CN104138762A - Preparation method and application of cubic-structure CuCr2O4 visible light photocatalyst - Google Patents

Preparation method and application of cubic-structure CuCr2O4 visible light photocatalyst Download PDF

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CN104138762A
CN104138762A CN201410353190.5A CN201410353190A CN104138762A CN 104138762 A CN104138762 A CN 104138762A CN 201410353190 A CN201410353190 A CN 201410353190A CN 104138762 A CN104138762 A CN 104138762A
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cucr
preparation
visible
cubic structure
light photocatalyst
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袁文辉
刘晓霞
李莉
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South China University of Technology SCUT
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South China University of Technology SCUT
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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

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Abstract

The invention discloses a preparation method and application of a cubic-structure CuCr2O4 visible light photocatalyst. The preparation method includes the steps that cupric nitrate and chromic nitrate are dissolved in deionized water, sodium hydroxide is added to adjust the pH value of the solution, the solution is heated to a certain temperature and evenly stirred at the temperature to obtain a suspension, the suspension is moved to an autoclave for being subjected to hydrothermal reaction, after the reaction is finished, a reaction product is centrifuged, washed, dried and grinded to obtain a precursor, and the precursor is calcinated at a certain temperature for certain time to obtain the cubic-structure CuCr2O4 visible light photocatalyst. The cubic-structure CuCr2O4 visible light photocatalyst of a square crystalline phase is prepared by adopting the hydrothermal synthesis method, the preparation technology is simple and low in cost, the preparation process is free of pollutant discharge, the prepared photocatalyst is high in photocatalytic activity and capable of being effectively used for degrading organic dyestuff pollutants in waste water.

