CN102553590B - Abandoned shell/nanometer Cu2O composite photocatalyst material as well as preparation and application thereof - Google Patents
Abandoned shell/nanometer Cu2O composite photocatalyst material as well as preparation and application thereof Download PDFInfo
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- CN102553590B CN102553590B CN201010281703.8A CN201010281703A CN102553590B CN 102553590 B CN102553590 B CN 102553590B CN 201010281703 A CN201010281703 A CN 201010281703A CN 102553590 B CN102553590 B CN 102553590B
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention provides an abandoned shell/nanometer Cu2O composite photocatalyst material as well as a preparation method and application of the photocatalyst material. The preparation method mainly comprises the steps of activation of shells and in-situ hydrolysis and load of nanometer Cu2O and concretely comprises the steps of: activating the abandoned shells at a high temperature to enhance the alkalinity and porosity, adsorbing and in situ hydrolyzing univalent copper ions in solution by utilizing the developed porosity and alkalinity of the activated shells, drying, dehydrating, tightly loading nanoscale globular Cu2O particles on the surface of the shells and synthetizing the composite photocatalyst material. The invention relates to resource recovery and high-value utilization of wastes on raw materials, utilization of visible light and sunlight on energy and treatment of organic pollutants difficult to degrade by water body on application. The nanometer Cu2O/shell composite photocatalyst material has important significance in environmental protection and the activity of the composite photocatalyst material is greatly superior to that of the nanometer Cu2O.
Description
Technical field
The invention belongs to the function nano material synthesis technology in solid waste resource utilization field, particularly there is the shell loaded with nano Cu of photochemical catalysis performance
2the preparation method of O composite and application.
Background technology
The a large amount of discarded shell that mariculture industry and marine product processing industry produce is arbitrarily abandoned and is toppled over a kind of improper disposal of wasting resource and contaminated environment, and its recycling is the key that shell is rationally disposed.In shell, contain 95% calcium carbonate and a small amount of organic matter.At present the resource utilization method of shell is mainly contained to shellwork processing, development animal feed, exploitation biological medicine etc.High, the even aperture distribution of shell porosity under micro-meter scale, specific area through calcining are large, and these features make its novel inorganic material for water treatment as a kind of excellence become possibility.The shellfish material wide material sources of porous and have good absorption property, are applicable to serving as the carrier of nano material.
Being applied in the semiconductor nano photocatalysis material of water body persistent organic pollutants process field, nanometer Cu
2o receives publicity as a kind of Metal-vacancy p-type conductor photocatalysis material.Nanometer Cu
2, between 2.0～2.2eV, can, by the optical excitation of wavelength≤600nm, there be response in O forbidden band to ultraviolet and visible ray, sets it as catalysis material solar radiation is had to higher utilization rate.Nanometer Cu at present
2the preparation method of O mainly contains polyalcohol method, electrolysis, reducing process, Hydrolyze method etc.Polyalcohol method, electrolysis and reducing process all need poisonous organic reagent, and reaction condition complexity; Hydrolyze method can be prepared nanometer Cu at normal temperatures
2o also avoids the use of poisonous organic reagent.Nanoscale Cu
2o particle is very easily reunited and is difficult for precipitation in the aqueous solution, and electronics and hole separative efficiency reduce greatly, and catalytic degradation activity is affected; And, nanometer Cu
2o particle only has better degradation treatment effect to extremely low concentration organic sewage, high to the concentration of wastewater requirement that is applicable to processing, and is difficult for carrying out Separation of Solid and Liquid.Therefore, the difficult precipitability of the minor fluctuations of water quality or catalyst all may make nanometer Cu
2effluent quality after O particle photodissociation organic wastewater does not still reach national standard requirement.
Due to nanometer Cu
2the direct utilization of O particle is restricted, and is necessary its being fixed.At present, there is research to adopt zeolite, montmorillonite, CNT, glass fibre, float pearl, cationic ion-exchange resin, shitosan etc. and realize the fixing of nano cuprous oxide as carrier, but utilize polyalcohol method, electrolysis and reducing process etc. to carry out load more, be difficult to avoid using and discharging of poisonous organic reagent.
