CN102580742B - Activated carbon-loaded cuprous oxide photocatalyst and preparation method thereof - Google Patents
Activated carbon-loaded cuprous oxide photocatalyst and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 82
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 title claims abstract description 25
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 title claims abstract description 25
- 229940112669 cuprous oxide Drugs 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 11
- 239000002957 persistent organic pollutant Substances 0.000 claims abstract description 5
- 150000002989 phenols Chemical class 0.000 claims abstract description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims abstract 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical group OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 10
- 239000000243 solution Substances 0.000 claims description 10
- 230000007935 neutral effect Effects 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 6
- 150000001299 aldehydes Chemical class 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- 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 2
- 239000008103 glucose Substances 0.000 claims description 2
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 235000011114 ammonium hydroxide Nutrition 0.000 claims 1
- 239000007853 buffer solution Substances 0.000 claims 1
- 239000003054 catalyst Substances 0.000 abstract description 33
- 239000002351 wastewater Substances 0.000 abstract description 14
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000007254 oxidation reaction Methods 0.000 abstract description 9
- 230000015556 catabolic process Effects 0.000 abstract description 8
- 238000006731 degradation reaction Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 6
- 238000004887 air purification Methods 0.000 abstract description 4
- 239000003344 environmental pollutant Substances 0.000 abstract description 4
- 231100000719 pollutant Toxicity 0.000 abstract description 4
- 238000006243 chemical reaction Methods 0.000 abstract description 3
- 230000009286 beneficial effect Effects 0.000 abstract description 2
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 229910000365 copper sulfate Inorganic materials 0.000 abstract 1
- 229910052799 carbon Inorganic materials 0.000 description 24
- 238000000034 method Methods 0.000 description 14
- 239000010949 copper Substances 0.000 description 13
- 239000000975 dye Substances 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 8
- 239000004065 semiconductor Substances 0.000 description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 229910010413 TiO 2 Inorganic materials 0.000 description 5
- 238000007598 dipping method Methods 0.000 description 5
- 238000005303 weighing Methods 0.000 description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 4
- 238000002835 absorbance Methods 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000007146 photocatalysis Methods 0.000 description 4
- 238000011084 recovery Methods 0.000 description 4
- 238000011282 treatment Methods 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- 238000004043 dyeing Methods 0.000 description 3
- 230000010355 oscillation Effects 0.000 description 3
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 239000005083 Zinc sulfide Substances 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 2
- 239000000356 contaminant Substances 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000010919 dye waste Substances 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 238000005470 impregnation Methods 0.000 description 2
- 230000004298 light response Effects 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 239000005416 organic matter Substances 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000006479 redox reaction Methods 0.000 description 2
- STZCRXQWRGQSJD-UHFFFAOYSA-M sodium;4-[[4-(dimethylamino)phenyl]diazenyl]benzenesulfonate Chemical compound [Na+].C1=CC(N(C)C)=CC=C1N=NC1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-UHFFFAOYSA-M 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000004065 wastewater treatment Methods 0.000 description 2
- 239000005749 Copper compound Substances 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 206010070834 Sensitisation Diseases 0.000 description 1
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 230000003373 anti-fouling effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000010165 autogamy Effects 0.000 description 1
- 239000003899 bactericide agent Substances 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 229910002090 carbon oxide Inorganic materials 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001311 chemical methods and process Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002894 chemical waste Substances 0.000 description 1
- 238000005345 coagulation Methods 0.000 description 1
- 230000015271 coagulation Effects 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000004939 coking Methods 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 150000001880 copper compounds Chemical class 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 210000003298 dental enamel Anatomy 0.000 description 1
- 239000002781 deodorant agent Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 230000005684 electric field Effects 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 125000000623 heterocyclic group Chemical group 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- -1 hydroxyl radical free radical Chemical class 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000001089 mineralizing effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 1
- 125000003367 polycyclic group Chemical group 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000037452 priming Effects 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000008313 sensitization Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000167 toxic agent Toxicity 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
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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
本发明提供的活性炭负载氧化亚铜光催化剂可用作酚类等有机污染物的降解和空气净化的光催化剂，它是用处理过的活性炭浸渍在硫酸铜溶液中，由C6O12O6或Na2SO3还原制备而成。本发明的有益效果：活性炭负载氧化亚铜光催化剂的制备是以硫酸铜为原料，以活性炭为载体，将氧化亚铜载到活性炭上，催化剂制备方法简便、价格低廉、稳定性好、光催化活性高。用该催化剂催化氧化酚类等废水和室内空气净化，可在紫外-可见光条件下直接进行，易于操作，反应条件温和，污染物的去除率高。The activated carbon-supported cuprous oxide photocatalyst provided by the invention can be used as a photocatalyst for the degradation of organic pollutants such as phenols and for air purification . Or Na 2 SO 3 reduction prepared. Beneficial effects of the present invention: the preparation of activated carbon-supported cuprous oxide photocatalyst uses copper sulfate as raw material, activated carbon as carrier, and cuprous oxide is loaded on activated carbon. High activity. Using the catalyst to catalyze the oxidation of phenolic waste water and indoor air purification can be carried out directly under the condition of ultraviolet-visible light, easy to operate, mild in reaction conditions, and high in the removal rate of pollutants.
