CN102553590A - 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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- CN102553590A CN102553590A CN2010102817038A CN201010281703A CN102553590A CN 102553590 A CN102553590 A CN 102553590A CN 2010102817038 A CN2010102817038 A CN 2010102817038A CN 201010281703 A CN201010281703 A CN 201010281703A CN 102553590 A CN102553590 A CN 102553590A
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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
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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 reclamation of solid wastes and utilize the function nano material synthesis technology in field, the shell loaded with nano Cu that particularly has the 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.Contain 95% calcium carbonate and a small amount of organic matter in the shell.Resource utilization method to shell mainly contains shellwork processing, development animal feed, exploitation biological medicine etc. at present.Shell porosity height, even aperture distribution, specific area under micro-meter scale through calcining are big, and these characteristics 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 fit to serve as the carrier of nano material.
In the semiconductor nano catalysis material that is applied to water body persistent organic pollutants process field, nanometer Cu
2O receives publicity as the vacant p type conductor photocatalysis material of a kind of metal.Nanometer Cu
2Can there be response in the O forbidden band to ultraviolet and visible light by the optical excitation of wavelength≤600nm between 2.0～2.2eV, it is had higher utilization rate as catalysis material to solar radiation.Present nanometer Cu
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 is complicated; Hydrolyze method can prepare nanometer Cu at normal temperatures
2O also avoids the use of poisonous organic reagent.Nanoscale Cu
2The O particle is very easily reunited in the aqueous solution and is difficult for deposition, and electronics and hole separative efficiency reduce greatly, and the catalytic degradation activity is affected; And, nanometer Cu
2The O particle only has better degradation treatment effect to the extremely low concentration organic sewage, the concentration of wastewater that is fit to handle is required height, and be difficult for carrying out Separation of Solid and Liquid.Therefore, the difficult precipitability of the minor fluctuations of water quality or catalyst all possibly make nanometer Cu
2Effluent quality behind the O particle photodissociation organic wastewater does not still reach the national standard requirement.
Because nanometer Cu
2The direct utilization of O particle is restricted, and is necessary it is carried out immobilization.At present; There is research to adopt zeolite, montmorillonite, CNT, glass fibre, floats fixing as carrier realization nano cuprous oxide such as pearl, cationic ion-exchange resin, shitosan; 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 combines the shell composition characteristic that it is carried out the high-temperature activation preliminary treatment, and the simple in-situ hydrolysis technology of adopting process is prepared nanometer Cu
2The O particle also makes it closely be carried on the shell carrier surface, synthesizing new composite photocatalyst functional material.This material is not only active high, but the organic dye waste water of catalytic degradation concentration≤250mg/L, and be easy to the sedimentation recovery, 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 objective of the invention is to utilize basicity that the shell self of high-temperature activation provides and porosity method loaded with nano Cu through in-situ hydrolysis
2O prepares nanometer Cu
2O/ shell composite photocatalyst material.Material settling out that this method has the reaction condition moderate notoxic, technological process is simple, generated time is short, prepare and active high advantage.
Principle of the present invention is: behind the shell high-temperature activation in water the surface be alkalescence, in little reaction system of forming by surfactant and electrolyte solution, a part of cuprous salt utilization OH that dissociates
-Form independently Cu through hydrolysis, dehydration
2The O particle also is deposited on shell surface:
Direct and the shelly facies mutual effect of another part cuprous salt forms combining form nanometer Cu through in-situ hydrolysis, dehydration
2The O particle forms new chemical bond simultaneously:
Concrete preparation technology comprises:
(1) shell activation in 900～1050 ℃ of scopes, crushing screening.
(2) stir down and in 200mL concentration is the NaCl solution of 2.0～5.0mol/L, to add a certain amount of neopelex (its concentration is 3.0～5.0g/L) to form the little reaction systems of Thermodynamically stables; Add CuCl and activation oyster shell whiting (neopelex, CuCl, activation oyster shell whiting three's mass ratio is 1: 1～2: 2～4) more successively, continue to stir 10～30min and be hydrolyzed.
(3) suspension that step (2) is obtained dehydrates under 60 ℃ after suction filtration separation, ultrasonic washing, redistilled water repeatedly clean, and 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, but and the organic dye waste water of catalytic degradation concentration≤250mg/L.
Description of 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 the visible light source radiation, wherein the initial concentration of different B-3G dyestuff represented in each letter: 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 the solar source radiation, wherein the initial concentration of different B-3G dyestuff represented in each letter: a, 20mg/L; B, 50mg/L; C, 100mg/L; D, 200mg/L; E, 60mg/L (add pure Cu
2O).
