CN110180579A - Multistage SnS2Nano flower and C3N4Quantum dot composite material and the preparation method and application thereof - Google Patents
Multistage SnS2Nano flower and C3N4Quantum dot composite material and the preparation method and application thereof Download PDFInfo
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- CN110180579A CN110180579A CN201910595032.3A CN201910595032A CN110180579A CN 110180579 A CN110180579 A CN 110180579A CN 201910595032 A CN201910595032 A CN 201910595032A CN 110180579 A CN110180579 A CN 110180579A
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- 239000002131 composite material Substances 0.000 title claims abstract description 105
- 238000002360 preparation method Methods 0.000 title claims abstract description 55
- 239000002057 nanoflower Substances 0.000 claims abstract description 128
- 239000002096 quantum dot Substances 0.000 claims abstract description 128
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 41
- 238000006731 degradation reaction Methods 0.000 claims abstract description 12
- 230000015556 catabolic process Effects 0.000 claims abstract description 11
- 239000005416 organic matter Substances 0.000 claims abstract 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 36
- 239000008367 deionised water Substances 0.000 claims description 34
- 229910021641 deionized water Inorganic materials 0.000 claims description 34
- 238000006243 chemical reaction Methods 0.000 claims description 32
- 239000011259 mixed solution Substances 0.000 claims description 28
- 239000000243 solution Substances 0.000 claims description 28
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 26
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 24
- 239000007787 solid Substances 0.000 claims description 21
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 20
- 238000002156 mixing Methods 0.000 claims description 17
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical group N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 15
- 238000001035 drying Methods 0.000 claims description 14
- 230000001376 precipitating effect Effects 0.000 claims description 14
- 239000004201 L-cysteine Substances 0.000 claims description 10
- 235000013878 L-cysteine Nutrition 0.000 claims description 10
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 10
- 239000004202 carbamide Substances 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 9
- 229910021627 Tin(IV) chloride Inorganic materials 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000000203 mixture Substances 0.000 claims description 4
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical group C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 3
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 abstract description 27
- 238000000034 method Methods 0.000 abstract description 17
- 229940106691 bisphenol a Drugs 0.000 abstract description 13
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 11
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 abstract description 6
- 229940012189 methyl orange Drugs 0.000 abstract description 6
- 239000004065 semiconductor Substances 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 33
- 239000003054 catalyst Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 12
- 238000013019 agitation Methods 0.000 description 11
- 239000002994 raw material Substances 0.000 description 10
- 230000001699 photocatalysis Effects 0.000 description 9
- 230000008569 process Effects 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 239000013078 crystal Substances 0.000 description 8
- 239000000843 powder Substances 0.000 description 8
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 8
- 238000001514 detection method Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 229960004756 ethanol Drugs 0.000 description 7
- 239000002135 nanosheet Substances 0.000 description 7
- 239000012071 phase Substances 0.000 description 7
- 238000007146 photocatalysis Methods 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- 239000001508 potassium citrate Substances 0.000 description 6
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 6
- 241000209094 Oryza Species 0.000 description 4
- 235000007164 Oryza sativa Nutrition 0.000 description 4
- 238000004847 absorption spectroscopy Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000007791 liquid phase Substances 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 235000009566 rice Nutrition 0.000 description 4
- 239000002023 wood Substances 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
- 239000007864 aqueous solution Substances 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 150000004770 chalcogenides Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 230000005284 excitation Effects 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000000703 high-speed centrifugation Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229960002635 potassium citrate Drugs 0.000 description 3
- 235000011082 potassium citrates Nutrition 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000000227 grinding Methods 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000005070 sampling Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007405 data analysis Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 230000007850 degeneration Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000023004 detection of visible light Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000000598 endocrine disruptor Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine powder Natural products NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 1
- 238000000634 powder X-ray diffraction Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
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- 238000010189 synthetic method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- RBNWAMSGVWEHFP-UHFFFAOYSA-N trans-p-Menthane-1,8-diol Chemical compound CC(C)(O)C1CCC(C)(O)CC1 RBNWAMSGVWEHFP-UHFFFAOYSA-N 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000002211 ultraviolet spectrum Methods 0.000 description 1
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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
- B01J27/24—Nitrogen compounds
-
- B01J35/23—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- 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
- C02F2101/345—Phenols
-
- 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
Abstract
The present invention discloses a kind of multistage SnS2Nano flower and C3N4Quantum dot composite material is related to Photocatalitic Technique of Semiconductor field, and composite material is multi-stage nano flower-shape looks, and size is distributed in 4~6 μm, C3N4The size of quantum dot is distributed in 3~9nm.The present invention also provides the preparation methods of composite material, comprising the following steps: (1) C3N4The preparation of quantum dot；(2) multistage SnS2The preparation of nano flower；(3) multistage SnS2Nano flower and C3N4The preparation of quantum dot composite material, the present invention also provides multistage SnS2Nano flower and C3N4Application of the quantum dot composite material in organic matter degradation, the beneficial effects of the present invention are: composite material prepared by the present invention can be to the bisphenol-A and the good photocatalytic degradation of methyl orange realization in water body, and can be used repeatedly, and has cyclical stability.
Description
Technical field
The present invention relates to Photocatalitic Technique of Semiconductor fields, and in particular to a kind of multistage SnS2Nano flower and C3N4Quantum dot
Composite material and preparation method and application.