Description
Technical field
The present invention relates to a kind of activated carbon supported type photochemical catalyst and preparation method thereof, this catalyst is applicable to the purification method of wastewater treatments such as dyestuff and indoor pollution air.
Background technology
China is first big country of DYE PRODUCTION and consumption, and dye well dyeing waste water contaminant capacity is big and wide.The dye well dyeing waste water has characteristics such as the water yield is big, colourity is high, complex chemical composition, bio-refractory, is one of bigger industrial wastewater of difficulty of governance.BOD, COD, organic toxic substance and colourity etc. are the major pollutants in this class waste water, if these pollutants are unprocessed or deal with improperly with discharge of wastewater, will produce severe contamination to water body.Usually, the dye well dyeing waste water generally adopts filtration, coagulation, is precipitated as main physico-chemical process, because this class waste water contains a large amount of biodegradable aromatic series organic matter, heterocycle and polycyclic compounds of being difficult to, and content is higher, and the domestic and international at present processing to this type of waste water does not all have desirable processing method.The photocatalytic oxidation degradation of dye waste water is the hot technology that latest developments are got up.Photocatalysis oxidation technique utilizes ultraviolet light or visible light irradiation to have the semiconductor light-catalyst of photocatalytic activity, belongs to metal oxide semiconductor, sulfide or composite oxides etc. more.As titanium dioxide (TiO
2), zinc oxide (ZnO), zinc sulphide (ZnS), tungstic acid (WO
3), cadmium sulfide (CdS), bismuth oxide (Bi
2O
3) etc., semi-conductive intragranular contains band structure, it can be with usually by a low energy valence band (Valent band who is full of electronics, VB) and high energy conduction band (the Conduct band of a sky, CV) constitute, separated by the forbidden band between valence band and the conduction band, the size in this zone is called energy gap, it can differ from and be that band-gap energy, semi-conductive band-gap energy are generally 0. 2～3. 0 eV.When catalyst was penetrated in the illumination that is equal to or greater than band-gap energy with energy, the electronics on the valence band was excited, and crossed the forbidden band and entered conduction band, produced corresponding hole simultaneously on valence band, and promptly light induced electron/hole is to (e
-/ h
+).Light induced electron on conduction band has stronger reducing power, and the photohole on valence band has very strong oxidisability.Because the discontinuity of semiconductor energy gap, the life-span in electronics and hole is longer, moves under electric field action or by the mode of diffusion, and is adsorbed on the lip-deep material generation of catalyst particle redox reaction, is perhaps captured by the lattice surface defective.Hole and electronics in catalyst inside or the surface also may be directly compound.Under illumination condition, the photocatalytic process on the semiconductor can be divided into for four steps to be finished: the absorption electrons/ by light is separated; The absorption of reactant; Redox reaction; The product desorption.In this process, because the photohole that the ultraviolet excitation semiconductor produces and move to semiconductor surface and captured the back by water or hydroxyl and form hydroxyl radical free radical and have very strong oxidability, can the most organic pollutions of oxidation and to make it permineralization be CO
2, as all kinds of organic pollutions such as dyestuff, aldehydes matter, alkene, aldehydes, Polychlorinated biphenyls, surfactants.
At present, adopting maximum semiconductor light-catalysts is TiO
2Titanium dioxide has physical characteristics such as high specific area, high density, blemish and high surface energy and nontoxic, stable, chemical property such as catalytic activity is high, reaction speed is fast, simultaneously low and can make the thorough mineralizing and degrading of organic matter to the selectivity of organic pollutant degradation again, do not cause advantages such as secondary pollution, in the actual production life is used, be widely used.But because TiO
2Greater band gap (Eg=3.2 eV), can only be by ultraviolet excitation (λ＜387 nm), and sunshine medium ultraviolet light only accounts for 3～4 % of sunshine gross energy, has greatly limited its research and application.If adopt artificial ultraviolet source, then need expensive equipment, thereby improve TiO
2Photochemical catalyst visible light-responded or develop meaning and the broad prospect of application that all kinds of visible light responsive photocatalysts have particular importance, and can derive many new industries simultaneously.Main method has: 1) adopt doped transition metal ions TiO
2The preparation visible light catalyst; 2) by transition metal and nonmetalloid codope; 3) by nonmetalloid calking and displacement doped Ti O
2Realize that the visible light catalytic effect is considered to a key progress.Yet with l) method is the same, the activity of the photochemical catalyst of acquisition under visible light be well below the activity of business-like Degussa P25 under ultraviolet light, and its used light source still has tangible ultraviolet light, and the activity under ultraviolet light the two is approaching; 4) utilize dye sensitization TiO
2Realize the visible light catalytic effect.This respect scientist has made a large amount of elaborations, has obtained the impressive progress of dyestuff contaminant degraded under excited by visible light.