The present invention carries out high-temperature activation pretreatment in conjunction with shell composition characteristic to it, and the simple in-situ hydrolysis technology of adopting process is prepared nanometer Cu
2o particle also makes it closely be carried on shell carrier surface, synthesizing new composite photocatalyst functional material.This material is not only active high, organic dye waste water that can catalytic degradation concentration≤250mg/L, and be easy to sedimentation and reclaim, improve the recycling rate of waterused of effluent quality and material.This technical method has been realized resource, the higher value application of discarded shell simultaneously.
Summary of the invention
The object of the invention is to utilize basicity and the porosity that the shell self of high-temperature activation provides to pass through the method loaded with nano Cu of in-situ hydrolysis
2o, prepares nanometer Cu
2o/ shell composite photocatalyst material.The material settling out that this method has advantages of reaction condition moderate notoxic, technological process is simple, generated time is short, prepare and active high.
Principle of the present invention is: after shell high-temperature activation, in water, surface is alkalescence, in the micro-reaction system by surfactant and electrolyte solution compositions, and a part of cuprous salt utilization OH that dissociates
-form independently Cu through hydrolysis, dehydration
2o particle is also deposited on shell surface:
Another part cuprous salt directly with shelly facies mutual effect, through in-situ hydrolysis, dehydration formation combining form nanometer Cu
2o particle forms new chemical bond simultaneously:
Concrete preparation technology comprises:
(1) shell activates within the scope of 900～1050 DEG C, pulverizes and sieves.
(2) in the NaCl solution that is 2.0～5.0mol/L to 200mL concentration under stirring, add a certain amount of neopelex (its concentration is 3.0～5.0g/L) to form the micro-reaction system of Thermodynamically stable, add successively again CuCl and activation oyster shell whiting (neopelex, CuCl, activation oyster shell whiting three's mass ratio is 1: 1～2: 2～4), continue to stir 10～30min and be hydrolyzed.
(3) suspension step (2) being obtained, after suction filtration separation, ultrasonic washing, redistilled water repeatedly clean, dehydrates at 60 DEG C, obtains nanometer Cu
2o/ shell composite photocatalyst material.
Experiment showed, the nanometer Cu that the present invention obtains
2o/ shell composite photocatalyst material catalytic activity is high, be easy to sedimentation separation, and organic dye waste water that can catalytic degradation concentration≤250mg/L.
Brief description of the drawings
Fig. 1 is nanometer Cu
2the ESEM picture of O/ shell composite photocatalyst material.
Fig. 2 is nanometer Cu
2the X-ray diffractogram of O/ shell composite photocatalyst material.
Fig. 3 is nanometer Cu
2the degradation and decolorization design sketch of O/ shell composite photocatalytic activity scarlet dye B-3G.(1) be the decolouring clearance of B-3G under visible light source radiation, wherein each letter represents the initial concentration of different B-3G dyestuff: a, 30mg/L; B, 60mg/L; C, 130mg/L; D, 220mg/L; E, 30mg/L (add pure Cu
2o); (2) be the decolouring clearance of B-3G under solar source radiation, wherein each letter represents the initial concentration of different B-3G dyestuff: a, 20mg/L; B, 50mg/L; C, 100mg/L; D, 200mg/L; E, 60mg/L (add pure Cu
2o).
Detailed description of the invention
By through overpickling (be 0.1% by mass concentration watery hydrochloric acid soak 0.5h), dried pearl shell calcining and activating 2h pulverized 100 mesh sieves at 1050 DEG C in Muffle furnace; In the micro-reaction system of 200mL, NaCl concentration is that 2.0mol/L, neopelex concentration are 5.0g/L, adds the pearl shell powder after 2.0gCuCl and 2.0g activation under magnetic agitation.Neopelex, CuCl, activation oyster shell whiting three mass ratio are 1: 2: 2.Suction filtration, supersound washing (ultrasonic cleaner vibration 5min), 5 washings after lasting stirring hydrolysis 30min, gained brown color solid dehydrates 6h and obtains nanometer Cu at 60 DEG C
2o/ shell composite photocatalyst material.The nanometer Cu of load
2o particle is spherical, and particle diameter is less than 100nm.Fig. 1 and Fig. 2 are respectively ESEM picture and the X-ray diffractogram of the present embodiment products obtained therefrom.