Background technique
An important factor for energy problem and environmental problem are obstruction human social developments, and photocatalysis technology is considered as solution
Certainly one of the potential strategy of energy and environmental problem.In photocatalysis technology, it is most important that can be by the excitation of sunlight
Promote the progress of chemical reaction and itself is not involved in the photosensitive response catalyst material of reaction.In numerous studied catalyst materials
In material, TiO2It is environmental-friendly since its is cheap and easy to get, and there is good anti-light corrosivity and catalytic activity and be considered as mesh
Preceding most potential catalysis material.However, TiO2The drawbacks of there is itself.Firstly, TiO2It is often needed when as photochemical catalyst
Will be using ultraviolet light as excitation light source, thus use is difficult to realize in reality on a large scale to it.Secondly, TiO2Nanoparticle
Sub- size is minimum, in water the emulsion of colloid easy to form, causes the later period very difficult to the separation of catalyst, and generate
Consequence is then the secondary pollution for being easy to cause catalyst.
In order to avoid the generation of these problems, sight has been turned to other by the older generations can be using visible light as excitation light source
Material.SnS2As typical stratiform chalcogenide, due to cheap and easy to get, toxicity is low, in aqueous solution stability height with
And the narrow equal intrinsic properties of band gap and receive the concern of photocatalysis field researcher.However, although SnS2Can efficiently use can
It is light-exposed, but the light induced electron that its narrowband gap structure having is promoted again in conduction band returns to valence band easily, it means that catalysis
It is compound in photosensitive response material that the catalytic efficiency of agent is still limited by light induced electron and hole.
In order to solve this problem, scientist attempts will equally have the carbonitride (C of superior photocatalytic activity3N4) introduce
SnS2Photocatalytic system, it is intended to obtain SnS2With C3N4Composite material.The calculated results prove, ideal SnS2With C3N4It is compound
Material is capable of forming Z- type hetero-junctions, and Z- type hetero-junctions can make light induced electron by SnS2It is transferred to C3N4On, bring result is then
It is to cause to be located at C since crystal phase interfacial effect exists3N4The light induced electron of conduction band bottom end is difficult to and is located at SnS2On hole it is multiple
It closes, photo-generated carrier survival ability is improved, to promote photocatalytic activity.By unremitting effort, SnS2With C3N4Nanometer sheet
Composite material successfully prepared.It is experimentally confirmed that SnS2With C3N4The composite material of nanometer sheet not only efficiently avoids TiO2
Existing drawback that can not be small using visible light and partial size, and pure phase chalcogenide photoproduction is alleviated to a certain extent
The fast disadvantage of Carrier recombination.
However, still there are serious technological deficiencies for current prepared material: due to crystal structure characteristic, SnS2Often
It is easily formed multistage layer structure, in the SnS being currently reported2With C3N4SnS in the composite material of nanometer sheet2It is as multistage
Laminar nano floral structure, this structure and C3N4Nanometer sheet compound tense contact area is extremely limited, causes photohole from SnS2It is past
C3N4On transition process it is slow, it is difficult to the advantage for utmostly realizing Z- type hetero-junctions, therefore to SnS2With C3N4Composite construction
Redesign still have important science and realistic meaning.
Summary of the invention
Present invention solves the technical problem that one of be to provide a kind of multistage SnS2Nano flower and C3N4Quantum dot composite wood
Material.
The present invention adopts the following technical solutions solves above-mentioned technical problem:
The present invention provides a kind of multistage SnS2Nano flower and C3N4Quantum dot composite material, the composite material are received for multistage
Popped rice pattern, size are distributed in 4~6 μm, C3N4The size of quantum dot is distributed in 3~9nm.
Preferably, the composite material preparation method the following steps are included:
(1)C3N4The preparation of quantum dot
Citric acid and urea are mixed by the weight ratio of 1-2:2-4 and are placed in deionized water, is formed after stirring transparent
Solution；Mixed solution is heated, brown carbonitride solid is formed；Solid sample is dried, by the solid after drying
After sample is dissolved in acetone and the mixed solution of deionized water, mixed solution is centrifuged, takes supernatant, supernatant is pressed with dehydrated alcohol
Volume ratio 1-2:12-20 is mixed, and precipitating is taken after centrifugation, and precipitating is C3N4Quantum dot；
(2) multistage SnS2The preparation of nano flower
Take SnCl4, L-cysteine and bipyridyl, deionized water is added and is mixed, mixed solution is placed at 180 DEG C
Under the conditions of heat, be cooled to room temperature after reaction, obtain brown color sample, obtained brown color sample is obtained by drying to more
Grade SnS2Nano flower；
(3) multistage SnS2Nano flower and C3N4The preparation of quantum dot composite material
Take C3N4Quantum dot is placed in dehydrated alcohol, with multistage SnS2Nano flower mixing, is stirred to react 24-30h, wait react
After dry to get arrive multistage SnS2Nano flower and C3N4Quantum dot composite material.
Preferably, the mixed solution of citric acid, urea and deionized water in step (1) is stirred into 10-20min.
Preferably, mixed solution is put into micro-wave oven in the step (1) and heats 4-6min under 650-800W power.
Preferably, solid sample is put into vacuum oven in the step (1), the dry 1h at 60-80 DEG C.
Preferably, deionized water and the volume ratio of acetone are 1-2:5-10 in the step (1).
