CN110479275A - A kind of preparation and its application loading super-small composite Nano catalysis material device - Google Patents
A kind of preparation and its application loading super-small composite Nano catalysis material device Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 48
- 238000006555 catalytic reaction Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000011068 loading method Methods 0.000 title claims abstract description 6
- 239000002131 composite material Substances 0.000 title abstract description 6
- 239000011521 glass Substances 0.000 claims abstract description 51
- 238000006731 degradation reaction Methods 0.000 claims abstract description 43
- 238000000034 method Methods 0.000 claims abstract description 41
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 38
- 239000002351 wastewater Substances 0.000 claims abstract description 37
- 230000015556 catabolic process Effects 0.000 claims abstract description 34
- 230000003197 catalytic effect Effects 0.000 claims abstract description 27
- 230000008569 process Effects 0.000 claims abstract description 20
- 230000004913 activation Effects 0.000 claims abstract description 10
- 239000013256 coordination polymer Substances 0.000 claims abstract description 8
- 229920001795 coordination polymer Polymers 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 4
- 229910002451 CoOx Inorganic materials 0.000 claims description 39
- 229920001940 conductive polymer Polymers 0.000 claims description 26
- 238000009616 inductively coupled plasma Methods 0.000 claims description 26
- 230000010287 polarization Effects 0.000 claims description 23
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 17
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 15
- 229910021389 graphene Inorganic materials 0.000 claims description 14
- 239000003446 ligand Substances 0.000 claims description 10
- 239000002105 nanoparticle Substances 0.000 claims description 10
- 229910021645 metal ion Inorganic materials 0.000 claims description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003792 electrolyte Substances 0.000 claims description 6
- 150000002460 imidazoles Chemical class 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 5
- 150000001455 metallic ions Chemical class 0.000 claims description 5
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 4
- YCIMNLLNPGFGHC-UHFFFAOYSA-N catechol Chemical compound OC1=CC=CC=C1O YCIMNLLNPGFGHC-UHFFFAOYSA-N 0.000 claims description 4
- 230000008859 change Effects 0.000 claims description 4
- 238000001548 drop coating Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910052697 platinum Inorganic materials 0.000 claims description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 4
- PJZLSMMERMMQBJ-UHFFFAOYSA-N 3,5-ditert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC(O)=C(O)C(C(C)(C)C)=C1 PJZLSMMERMMQBJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910001429 cobalt ion Inorganic materials 0.000 claims description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 claims description 3
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims description 2
- 235000007164 Oryza sativa Nutrition 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 229910001431 copper ion Inorganic materials 0.000 claims description 2
- 235000009566 rice Nutrition 0.000 claims description 2
- 239000000975 dye Substances 0.000 abstract description 25
- 238000012544 monitoring process Methods 0.000 abstract description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 13
- 230000015572 biosynthetic process Effects 0.000 abstract description 8
- 239000002086 nanomaterial Substances 0.000 abstract description 8
- 239000007800 oxidant agent Substances 0.000 abstract description 8
- 230000001590 oxidative effect Effects 0.000 abstract description 8
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 230000005518 electrochemistry Effects 0.000 abstract description 5
- 230000000593 degrading effect Effects 0.000 abstract description 4
- 239000010919 dye waste Substances 0.000 abstract description 3
- 239000010842 industrial wastewater Substances 0.000 abstract description 3
- 238000004886 process control Methods 0.000 abstract description 3
- 238000004065 wastewater treatment Methods 0.000 abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 abstract description 2
- 150000004706 metal oxides Chemical class 0.000 abstract description 2
- 229910000428 cobalt oxide Inorganic materials 0.000 description 33
- 239000003054 catalyst Substances 0.000 description 24
- 238000006243 chemical reaction Methods 0.000 description 11
- 238000004043 dyeing Methods 0.000 description 8
- 238000005457 optimization Methods 0.000 description 8
- 238000002835 absorbance Methods 0.000 description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 6
- 239000002537 cosmetic Substances 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 description 5
- 229960000907 methylthioninium chloride Drugs 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- -1 Ethyl alcohol Chemical compound 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000000825 ultraviolet detection Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 238000009303 advanced oxidation process reaction Methods 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 229910052799 carbon Inorganic materials 0.000 description 3