Description

A kind of cubic structure CuCr 2o 4the preparation method of visible-light photocatalyst and application
Technical field
The invention belongs to the preparing technical field of catalysis material, be specifically related to a kind of cubic structure CuCr 2o 4the preparation method of visible-light photocatalyst and application.
Background technology
Along with science and technology and industrial fast development, the problem of environmental pollution of facing mankind also becomes increasingly conspicuous, and environmental protection more and more gets more and more people's extensive concerning.Photocatalysis technology has been brought into play important function aspect environmental protection, and utilizing semi-conducting material is a kind of very promising technology as photocatalyst for degrading atmosphere and organic pollutants.Current most of photocatalysis is all around TiO 2launch, but due to TiO 2there is wider energy gap, only at ultraviolet region, have absorption, and its quantum efficiency is low, thereby has limited to a great extent its application in photocatalysis field.People attempt to improve TiO by methods such as photoactivate, doping 2visible ray utilization rate and photocatalysis efficiency, though obtain certain effect, effect is very not remarkable.Find novel visible photochemical catalyst and become the development trend in this field at present.
The CuCr with spinel structure 2o 4be a kind of very important visible light-responded p-type semiconductor light-catalyst, its energy gap is about 1.4eV, can absorb efficiently and utilize solar energy.Due to CuCr 2o 4the stability of structure and visible light-responded, in recent decades, it has been widely used in the fields such as organic pollution in photodissociation aquatic products hydrogen and photocatalytic degradation atmosphere or water under hydrogenization, alkylating and visible ray.Yet the pattern of material physicochemical properties are corresponding thereto closely related, adopt the synthetic traditional chondritic CuCr of high temperature solid-state method, sol-gel process and coprecipitation 2o 4the catalytic rate of photochemical catalyst is slow, and catalytic activity needs further to be improved, and therefore special construction CuCr is prepared in research 2o 4straightforward procedure and improve its catalytic activity and become one of the study hotspot in this field.
Summary of the invention
In order to overcome the shortcoming and deficiency of prior art, primary and foremost purpose of the present invention is to provide a kind of cubic structure CuCr 2o 4the preparation method of visible-light photocatalyst.
Another object of the present invention is to provide the cubic structure obtaining by above-mentioned preparation method CuCr 2o 4visible-light photocatalyst.Good, the visible light-responded wide ranges of this catalyst stability, photocatalytic activity are high.
A further object of the present invention is to provide described cubic structure CuCr 2o 4the application of visible-light photocatalyst organic dyestuff in degrading waste water.
Object of the present invention is achieved through the following technical solutions: a kind of cubic structure CuCr 2o 4the preparation method of visible-light photocatalyst, comprises the following steps:
(1) copper nitrate and chromic nitrate are dissolved in deionized water, stir, obtain mixed solution, then the pH value of mixed solution is adjusted to 10～11; The mol ratio of controlling copper nitrate and chromic nitrate is 1:(1.8～2.2);
(2) solution obtaining in step (1) is heated to 70～80 ℃, and stirs and obtain suspension at this temperature;
(3) suspension step (2) being made carries out hydro-thermal reaction, after reaction finishes, cooling; Controlling hydrothermal temperature is 160～200 ℃, and the hydro-thermal reaction time is 9～13h;
(4) product obtaining after step (3) is cooling carries out centrifugation, gets precipitation, with deionized water and absolute ethanol washing precipitation several times, dry, obtains precursor after grinding;
(5) precursor step (4) being obtained, in 550～650 ℃ of roasting 3.5～4.5h, makes cubic structure CuCr 2o 4visible-light photocatalyst.
Preferably, the final concentration of the copper nitrate described in step (1) and chromic nitrate is respectively 0.05～0.1mol/L and 0.1～0.2mol/L;
PH value described in step (1) preferably regulates by sodium hydroxide solution;
The concentration of described sodium hydroxide solution is preferably 4～6mol/L;
The time of the stirring described in step (1) is 15～20min;
The time of the stirring described in step (2) is 3～4h;
It is cooling that cooling mode described in step (3) is preferably nature;
Centrifugal condition described in step (4) is the centrifugal 10～15min of 8000～10000r/min;
Dry condition described in step (4) is 70～90 ℃ of dry 4～6h.
A kind of cubic structure CuCr 2o 4visible-light photocatalyst, is made by above-mentioned preparation method, prepared CuCr 2o 4crystal is the cubic structure nano particle of tetragonal phase, and particle diameter is about 15～30nm, and specific area is 12～15m 2g -1, there is strong visible absorption ability, wide visible light-responded scope, highlight catalytic active and good stability.