Preferably, the bipyridyl in the step (2) is 2,2- bipyridyl or 4,4- bipyridyl.
Preferably, SnCl in the step (2)4, the mass ratio of L-cysteine and bipyridyl is 1.05-3.15:1-3:
0.05-2。
Preferably, the sample deionized water and dehydrated alcohol that are cooled to room temperature after reaction in step (2) are centrifuged
Washing.
Preferably, the brown color sample that step (2) obtains is dried under the conditions of 60-80 DEG C.
Present invention solves the technical problem that two be to provide a kind of multistage SnS2Nano flower and C3N4Quantum dot composite material
Preparation method, comprising the following steps:
(1)C3N4The preparation of quantum dot
Citric acid and urea are mixed by the weight ratio of 1-2:2-4 and are placed in deionized water, is formed after stirring transparent
Solution；Mixed solution is heated, brown carbonitride solid is formed；Solid sample is dried, by the solid after drying
Sample is dissolved in the mixed solution of acetone and deionized water, is centrifuged to mixed solution, takes supernatant, and supernatant and dehydrated alcohol press body
Product is mixed than 1-2:12-20, and precipitating is taken after centrifugation, and precipitating is C3N4Quantum dot；
(2) multistage SnS2The preparation of nano flower
Take tin tetrachloride (SnCl4), L-cysteine and bipyridyl, deionized water is added and is mixed, by mixed solution
It heats under the conditions of being placed at 180 DEG C, is cooled to room temperature after reaction, obtain brown color sample, the brown color sample that will be obtained
It is obtained by drying to arrive multistage SnS2Nano flower；
(3) multistage SnS2Nano flower and C3N4The preparation of quantum dot composite material
Take C3N4Quantum dot is placed in dehydrated alcohol, with multistage SnS2Nano flower mixing, and 24-30h is stirred, reaction terminates
After dry to get to multistage SnS2Nano flower and C3N4Quantum dot composite material.
Preferably, the mixed solution of citric acid, urea and deionized water in step (1) is stirred into 10-20min.
Preferably, mixed solution is put into micro-wave oven and heats 4-6min under 650-800W power.
Preferably, solid sample is put into vacuum oven, the dry 1h at 60-80 DEG C.
Preferably, deionized water and the volume ratio of acetone are 1-2:5-10 in the step (1).
Preferably, the bipyridyl in the step (2) is 2,2- bipyridyl or 4,4- bipyridyl.
Preferably, SnCl in the step (2)4, the mass ratio of L-cysteine and bipyridyl is 1.05-3.15:1-3:
0.05-2。
Preferably, the sample deionized water and dehydrated alcohol that are cooled to room temperature after reaction in step (2) are centrifuged
Washing.
Preferably, the brown color sample that step (2) obtains is dried under the conditions of 60-80 DEG C.
Present invention solves the technical problem that three be to provide multistage SnS2Nano flower and C3N4Quantum dot composite material is having
Application in the degradation of machine object.
The beneficial effects of the present invention are:
(1) present invention passes through multi-step synthetic methods for C3N4Quantum dot is attached to SnS2Nanometer flower surface, prepares multistage SnS2
Nano flower and C3N4Quantum dot composite material, the composite material can be to Organic Pollutants In Waters (with Typical Endocrine Disrupting Chemicals
For bisphenol-A and typical industry methyl orange) realize good photocatalytic degradation, and can be used repeatedly, there is circulation
Stability；
(2) the multistage SnS with relatively narrow bandgap structure prepared by the present invention2Nano flower and C3N4Quantum dot composite wood
Expect photochemical catalyst, can not only effectively avoid TiO2Can not be using visible light and the small drawback of partial size, and alleviate pure phase
The compound fast disadvantage of chalcogenide photo-generated carrier；More importantly solving currently existing multistage SnS2Layer structure
With C3N4SnS existing for nanosheet composite material2With C3N4The small disadvantage of contact area.In the photocatalytic process, multistage SnS2It receives
Popped rice and C3N4The huge contact area of quantum dot can ensure light induced electron success from transfer SnS2To C3N4On, utmostly send out
Interfacial effect effect has been waved, the compound of light induced electron and hole has been constrained, increases effective time-to-live of photo-generated carrier, from
And realize efficient catalytic effect.
Detailed description of the invention
Fig. 1 is multistage SnS obtained in the embodiment of the present invention 12Nano flower and C3N4The X-ray powder of quantum dot composite material
Last diffraction pattern；
Fig. 2 is multistage SnS obtained in the embodiment of the present invention 12Nano flower and C3N4Quantum dot composite material is under 2 μm
Transmission electron microscope picture；
Fig. 3 is multistage SnS obtained in the embodiment of the present invention 12Nano flower and C3N4Quantum dot composite material is at 10nm
Transmission electron microscope picture；
Fig. 4 is multistage SnS obtained in the embodiment of the present invention 12Nano flower and C3N4The UV, visible light of quantum dot composite material
Spectrum (UV-vis) figure；
Fig. 5 is multistage SnS obtained in the embodiment of the present invention 12Nano flower and C3N4The bandgap structure of quantum dot composite material
Figure；
Fig. 6 is multistage SnS obtained in the embodiment of the present invention 12Nano flower and C3N4The AC impedance of quantum dot composite material
Figure；
Fig. 7 is the density of states state diagram of the composite material prepared in embodiment 1；
Fig. 8 is the C prepared in embodiment 13N4The density of states state diagram of quantum dot；
Fig. 9 is the multistage SnS prepared in embodiment 12The density of states state diagram of nano flower；
Figure 10 is multistage SnS obtained in the embodiment of the present invention 12Nano flower and C3N4Quantum dot composite material photochemical catalyst
To the photocatalytic degradation effect figure of bisphenol-A；S1 represents comparative example 1 in figure；S3 represents comparative example 3, and S4 represents comparative example 4, S5 generation
Table comparative example 5, S6 represent comparative example 6；
Figure 11 is the multistage SnS prepared in the embodiment of the present invention 12Nano flower and C3N4Quantum dot composite material is to methyl orange
Photocatalytic degradation effect figure；S1 represents comparative example 1 in figure；S3 represents comparative example 3, and S4 represents comparative example 4, and S5 represents comparative example
5, S6 represent comparative example 6；
Figure 12 is the multistage SnS prepared in the embodiment of the present invention 12Nano flower and C3N4The cycle down of quantum dot composite material
Solve test curve figure.