- 235000013339 cereals Nutrition 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- DLHSXQSAISCVNN-UHFFFAOYSA-M hydroxy(oxo)cobalt Chemical compound O[Co]=O DLHSXQSAISCVNN-UHFFFAOYSA-M 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002114 nanocomposite Substances 0.000 description 3
- NJPPVKZQTLUDBO-UHFFFAOYSA-N novaluron Chemical compound C1=C(Cl)C(OC(F)(F)C(OC(F)(F)F)F)=CC=C1NC(=O)NC(=O)C1=C(F)C=CC=C1F NJPPVKZQTLUDBO-UHFFFAOYSA-N 0.000 description 3
- 239000013110 organic ligand Substances 0.000 description 3
- 239000001103 potassium chloride Substances 0.000 description 3
- 235000011164 potassium chloride Nutrition 0.000 description 3
- BJEMXPVDXFSROA-UHFFFAOYSA-N 3-butylbenzene-1,2-diol Chemical compound CCCCC1=CC=CC(O)=C1O BJEMXPVDXFSROA-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 241000446313 Lamella Species 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 238000012805 post-processing Methods 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 150000005206 1,2-dihydroxybenzenes Chemical class 0.000 description 1
- 229910014033 C-OH Inorganic materials 0.000 description 1
- JGLMVXWAHNTPRF-CMDGGOBGSA-N CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O Chemical compound CCN1N=C(C)C=C1C(=O)NC1=NC2=CC(=CC(OC)=C2N1C\C=C\CN1C(NC(=O)C2=CC(C)=NN2CC)=NC2=CC(=CC(OCCCN3CCOCC3)=C12)C(N)=O)C(N)=O JGLMVXWAHNTPRF-CMDGGOBGSA-N 0.000 description 1
- 229910014570 C—OH Inorganic materials 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 1
- 238000004566 IR spectroscopy Methods 0.000 description 1
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 1
- 239000006096 absorbing agent Substances 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000001133 acceleration Effects 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- XLYOFNOQVPJJNP-DYCDLGHISA-N deuterium hydrogen oxide Chemical compound [2H]O XLYOFNOQVPJJNP-DYCDLGHISA-N 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000036541 health Effects 0.000 description 1
- 230000036571 hydration Effects 0.000 description 1
- 238000006703 hydration reaction Methods 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 1
- 239000002440 industrial waste Substances 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- VUZPPFZMUPKLLV-UHFFFAOYSA-N methane;hydrate Chemical compound C.O VUZPPFZMUPKLLV-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000010355 oscillation Effects 0.000 description 1
- 238000010422 painting Methods 0.000 description 1
- FHHJDRFHHWUPDG-UHFFFAOYSA-L peroxysulfate(2-) Chemical compound [O-]OS([O-])(=O)=O FHHJDRFHHWUPDG-UHFFFAOYSA-L 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000010957 pewter Substances 0.000 description 1
- 229910000498 pewter Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
- HDMGAZBPFLDBCX-UHFFFAOYSA-M potassium;sulfooxy sulfate Chemical compound [K+].OS(=O)(=O)OOS([O-])(=O)=O HDMGAZBPFLDBCX-UHFFFAOYSA-M 0.000 description 1
- 238000003918 potentiometric titration Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 150000003254 radicals Chemical class 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 239000004317 sodium nitrate Substances 0.000 description 1
- 235000010344 sodium nitrate Nutrition 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000003419 tautomerization reaction Methods 0.000 description 1
- 229910021642 ultra pure water Inorganic materials 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000000870 ultraviolet spectroscopy Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000008096 xylene Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/23—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/348—Electrochemical processes, e.g. electrochemical deposition or anodisation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
Abstract
The invention discloses one kind using the unlimited coordination polymer nano material of conductivity type as presoma, is post-processed by electrochemistry, the method that super-small metal oxide nanocatalyst material is prepared in situ in conductive glass surface in one-step method.And above-mentioned electro-conductive glass element is utilized on this basis, a kind of load super-small composite Nano catalysis material device is constructed, and be applied to the real-time degrading monitoring of waste water from dyestuff and process adjustment.Preparation method provided by the invention is easy, mild condition, and the super-small nano material catalytic performance of synthesis is superior, can effective activation oxidant, realize the efficient degradation to dyestuff.In addition, stability is good, is easily assembled, and realizes the real-time monitoring of different colorful wastewater actual sample degradation processes using the device for the electro-conductive glass building for loading above-mentioned nanocatalyst.This realizes that the assessment and process control in During Industrial Wastewater Treatment Process are of great significance, has a good application prospect in terms of handling industrial dye waste water for developing on-line monitoring equipment.