Nanometer Cu
2in the test tube that O/ shell composite Photocatalytic activity scarlet dye B-3G is 18mm at diameter, carry out, catalyst amounts is 2g/L, passes into air stirring reaction system, provides oxygen as electron capture agent simultaneously.Visible light catalytic process is taking 500w iodine-tungsten lamp as light source, and average intensity is 127000lux; Natural daylight catalytic process is taking sunshine as light source, and average intensity is 64300lux.Fig. 3 shows, nanometer Cu
2o/ shell composite photocatalyst material all shows the excellent properties of degrading active dye under visible ray and sunshine.Through 90min radiation, the decolouring clearance that concentration is less than the B-3G dyestuff of 130mg/L all can reach more than 99% under visible ray and sunshine, the decolouring clearance of low concentration B-3G can reach 100%, and the decolouring clearance of the B-3G that concentration is greater than 200mg/L after visible radiation 90min and solar radiation 180min also can reach respectively 98% and 97%.Nanometer Cu
2the activity of O/ shell composite photocatalyst material is better than pure nanometer Cu greatly
2o.
By through overpickling (be 0.05% by mass concentration watery hydrochloric acid soak 1h), dried CONCHA MERETRICID SEU CYCLINAE calcining and activating 2h pulverized 100 mesh sieves at 900 DEG C in Muffle furnace; In the micro-reaction system of 100mL, NaCl concentration is that 4.0mol/L, neopelex concentration are 5.0g/L, adds the CONCHA MERETRICID SEU CYCLINAE powder after 1.0gCuCl and 1.0g activation under magnetic agitation.Neopelex, CuCl, activation oyster shell whiting three mass ratio are 1: 2: 2.After lasting stirring hydrolysis 10min, through suction filtration, supersound washing (ultrasonic cleaner vibration 3min), 5 washings, gained brown color solid product dehydrates 6h at 60 DEG C.
Photocatalysis is tested Boiling tube taking diameter as 38mm as reactor, taking 500w iodine-tungsten lamp as light source, passes into airlight according to after 90min, and can make concentration is that the decolouring clearance of the B-3G dyestuff of 60mg/L reaches 98%.
Embodiment 3
By through overpickling (be 0.1% by mass concentration watery hydrochloric acid soak 0.5h), dried oyster shell calcining and activating 2h pulverized 100 mesh sieves at 1050 DEG C in Muffle furnace, in the micro-reaction system of 100mL, NaCl concentration is that 2.0mol/L, neopelex concentration are 5.0g/L, adds the oyster shell powder after 1.0gCuCl and 1.0g activation under magnetic agitation.Neopelex, CuCl, activation oyster shell whiting three mass ratio are 1: 2: 2.After lasting stirring hydrolysis 20min, through suction filtration, supersound washing (ultrasonic cleaner vibration 2min), 4 washings, gained brown color solid product dehydrates 6h at 60 DEG C.
Photocatalysis is tested test tube taking diameter as 18mm as reactor, taking visible ray as light source, passes into air stirring, catalytic degradation actual dying after illumination 120min.Table 1 shows, under visible radiation, and nanometer Cu
2o/ shell composite can make actual dying catalytic degradation, and wherein, to COD and the lower water sample 2 of colourity, its COD and chroma removal rate reach respectively 73.05% and 96.15%, and the present invention is suitable for the advanced treating of dyeing waste water as shown in Table 1.
Table 1 nanometer Cu
2o/ shell composite visible light photocatalytic degradation actual dying situation
(processing stage that water sample 1 being taken from respectively Qingdao printing and dyeing mill different sewage with water sample 2)
Claims (6)
1. a discarded shell loaded with nano Cu
2the preparation method of O composite photocatalyst material, is characterized in that:
Its preparation process is as follows, to the oyster shell whiting that adds CuCl and high-temperature activation in the micro-reaction system of the Thermodynamically stable being formed by NaCl and neopelex, continue to stir, utilize the flourishing hole of activation oyster shell whiting and basicity make cuprous salt hydrolysis and are closely carried on oyster shell whiting surface; Through Separation of Solid and Liquid, ultrasonic washing, distilled water flushing, dehydrate after, synthesis of nano Cu
2o/ shell composite photocatalyst material.
