CN106111137B - A kind of preparation method and applications of carbon quantum dot-cuprous oxide composite material - Google Patents
A kind of preparation method and applications of carbon quantum dot-cuprous oxide composite material Download PDFInfo
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- CN106111137B CN106111137B CN201610453856.3A CN201610453856A CN106111137B CN 106111137 B CN106111137 B CN 106111137B CN 201610453856 A CN201610453856 A CN 201610453856A CN 106111137 B CN106111137 B CN 106111137B
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- cuprous oxide
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- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 41
- 239000002131 composite material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims description 34
- 229910052799 carbon Inorganic materials 0.000 title claims description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 21
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 7
- 239000008103 glucose Substances 0.000 claims abstract description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 10
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid group Chemical group C(CC(O)(C(=O)O)CC(=O)O)(=O)O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 6
- 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 claims description 5
- 229940012189 methyl orange Drugs 0.000 claims description 5
- 238000005406 washing Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 238000000502 dialysis Methods 0.000 claims description 4
- 239000008236 heating water Substances 0.000 claims description 4
- 235000015165 citric acid Nutrition 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000725 suspension Substances 0.000 claims description 3
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 3
- 239000012498 ultrapure water Substances 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 2
- 229910000366 copper(II) sulfate Inorganic materials 0.000 claims description 2
- 239000004337 magnesium citrate Substances 0.000 claims description 2
- 229960005336 magnesium citrate Drugs 0.000 claims description 2
- 235000002538 magnesium citrate Nutrition 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000001508 potassium citrate Substances 0.000 claims description 2
- 229960002635 potassium citrate Drugs 0.000 claims description 2
- 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 claims description 2
- 235000011082 potassium citrates Nutrition 0.000 claims description 2
- 150000003384 small molecules Chemical class 0.000 claims description 2
- 239000001509 sodium citrate Substances 0.000 claims description 2
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims description 2
- PLSARIKBYIPYPF-UHFFFAOYSA-H trimagnesium dicitrate Chemical compound [Mg+2].[Mg+2].[Mg+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O PLSARIKBYIPYPF-UHFFFAOYSA-H 0.000 claims description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 239000000975 dye Substances 0.000 claims 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims 1
- 235000005979 Citrus limon Nutrition 0.000 claims 1
- 244000248349 Citrus limon Species 0.000 claims 1
- 239000011575 calcium Substances 0.000 claims 1
- 229910052791 calcium Inorganic materials 0.000 claims 1
- 238000000926 separation method Methods 0.000 claims 1
- 235000011083 sodium citrates Nutrition 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 12
- 238000007146 photocatalysis Methods 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 10
- 230000008569 process Effects 0.000 abstract description 4
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 238000003912 environmental pollution Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 239000000463 material Substances 0.000 description 11
- 150000001875 compounds Chemical class 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 9
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000015556 catabolic process Effects 0.000 description 3
- 238000006731 degradation reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000004408 titanium dioxide Substances 0.000 description 3
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 235000013877 carbamide Nutrition 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 230000007096 poisonous effect Effects 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000003643 water by type Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- FNAQSUUGMSOBHW-UHFFFAOYSA-H calcium citrate Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O.[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O FNAQSUUGMSOBHW-UHFFFAOYSA-H 0.000 description 1
- 239000001354 calcium citrate Substances 0.000 description 1
- 229960004256 calcium citrate Drugs 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000010531 catalytic reduction reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910001922 gold oxide Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000012779 reinforcing material Substances 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- FJOLTQXXWSRAIX-UHFFFAOYSA-K silver phosphate Chemical compound [Ag+].[Ag+].[Ag+].[O-]P([O-])([O-])=O FJOLTQXXWSRAIX-UHFFFAOYSA-K 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 150000003467 sulfuric acid derivatives Chemical class 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 235000013337 tricalcium citrate Nutrition 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 150000003672 ureas Chemical class 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of preparation method of carbon quantum dot cuprous oxide composite material and its as the application of photochemical catalyst.The preparation method of the present invention does not add any surfactant, is an a kind of step in-situ preparation method simple and easy to control using glucose as reducing agent, and simple process and low cost is honest and clean, highly practical, is convenient for high-volume industrial production；Obtained composite material morphology controllable, photocatalysis efficiency are high, using solar energy and are curbing environmental pollution etc. and to have good application prospect.
