CN110227457A - A kind of preparation method of low temperature liquid phase precipitation method cuprous oxide visible light photochemical catalyst - Google Patents
A kind of preparation method of low temperature liquid phase precipitation method cuprous oxide visible light photochemical catalyst Download PDFInfo
- Publication number
- CN110227457A CN110227457A CN201910558453.9A CN201910558453A CN110227457A CN 110227457 A CN110227457 A CN 110227457A CN 201910558453 A CN201910558453 A CN 201910558453A CN 110227457 A CN110227457 A CN 110227457A
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- CN
- China
- Prior art keywords
- cuprous oxide
- visible light
- dyestuff
- low temperature
- liquid phase
- Prior art date
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- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 116
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 81
- 238000000034 method Methods 0.000 title claims abstract description 49
- 239000003054 catalyst Substances 0.000 title claims abstract description 26
- 239000007791 liquid phase Substances 0.000 title claims abstract description 19
- 238000001556 precipitation Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000000975 dye Substances 0.000 claims abstract description 85
- 230000001699 photocatalysis Effects 0.000 claims abstract description 45
- 239000011941 photocatalyst Substances 0.000 claims abstract description 39
- 230000015556 catabolic process Effects 0.000 claims abstract description 34
- 238000006731 degradation reaction Methods 0.000 claims abstract description 34
- 238000007146 photocatalysis Methods 0.000 claims abstract description 33
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims abstract description 18
- 150000007524 organic acids Chemical class 0.000 claims abstract description 13
- 238000004064 recycling Methods 0.000 claims abstract description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 52
- 239000000243 solution Substances 0.000 claims description 41
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 19
- 239000008367 deionised water Substances 0.000 claims description 14
- 229910021641 deionized water Inorganic materials 0.000 claims description 14
- 238000006243 chemical reaction Methods 0.000 claims description 13
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 claims description 12
- 239000003638 chemical reducing agent Substances 0.000 claims description 12
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- 239000011668 ascorbic acid Substances 0.000 claims description 10
- 229960005070 ascorbic acid Drugs 0.000 claims description 10
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000013078 crystal Substances 0.000 claims 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 description 8
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- 239000008103 glucose Substances 0.000 claims description 8
- 238000000926 separation method Methods 0.000 claims description 8
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 230000008859 change Effects 0.000 claims description 7
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 7
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 7
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 6
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 6
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 5
- 239000000843 powder Substances 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N 4-hydroxybenzoic acid Chemical compound OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Malonic acid Chemical compound OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 4
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- 229940012189 methyl orange Drugs 0.000 claims description 4
- DNUYOWCKBJFOGS-UHFFFAOYSA-N 2-[[10-(2,2-dicarboxyethyl)anthracen-9-yl]methyl]propanedioic acid Chemical compound C1=CC=C2C(CC(C(=O)O)C(O)=O)=C(C=CC=C3)C3=C(CC(C(O)=O)C(O)=O)C2=C1 DNUYOWCKBJFOGS-UHFFFAOYSA-N 0.000 claims description 3
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 3
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Classifications
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- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- 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
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Abstract
The present invention relates to a kind of preparation methods of low temperature liquid phase precipitation method cuprous oxide visible light photochemical catalyst, cuprous oxide photocatalyst is prepared using organic acid assistant regulating and controlling and the low temperature liquid phase precipitation method, the rate of release for reducing copper ion, the speed of growth, structure and the pattern for regulating and controlling cuprous oxide nucleus are acted on using the ligand complex of organic acid and copper ion, white LED lamp is used to carry out photocatalytic degradation to dye solution for simulated visible light light source.Operation is simple for cuprous oxide photocatalyst preparation method of the invention, without being added macromolecule or surfactant, low temperature or reacts under room temperature, low energy consumption, and the reaction time is short.When white LED lamp 30~50min of illumination, cuprous oxide photocatalyst basically reaches balance to the photocatalytic degradation of dye solution, when white LED lamp illumination 50min, cuprous oxide photocatalyst respectively reaches 78~99% and 40~60% to the photocatalysis dyestuff degradation rate of 10mg/L and 50mg/L dye solution, 5 times the photocatalysis dyestuff degradation rate for recycling rear cuprous oxide photocatalyst is the 75~90% of first time photocatalysis dyestuff degradation rate, can be widely applied to the fields such as dyestuff Photocatalytic Activity for Degradation and waste water from dyestuff pollution control.