The specific embodiment
Will be through overpickling (using mass concentration is that 0.1% watery hydrochloric acid soaks 0.5h), dried pearl shell 1050 ℃ of following calcining and activating 2h and pulverized 100 mesh sieves in Muffle furnace; NaCl concentration is that 2.0mol/L, neopelex concentration are 5.0g/L in the little reaction system of 200mL, the pearl shell powder under the magnetic agitation after adding 2.0gCuCl and the 2.0g activation.Neopelex, CuCl, activation oyster shell whiting three mass ratio are 1: 2: 2.Suction filtration, supersound washing (ultrasonic cleaner vibration 5min), 5 washings behind the lasting stirring hydrolysis 30min, the pale brown look solid of gained dehydrates 6h and promptly gets nanometer Cu under 60 ℃
2O/ shell composite photocatalyst material.The nanometer Cu of load
2The O particle is spherical, and particle diameter is less than 100nm.Fig. 1 and Fig. 2 are respectively the ESEM picture and the X-ray diffractogram of present embodiment products obtained therefrom.
Nanometer Cu
2O/ shell composite photocatalytic degradation active scarlet dye B-3G carries out in diameter is the test tube of 18mm, and catalyst amounts is 2g/L, and bubbling air stirring reaction system provides oxygen as the electron capture agent simultaneously.The visible light catalytic process is a light source with the 500w iodine-tungsten lamp, and average intensity is 127000lux; The natural daylight catalytic process is light source with the sunshine, 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 light and sunshine.Through the 90min radiation; Concentration all can reach more than 99% less than the decolouring clearance of the B-3G dyestuff of 130mg/L under visible light and sunshine; The decolouring clearance of low concentration B-3G can reach 100%, and concentration also can reach 98% and 97% respectively greater than the decolouring clearance of B-3G behind visible radiation 90min and solar radiation 180min of 200mg/L.Nanometer Cu
2The activity of O/ shell composite photocatalyst material is superior to pure nanometer Cu greatly
2O.
Will be through overpickling (using mass concentration is that 0.05% watery hydrochloric acid soaks 1h), dried CONCHA MERETRICID SEU CYCLINAE 900 ℃ of following calcining and activating 2h and pulverized 100 mesh sieves in Muffle furnace; NaCl concentration is that 4.0mol/L, neopelex concentration are 5.0g/L in the little reaction system of 100mL, the CONCHA MERETRICID SEU CYCLINAE powder under the magnetic agitation after adding 1.0gCuCl and the 1.0g activation.Neopelex, CuCl, activation oyster shell whiting three mass ratio are 1: 2: 2.Continue to stir hydrolysis 10min after suction filtration, supersound washing (ultrasonic cleaner vibration 3min), 5 washings, the pale brown look solid product of gained dehydrates 6h under 60 ℃.
Photocatalysis experiment is that the Boiling tube of 38mm is reactor, is light source with the 500w iodine-tungsten lamp with the diameter, and behind the bubbling air illumination 90min, can make concentration is that the decolouring clearance of the B-3G dyestuff of 60mg/L reaches 98%.
Embodiment 3
Will be through overpickling (using mass concentration is that 0.1% watery hydrochloric acid soaks 0.5h), dried oyster shell 1050 ℃ of following calcining and activating 2h and pulverized 100 mesh sieves in Muffle furnace; NaCl concentration is that 2.0mol/L, neopelex concentration are 5.0g/L in the little reaction system of 100mL, the oyster shell powder under the magnetic agitation after adding 1.0gCuCl and the 1.0g activation.Neopelex, CuCl, activation oyster shell whiting three mass ratio are 1: 2: 2.Continue to stir hydrolysis 20min after suction filtration, supersound washing (ultrasonic cleaner vibration 2min), 4 washings, the pale brown look solid product of gained dehydrates 6h under 60 ℃.
The photocatalysis experiment is that the test tube of 18mm is reactor, is light source with the visible light that bubbling air stirs, catalytic degradation actual dying behind the illumination 120min with the diameter.Table 1 shows, under the visible radiation, and nanometer Cu
2O/ shell composite can make the actual dying catalytic degradation, and wherein to COD and the lower water sample 2 of colourity, its COD and chroma removal rate reach 73.05% and 96.15% respectively, but is suitable for the advanced treating of dyeing waste water by the invention of table 1 knowledge capital.
