reacted in the reactor is 160 DEG C, and the reaction time is 12 hours；The temperature of the roasting
For 400 DEG C, the time of the roasting is 2 hours.
6. the preparation method of three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst according to claim 2, its feature exists
In in step 1, the temperature of the drying is 80 DEG C, and the time of the drying is 10 hours.
7. the preparation method of three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst according to claim 2, its feature exists
In in step 2, the weight/mass percentage composition of cadmium sulfide is 1~7% in the cadmium sulfide/bismuth oxybromide mixture.
8. the preparation method of three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst according to claim 2, its feature exists
In in step 2, the molar concentration of the three-dimensional cadmium sulfide/bismuth oxybromide hetero-junctions precursor liquid is 0.016~0.02mol/L.
9. the preparation method of three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst according to claim 2, its feature exists
In in step 2, the reaction temperature reacted in the reactor is 140 DEG C, and the reaction time is 12 hours.
10. three-dimensional cadmium sulfide/bismuth oxybromide heterojunction photocatalyst according to prepared by any one of claim 2 to 9 is in light
Catalysis reduction CO2In application.
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| CN109529890A (en) * | 2018-11-06 | 2019-03-29 | 常州大学 | A kind of preparation method of zinc-cadmium sulfide/bismuth oxybromide composite visible light catalyst |
| CN110302814A (en) * | 2019-08-02 | 2019-10-08 | 谢明财 | A kind of compound assemble method of CdS Semiconductor Nanometer Particles |
| CN110911170A (en) * | 2019-12-02 | 2020-03-24 | 武汉轻工大学 | Photo-anode material with molybdenum sulfide modified bismuth oxybromide in two-dimensional structure and preparation method thereof |
| CN110911170B (en) * | 2019-12-02 | 2021-09-07 | 武汉轻工大学 | Photo-anode material with molybdenum sulfide modified bismuth oxybromide in two-dimensional structure and preparation method thereof |
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