2. preparation method as claimed in claim 1, is characterized in that:
Discarded shell is selected CONCHA MERETRICID SEU CYCLINAE, oyster shell or pearl shell, and shell activation temperature is 900～1050 DEG C, and soak time 1～4 hour is crossed 80～150 mesh sieves after activation.
3. preparation method as claimed in claim 1, is characterized in that: the concentration of the NaCl electrolyte solution in the micro-reaction system of Thermodynamically stable is 2.0～5.0mol/L, and the concentration of neopelex is 3.0～5.0g/L; Neopelex, CuCl and activation oyster shell whiting three mass ratio are 1: 1～2: 2～4.
4. preparation method as claimed in claim 1, is characterized in that: continuing to stir hydrolysis time is 10～30min.
5. preparation method as claimed in claim 1, is characterized in that: hydrolysate need be through ultrasonic washing to remove unnecessary surfactant and Cl
-; After oyster shell whiting Separation of Solid and Liquid after load in the aqueous solution with ultrasonic cleaner vibration 2～5min, carry out 4～6 washings again, then dehydrate in 40～70 DEG C.
6. preparation method as claimed in claim 1, is characterized in that: composite photocatalyst material has photochemical catalysis performance, can be applied to the organic dye waste water of catalytic degradation concentration≤250mg/L.
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| CN201010281703.8A CN102553590B (en) | 2010-09-11 | 2010-09-11 | Abandoned shell/nanometer Cu2O composite photocatalyst material as well as preparation and application thereof |
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| CN102553590B true CN102553590B (en) | 2014-06-11 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103191738A (en) * | 2013-04-09 | 2013-07-10 | 云南大学 | Glass fiber loading cuprous oxide visible light catalyst and application thereof |
| CN103894197B (en) * | 2014-04-09 | 2015-09-02 | 厦门大学嘉庚学院 | One utilizes extra large oyster shell loaded with nano Cu 2o-TiO 2the preparation method of optic catalytic composite material |
| CN105016630B (en) * | 2015-07-16 | 2017-07-21 | 北京新源环境有限公司 | The sulfydryl grafting repaired for soil pollution and the preparation method of the resurrection glass fibre of photocatalyst |
| CN105664943A (en) * | 2016-01-29 | 2016-06-15 | 上海交通大学 | Preparation method of cubic cuprous oxide/graphene nanocomposite |
| CN106675524B (en) * | 2016-07-13 | 2019-05-17 | 北京化工大学 | A kind of multi-functional phase-change material micro-capsule and preparation method thereof |
| CN106824994A (en) * | 2017-02-15 | 2017-06-13 | 上海浦东路桥建设股份有限公司 | Shell class waste material turns to the process of road engineering material |
| CN109529864B (en) * | 2018-11-14 | 2021-06-18 | 浙江海洋大学 | alpha-Fe2O3/Bi2WO6Shell composite photocatalyst and preparation method thereof |
| CN110394186B (en) * | 2019-07-03 | 2022-04-22 | 浙江海洋大学 | Preparation method of carbon nitride/mussel shell nonmetal composite micro-nano photocatalytic material |
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| CN101352676A (en) * | 2008-03-03 | 2009-01-28 | 广东海洋大学 | Method for preparing nano zinc oxide using shell powder as carrier |
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Patent Citations (2)
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|---|---|---|---|---|
| CN101352676A (en) * | 2008-03-03 | 2009-01-28 | 广东海洋大学 | Method for preparing nano zinc oxide using shell powder as carrier |
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Non-Patent Citations (2)
| Title |
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| 沸石负载Cu2O光催化剂的制备及其性能研究;陈茂荣等;《武汉工程大学学报》;20091231;第31卷(第12期);28-31 * |
| 陈茂荣等.沸石负载Cu2O光催化剂的制备及其性能研究.《武汉工程大学学报》.2009,第31卷(第12期),28-31. |
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