Description
Technical field
The present invention relates to a kind of preparation for loading super-small composite Nano catalysis material device and its in waste water from dyestuff reality
When degrading monitoring in application.
Background technique
With the rapid development of social economy and the acceleration of process of industrialization, water environmental problems are increasingly sharpened.Wherein, industrial
The discharge of pollutant effluents not only breaks up the balance of aquatic ecosystem, or even directly generates threat to the life and health of the mankind.Cause
This, develops the processing technique of clean and effective, realizes most important to the efficiently removal of poisonous and harmful substance in industrial wastewater.
In view of the above-mentioned problems, in recent years, such as adsorbing, condense, biodegrade, the pollutants such as UF membrane and electrochemical degradation
Treatment process is constantly proposed.Wherein, the environmental type that organic pollutant directly can be converted to carbon dioxide and water is high
Grade oxidation technology (advanced oxidationprocesses, AOP) has received widespread attention.Recently, based on novel oxidized
Agent potassium hydrogen persulfate (peroxymonosulfate, PMS) generates potentiometric titrations (SO4 -) in combination with cobalt oxide
(CoOx) the AOP technique of catalyst achieves certain progress, it is successfully realized quick, the efficient drop to waste water from dyestuff
Solution.However, wherein there are still some critical issues with challenge it is urgently to be resolved, for example, how to further increase waste water from dyestuff
How treatment effeciency realizes powdered nano-catalyst material CoOxRecycling and reusing to avoid secondary pollution etc., therefore
The CoO that the suitable simple mild method of stromal surface development prepares ultra-small grain size and is evenly distributedxNano catalytic material is gone forward side by side
One step is element using above-mentioned substrate, and it is necessary for designing and developing new dye waste water catalytic degradation device.
Unlimited coordination polymer (infinite coordinationpolymers, ICPs) material be by metal ion or
Metal ion cluster and multiple tooth bridge ligand self assembly and form a kind of novel organic-inorganic hybrid nanomaterials, sensing, urging
Change, optics, gas storage, ion exchange, valence tautomerism and pharmaceutical carrier etc. all show huge application prospect.
However, so far, using unlimited coordination polymer as presoma, preparing the efficient of super-small by electrochemistry post-processing
Nano catalytic material, and develop portable device, realize to degradation real-time monitoring and the process optimization of waste water from dyestuff there is not yet
Report.
Summary of the invention
An object of the present invention is to provide a kind of CoO that super-small is prepared using electrochemical polarizationx、CoOx/ GO receives
The method of rice catalyst:
Using electric conductivity ICPs nano material as presoma, doped or undoped graphene oxide (graphene oxide,
GO), after dry, by activation polarization, the CoO of super-small is prepared in situ in ITO conductive glass surfacex、CoOx/ GO nanometers
Catalyst.
On address in following any the method or application, the ICPs is a kind of novel organic coordination polymer nanometer
Particle, including ligand and central metallic ions.
Wherein, the ligand is bix (bis- (imidazoles -1- methyl) benzene of Isosorbide-5-Nitrae -) and 3,5-, bis- uncle with redox active
One of butyl catechol and the similar catechol with coordination ability are a variety of；It preferably, is bix
(bis- (imidazoles -1- methyl) benzene of Isosorbide-5-Nitrae -) and 3,5- ditertiarybutyl catechol with redox active.
Wherein, the central metallic ions are the metal ion, including cobalt ions, copper ion etc. of variable valence；Preferably,
For cobalt ions.
Wherein, the ligand and central metal ion molar ratio are 2:1.