Catalytic wet air oxidation is a kind of treatment technology of handling organic wastewater that last century, the eighties grew up in the world, but costs an arm and a leg, and makes its application be subjected to great restriction.Photocatalysis oxidation technique is that the organic wastewater and the indoor air purification that grow up over past ten years are handled one of important method.Cuprous oxide (Cu
2O) be the p type semi-conducting material of direct band gap, of many uses.At the bactericide of coatings industry as marine antifouling priming paint; Be used for red glass and red enamel colouring agent in glass industry; Be used as catalyst in organic industry.Existing bibliographical information (the Li-Li Ma et al of cuprous oxide that utilize as the photocatalyst for degrading organic dye waste water, Materials Research Bulletin 45 (2010) 961 – 968), invention (the Fukumoto that copper compound matrix activated carbon deodorant is also arranged, Kazuhiro et al, JP 2004166920) and activated charcoal carried copper oxide (CuO) be used for the invention (CN 1876232A) of coking chemical waste water.Although photocatalysis oxidation technique has treatment effect preferably, this technology will realize that industrialization also need be in selection visible light response catalyst active component, the separation that solves catalyst, aspect the making a breakthrough property achievements such as selection of carrier to waste water from dyestuff, indoor pollution air etc.
Summary of the invention
Technical problem to be solved by this invention is: propose a kind of dye wastewater treatment using and indoor pollution air visible light response catalyst and preparation method thereof, and carry out the processing that Treatment by Photocatalysis Oxidation has waste water from dyestuff and indoor air pollutants with shaped activated carbon loaded catalysts such as this powdery and particles.
Technical scheme of the present invention:
A kind of powder or granular active carbon load cuprous oxide photochemical catalyst, its component and content are:
The cuprous oxide weight percent content is 1.0-5.0%, and the active carbon weight percent content is 95.0-99.0%.
A kind of preparation method of activated carbon supported cuprous oxide photochemical catalyst, this method may further comprise the steps:
(1) filters after active carbon is stirred 24h with 3mol/L ammonia spirit dipping, be washed till neutrality with distilled water;
(2) with step (1) processed active carbon 5mol/L HNO
3Solution impregnation is filtered after stirring 24h, is washed till neutrality with distilled water, puts into baking oven, and is in 110 ℃ of oven dry, standby;
(3) take by weighing the CuSO that a certain amount of pretreated active carbon impregnated in 0.04mol/L ~ 0.2 mol/L respectively
4In the solution, be 90rpm at rotating speed, temperature is in 25 ℃ the constant temperature culture oscillator behind the dipping 24h, filters.
(4) active carbon that step (3) is obtained is transferred to proper C
6H
12O
6In NaOH solution, place the constant temperature culture oscillator again, temperature is 30 ℃, rotating speed is rotational oscillation 24h under the 90rpm condition, takes out washing to neutral.
(5) loaded Cu that step (4) is obtained
2The active carbon of O changes dry 3h in 80 ℃ the vacuum drying chamber over to, makes activated carbon supported cuprous oxide photochemical catalyst.
The present invention compares the beneficial effect that is had with prior art:
The preparation of activated carbon supported cuprous oxide photochemical catalyst is to be raw material with copper sulphate, is carrier with the active carbon, and cuprous oxide is downloaded on the active carbon, and method for preparing catalyst is easy, cheap, good stability, photocatalytic activity height.With waste water and indoor air purifications such as this catalyst oxidation phenols, can under the ultraviolet-visible optical condition, directly carry out easy operating, reaction condition gentleness, the clearance height of pollutant.
Description of drawings
Fig. 1 is a column-shaped active carbon SEM pattern.
Fig. 2 is a column-shaped active carbon surface scan electron microscope pattern.
Fig. 3 a is Cu
2The bar-shaped Cu of O carried-type active carbon surface
2O SEM pattern
Fig. 3 b is the energy spectrogram of Fig. 3 a.
Fig. 4 is Cu
2The starlike Cu of O carried-type active carbon surface
2O SEM pattern.
Fig. 5 is Cu
2The relevant x-ray diffraction pattern of O carried active carbon.