Specific embodiment
The present invention is described in further details below with reference to Figure of description and embodiment.
Test material and reagent as used in the following examples etc., unless otherwise specified, commercially obtain.
In the examples where no specific technique or condition is specified, can according to the literature in the art described technology or
Condition is carried out according to product description.
Embodiment 1
Prepare multistage SnS2Nano flower and C3N4Quantum dot composite material
(1)C3N4The preparation of quantum dot
3g citric acid is mixed with 6g urea and is placed in 20mL deionized water, magnetic agitation 20min is allowed to mix well, shape
At clear solution, solution is placed in micro-wave oven, 5min is heated under 650W power, former clear solution becomes grain after reaction
Diameter scrapes solid in the brown carbonitride solid of 20~2000 mesh, grinds 10min, places it in vacuum oven, at 60 DEG C
Lower heating 1h, the sample powder obtained after reaction are dissolved in the mixture of acetone and deionized water, deionized water and acetone body
Product is centrifuged 20min, removal partial size is greater than the particle C of 10nm than being 1:5 under 3000rpm revolving speed3N4, then will be upper after centrifugation
Clear liquid and dehydrated alcohol are miscible with the volume ratio of 1:12, and high speed centrifugation washs 30min under 12000rpm revolving speed, and precipitating is
C3N4Quantum dot, by C3N4Quantum dot is stored in spare in dehydrated alcohol, C3N4The concentration of quantum dot in ethanol is 5mg/ml.
(2) multistage SnS2The preparation of nano flower
By 1.05g SnCl4, 1g L-cysteine and 0.05g2,2- bipyridyl mixing be placed in 30mL ionized water, magnetic
Power stirs 20min, and mixed solution is placed in 50ml reaction kettle, heats at 180 DEG C for 24 hours, naturally cools to after reaction
Room temperature, with deionized water and dehydrated alcohol, circular centrifugal washing sample 3 times under the revolving speed of 7000rpm, obtain brown color sample,
Sample is obtained by drying under conditions of 60 DEG C after washing arrives multistage SnS2Nano flower.
(3) multistage SnS2Nano flower and C3N4The preparation of quantum dot composite material
By 0.5g multistage SnS2Nano flower is placed in C3N4In the ethanol solution of quantum dot, magnetic agitation for 24 hours, after reaction
It is centrifuged reaction solution at 6000rpm to be precipitated, precipitating circular centrifugal is washed 3 times at 6000rpm with dehydrated alcohol, it will
Sample after washing dries 10h under conditions of 60 DEG C to get multistage SnS is arrived2Nano flower and C3N4Quantum dot composite material.
Experimental result: Fig. 1 is X-ray powder diffraction figure, and Fig. 2 and Fig. 3 are transmission electron microscope figure, can from Fig. 1
Multistage SnS out2Nano flower and C3N4Quantum dot composite material maintains pure phase SnS2Crystal form and crystal phase, this illustrates C3N4Quantum dot
Only it is attached to SnS2Surface, and it is not embedded into SnS2Its crystal structure is caused to change in lattice；Fig. 2 and Fig. 3 is multi-stage nano flower-shape
Looks, wherein multistage SnS2Nanostructure is nano flower spherical shape looks, having a size of 4~6 μm, C3N4Quantum dot is attached to SnS2Nano flower
Surface, C3N4Quantum dot size is distributed in 3~9nm.Fig. 2 and Fig. 3 not only illustrates multistage SnS2Nano flower and C3N4Quantum dot is compound
Material has the volume that is easily recycled, and verifying C3N4Quantum dot is only attached to SnS2Surface, this complex method are maximum
Degree has played the advantage of Z- type hetero-junctions, and two kinds of intrinsic special types of material are performed to maximum, facilitate integral composite light
The promotion of catalytic effect.
Embodiment 2
Prepare multistage SnS2Nano flower and C3N4Quantum dot composite material
(1)C3N4The preparation of quantum dot
3g citric acid is mixed with 12g urea and is placed in 20mL deionized water, magnetic agitation 10min is allowed to mix well,
Clear solution is formed, solution is placed in micro-wave oven, 6min is heated under 650W power, former clear solution becomes after reaction
Partial size scrapes solid in the brown carbonitride solid of 20~2000 mesh, grinds 10min, places it in vacuum oven, 80
1h is heated at DEG C, the sample powder obtained after reaction is dissolved in the mixture of acetone and deionized water, deionized water and acetone
Volume ratio is 1:5, and 20min is centrifuged under 3000rpm revolving speed, and removal partial size is greater than the particle C of 10nm3N4, then will be after centrifugation
Supernatant and dehydrated alcohol are miscible with the volume ratio of 1:12, and high speed centrifugation washs 30min under 12000rpm revolving speed, and precipitating is
C3N4Quantum dot, by C3N4Quantum dot is stored in spare in dehydrated alcohol, C3N4The concentration of quantum dot in ethanol is 5mg/ml.