Described cubic structure CuCr 2o 4the application of visible-light photocatalyst organic dyestuff in degrading waste water.CuCr in the application of organic dyestuff in degrading waste water 2o 4with H 2o 2mol ratio be 1:(4～6), H 2o 2in degradation process, be mainly to catch light induced electron, hydroxyl radical free radical (OH) is provided.
Mechanism of the present invention is:
CuCr 2O 4+hν→CuCr 2O 4(h ++e -) (1)
H 2O 2+CuCr 2O 4(e -)→OH ·+OH -+CuCr 2O 4 (2)
OH .+ organic dyestuff → catabolite (3)
The present invention has following advantage and effect with respect to prior art:
(1) the present invention has prepared the cubic structure CuCr of tetragonal phase by hydrothermal synthesis method 2o 4, pattern homogeneous, purity is high.
(2) it is cheap and easy to get, with low cost that the present invention prepares the raw material of use, and technique is simple, preparation process non-pollution discharge.
(3) cubic structure CuCr of the present invention 2o 4visible-light photocatalyst has good stability, wide visible light-responded scope, highlight catalytic active, is applicable to the fields such as solar energy trans-utilization and environmental improvement, as the degraded that contains rhodamine B organic dyestuff industrial wastewater.
Accompanying drawing explanation
Fig. 1 is the cubic structure CuCr of embodiment 1 preparation 2o 4the cubic structure CuCr of preparation in visible-light photocatalyst and embodiment 1 2o 4the CuCr that visible-light photocatalyst circulates and reclaims after the rhodamine B degradation aqueous solution 5 times under same experimental conditions 2o 4x-ray diffractogram.
Fig. 2 is the cubic structure CuCr of embodiment 1 preparation 2o 4the transmission electron microscope picture of visible-light photocatalyst.
Fig. 3 is the cubic structure CuCr of embodiment 1 preparation 2o 4the UV-Vis DRS spectrogram of visible-light photocatalyst.
Fig. 4 is the cubic structure CuCr of embodiment 1 preparation 2o 4the concentration time changing curve figure of visible-light photocatalyst rhodamine B degradation under radiation of visible light.
The specific embodiment
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this.
Embodiment 1
A kind of cubic structure CuCr 2o 4the preparation method of visible-light photocatalyst, comprises the following steps:
(1) 5mmol copper nitrate and 10mmol chromic nitrate are dissolved in 50mL deionized water, stir 20min, obtain mixed solution, then to it, adding the sodium hydroxide solution of 5mol/L to regulate the pH value of mixed solution is 10.3;
(2) solution obtaining in step (1) is heated to 70 ℃, and at this temperature, stirs 4h and obtain suspension;
(3) suspension step (2) being made be transferred to reactor (purchased from Guangzhou Yu Hua Instrument Ltd., model: KH-100), at the Water Under thermal response 11h of 180 ℃, reaction finish after, naturally cool to room temperature;
(4) step (3) product is carried out to centrifugation, centrifugation rate is 9000r/min, centrifugal 12min, and the precipitate with deionized water washing obtaining after centrifugal is to neutral, then uses absolute ethanol washing 3 times, under 80 ℃ of conditions, dry 5h, obtains precursor after grinding;
(5) precursor step (4) being obtained is 600 ℃ of roasting 4h in Muffle furnace, make cubic structure CuCr 2o 4visible-light photocatalyst.
Fig. 1 (a) is the cubic structure CuCr of preparation in embodiment 1 2o 4the X-ray diffractogram of visible-light photocatalyst.From Fig. 1 (a), prepared CuCr 2o 4the characteristic diffraction peak of sample and CuCr 2o 4standard card JCPDS No.34-0424's is in full accord, and retrieval obtains prepared CuCr 2o 4crystal is tetragonal phase, and CuO, Cr do not detected 2o 3and the diffraction maximum of other impurity, this shows successfully to have prepared the CuCr of tetragonal phase 2o 4photochemical catalyst, and the product making is purer; According to Scherrer equation, calculate prepared CuCr 2o 4the particle diameter of nano particle is about 15 nm～30 nm; Fig. 1 (b) is the cubic structure CuCr of preparation in embodiment 1 2o 4visible-light photocatalyst circulates after the rhodamine B degradation aqueous solution (20mg/L) 5 times and reclaims the CuCr obtaining under same experimental conditions 2o 4x-ray diffractogram, from Fig. 1 (b), can find out, recycle and reclaim the CuCr obtaining after 5 times 2o 4the characteristic diffraction peak of visible-light photocatalyst is consistent with Fig. 1 (a), and prepared cubic structure CuCr is described 2o 4visible-light photocatalyst has good stability; From Fig. 2 transmission electron microscope photo, can observe obvious cubic structure, confirm by the legal cubic structure CuCr that successfully makes of hydro-thermal 2o 4photochemical catalyst, and the cubic structure CuCr making 2o 4particle belongs to Nano grade, is evenly distributed, pattern homogeneous; From the UV-Vis DRS collection of illustrative plates of Fig. 3, prepared cube CuCr 2o 4sample has strong absorption in whole visible-range, and the cubic structure CuCr making is described 2o 4there is wide visible light-responded scope and visible light catalysis activity.
Embodiment 2
A kind of cubic structure CuCr 2o 4the preparation method of visible-light photocatalyst, comprises the following steps:
(1) 2.5mmol copper nitrate and 5.5mmol chromic nitrate are dissolved in 50mL deionized water, stir 15min, obtain mixed solution, then to it, adding the sodium hydroxide solution of 4mol/L to regulate the pH value of mixed solution is 11;
(2) solution obtaining in step (1) is heated to 80 ℃, and at this temperature, stirs 3.5h and obtain suspension;
(3) suspension step (2) being made is transferred in reactor, at the Water Under thermal response 13h of 160 ℃, after reaction finishes, naturally cools to room temperature;
(4) step (3) product is carried out to centrifugation, centrifugation rate is 10000r/min, centrifugal 10min, and the precipitate with deionized water washing obtaining after centrifugal is to neutral, then uses absolute ethanol washing 3 times, under 90 ℃ of conditions, dry 4h, obtains precursor after grinding;
(5) precursor step (4) being obtained is 550 ℃ of roasting 4.5h in Muffle furnace, make cubic structure CuCr 2o 4visible-light photocatalyst.
Cubic structure CuCr in the present embodiment 2o 4the X-ray diffractogram of visible-light photocatalyst, transmission electron microscope picture and UV-Vis DRS spectrogram are similar to Fig. 1～3.
Embodiment 3
A kind of cubic structure CuCr 2o 4the preparation method of visible-light photocatalyst, comprises the following steps:
(1) 5mmol copper nitrate and 9mmol chromic nitrate are dissolved in 50mL deionized water, stir 20min, obtain mixed solution, then to it, adding the sodium hydroxide solution of 6mol/L to regulate the pH value of mixed solution is 10;
(2) solution obtaining in step (1) is heated to 75 ℃, and at this temperature, stirs 3h and obtain suspension;
(3) suspension step (2) being made is transferred in reactor, at the Water Under thermal response 9h of 200 ℃, after reaction finishes, naturally cools to room temperature;
(4) step (3) product is carried out to centrifugation, centrifugation rate is 8000r/min, centrifugal 15min, and the precipitate with deionized water washing obtaining after centrifugal is to neutral, then uses absolute ethanol washing 3 times, under 70 ℃ of conditions, dry 6h, obtains precursor after grinding;
(5) precursor step (4) being obtained is 650 ℃ of roasting 3.5h in Muffle furnace, make a cube CuCr 2o 4visible-light photocatalyst.
Cubic structure CuCr in the present embodiment 2o 4the X-ray diffractogram of visible-light photocatalyst, transmission electron microscope picture and UV-Vis DRS spectrogram are similar to Fig. 1～3.
Application Example
Use the cubic structure CuCr of preparation 2o 4visible-light photocatalyst is catalytic degradation organic dyestuff under sunshine: the rhodamine B aqueous solution of take is evaluated the photocatalytic activity of this catalyst as simulating sewage.Experiment condition is set to: (1) is by the 20mg cubic structure CuCr of preparation in embodiment 1 2o 4it is 20mgL that visible-light photocatalyst is distributed to 50mL concentration -1the rhodamine B aqueous solution in, before illumination reaction, first suspension is placed in to dark surrounds magnetic agitation 30min so that system reaches adsorption/desorption balance, then in suspension, add 50 μ L H 2o 2(30%, mass fraction), continues to stir 3min; (2) open simulated solar light source, after each illumination 15min, sample, centrifuging and taking supernatant liquor, detects the variation of upper strata ultraviolet-visible absorbance of rhodamine B solution in the stillness of night.
Fig. 4 is cubic structure CuCr in embodiment 1 2o 4the concentration time changing curve figure of rhodamine B degradation under visible-light photocatalyst radiation of visible light.Known in conjunction with Fig. 4, in contrast experiment, with H 2o 2(50 μ L) and pure cubic structure CuCr 2o 4(20mg), while being photochemical catalyst, after radiation of visible light 60min, the degradation rate of rhodamine B is respectively 10.8% and 6.4%, and H is described 2o 2with pure cubic structure CuCr 2o 4catalytic degradation activity to rhodamine B is very low, for the pure cubic structure CuCr with strong visible absorption 2o 4low catalytic degradation activity be mainly because its light induced electron-hole is to very easily compound; And at H 2o 2under the condition existing with cubic structure CuCr 2o 4(20mg) while being photochemical catalyst, at 60min only to the degradation rate of rhodamine B up to 96.8%, this shows cubic structure CuCr 2o 4visible-light photocatalyst is at H 2o 2assistance under there is high visible light catalysis activity, and degradation rate is very fast.H 2o 2effect in this catalytic degradation process is mainly to generate OH by catching light induced electron, thereby has effectively suppressed the right separation in light induced electron-hole, improves CuCr 2o 4the photocatalytic activity of visible-light photocatalyst.Therefore the cubic structure CuCr that, prepared by the present invention 2o 4visible-light photocatalyst is at H 2o 2assistance under can be effectively applied to Visible Light Induced Photocatalytic organic pollution.
Above-described embodiment is preferably embodiment of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under Spirit Essence of the present invention and principle, substitutes, combination, simplify; all should be equivalent substitute mode, within being included in protection scope of the present invention.