Description
Technical field
The invention belongs to visible light catalytic material fields, and in particular to a kind of carbon quantum dot-cuprous oxide composite material
Preparation method and its application as photochemical catalyst.
Background technology
Based on the photochemical catalyst of semiconductor because solar energy and environment purification can be efficiently used in terms of advantage, attracted
The concern of more and more scholars.Cuprous oxide is a kind of typical narrow gap semiconductor (band gap magnitude is about 2.17eV), energy
It is enough by most excited by visible light, and, preparation method cheap with manufacturing cost be green non-poisonous and the earth on copper reserves it is rich
Rich, the advantages that can largely preparing, therefore have a wide range of applications potentiality in the photocatalysis field of visible light.However, due in light
According on lower cuprous oxide photoproduction electrons and holes it is quick compound so that the photo-catalysis capability of cuprous oxide also needs to further
It is promoted, photocatalytic degradation efficiency needs further increase.Studies have shown that by the way that cuprous oxide is compound with other materials, it can
Effectively to prevent the compound of electrons and holes in cuprous oxide, photocatalysis efficiency is greatly improved.Wang Hui et al. exist
It is reported on 23 (2011) 4587-4598 of Chemistry of Materials compound with cuprous oxide using gold nano grain
The method for preparing gold/cuprous oxide nucleocapsid to improve cuprous oxide photocatalysis efficiency；Luo Shenglian et al. exist
It is reported on Environmental Science＆Technology 44 (2010) 7461-7646 and utilizes titanium dioxide semiconductor
The method for improving visible light catalytic efficiency after compound with cuprous oxide；Tang Junwang et al. are in ChemSusChem 7
(2014) it is reported on 1086-1093 and utilizes the compound rear raising photo catalytic reduction titanium dioxide of redox graphene and cuprous oxide
The method of carbon efficiencies.In many reports, using carbon material such as graphene and carbon nanotube etc., and cuprous oxide is compound improves
The advantages that its photocatalysis performance has photocatalysis performance excellent, and preparation method is simple, green non-pollution, therefore receive increasingly
The concern of more scholars.
Carbon quantum dot (CQDs) is the emerging carbon nanomaterial that a kind of size is less than 10nm, because of excellent optical property, good
Good biocompatibility, it is green non-poisonous the advantages that and receive much attention.Recent studies indicate that utilizing carbon quantum dot and semiconductor
(for example, carbon quantum dot/titanium dioxide, carbon quantum dot/zinc oxide, carbon quantum dot/silver orthophosphate etc.) can be significantly after Material cladding
Improve the photocatalysis performance of semiconductor.Its specific mechanism is, under light illumination, semiconductor will produce electrons and holes, on semiconductor
Carbon quantum dot can be with the transmission of charge in reinforcing material, and the hole for hindering photoinduction on semiconductor to generate and electronics are compound,
To greatly improve the photocatalysis efficiency of material.However, presently, there are carbon quantum dot/semiconductor composite it is mostly ultraviolet
Photochemical catalyst, therefore there is an urgent need to provide a kind of method that simple low cost prepares visible light or even near infrared light catalyst.
Invention content
In view of the drawbacks described above of the prior art, the purpose of the present invention is to provide a kind of simple controllable carbon quantum dots-
The preparation method of cuprous oxide composite material and its application as photochemical catalyst.
To achieve the above object, the present invention provides a kind of carbon quantum dot preparing morphology controllable-cuprous oxide composite woods
The method of material does not add surfactant, using the mild glucose of green as reducing agent, at a certain temperature fabricated in situ carbon
Quantum dot-cuprous oxide composite material.