Table 1 nanometer Cu
2O/ shell composite visible light photocatalytic degradation actual dying situation
(processing stage that water sample 1 being taken from Qingdao printing and dyeing mill different sewage respectively with water sample 2)
Claims (8)
1. discarded shell loaded with nano Cu
2The O composite photocatalyst material is characterized in that:
Its preparation process is following; The oyster shell whiting that in the little reaction system of the Thermodynamically stable of forming by NaCl and neopelex, adds CuCl and high-temperature activation; Continue to stir, utilize the flourishing hole of activation oyster shell whiting and basicity to make the cuprous salt hydrolysis and closely be carried on the 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. material according to claim 1, it is characterized in that: the concentration of the NaCl electrolyte solution in the little reaction system of Thermodynamically stable is 2.0～5.0mol/L, 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.
3. the preparation method of the described composite photocatalyst material of claim 1 is characterized in that:
Its preparation process is following; The oyster shell whiting that in the little reaction system of the Thermodynamically stable of forming by NaCl and neopelex, adds CuCl and high-temperature activation; Continue to stir, utilize the flourishing hole of activation oyster shell whiting and basicity to make the cuprous salt hydrolysis and closely be carried on the 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.
4. preparation method as claimed in claim 3 is characterized in that:
Discarded shell can be selected CONCHA MERETRICID SEU CYCLINAE, oyster shell or pearl shell for use, and the shell activation temperature is 900～1050 ℃, and soak time 1～4 hour is crossed 80～150 mesh sieves after the activation.
5. preparation method as claimed in claim 3 is characterized in that: the concentration of the NaCl electrolyte solution in the little 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.
6. preparation method as claimed in claim 3 is characterized in that: continuing to stir hydrolysis time is 10～30min.
7. preparation method as claimed in claim 3 is characterized in that: hydrolysate need pass through ultrasonic washing to remove unnecessary surfactant and Cl
-After the oyster shell whiting Separation of Solid and Liquid after the load in the aqueous solution with ultrasonic cleaner vibration 2～5min, again carry out 4～6 washings, dehydrate in 40～70 ℃ then.
8. the application of the said composite photocatalyst material of claim 1, it has the photochemical catalysis performance, but 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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|---|---|---|---|
| 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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Cited By (8)
| 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 |
| CN103894197A (en) * | 2014-04-09 | 2014-07-02 | 厦门大学嘉庚学院 | Preparation method for oyster shell-supporting nanometer Cu2O-TiO2 photocatalytic composite material |
| CN105016630A (en) * | 2015-07-16 | 2015-11-04 | 北京新源环境有限公司 | Preparation method of sulfydryl-grafted and photocatalyst-loaded high silica glass fiber for soil pollution remediation |
| CN105664943A (en) * | 2016-01-29 | 2016-06-15 | 上海交通大学 | Preparation method of cubic cuprous oxide/graphene nanocomposite |
| CN106675524A (en) * | 2016-07-13 | 2017-05-17 | 北京化工大学 | Multifunctional phase change material microcapsule 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 |
| CN109529864A (en) * | 2018-11-14 | 2019-03-29 | 浙江海洋大学 | A kind of α-Fe2O3/Bi2WO6/ shell composite photo-catalyst and preparation method thereof |
| CN110394186A (en) * | 2019-07-03 | 2019-11-01 | 浙江海洋大学 | A kind of preparation method of the nonmetallic composite micro-nano rice catalysis material of carbonitride/mussel shell |
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Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103191738A (en) * | 2013-04-09 | 2013-07-10 | 云南大学 | Glass fiber loading cuprous oxide visible light catalyst and application thereof |
| CN103894197A (en) * | 2014-04-09 | 2014-07-02 | 厦门大学嘉庚学院 | Preparation method for oyster shell-supporting nanometer Cu2O-TiO2 photocatalytic composite material |
| 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 |
| CN105016630A (en) * | 2015-07-16 | 2015-11-04 | 北京新源环境有限公司 | Preparation method of sulfydryl-grafted and photocatalyst-loaded high silica glass fiber for soil pollution remediation |
| CN105664943A (en) * | 2016-01-29 | 2016-06-15 | 上海交通大学 | Preparation method of cubic cuprous oxide/graphene nanocomposite |
| CN106675524A (en) * | 2016-07-13 | 2017-05-17 | 北京化工大学 | Multifunctional phase change material microcapsule and preparation method thereof |
| 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 |
| CN109529864A (en) * | 2018-11-14 | 2019-03-29 | 浙江海洋大学 | A kind of α-Fe2O3/Bi2WO6/ shell composite photo-catalyst and preparation method thereof |
| CN109529864B (en) * | 2018-11-14 | 2021-06-18 | 浙江海洋大学 | alpha-Fe2O3/Bi2WO6Shell composite photocatalyst and preparation method thereof |
| CN110394186A (en) * | 2019-07-03 | 2019-11-01 | 浙江海洋大学 | A kind of preparation method of the nonmetallic composite micro-nano rice catalysis material of carbonitride/mussel shell |
| 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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