Description
One, technical field
The present invention relates to a kind of preparation method of low temperature liquid phase precipitation method cuprous oxide visible light photochemical catalyst, systems of the present invention
Standby low temperature liquid phase precipitation method cuprous oxide visible light photochemical catalyst is suitable for the Photocatalytic Activity for Degradation of dyestuff, can answer extensively
The fields such as visible light light degradation and dye environment pollution control for dyestuff.
Two, background technique
Waste water from dyestuff is mainly derived from dye and dye intermediate production industry and weaving, leather, papermaking, rubber, plastics,
The different industries such as cosmetics, pharmacy and food, with complicated composition, water and change of water quality are big, coloration is high, COD and BOD concentration
High, the features such as suspended matter is more, recalcitrant substance is more, be one of industrial wastewater difficult to deal with.The annual output of China's dyestuff
About 150,000 tons, the 16.7%-18.7% of Zhan Quanqiu dyestuff annual output, wherein there is 10%~15% dyestuff producing and making
With can be discharged into environment in the process, these dyestuff majorities are extremely stable, into environment waters after be difficult to natural degradation, cause to get dirty
Contaminating waters oxygen content reduces, and it is incident to hinder light, and then influence the normal activities of aquatile, destroys the ecology of water body
Balance, more seriously dyestuff is mostly noxious material, has carcinogenic teratogenic effect, is discharged into the healthy structure in environment to the mankind
It is threatened at great, therefore dyeing waste water is all the reluctant industrial wastewater in various countries in the world for a long time, at environment-friendly high-efficiency
Reason waste water from dyestuff has become today's society great environmental problem urgently to be resolved.
The method of processing waste water from dyestuff mainly has chemistry, biology, physical method etc. at present.It is easy to operate to precipitate flocculence, at
This is low, but a large amount of sludge generated increase operation cost.Electricity is consumed when Treatment of Wastewater by Electrolysis and metal electrode amount is big.Photocatalysis
Oxidation is only good to low concentration waste water from dyestuff effect.The more single and microorganism of bioanalysis selectivity is environmentally sensitive.Absorption method operation
Simply, at low cost, effect is good, adsorbent is easily recycled.The active charcoal of common adsorbent, mineral, resinae adsorbent
Deng.Activated carbon adsorption power is strong, and removal rate is high, but at high cost, is normally only used for the lower treatment of dyeing wastewater of concentration or depth
Reason.Mineral include natural zeolite, bentonite etc., and ion-exchange capacity and absorption property are preferable, but activity is low, and regeneration is difficult.
And resinae adsorbent treatment effeciency is high, can regenerate under certain condition, can still keep efficiently, being suitable for waste water from dyestuff after regeneration
Processing, but higher cost.
Since Fujishima] find that TiO2 photocatalytic water is used to, conductor photocatalysis material starts to be widely used in ring
Border purification, wastewater treatment and solar energy conversion etc..TiO2 has photocatalytic activity height, stability good, cheap, less toxic
The advantages that property, but its band gap is larger, can only absorb ultraviolet light, can not efficiently use solar energy, significantly limits photocatalysis and answers
With therefore, people have been working hard the catalysis material found and have visible light absorption capacity.Cuprous oxide is a kind of very heavy
The p-type semiconductor material wanted, forbidden bandwidth are about 2.17eV, can be by excited by visible light, can be effective under the irradiation of sunlight
Real estate gives birth to photo-generated carrier, and energy transformation ratio is theoretically up to 12%.3d and 4s track in cuprous oxide lattice is due to copper original
The distance between son and be no longer overlapped, form the valence band being full of entirely by one in system and an empty conduction band constituted half
Conductor energy band, make its performance show good photocatalytic activity, adsorptivity, electro-chemical activity, air-sensitive property and other urge
Change activity, therefore the research of cuprous oxide photocatalyst becomes the research hotspot and emphasis in the whole world.