(2) multistage SnS2The preparation of nano flower
By 3.15g SnCl4, 2g L-cysteine and 0.05g2,2- bipyridyl mixing be placed in 30mL ionized water, magnetic
Power stirs 20min, and mixed solution is placed in 50ml reaction kettle, heats at 180 DEG C for 24 hours, naturally cools to after reaction
Room temperature, with deionized water and dehydrated alcohol, circular centrifugal washing sample 3 times under the revolving speed of 7000rpm, obtain brown color sample,
Sample is obtained by drying under conditions of 60 DEG C after washing arrives multistage SnS2Nano flower.
(3) multistage SnS2Nano flower and C3N4The preparation of quantum dot composite material
By 0.5g multistage SnS2Nano flower is placed in C3N4In the ethanol solution of quantum dot, magnetic agitation for 24 hours, after reaction
It is centrifuged reaction solution at 6000rpm to be precipitated, precipitating circular centrifugal is washed 3 times at 6000rpm with dehydrated alcohol, it will
Sample after washing dries 10h under conditions of 60 DEG C to get multistage SnS is arrived2Nano flower and C3N4Quantum dot composite material.
Embodiment 3
Prepare multistage SnS2Nano flower and C3N4Quantum dot composite material
(1)C3N4The preparation of quantum dot
6g citric acid is mixed with 6g urea and is placed in 20mL deionized water, magnetic agitation 10min is allowed to mix well, shape
At clear solution, solution is placed in micro-wave oven, 6min is heated under 650W power, former clear solution becomes grain after reaction
Diameter scrapes solid in the brown carbonitride solid of 20~2000 mesh, grinds 10min, places it in vacuum oven, at 60 DEG C
Lower heating 1h, the sample powder obtained after reaction are dissolved in the mixture of acetone and deionized water, deionized water and acetone body
Product is centrifuged 20min, removal partial size is greater than the particle C of 10nm than being 1:6 under 3000rpm revolving speed3N4, then will be upper after centrifugation
Clear liquid and dehydrated alcohol are miscible with the volume ratio of 1:15, and high speed centrifugation washs 30min under 12000rpm revolving speed, and precipitating is
C3N4Quantum dot, by C3N4Quantum dot is stored in spare in dehydrated alcohol, C3N4The concentration of quantum dot in ethanol is 5mg/ml.
(2) multistage SnS2The preparation of nano flower
By 2g SnCl4, 3g L-cysteine and 2g 2, the mixing of 2- bipyridyl is placed in 30mL ionized water, and magnetic force stirs
20min is mixed, mixed solution is placed in 50ml reaction kettle, is heated at 180 DEG C for 24 hours, after reaction cooled to room temperature,
With deionized water and dehydrated alcohol, circular centrifugal washing sample 3 times under the revolving speed of 7000rpm, obtain brown color sample, will wash
It is obtained by drying to multistage SnS under conditions of 60 DEG C to wash rear sample2Nano flower.
(3) multistage SnS2Nano flower and C3N4The preparation of quantum dot composite material
By 0.5g multistage SnS2Nano flower is placed in C3N4In the ethanol solution of quantum dot, magnetic agitation for 24 hours, after reaction
It is centrifuged reaction solution at 6000rpm to be precipitated, precipitating circular centrifugal is washed 3 times at 6000rpm with dehydrated alcohol, it will
Sample after washing dries 10h under conditions of 60 DEG C to get multistage SnS is arrived2Nano flower and C3N4Quantum dot composite material.
Comparative example 1
Prepare multistage SnS2Nano flower: multistage SnS in preparation method and embodiment 12The preparation method of nano flower is identical.
Comparative example 2
Prepare C3N4Quantum dot: C in preparation method and embodiment 13N4The preparation method of quantum dot is identical.
Comparative example 3
Prepare multistage SnS2Nano flower and C3N4Nanosheet composite material:
(1)C3N4Nanometer piece preparation method: weighing a certain amount of melamine powder, with 550 DEG C of annealing 2h in Muffle furnace,
Heating rate is 5 DEG C/min, and cooling rate is 3 DEG C/min, and C can be obtained3N4Nanometer sheet powder.
(2) multistage SnS2Multistage SnS in the preparation method and embodiment 1 of nano flower2The preparation method of nano flower is identical.
(3) multistage SnS2Nano flower and C3N4The preparation method of nanosheet composite material:
By 0.5g multistage SnS2Nano flower and 0.1gC3N4Nanometer sheet powder is placed in 50ml beaker, and 30ml deionization is added
Water magnetic agitation 30 minutes, solution is put into reaction kettle, in 180 DEG C of heating 2h, cooled to room temperature after reaction,
With deionized water and dehydrated alcohol, circular centrifugal washing sample 3 times under the revolving speed of 7000rpm, obtain dark-brown sample, will wash
It is obtained by drying to multistage SnS under conditions of 60 DEG C to wash rear sample2Nano flower and C3N4Nanosheet composite material.