Claims (10)

1. a cubic structure CuCr 2o 4the preparation method of visible-light photocatalyst, is characterized in that comprising the following steps:
(1) copper nitrate and chromic nitrate are dissolved in deionized water, stir, obtain mixed solution, then the pH value of mixed solution is adjusted to 10～11; The mol ratio of controlling copper nitrate and chromic nitrate is 1:(1.8～2.2);
(2) solution obtaining in step (1) is heated to 70～80 ℃, and stirs and obtain suspension at this temperature;
(3) suspension step (2) being made carries out hydro-thermal reaction, after reaction finishes, cooling; Controlling hydrothermal temperature is 160～200 ℃, and the hydro-thermal reaction time is 9～13h;
(4) product obtaining after step (3) is cooling carries out centrifugation, gets precipitation, with deionized water and absolute ethanol washing precipitation several times, dry, obtains precursor after grinding;
(5) precursor step (4) being obtained, in 550～650 ℃ of roasting 3.5～4.5h, makes cubic structure CuCr 2o 4visible-light photocatalyst.
2. preparation method according to claim 1, is characterized in that: the final concentration of the copper nitrate described in step (1) and chromic nitrate is respectively 0.05～0.1mol/L and 0.1～0.2mol/L.
3. preparation method according to claim 1, is characterized in that: the pH value described in step (1) regulates by sodium hydroxide solution;
The concentration of described sodium hydroxide solution is 4～6mol/L.
4. preparation method according to claim 1, is characterized in that:
The time of the stirring described in step (1) is 15～20min;
The time of the stirring described in step (2) is 3～4h.
5. preparation method according to claim 1, is characterized in that: the centrifugal condition described in step (4) is the centrifugal 10～15min of 8000～10000r/min.
6. preparation method according to claim 1, is characterized in that: the dry condition described in step (4) is 70～90 ℃ of dry 4～6h.
7. a cubic structure CuCr 2o 4visible-light photocatalyst, is prepared by the preparation method described in claim 1～6 any one.
8. cubic structure CuCr according to claim 7 2o 4visible-light photocatalyst, is characterized in that: prepared CuCr 2o 4crystal is the cubic structure nano particle of tetragonal phase, and particle diameter is 15～30nm, and specific area is 12～15m 2g -1.
9. the cubic structure CuCr described in claim 7 or 8 2o 4the application of visible-light photocatalyst organic dyestuff in degrading waste water.
10. application according to claim 9, is characterized in that: CuCr 2o 4with H 2o 2mol ratio be 1:(4～6).
CN201410353190.5A 2014-07-23 2014-07-23 Preparation method and application of cubic-structure CuCr2O4 visible light photocatalyst Pending CN104138762A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107376929A (en) * 2017-08-09 2017-11-24 南京工业大学 Catalytic combustion catalyst, preparation and application thereof
CN108404927A (en) * 2018-03-13 2018-08-17 湘潭大学 The method of dye wastewater degradation catalyst, preparation method and degrading waste water
CN108796460A (en) * 2018-06-11 2018-11-13 佛山腾鲤新能源科技有限公司 A kind of preparation method of solar selectively adsorption layer
CN111777099A (en) * 2020-06-28 2020-10-16 陕西师范大学 Preparation method of cubic spinel type nano flaky copper chromite
CN115385377A (en) * 2022-08-25 2022-11-25 湖南汇帮环保科技有限公司 Preparation method of copper chromite for laser etching chemical plating aid

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1426965A (en) * 2001-12-17 2003-07-02 上海润基科技发展有限公司 Preparation of nano copper chromite using microemulsion method
CN101367044A (en) * 2008-07-18 2009-02-18 清华大学 Method for preparing nano-catalyst copper chromite and copper ferrite
CN101610840A (en) * 2007-02-14 2009-12-23 伊士曼化工公司 Palladium-palladium-copper chromite hydrogenation catalysts
CN102500389A (en) * 2011-11-03 2012-06-20 北京化工大学 Copper chromite/carbon nanotube nano-composite catalyst, preparation method and application

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1426965A (en) * 2001-12-17 2003-07-02 上海润基科技发展有限公司 Preparation of nano copper chromite using microemulsion method
CN101610840A (en) * 2007-02-14 2009-12-23 伊士曼化工公司 Palladium-palladium-copper chromite hydrogenation catalysts
CN101367044A (en) * 2008-07-18 2009-02-18 清华大学 Method for preparing nano-catalyst copper chromite and copper ferrite
CN102500389A (en) * 2011-11-03 2012-06-20 北京化工大学 Copper chromite/carbon nanotube nano-composite catalyst, preparation method and application

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
SHAHID KHAN DURRANI, ET AL.: ""Hydrothermal synthesis and characterization of nanosized transition metal chromite spinels"", 《TURK J CHEM》, vol. 36, 31 December 2012 (2012-12-31), pages 111 - 120 *
胡志强等: ""尖晶石型CuCr_2O_4纳米粉体的制备及应用"", 《陶瓷学报》, vol. 31, no. 4, 31 December 2010 (2010-12-31), pages 512 - 516 *

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN107376929A (en) * 2017-08-09 2017-11-24 南京工业大学 Catalytic combustion catalyst, preparation and application thereof
CN108404927A (en) * 2018-03-13 2018-08-17 湘潭大学 The method of dye wastewater degradation catalyst, preparation method and degrading waste water
CN108796460A (en) * 2018-06-11 2018-11-13 佛山腾鲤新能源科技有限公司 A kind of preparation method of solar selectively adsorption layer
CN111777099A (en) * 2020-06-28 2020-10-16 陕西师范大学 Preparation method of cubic spinel type nano flaky copper chromite
CN111777099B (en) * 2020-06-28 2022-07-01 陕西师范大学 Preparation method of cubic spinel type nano flaky copper chromite
CN115385377A (en) * 2022-08-25 2022-11-25 湖南汇帮环保科技有限公司 Preparation method of copper chromite for laser etching chemical plating aid
CN115385377B (en) * 2022-08-25 2023-10-24 湖南汇帮环保科技有限公司 Preparation method of copper chromite for laser engraving chemical plating auxiliary

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