The main preparation methods of cuprous oxide have vapor phase method, solid phase method and liquid phase method at present.Vapor phase method is solid anti-
It is chemically reacted after answering object to be converted to gaseous material under heating conditions, ultimately produces new solid matter and be deposited on substrate
Surface obtain thin-film material.The substance uniformity adulterated in the thin-film material that this method prepares is good and purity is higher, is
The major way of thin-film material is industrially prepared now.It is prepared by the method that Medina and Markworth passes through vapor deposition respectively
Cuprous oxide film is gone out.Zhang etc. prepares the cuprous nano knot of cube by the method on a sapphire substrate
Structure.Solid phase method major advantage is to preferably control the temperature of reaction and without using solvent, also have highly selective, high
Yield, synthesis technology are simple etc..But the energy consumption of the method is big, environmental pollution is serious, and product purity is low, particle size
Greatly, production efficiency is low.Solid phase method mainly has low-temperature solid-phase method, mechanochemical reaction and metallurgy sintered method etc..It opens bright equal using low temperature
Solid phase method has prepared cuprous oxide nanorods.Ye et al. is sub- using the nanometer powdery oxidation that solid phase method is prepared for various one-components
Copper.
Because prepared by liquid phase method, cuprous oxide is simple to operate, low in cost, reaction condition is mild and technique in recent years
Comparative maturity causes the great interest of people.People have prepared the cuprous oxide with different structure and pattern at present,
Substantially increase the performances such as photocatalysis, air-sensitive, the electrochemistry of cuprous oxide.Liquid phase method includes hydro-thermal method, chemical precipitation method and electricity
Chemical method.Hydro-thermal method refers to the synthetic method using water as solvent, reacted under higher temperature and elevated pressures.Zhu returns victory et al.
The spherical cuprous oxide powder that partial size is about 200nm is prepared using hydro-thermal method.Hua et al. using hydro-thermal method be prepared for cube,
Octahedra and granatohedron Cu2O.Feng et al. is dissolved in NaOH solution with by ethylenediamine EDA, is added copper nitrate and is obtained
To copper-ethylenediamine complex compound, it is prepared for the Cu2O of hollow octahedron and spherical structure using hydro-thermal method, passes through photocatalytic degradation
The Cu2O that methyl orange and Congo red two kinds of organic dyestuff demonstrate hollow octahedral structure has better photocatalytic activity.Leng
Et al. a certain amount of copper acetate is added in the mixed solution of ultrapure water and dehydrated alcohol using hydro-thermal method, NaOH is then added
Solution stirs 10min, is eventually adding reducing agent glucose and has obtained the five decahedron knot of Cu2O of exposed high index { 311 } crystal face
Structure.Valodkar has the Cu2O skeleton of nano-scale using hydro-thermal method preparation using starch as reducing agent and stabilizer,
It was found that the size of the diameter of spherical shape Cu2O nano particle and one-dimensional dendron shape Cu2O nanostructure is about 50nm.Al-Ghamdi etc.
People has the nano cuprous oxide of octahedral structure using the preparation of microwave hydrothermal reaction at low temperature, and having a size of 71nm, gap E g is about
2.43eV.Khan et al. is prepared for the oxidation with multi-branched nanostructure using hydrothermal reaction at low temperature using glucose as reducing agent
It is cuprous.Electrochemical process is primarily referred to as cathodic protection, i.e. sacrificial anode and the method for protecting cathode, and protected metal is made to become yin
Pole and be protected.Electrochemical process prepares Cu2O and typically refers to make anode with metal copper plate and in the solution containing bivalent cupric ion
Middle electrolysis, to obtain the higher Cu2O nanoparticle of purity on cathode.Electrochemical process prepares Cu2O with easy to operate, anti-
The advantages that shorter, product quality is high between seasonable, but the electricity consumed is big, obtained Product yields are low, thus are not suitable in work
It is widely applied in industry.Method copper nitrate, NH4C1 the and KCl solution reaction of Zhong et al. electrochemical deposition are first in matrix
On obtain Cu2O nanometer stick array, as the effect of NH4C1 finally obtains Cu2O nano-tube array.Kevin et al. electrochemistry
Method deposited one layer of Cu2O in the matrix with ZnO nano-wire.Wang et al. uses the matrix with ZnO nanorod as work
Make electrode, quilt has been obtained in DMSO (dimethyl alum) solution at 60 DEG C containing copper nitrate by the method for electrochemical deposition
The Cu2O/ZnO nanometer stick array of Cu2O sensitization, finds prepared Cu2O/ZnO nanometer stick array table under simulated solar irradiation
Reveal significant photocatalysis antibacterial performance.