Comparative example 4
Multistage SnS is prepared by raw material of potassium citrate2Nano flower and C3N4Quantum dot composite material: preparation method and reality
Apply multistage SnS in example 12Nano flower and C3N4The preparation method of quantum dot composite material is identical, in addition to that will prepare C3N4Quantum dot
Citric acid such as changes at the potassium citrate of weight.
Comparative example 5
It is that raw material prepares multistage SnS with polyvinylpyrrolidone (PVP)2Nano flower and C3N4Quantum dot composite material: it is made
Multistage SnS in Preparation Method and embodiment 12Nano flower and C3N4The preparation method of quantum dot composite material is identical, more in addition to that will prepare
Grade SnS2The 2,2- bipyridyl of nano flower at etc. weight PVP.
Comparative example 6
Multistage SnS2Nano flower and C3N4The mixing material of quantum dot: multistage SnS in preparation method and embodiment 12Nanometer
Colored and C3N4The preparation method of quantum dot composite material is identical, in addition to the step (3) in embodiment 1 is changed to that the multistage of weight will be waited
SnS2C after nano flower and cooling drying3N4Quantum dot directly mixes, grinding uniformly to get arrive multistage SnS2Nano flower and C3N4
The mixing material of quantum dot.
Embodiment 4
Multistage SnS prepared by embodiment 12Nano flower and C3N4Quantum dot composite material carries out uv-vis spectra, band gap
And AC impedance detection:
(1) uv-vis spectra detection process:
Weigh 0.5g multistage SnS2Nano flower and C3N4Quantum dot composite material, being pressed into diameter is 1cm, with a thickness of 0.2cm
Disk, detected with uv-vis spectra.
(2) band gap determines: being obtained by ultraviolet spectrum data analysis.
(3) AC impedance detects:
By 0.1g multistage SnS2Nano flower and C3N4Quantum dot composite material is placed in agate mortar, and 0.5ml terpinol is added dropwise
With 2ml dehydrated alcohol, grinding until formed viscous solution, with scalpel scrape embrane method by viscous solution blade coating 1 × 2cm FTO
On electro-conductive glass, blade coating area is 0.25cm2, the FTO electro-conductive glass after film is placed in vacuum drying oven, under vacuum conditions
200 ° of heating 1h inject electrolyte after natural cooling into the FTO electro-conductive glass of two panels film, and pass through electrochemical workstation and survey
Measure AC impedance.
Experimental result: Fig. 4 is multistage SnS2Nano flower and C3N4Ultraviolet-visible spectrogram, Fig. 5 of quantum dot composite material be
Bandgap structure figure and Fig. 6 are AC impedance figure, as can be seen from Figure 4 and Figure 5 multistage SnS2Nano flower and C3N4Quantum dot composite wood
For material in visible region strong absworption peak, band gap is 2.03~2.35eV.This illustrates multistage SnS2Nano flower and C3N4Quantum dot is compound
Material can make full use of visible light, and which overcome TiO2The defect of visible light can not be utilized.From fig. 6, it can be seen that multistage SnS2
Nano flower and C3N4Quantum dot composite material electronics transfer impedance is 2.34k Ω, for inorganic semiconductor, this impedance data
Prove that composite material has lesser electronics transfer impedance, this is conducive to the migration of carrier, can effectively facilitate both hole and electron
Pair separation.
Embodiment 5
Multistage SnS prepared by embodiment 12Nano flower and C3N4Quantum dot composite material carries out density of states theoretical modeling meter
It calculates
Theoretical calculation process: first-principles calculations method is utilized, multistage SnS is constructed2Nano flower and C3N4Quantum dot is compound
The theoretical model of material calculates multistage SnS using supercomputer computer2Nano flower and C3N4Quantum dot composite material, multistage SnS2
Nano flower and C3N4Multistage SnS in quantum dot composite material2With multistage SnS2Nano flower and C3N4C in quantum dot composite material3N4Amount
The density of states of son point.
The calculated results: Fig. 7, Fig. 8 and Fig. 9 are density of states state.It can be seen that composite wood by Fig. 7, Fig. 8 and Fig. 9
The conduction band low side of material is in C3N4On quantum dot, and the valence band top of composite material is in multistage SnS2Nano flower, this illustrates this structure
Composite material can effectively disperse light induced electron on two different components, and the fast of Pair production can be effectively relieved in this
Conjunction is replied immediately, photocatalysis efficiency is promoted.