The preparation method of carbon quantum dot-cuprous oxide composite material of the present invention, includes the following steps：
Step 1: weighing a certain amount of carbon source and nitrogen source, microwave heating reaction is carried out after soluble in water, obtained product adds
After water-dispersed, insoluble matter is removed by centrifugation first, then unreacted small molecule reaction object is removed by dialysing, obtains
Carbon quantum dot solution；
Copper-bath is obtained Step 2: being dispersed with stirring anhydrous cupric sulfate in water, a certain amount of carbon amounts is added
Son point solution, is uniformly mixed；
Step 3: the solution heating water bath that step 2 is obtained, is then added sodium hydroxide solution, is immediately generated in solution
Precipitation；
It is after the reaction was continued 3 hours, product is anti-Step 4: glucose solution is added in the suspension obtained to step 3
Multiple centrifugation, washing are multiple, and carbon quantum dot-cuprous oxide composite material is obtained after dry.
Preferably, in step 1, the microwave heating reaction is heated using household microwave oven, the work(of the micro-wave oven
Rate is 600~1000W, and the time of the microwave heating reaction is 3~15 minutes.The carbon source be selected from citric acid, sodium citrate,
One or more of magnesium citrate, calcium citrate, potassium citrate；The nitrogen source is urea；The matter of the carbon source and the nitrogen source
Amount is than being 0.5:1~2:1.The rotating speed of the centrifugation is 6000~10000 revs/min, and the time is 30 minutes；The dialysis
Dialysis bag retention molecular weight used is 500Da.
Preferably, in step 2, it is described stirring be mechanical agitation, a concentration of 0.5~1mol/L of the copper-bath,
The volume for the carbon quantum dot solution being added is 0.5~30mL.
Preferably, in step 3, the temperature of the heating water bath is 50~70 DEG C, the sodium hydroxide solution of addition
A concentration of 0.5~2mol/L, volume 10mL, and to be slowly added dropwise dropwise.
Preferably, in step 4, a concentration of 0.1~0.5mol/L of the glucose solution, volume 10mL, and be fast
It injects fastly.The rotating speed of the centrifugation is 3000~8000 revs/min, every time 3~5 minutes；The washing is to use ultra-pure water
With absolute ethyl alcohol alternately washing 3~5 times；The drying is 30~60 DEG C and is dried in vacuo 6~8 hours.
Compared with prior art, the present invention has the advantages that：Simple process and low cost is honest and clean, highly practical, is convenient for
High-volume industrial production；Obtained composite material morphology controllable, photocatalysis efficiency are high, using solar energy and are curbing environmental pollution
Aspect has good application prospect.For example, the composite material that the present invention obtains can use photocatalyst, it to be used for degradating organic dye
And other organic pollutions.
The technique effect of the design of the present invention, specific example and generation is described further below with reference to attached drawing, with
It is fully understood from the present invention.The purpose for providing these explanations is only that and helps explain the present invention, should not be taken to limit the present invention
The scope of the claims.
Description of the drawings
Fig. 1 is the scanning electron microscope of the carbon quantum dot-cuprous oxide composite material of a preferred embodiment of the present invention
Photo；
Fig. 2 is the transmission electron microscope of the carbon quantum dot-cuprous oxide composite material of a preferred embodiment of the present invention
Photo；
Fig. 3 is the X-ray diffractogram of the carbon quantum dot-cuprous oxide composite material of a preferred embodiment of the present invention；
Fig. 4 is the UV-Vis DRS of the carbon quantum dot-cuprous oxide composite material of a preferred embodiment of the present invention
Figure；
Fig. 5 is the carbon quantum dot-cuprous oxide composite material photo-catalytic degradation of methyl-orange of a preferred embodiment of the present invention
Degradation curve figure.
Specific implementation mode
It elaborates below in conjunction with the accompanying drawings to the embodiment of the present invention, the present embodiment before being with technical solution of the present invention
It puts and is implemented, give detailed embodiment and specific operating process, but protection scope of the present invention is not limited to down
The embodiment stated.