Copper acetate is reacted a period of time using 70 DEG C of chemical precipitation method by Sun et al. with NaOH, and glucose is then added and obtains
To the Cu2O with 50 face body structures.Yu et al. is by using SDS aqueous solution as soft template, and hydrazine hydrate is reducing agent, using change
It learns the precipitation method and obtains the Cu2O of hollow porous spherical structure.When being added without SDS soft template, finally obtained is Cu2O octahedron knot
Structure, the cuprous oxide for being found to have hollow porous spherical structure have excellent visible light catalysis activity.Michael et al. chlorination
For copper as copper source, SDS is surfactant, is finally restored to obtain cuprous nano particle with hydroxylamine hydrochloride.Pass through tune
The amount that hydroxylamine hydrochloride is added in section has respectively obtained cube, octahedron, the octahedron shortened and granatohedron pattern
The photocatalytic activity of Cu2O nanoparticle, discovery granatohedron nanoparticle is better than cube nanoparticle.Zhang et al.
A certain amount of PVP is dissolved in CuCl2 solution, then be added NaOH solution stirring a period of time after be added ascorbic acid solution into
Row reduction realizes Cu2O from cube, the cube shortened, cubes eight by the molar ratio of simple adjustment PVP and CuCI2
Face body, the octahedral Morphology of octahedra most Zhongdao shortened, find the Cu2O of octahedral structure due to { 111 } crystal face
Exposure makes it adsorb the Cu2O nanoparticle that the performance of methyl orange dye is better than other patterns.Zeng et al. first with ascorbic acid also
Former copper chloride obtains the Cu2O cube nucleus of top rake, is then dispersed in the mixed aqueous solution of copper nitrate and ammonium nitrate,
NaOH solution is added dropwise again, is eventually adding ascorbic acid solution and restores to obtain the Cu2O with core-shell structure.Tang Aidong etc. is using letter
Single chemical precipitation method is prepared for the octahedra cuprous oxide powder with spherical shape.Copper acetate, hair are restored by reducing agent of hydrazine hydrate
Existing sodium hydroxide plays the role of very important in terms of control crystal particle diameter and pattern.Liu is precious just to be waited using copper sulphate as copper
Source, polyvinylpyrrolidone (PVP) are surfactant, prepare nano oxidized Asia by reducing agent of hydrazine hydrate in aqueous solution
The tiny balloon that copper particle is constituted.Cuprous oxide tiny balloon shell thickness 20-3Onm, diameter 170-220nm, in 400-700nm wave
Long range has stronger absorption, has apparent photocatalytic degradation effect to sanitary sewage.Wang Yuejun etc. with Cu (OH) 2 be presoma,
With glucose reduction sulfuric acid copper for the monodisperse spherical Cu2O powder of different-grain diameter, find with reaction temperature and glucose
The grain diameter of the raising of concentration, cuprous oxide reduces, and with the raising of naoh concentration, cuprous oxide grain diameter increases
Greatly.Wang et al. prepares 2 nano wire of Cu (OH) using CuSO4 and ammonium hydroxide as raw material, then uses hydrazine hydrate reduction Cu at room temperature
(OH) 2 nano wires are prepared for Cu2O nano wire, and nanowire diameter is about 5-15nm, and length is up to some tens of pm.Liu Yifan et al.
It is prepared for orange-yellow Monodispersion with hydrazine hydrate reduction acetic acid copper solution, this colloidal sol is sufficiently stable, does not sink for a long time
Drop.Murphy et al. prepares the Cu2O crystal of nanocube in NaOH solution with SODIUM ASCORBATE reduction CuSO4 solution,
The partial size of Cu2O crystal is controlled using the concentration of hexadecyl trimethyl ammonium bromide, hexadecyl trimethyl ammonium bromide is worked as in discovery
Concentration when increasing to 0.1M from 0.01M, the partial size of the Cu2O crystal of nanocube increases to 450nm from 200nm.Wu et al.
Copper sulphate, glucose and sodium tartrate mixed liquor are put into conical flask, NaOH is then added and adjusts pH to 12, passes through microwave spoke
According to having obtained the star Cu2O nanoparticle of controllable pattern.Liu et al. people is using microwave method and does not have with any template or surface
Activating agent has only prepared the shaggy spherical oxidation Asia of self assembly by adjusting the concentration of temperature and acetic acid copper solution
Steel structure.Xu et al. has prepared certain density acetic acid copper solution, then sequentially adds beta-cyclodextrin and ascorbic acid ultrasound is closed
At porous Cu2O nanometers of spherical structure.