Embodiment 6
It can to the material progress prepared in embodiment 1, comparative example 1, comparative example 3, comparative example 4, comparative example 5 and comparative example 6
Light-exposed catalytic degradation incretion interferent (bisphenol-A) detection
(1) bisphenol-A (BPA) aqueous solution configures: weighing 0.228g bisphenol-A crystal powder and is dissolved in 1L deionized water, stirs
2h is stood more than for 24 hours after sufficiently dissolving mixing, and being such as precipitated without crystal can be used, and the concentration of bisphenol-A solution is at this time
1mmol/L。
(2) photocatalytic degradation experimentation:
A. the multistage SnS prepared in 50mg embodiment 1 is weighed2Nano flower and C3N4Quantum dot composite material photochemical catalyst adds
Enter to 50ml, in the bisphenol-A solution of 1mmol/L concentration；The composite material prepared in embodiment 1 is substituted for comparative example 1 respectively
The multistage SnS of middle preparation2Nano flower and C3N4The multistage SnS prepared in nanometer sheet mixing material and comparative example 22Nano flower；
B. the mixed solution of step a is packed into photocatalytic degradation and reacts instrument, the lower magnetic agitation of dark reacts 2h, every 30min
Sampling is crossed 0.45 μm of film and is fitted into liquid phase bottle, and ultraviolet-visible absorption spectroscopy detection is waited, this process is to reach catalyst pair
The adsorption equilibrium of BPA.Use the xenon lamp of 500W simulated solar irradiation as light source (intensity of light source 7mW/cm2, light source is away from reaction unit
About 3cm), magnetic agitation is carried out while being irradiated to mixed solution, is sampled every 30min, is crossed 0.45 μm of film and is packed into
In liquid phase bottle, ultraviolet-visible absorption spectroscopy detection is waited.
Experimental result: Figure 10 is multistage SnS2Nano flower and C3N4Quantum dot composite material photochemical catalyst urges the light of bisphenol-A
Change degradation effect figure, S1 represents the multistage SnS prepared in comparative example 12Nano flower, S3 represent the multistage SnS prepared in comparative example 32
Nano flower and C3N4Nanosheet composite material, S4 represent prepared in comparative example 4 using potassium citrate as raw material prepare multistage SnS2It receives
Popped rice and C3N4Quantum dot composite material, S5 represent prepared in comparative example 5 using PVP as raw material prepare multistage SnS2Nano flower with
C3N4Quantum dot composite material, S6 represent the multistage SnS prepared in comparative example 62Nano flower and C3N4The mixing material of quantum dot.
It is 10 to 50ml concentration in 3h from fig. 10 it can be seen that being irradiated using 500W xenon lamp as light source analogy sunlight- 5The bisphenol-A degradation rate of M reaches 97% or more, multistage SnS2Nano flower and C3N4Quantum dot composite material photochemical catalyst is right in 3h
The degradation rate of BPA is multistage SnS respectively212.3 times of nano flower are multistage SnS2Nano flower and C3N4Nanosheet composite material
7.1 times, be to prepare multistage SnS by raw material of potassium citrate2Nano flower and C3N41.3 times of quantum dot composite material, are with PVP
Multistage SnS is prepared for raw material2Nano flower and C3N43.5 times of quantum dot composite material are multistage SnS2Nano flower and C3N4Quantum
8.9 times of the mixing material of point.
Photocatalysis result explanation, relative to the potassium citrate used in traditional preparation methods, PVP and solid-state mixing side
Method prepares C by raw material of citric acid in the preparation method being related in the application3N4Quantum point process, using bipyridyl as raw material
Prepare multistage SnS2Nano flower and by multistage SnS2Nano flower is immersed into C3N4Quantum dot ethanol solution prepares multistage SnS2Nanometer
Colored and C3N4Quantum dot composite material process be it is essential, these new technologies to obtain high efficiency photocatalysis activity have it is important
Contribution function.
Embodiment 7
To the multistage SnS prepared in embodiment 1, comparative example 1, comparative example 3, comparative example 4, comparative example 5 and comparative example 62It receives
Popped rice and C3N4Quantum dot composite material carries out the detection of visible light photocatalytic degradation industrial dye methyl orange
(1) methyl orange aqueous solution configures: weighing 0.327g methyl orange powder and is dissolved in 1L deionized water, 1h is stirred, wait fill
It is stood more than for 24 hours after dividing dissolution mixing, it is usable for being such as precipitated without crystal, and the concentration of methyl orange solution is 1mmol/L at this time；
(2) photocatalytic degradation experimentation:
A. the multistage SnS prepared in 50mg embodiment 1 is weighed2Nano flower and C3N4Quantum dot composite material photochemical catalyst adds
Enter to 50ml, in the methyl orange solution of 1mmol/L concentration；
B. the mixed solution of step a is packed into photocatalytic degradation and reacts instrument, the lower magnetic agitation of dark reacts 2h, every 30min
Sampling is crossed 0.45 μm of film and is fitted into liquid phase bottle, and ultraviolet-visible absorption spectroscopy detection is waited, this process is to reach catalyst pair
The adsorption equilibrium of BPA.Use the xenon lamp of 500W simulated solar irradiation as light source (intensity of light source 7mW/cm2, light source is away from reaction unit
About 3cm), magnetic agitation is carried out while being irradiated to mixed solution, is sampled every 30min, is crossed 0.45 μm of film and is packed into
In liquid phase bottle, ultraviolet-visible absorption spectroscopy detection is waited.
Experimental result: as shown in figure 11,350W xenon lamp is irradiated as light source analogy sunlight, is to 50ml concentration in 3h
10-5The industrial dye catalytic degradation efficiency of M reaches 99% or more, compared to the multistage SnS of single-phase2Nano flower, multistage SnS2
Nano flower and C3N4Quantum dot composite material is multistage SnS to the photocatalytic degradation efficiency of industrial dye24.1 times of nano flower are
Multistage SnS2Nano flower and C3N41.6 times of nanosheet composite material are to prepare multistage SnS by raw material of potassium citrate2Nano flower
With C3N42.1 times of quantum dot composite material are to prepare multistage SnS by raw material of PVP2Nano flower and C3N4Quantum dot composite material
2.2 times, be multistage SnS2Nano flower and C3N41.2 times of the mixing material of quantum dot.