Embodiment 1
3g citric acids and 3g ureas are dissolved under ultrasound in 10mL ultra-pure waters, are placed in the household microwave oven of 800W by step 1
Middle heating 5min, Temperature fall；It is added ultra-pure water into the said goods, after ultrasonic disperse, is centrifuged 30 minutes with 8000 revs/min
Afterwards, supernatant is fitted into the bag filter of 500Da and is dialysed 2-3 days, obtain carbon quantum dot solution；
0.3g anhydrous cupric sulfates are dissolved under tool stirring in 50mL ultra-pure waters, the above-mentioned carbon quantums of 10mL are added by step 2
Point solution, stirs evenly；
Above-mentioned solution water-bath is warming up to 60 DEG C by step 3, and the sodium hydroxide solution of 10mL 1mol/L is added dropwise dropwise；
Step 4, it is above-mentioned be added dropwise to complete after, the glucose for injecting 10mL 0.3mol/L immediately into obtained suspension is molten
Liquid, continues mechanical agitation 3 hours；The said goods are cooled to room temperature, are centrifuged 10 minutes with 3000 revs/min, continue with water and
Ethyl alcohol after eccentric cleaning, is placed in drying 6 hours in 60 DEG C of vacuum drying chambers, obtains carbon quantum dot-cuprous oxide composite wood successively
Material.
The carbon of the present invention it can be seen from the electron scanning micrograph of Fig. 1 and the transmission electron microscope photo of Fig. 2
Quantum dot-cuprous oxide composite material is the cube pattern of size uniformity.By the X-ray diffractogram of Fig. 3 it is found that the present invention obtains
To carbon quantum dot-cuprous oxide composite material in, the crystallinity of cuprous oxide is very high, and without impurity peaks, thus purity is also very
It is high.Relative to pure cuprous oxide material, carbon quantum dot-oxygen of the invention it can be seen from the UV-vis DRS figure of Fig. 4
Change cuprous composite material in the visible region of 460~800nm, absorbance is apparently higher than pure cuprous oxide material；Especially exist
The near infrared region of 780~800nm still shows stronger absorption, this is estimable.
The carbon quantum dot of embodiment 1-cuprous oxide composite material is used to study the visible light photocatalytic degradation of methyl orange.
The composite material powder 50mg that embodiment 1 is obtained is added in the 10mg/mL methyl orange solutions of 50mL, be protected from light stirring 20 minutes with
Reach adsorption equilibrium, then carries out radiation of visible light, sampling in every 10 minutes is primary, observes 60 minutes altogether, result such as Fig. 5 institutes
Show.Obviously, carbon quantum dot of the invention-cuprous oxide composite material under visible light shows the photocatalytic degradation of methyl orange
Extremely strong activity, 60 minutes degradation rates are up to 90% or so；Opposite, pure 60 minutes degradation rates of cuprous oxide material
Only 5% or so, it is sufficient to which the display present invention produces significant advantageous effects by carbon quantum dot and cuprous oxide are compound.
The preparation method of the present invention, the carbon quantum dot-oxidation that can be controlled by adjusting the dosage of carbon quantum dot are sub-
The size and shape of carbon/carbon-copper composite material.The preparation method is simple for process, highly practical, and carbon quantum dot-cuprous oxide of preparation is multiple
The size and shape of condensation material is controllable, and photocatalysis efficiency is high, has preferable application prospect in terms of environmental improvement.
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that those skilled in the art without
It needs creative work according to the present invention can conceive and makes many modifications and variations.Therefore, all technologies in the art
Personnel are available by logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Technical solution, all should be in the protection domain being defined in the patent claims.