Correlative study shows that organic acid can form complex, regulation gold as co-ordination complex with metal cation
Belong to the rate of release of cation, to regulate and control the speed of growth of crystal nucleus, structure and pattern, is conducive to improve photochemical catalyst
Photocatalysis performance.Although cuprous oxide photocatalyst gets more and more extensive concerning of people and is increasingly becoming research both domestic and external
Hot spot, but the research of cuprous oxide photocatalyst is prepared using organic acid regulation both at home and abroad at present and is reported seldom.
Three, summary of the invention
In view of this, the object of the invention is to be to provide a kind of low temperature liquid phase precipitation method cuprous oxide visible light light to urge
The preparation method of agent.The present invention prepares cuprous oxide photocatalyst using organic acid assistant regulating and controlling and the low temperature liquid phase precipitation method,
The growth speed for being acted on using the ligand complex of organic acid and copper ion and reducing the hydrolysis rate of copper ion, regulate and control cuprous oxide nucleus
Degree, structure and pattern, are able to achieve using absorption property and cuprous oxide photocatalytic of the cuprous oxide photocatalyst to dyestuff
The synergistic effect of the absorption enrichment and visible light photocatalytic degradation of dyestuff, is efficient, stable cuprous oxide visible light photochemical catalyst
Provide New methods in working.
Purpose according to the present invention proposes a kind of preparation of low temperature liquid phase precipitation method cuprous oxide visible light photochemical catalyst
Method, feature have following processing step:
A) mantoquita and organic acid are dissolved in deionized water, addition mass concentration is after 25 DEG C of constant temperature stir 0.5~1.5h
20% sodium hydroxide solution, 25 DEG C of constant temperature stir, and the reducing agent aqueous solution that mass concentration is 20% is added after 15~45min, and 25
~60 DEG C of constant temperature are stirred to react 1~4h, and product is centrifuged after reaction, is washed with deionized water and dehydrated alcohol
It 3~5 times, is dried after centrifuge separation, grinds, obtain cuprous oxide visible light photochemical catalyst；The mass ratio of mantoquita and deionized water
For 1~10:50~100, mantoquita, organic acid, sodium hydroxide and reducing agent molar ratio be 1:0.5~2:2~6:0.5~2.
B) when 30~50min of white LED lamp illumination, cuprous oxide photocatalyst is basic to the photocatalytic degradation of dye solution
Reach balance, when white LED lamp illumination 50min, cuprous oxide photocatalyst urges the light of 10mg/L and 50mg/L dye solution
Change dyestuff degradation rate and respectively reach 78~99% and 40~60%, recycles the photocatalysis of rear cuprous oxide photocatalyst for 5 times
Dyestuff degradation rate is the 75~90% of first time photocatalysis dyestuff degradation rate.
Organic acid of the present invention is selected from ethanedioic acid, malonic acid, benzoic acid, phthalic acid, terephthalic acid (TPA), isophthalic
Dioctyl phthalate, P-hydroxybenzoic acid, septichen and m-hydroxybenzoic acid.
White LED lamp power of the present invention is 20~30 watts, and service life 30,000~100,000 hour, colour temperature is 4500
Between~7000, formed by the yellow light combine that the blue light of wavelength 400~500 is sent out with the fluorescent powder being stimulated by blue light.
Dyestuff of the present invention is selected from methyl orange, methylene blue, crystal violet and rhodamine B.
Mantoquita of the present invention is selected from copper sulphate, copper chloride and copper nitrate.
Reducing agent of the present invention is selected from ascorbic acid, glucose and hydrazine hydrate.
Advantages of the present invention and effect are:
1) present invention prepares cuprous oxide photocatalyst using organic acid assistant regulating and controlling and the low temperature liquid phase precipitation method, using having
The effect of the ligand complex of machine acid and copper ion reduces the rate of release of copper ion, the speed of growth for regulating and controlling cuprous oxide nucleus, knot
Structure and pattern are able to achieve dyestuff using absorption property and cuprous oxide photocatalytic of the cuprous oxide photocatalyst to dyestuff
The synergistic effect of absorption enrichment and visible light photocatalytic degradation, provides for efficient, stable cuprous oxide visible light photochemical catalyst
New methods in working.