Preferably, the ligand bix (bis- (imidazoles -1- methyl) benzene of Isosorbide-5-Nitrae -) and 3,5-, bis- uncle with redox active
Butyl catechol and central metal ion molar ratio are 1:1:1.
Wherein, the concentration of the ICPs is 1-4mg/mL；It preferably, is 3.33mg/mL.
Wherein, the concentration of the graphene oxide is 3-20mg/mL；It preferably, is 5mg/mL.
Wherein, when the ICPs is with graphene oxide doped, the mass ratio of ICPs and GO are (2:1)-(1:1)；Preferably,
For 7:5.
Wherein, the ITO electro-conductive glass is the ITO electro-conductive glass coated with indium-tin oxide coatings or the conductive painting of other coatings
The glass of layer.
Wherein, the temperature of the drying is 30-70 DEG C；It preferably, is 60 DEG C.
Wherein, the time of the drying is 5-15 minutes；Preferably, it is 10 minutes.
Wherein, the system used in the polarization process is three-electrode system, reference electrode: Ag/AgCl；To electrode: platinum
Silk；Working electrode: the ITO electro-conductive glass of drop coating ICPs/GO.
Wherein, the polarized electrolyte is 0.10mol L-1Klorvess Liquid (VEthyl alcohol: VWater=1:9, i.e. potassium chloride are molten
The ethyl alcohol and water for being 1:9 containing volume ratio in liquid), polarization potential is -1.1V, polarization time 1000s.
The present invention also provides the CoO of super-small prepared by the above methodx、CoOx/ GO nanocatalyst.
Wherein, the size of the nanocatalyst is 1.21 ± 0.28nm.
Another object of the present invention is to provide a kind of preparation method for loading super-small nano catalytic material device, with negative
Carry above-mentioned super-small CoOx、CoOxThe ITO electro-conductive glass of the nanocatalyst of/GO is element, prepares catalysis material device.
Wherein, the catalysis material device is by one piece of load C oOx(block is the bottom of as the ito glass of/GO nanocatalyst
Seat), two pieces of difference load C oOxThe ito glass (this two pieces sides endways as two) of/GO nanocatalyst and two panels is not
Load nanocatalyst ito glass (this two pieces sides endways as two because without supported catalytic materials,
Be it is transparent, just optical path is allowed to pass through, so as to ultraviolet detection) be spliced.
Wherein, the catalysis material device is by one piece of load C oOxThe ito glass (block is as pedestal) of nanocatalyst,
Two pieces of difference load C oOxThe ito glass (this two pieces sides endways as two) and the unsupported nanometer of two panels of nanocatalyst
Catalyst ito glass (this two pieces sides endways as two because without supported catalytic materials, be it is transparent,
Just optical path is allowed to pass through, so as to ultraviolet detection) it is spliced.
In a specific embodiment, the catalysis material device is loaded by one piece (1.0cm × 1.0cm × 0.1cm)
0.10mg CoOxThe ito glass of/GO, two pieces (1.2cm × 4.5cm × 0.1cm) load 0.20mg CoO respectivelyxThe ITO glass of/GO
The ito glass of glass and two panels (1.0cm × 4.5cm × 0.1cm) unsupported catalyst is spliced (such as ultraviolet sample detection pond
(pictorial diagram is shown in Fig. 1 C)), in conjunction with ultraviolet-visible spectrophotometer to two kinds of dyeing waste waters and a kind of cosmetics Wastewater Dyes
Degradation carries out real-time monitoring and process optimization.
The present invention also provides a kind of load super-small nano catalytic material devices.
Wherein, the nano catalytic material device is preferably ultraviolet sample detection pond.
Wherein, the catalysis material device is by one piece of load C oOx(block is conduct to the ito glass of/GO nanocatalyst
Pedestal), two pieces of difference load C oOxThe ito glass (this two pieces sides endways as two) of/GO nanocatalyst and two
The unsupported catalyst of piece ito glass (this two pieces sides endways as two because without supported catalytic materials,
Be it is transparent, just optical path is allowed to pass through, so as to ultraviolet detection) be spliced.