Embodiment 8
The experiment of visible light photocatalytic degradation bisphenol-A cyclical stability
Cyclical stability experimentation is consistent with the catalysis degeneration experiment in embodiment 3, only after primary degradation
By catalyst through centrifugation, washing, drying and etc. regain.After acquisition with the catalytic degradation process phase in embodiment 2
Same step re-starts degradation experiment, repeatedly three times.
Experimental result: as shown in figure 12, the multistage SnS prepared in embodiment 12Nano flower and C3N4Quantum dot composite material
Catalytic degradation efficiency after a number of uses is still constant, it was demonstrated that multistage SnS2Nano flower and C3N4Quantum dot composite material light is urged
Agent has good cyclical stability.
The above is only the preferred embodiment of the present invention, protection scope of the present invention is not limited merely to above-described embodiment,
It is within the scope of the invention with present inventive concept without the various process programs of substantial differences.
Claims (10)
1. a kind of multistage SnS2Nano flower and C3N4Quantum dot composite material, it is characterised in that: the composite material is multi-stage nano
Flower-shape looks, size are distributed in 4~6 μm, C3N4The size of quantum dot is distributed in 3~9nm.
2. multistage SnS according to claim 12Nano flower and C3N4Quantum dot composite material, it is characterised in that: described multiple
The preparation method of condensation material the following steps are included:
(1)C3N4The preparation of quantum dot
Citric acid and urea are mixed by the weight ratio of 1-2:2-4 and are placed in deionized water, forms clear solution after stirring；
Mixed solution is heated, brown carbonitride solid is formed；Solid sample is dried, the solid sample after drying is molten
In the mixed solution of acetone and deionized water, mixed solution is centrifuged, takes supernatant, supernatant and dehydrated alcohol 1- by volume
2:12-20 is mixed, and precipitating is taken after centrifugation, and precipitating is C3N4Quantum dot；
(2) multistage SnS2The preparation of nano flower
Take SnCl4, L-cysteine and bipyridyl, addition deionized water are mixed, mixed solution are placed under the conditions of 180 DEG C
Heating, is cooled to room temperature after reaction, obtains brown color sample, and obtained brown color sample is obtained by drying to multistage SnS2
Nano flower；
(3) multistage SnS2Nano flower and C3N4The preparation of quantum dot composite material
Take C3N4Quantum dot is placed in dehydrated alcohol, with multistage SnS2Nano flower mixing, is stirred to react 24-30h, to the end of reacting
After dry to get to multistage SnS2Nano flower and C3N4Quantum dot composite material.
3. preparing multistage SnS as described in claim 12Nano flower and C3N4The preparation method of quantum dot composite material, feature
It is: the following steps are included:
(1)C3N4The preparation of quantum dot
Citric acid and urea are mixed by the weight ratio of 1:2 and are placed in deionized water, forms clear solution after stirring；It will mix
It closes solution to be heated, forms solid sample；Solid sample is dried, the solid sample after drying is dissolved in acetone and is gone
The mixed solution of ionized water is centrifuged mixed solution, takes supernatant, 1:12 is mixed supernatant by volume with dehydrated alcohol
It closes, precipitating is taken after centrifugation, precipitating is C3N4Quantum dot；
(2) multistage SnS2The preparation of nano flower
Take SnCl4, mixed solution is placed at 180 DEG C of conditions by L-cysteine and bipyridyl, addition deionized water mixing
Lower heating, is cooled to room temperature after reaction, obtains brown color sample, and obtained brown color sample is obtained by drying to multistage
SnS2Nano flower；
(3) multistage SnS2Nano flower and C3N4The preparation of quantum dot composite material
Take C3N4Quantum dot is placed in dehydrated alcohol, with multistage SnS2Nano flower mixing, and is stirred, dry after reaction to get
To multistage SnS2Nano flower and C3N4Quantum dot composite material.
4. multistage SnS according to claim 32Nano flower and C3N4The preparation method of quantum dot composite material, feature exist
In: the mixed solution of citric acid, urea and deionized water in step (1) is stirred into 10-20min.
5. multistage SnS according to claim 32Nano flower and C3N4The preparation method of quantum dot composite material, feature exist
In: mixed solution is put into micro-wave oven in the step (1) and heats 4-6min under 650W power.
6. multistage SnS according to claim 32Nano flower and C3N4The preparation method of quantum dot composite material, feature exist
In: solid sample is put into vacuum oven in the step (1), the dry 1h at 60-80 DEG C.
7. multistage SnS according to claim 32Nano flower and C3N4The preparation method of quantum dot composite material, feature exist
In: deionized water and the volume ratio of acetone are 1-2:5-10 in the step (1).
8. multistage SnS according to claim 32Nano flower and C3N4The preparation method of quantum dot composite material, feature exist
In: the bipyridyl in the step (2) is 2,2- bipyridyl or 4,4- bipyridyl.
9. multistage SnS according to claim 32Nano flower and C3N4The preparation method of quantum dot composite material, feature exist
In: SnCl in the step (2)4, the mass ratio of L-cysteine and bipyridyl is 1.05-3.15:1-3:0.05-2.
10. multistage SnS described in claim 12Nano flower and C3N4Application of the quantum dot composite material in organic matter degradation.
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