2) operation is simple for cuprous oxide photocatalyst preparation method of the invention, low temperature or reacts under room temperature,
Low energy consumption, and the reaction time is short.
3) cuprous oxide photocatalyst Photocatalytic Activity for Degradation dyestuff speed of the invention is fast, photocatalysis dyestuff degradation rate
It is high with recycling performance.
4) traditional visible light photocatalysis experiment uses xenon lamp for simulated visible light light source, and ultraviolet thermoradiation efficiency is larger,
Service life is shorter (1500~3000 hours).The present invention is using white LED lamp as simulated visible light light source, thermoradiation efficiency
Very low, service life is very long (30,000~100,000 hours), more green and environmental-friendly compared with xenon lamp.
Cuprous oxide photocatalyst Photocatalytic Activity for Degradation dyestuff performance of the present invention and circular regeneration circulation
Utility measuring method is as follows.
Taking 100mL mass concentration is the dye solution of 10~50mg/L, and addition dosage is 0.05~0.15g cuprous oxide light
Catalyst is placed on magnetic stirring apparatus and stirs evenly, and white LED lamp is used to carry out photocatalytic degradation dye for simulated visible light light source
Material samples every 2~5min during light-catalyzed reaction, clear liquid is packed into cuvette after being filtered with filter, with UV, visible light point
Light photometer tests its absorbance in dyestuff maximum absorption wavelength, and cuprous oxide photocatalysis is investigated by the variation of dye strength
The dyestuff Photocatalytic Degradation Property of agent.
Photocatalytic activity (Y) calculation formula of dyestuff is as follows:
Y=(C0-Ct)/C0× 100%
In formula: C0For the dyestuff initial concentration before dye solution light-catalyzed reaction；CtWhen for dye solution light-catalyzed reaction t
Between after dye strength.
After cuprous oxide photocatalyst photocatalytic degradation of dye is primary, cuprous oxide photocatalyst is centrifugated, is washed,
Dried recovered carries out second of photocatalytic degradation of dye performance test under the same terms, carries out 5 circulation experiments in total, and with
First time photocatalytic degradation of dye performance compares, and investigates the recycling performance of cuprous oxide photocatalyst.
Four, specific embodiment
For a better understanding of the present invention, below with reference to the embodiment content that the present invention is further explained, described reality
A part of the embodiment that example is only the present patent application is applied, instead of all the embodiments.Based on the implementation in the present patent application
Example, every other embodiment obtained by those of ordinary skill in the art without making creative efforts belong to
The scope of protection of the invention.
Embodiment 1:
10g copper chloride and 5.1327g m-hydroxybenzoic acid are dissolved in 100g deionized water, added after 25 DEG C of constant temperature stirring 0.5h
Enter the sodium hydroxide solution that 29.8g mass concentration is 20%, 32.7g mass concentration, which is added, after 25 DEG C of constant temperature stirring 15min is
20% aqueous ascorbic acid, 25 DEG C of constant temperature are stirred to react 4h, product are centrifuged after reaction, uses deionization
Water and dehydrated alcohol wash 3 times, dry after centrifuge separation, grind, obtain cuprous oxide visible light photochemical catalyst.White LED lamp
When illumination 50min, cuprous oxide photocatalyst basically reaches balance, white LED lamp illumination to the photocatalytic degradation of dye solution
When 50min, cuprous oxide photocatalyst respectively reaches the photocatalysis dyestuff degradation rate of 10mg/L and 50mg/L dye solution
78% and 40%, 5 times the photocatalysis dyestuff degradation rate for recycling rear cuprous oxide photocatalyst is first time photocatalysis dyestuff
The 75% of degradation rate.