Claims (4)
1. a kind of preparation method of carbon quantum dot-cuprous oxide composite material, which is characterized in that the preparation method includes following
Step：
Step 1: weighing a certain amount of carbon source and nitrogen source, microwave heating reaction, the microwave heating reaction are carried out after soluble in water
It is heated using household microwave oven, the power of the micro-wave oven is 600~1000W, and the time of the microwave heating reaction is 3
~15 minutes, obtained product add it is water-dispersed after, first by centrifugation remove insoluble matter, then by dialyse removal it is not anti-
The small molecule reaction object answered, obtains carbon quantum dot solution, and the carbon source is selected from citric acid, sodium citrate, magnesium citrate, lemon
One or more of sour calcium, potassium citrate；The nitrogen source is urea；The mass ratio of the carbon source and the nitrogen source is 0.5:1~
2:1；
Copper-bath is obtained Step 2: being dispersed with stirring anhydrous cupric sulfate in water, a certain amount of carbon quantum dot is added
Solution is uniformly mixed, a concentration of 0.5~1mol/L of the copper-bath, the volume of the carbon quantum dot solution of addition
For 0.5~30mL；
Step 3: the solution heating water bath that step 2 is obtained, is then added sodium hydroxide solution, the temperature of the heating water bath
Be 50~70 DEG C, a concentration of 0.5~2mol/L of the sodium hydroxide solution of addition, volume 10mL, and for slowly by
Drop is added dropwise；
Step 4: glucose solution is added in the suspension obtained to step 3, continues mechanic whirl-nett reaction after 3 hours, will produce
Object is centrifuged repeatedly, washs, and the carbon quantum dot-cuprous oxide composite material, the concentration of the glucose solution are obtained after dry
For 0.1~0.5mol/L, volume 10mL, and rapidly to inject, the rotating speed of the centrifugation is 3000~8000 revs/min,
3~5 minutes every time；The washing is to use alternately washing 3~5 times of ultra-pure water and absolute ethyl alcohol；The drying is 30~60 DEG C
Vacuum drying 6~8 hours.
2. the preparation method of carbon quantum dot-cuprous oxide composite material as described in claim 1, wherein described in step 1 from
The rotating speed of heart separation is 6000~10000 revs/min, and the time is 30 minutes；Dialysis bag retention molecular weight used in the dialysis
For 500Da.
3. the carbon quantum dot obtained by any one of the claim 1-2 preparation methods-cuprous oxide composite material is as light
The application of catalyst.
4. carbon quantum dot as claimed in claim 3-application of the cuprous oxide composite material as photochemical catalyst, wherein the light
Catalyst is used for degradating organic dye, and the organic dyestuff is methyl orange.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610453856.3A CN106111137B (en) | 2016-06-21 | 2016-06-21 | A kind of preparation method and applications of carbon quantum dot-cuprous oxide composite material |
Applications Claiming Priority (1)
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| CN107511151B (en) * | 2017-09-08 | 2020-06-23 | 云南大学 | Carbon quantum dot/cuprous oxide compound (CQDs/Cu) as protein hydrolysis catalyst2O) and use thereof |
| CN108187722B (en) * | 2018-01-13 | 2020-11-10 | 常州大学 | Preparation method of nitrogen-doped carbon quantum dot/cuprous oxide composite photocatalyst |
| CN108816265B (en) * | 2018-06-08 | 2021-04-02 | 湖南大学 | Bismuth vanadate/nitrogen-doped carbon quantum dot/cuprous oxide double-Z-type photocatalyst and preparation method and application thereof |
| CN109939679B (en) * | 2019-04-12 | 2022-03-04 | 齐鲁工业大学 | Atomic-level dispersed copper CO2Transformation promoter, preparation method and application thereof |
| CN110358534A (en) * | 2019-06-28 | 2019-10-22 | 昆明理工大学 | A kind of preparation method that carbon quantum dot combined oxidation is cuprous |
| CN110508248B (en) * | 2019-08-30 | 2022-07-15 | 四川神州奥特农业科技有限公司 | Iodine adsorption material and preparation method thereof |
| CN111607387B (en) * | 2020-01-03 | 2023-07-25 | 华南师范大学 | Photocatalytic microsphere motor based on carbon dots and preparation method and application thereof |
| CN111229215B (en) * | 2020-03-09 | 2021-03-30 | 华东理工大学 | Metal high-dispersion supported catalyst based on carbon quantum dot induction and preparation method and application thereof |
| CN112536034B (en) * | 2020-11-22 | 2023-03-21 | 重庆交通大学 | CQDS/CuO@Cu 2 Preparation method of O-micron balls |
| CN112536022B (en) * | 2020-11-22 | 2023-04-07 | 重庆交通大学 | CQDS/Cu 2 Preparation method of S nanoflower |
| CN113413921B (en) * | 2021-07-30 | 2022-11-18 | 陕西科技大学 | ZIF-8 type composite photocatalyst and preparation method thereof |
| CN114768815A (en) * | 2022-04-28 | 2022-07-22 | 华南农业大学 | Rare earth-iron-carbon quantum dot composite material and preparation method and application thereof |
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