Fig. 6 is Cu
2The absorption spectrum of O carried active carbon degraded catechol.
The specific embodiment
Following embodiment further specifies activated carbon supported cuprous oxide photochemical catalyst provided by the invention, preparation method and application.
Activated carbon supported cuprous oxide photochemical catalyst and preparation method
(1) filters after active carbon is stirred 24h with 3mol/L ammonia spirit dipping, be washed till neutrality with distilled water;
(2) with step (1) processed active carbon 5mol/L HNO
3Solution impregnation is filtered after stirring 24h, is washed till neutrality with distilled water, puts into baking oven, and is in 110 ℃ of oven dry, standby;
(3) take by weighing the CuSO that the pretreated active carbon of 5g impregnated in 50mL 0.04mol/L
4In the solution, be 90rpm at rotating speed, temperature is in 25 ℃ the constant temperature culture oscillator behind the dipping 24h, filters.
(4) active carbon that step (3) is obtained is transferred to and contains 0.2g C
6H
12O
650mLNaOH(0.05mol/L) in the solution, place the constant temperature culture oscillator again, temperature is 30 ℃, rotating speed is rotational oscillation 24h under the 90rpm condition, filter product, washing is to neutral.
(5) loaded Cu that step (4) is obtained
2The active carbon of O changes dry 3h in 80 ℃ the vacuum drying chamber over to, makes activated carbon supported 1% cuprous oxide photochemical catalyst.
Step (1), (2) are identical with implementation method one;
(3) take by weighing the CuSO that the pretreated active carbon of 5g impregnated in 0.2mol/L
4In the solution, be 90rpm at rotating speed, temperature is in 25 ℃ the constant temperature culture oscillator behind the dipping 24h, filters.
(4) active carbon that step (3) is obtained is transferred to and contains 0.6g C
6H
12O
650mLNaOH(0.2mol/L) in the NaOH solution, place the constant temperature culture oscillator again, temperature is 30 ℃, rotating speed is rotational oscillation 24h under the 90rpm condition, filter product, washing is to neutral.
(5) loaded Cu that step (4) is obtained
2The active carbon of O changes dry 3h in 80 ℃ the vacuum drying chamber over to, makes activated carbon supported 5% cuprous oxide photochemical catalyst.
Step (1), (2) are identical with implementation method one;
(3) get 5g step (2) processed active carbon, 50mL 0.2mol/L CuSO
4With 50mL 0.05 mol/L Na
2SO
3Be positioned in the beaker of 500 mL and react, to cushioning liquid that wherein adds 300 mL pH=5 HAc-NaAc and 0.1g glucose, reaction 3h or microwave 30min under 70 ℃ of conditions, filter product, washing is to neutral.
(4) loaded Cu that step (3) is obtained
2The active carbon of O changes dry 3h in 80 ℃ the vacuum drying chamber over to, makes activated carbon supported 1% cuprous oxide photochemical catalyst.
Example with waste water such as activated carbon supported cuprous oxide photocatalyst treatment phenols.
Example 4
Take by weighing an amount of catechol solid and be configured to the catechol solution of 100mg/L, with the Cu of example 1 preparation
2O/AC is a photochemical catalyst, utilizes the incandescent lamp of 200W to be light source, is the maximum absorption wavelength of the catechol aqueous solution with 275 nm, surveys its absorbance.The photocatalytic degradation rate K of sample calculates with following formula:
K=[(A
0-A
t)/A
0]×100%
In the formula: A
O, the absorbance of initial sample; A
t, the absorbance of sample when the reaction time is t.Absorption spectrum after the degraded such as Fig. 6.Behind the degraded 2.5h, degradation rate reaches more than 80%.Use more than 4 times after the catalyst recovery after the recovery, degradation efficiency is constant substantially.
Example 5
Take by weighing the methyl orange solution of certain density autogamy, with the Cu of example 3 preparations
2O/AC is a photochemical catalyst, the photochemical reactor that utilizes Kaifeng Red Star scientific instrument factory to produce, and employing dominant wavelength is that the 300W mercury lamp of 365 nm is done radiation source, is the maximum absorption wavelength of methyl orange solution with 463nm, surveys its absorbance.The photocatalytic degradation rate K of sample presses example 4 methods and calculates.Behind the degraded 2h, degradation rate reaches more than 98%.Use more than 4 times after the catalyst recovery after the recovery, degradation efficiency is constant substantially.
By the degradation rate of example 4 and example 5 degradeds as can be known, the effect of activated carbon supported cuprous oxide catalysis degradable organic pollutant is remarkable.The activated carbon supported cuprous oxide photochemical catalyst its preparation method that the present invention makes is simple, cheap, good stability, to the clearance height of organic pollution, reusable, have good economic competitiveness.
Claims (4)
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