Embodiment 2:
2g copper nitrate and 2.605g benzoic acid are dissolved in 100g deionized water, 12.8g is added after 25 DEG C of constant temperature stirring 1.5h
The grape that 19.2g mass concentration is 20% is added after stirring 45min in the sodium hydroxide solution that mass concentration is 20%, 25 DEG C of constant temperature
Sugar aqueous solution, 60 DEG C of constant temperature are stirred to react 1h, product are centrifuged after reaction, with deionized water and dehydrated alcohol
Washing 5 times, is dried after centrifuge separation, is ground, is obtained cuprous oxide visible light photochemical catalyst；When white LED lamp illumination 45min,
Cuprous oxide photocatalyst basically reaches balance to the photocatalytic degradation of dye solution, when white LED lamp illumination 50min, oxidation
Cuprous photochemical catalyst respectively reaches 82.6% and 43.6% to the photocatalysis dyestuff degradation rate of 10mg/L and 50mg/L dye solution,
5 times the photocatalysis dyestuff degradation rate for recycling rear cuprous oxide photocatalyst is first time photocatalysis dyestuff degradation rate
78.4%.
Embodiment 3:
5g copper sulphate and 4.7479g septichen are dissolved in 100g deionized water, added after 25 DEG C of constant temperature stirring 1.5h
Enter the sodium hydroxide solution that 25g mass concentration is 20%, 27.5188g mass concentration, which is added, after 25 DEG C of constant temperature stirring 30min is
20% aqueous ascorbic acid, 25 DEG C of constant temperature are stirred to react 2h, product are centrifuged after reaction, uses deionization
Water and dehydrated alcohol wash 5 times, dry after centrifuge separation, grind, obtain cuprous oxide visible light photochemical catalyst；White LED lamp
When illumination 30min, cuprous oxide photocatalyst basically reaches balance, white LED lamp illumination to the photocatalytic degradation of dye solution
When 50min, cuprous oxide photocatalyst respectively reaches the photocatalysis dyestuff degradation rate of 10mg/L and 50mg/L dye solution
99% and 60%, 5 times the photocatalysis dyestuff degradation rate for recycling rear cuprous oxide photocatalyst is first time photocatalysis dyestuff
The 90% of degradation rate.
Embodiment 4:
4g copper sulphate and 2.25g ethanedioic acid are dissolved in 100g deionized water, 22.5g matter is added after 25 DEG C of constant temperature stirring 1.5h
The sodium hydroxide solution that concentration is 20% is measured, the water that 27.5188g mass concentration is 20% is added after 25 DEG C of constant temperature stirring 45min
Hydrazine aqueous solution is closed, 60 DEG C of constant temperature are stirred to react 4h, product is centrifuged after reaction, with deionized water and anhydrous second
Alcohol washs 5 times, dries after centrifuge separation, grinds, obtains cuprous oxide visible light photochemical catalyst；White LED lamp illumination 38min
When, cuprous oxide photocatalyst basically reaches balance to the photocatalytic degradation of dye solution, when white LED lamp illumination 50min, oxygen
Change cuprous photochemical catalyst and 94.3% and 51% respectively reached to the photocatalysis dyestuff degradation rate of 10mg/L and 50mg/L dye solution,
5 times the photocatalysis dyestuff degradation rate for recycling rear cuprous oxide photocatalyst is first time photocatalysis dyestuff degradation rate
82%.
Embodiment 5:
3g copper sulphate and 3.738g terephthalic acid (TPA) are dissolved in 100g deionized water, are added after 25 DEG C of constant temperature stirring 1.2h
The sodium hydroxide solution that 18.75g mass concentration is 20%, addition 18.1624g mass concentration is after 25 DEG C of constant temperature stir 40min
20% aqueous ascorbic acid, 25 DEG C of constant temperature are stirred to react 1.5h, product are centrifuged after reaction, spend from
Sub- water and dehydrated alcohol wash 5 times, dry after centrifuge separation, grind, obtain cuprous oxide visible light photochemical catalyst；White light LEDs
When light shines 35min, cuprous oxide photocatalyst basically reaches balance, white light LEDs light to the photocatalytic degradation of dye solution
When according to 50min, cuprous oxide photocatalyst respectively reaches the photocatalysis dyestuff degradation rate of 10mg/L and 50mg/L dye solution
95.8% and 53.2%, 5 times the photocatalysis dyestuff degradation rate for recycling rear cuprous oxide photocatalyst is first time photocatalysis
The 84% of dyestuff degradation rate.
Embodiment 6:
4g copper sulphate and 4.5686g phthalic acid are dissolved in 100g deionized water, are added after 25 DEG C of constant temperature stirring 1.5h
The sodium hydroxide solution that 22.5g mass concentration is 20%, addition 26.418g mass concentration is after 25 DEG C of constant temperature stir 35min
20% aqueous ascorbic acid, 25 DEG C of constant temperature are stirred to react 1.5h, product are centrifuged after reaction, spend from
Sub- water and dehydrated alcohol wash 5 times, dry after centrifuge separation, grind, obtain cuprous oxide visible light photochemical catalyst；White light LEDs
When light shines 50min, cuprous oxide photocatalyst distinguishes the photocatalysis dyestuff degradation rate of 10mg/L and 50mg/L dye solution
Reach 97.8% and 57.6%, 5 times the photocatalysis dyestuff degradation rate for recycling rear cuprous oxide photocatalyst is first time light
It is catalyzed the 86.3% of dyestuff degradation rate.
Claims (6)
1. a kind of preparation method of low temperature liquid phase precipitation method cuprous oxide visible light photochemical catalyst, it is characterised in that there is following technique
Step:
Mantoquita and organic acid are dissolved in deionized water, the hydrogen-oxygen that mass concentration is 20% is added after stirring 0.5~1.5h in 25 °C of constant temperature
Change sodium solution, the reducing agent aqueous solution that mass concentration is 20%, 25~60 °C of constant temperature are added after stirring 15~45min in 25 °C of constant temperature
It is stirred to react 1~4h, product is centrifuged after reaction, is washed 3~5 times with deionized water and dehydrated alcohol, from
It is dried after heart separation, grinds, obtain cuprous oxide visible light photochemical catalyst；Mantoquita and the mass ratio of deionized water are 1~10:50
~100, mantoquita, organic acid, sodium hydroxide and reducing agent molar ratio be 1:0.5~2:2~6:0.5~2, white light LEDs light
When according to 30~50min, cuprous oxide photocatalyst basically reaches balance, white light LEDs light to the photocatalytic degradation of dye solution
When according to 50min, cuprous oxide photocatalyst respectively reaches the photocatalysis dyestuff degradation rate of 10mg/L and 50mg/L dye solution
78~99% and 40~60%, 5 times the photocatalysis dyestuff degradation rate for recycling rear cuprous oxide photocatalyst is that first time light is urged
Change the 75~90% of dyestuff degradation rate.
2. a kind of preparation method of low temperature liquid phase precipitation method cuprous oxide visible light photochemical catalyst according to claim 1,
It is characterized by: the organic acid is selected from ethanedioic acid, malonic acid, benzoic acid, phthalic acid, terephthalic acid (TPA), isophthalic two
Formic acid, P-hydroxybenzoic acid, septichen, m-hydroxybenzoic acid.
3. a kind of preparation method of low temperature liquid phase precipitation method cuprous oxide visible light photochemical catalyst according to claim 1,
It is characterized by: the mantoquita is selected from copper sulphate, copper chloride and copper nitrate.
4. a kind of preparation method of low temperature liquid phase precipitation method cuprous oxide visible light photochemical catalyst according to claim 1,
It is characterized by: the reducing agent is selected from ascorbic acid, glucose and hydrazine hydrate.
5. a kind of preparation method of low temperature liquid phase precipitation method cuprous oxide visible light photochemical catalyst according to claim 1,
It is characterized by: the white LED lamp power is 20~30 watts, service life 30,000~100,000 hour, colour temperature 4500~
Between 7000, formed by the yellow light combine that the blue light of wavelength 400 ~ 500 is sent out with the fluorescent powder being stimulated by blue light.
6. a kind of preparation method of low temperature liquid phase precipitation method cuprous oxide visible light photochemical catalyst according to claim 1,
It is characterized by: the dyestuff is selected from methyl orange, methylene blue, crystal violet and rhodamine B.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN114762826A (en) * | 2021-07-21 | 2022-07-19 | 天津科技大学 | High index crystal plane Cu2Preparation method and application of O photocatalyst |
| CN114029079A (en) * | 2021-11-10 | 2022-02-11 | 牡丹江师范学院 | Preparation method of hollow micro-bead supported cerium or nitrogen-doped cuprous oxide photocatalyst |
| CN114029079B (en) * | 2021-11-10 | 2022-07-12 | 牡丹江师范学院 | Preparation method of hollow micro-bead supported cerium or nitrogen-doped cuprous oxide photocatalyst |
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