Wherein, the catalysis material device is by one piece of load C oOxThe ito glass (block is as pedestal) of nanocatalyst,
Two pieces of difference load C oOxThe ito glass (this two pieces sides endways as two) and the unsupported nanometer of two panels of nanocatalyst
Catalyst ito glass (this two pieces sides endways as two because without supported catalytic materials, be it is transparent,
Just optical path is allowed to pass through, so as to ultraviolet detection) it is spliced.
The present invention also provides the CoO of the super-smallx、CoOx/ GO nanocatalyst or load super-small nanometer are urged
Change application of the material devices in dye wastewater degradation.
The invention also provides the CoO using the super-smallx、CoOx/ GO nano-catalyst material or the extra small ruler of load
The method that very little nano catalytic material device carries out real-time monitoring and process optimization to dye wastewater degradation: in nano catalytic material device
Colored dyes reality sample, PMS are added in part, the variation by measuring solution absorbance calculates its degradation rate, real time information is obtained, and
Oxidant concentration or the adjusting regulation of other catalytic conditions are carried out according to above- mentioned information.
It is used as model dyestuff using methylene blue (methylene blue, MB), optimizes the CoO in degradation processx/ GO is used
Amount, PMS dosage, pH, temperature, using the time as abscissa in conjunction with ultraviolet-visible optical detection system, palliating degradation degree is ordinate,
The optimum condition of screening degradation MB, realizes the efficient degradation to organic dyestuff, that is, realizes to a variety of in colorful wastewater degradation process
The related application of the collection of multidate information and degradation process optimization.
The methylene blue solution concentration is 20mg mL-1, volume 2mL.
The CoOx/ GO dosage is 0.1-0.8mg；It preferably, is 0.5mg.
The PMS concentration is 0.25-2.0mmol L-1；It preferably, is 0.5mmol L-1。
The pH is 3-11；It preferably, is 7.
The temperature is 30-75 DEG C；It preferably, is 60 DEG C.
The wave-length coverage of the ultraviolet-visible optical detection system measurement is 350-750nm.
The palliating degradation degree uses Ct/C0It calculates, according to Lambert-Beer's law, A=ε bc, wherein A is absorbance (no list
Position), ε is that molar absorption coefficient (is fixed value, unit mol for a certain substance-1Cm L), b is absorber thickness
(the usually width of ultraviolet ware, fixed value, unit cm-1), c is that (unit is mol L to solution concentration-1).Therefore, A and c at
Direct ratio, Ct/C0A can be usedt/A0Instead of A0Initial absorbance value at specially methylene blue solution 664nm；AtIt then indicates a certain
When inscribe, absorbance value of the methylene blue solution at 664nm.
Compared with the preparation of Conventional nano catalysis material and its degradation in real wastewater samples are applied, the present invention has
The advantage of following protrusions:
(1) synthesis of nanocatalyst post-processes realization by electrochemistry at room temperature in the present invention, does not need to add
Add the dispersion aids such as surfactant, the removal of presoma is relatively clean, and method is simple and reliable, to the unlimited polycomplexation of conductivity type
The synthesis for closing object has certain universality, and actual application prospect is superior；
(2) present invention passes through central metallic ions and ligand using unlimited coordination polymer nano material as presoma
Coordination limits the growth of nanoparticle, the distance between strict control nanoparticle is (in this hair in last handling process
In bright unlimited coordination polymer, there are a metal ion species --- cobalt acetate, two kinds of organic ligands --- the bix (bis- (imidazoles-of Isosorbide-5-Nitrae-
1- methyl) benzene) and 3,5- ditertiarybutyl catechol, the presence meeting of the two ligands is so that there are distances between Co, rear
During face utilizes activation polarization, there is ethyl alcohol (V in electrolyteEthyl alcohol: VWater=1:9), according to " the phase patibhaga-nimitta in organic chemistry
It is molten " principle, two kinds of organic ligands, which can dissolve, to be fallen in electrolyte, metal Co is left behind, due to being infinitely to be coordinated before Co
Among polymer architecture, so Co just has distance each other after two kinds of organic ligands fall off), synthesized extra small ruler
Very little CoOxNanoparticle has preferable dispersibility and narrow size distribution, and catalytic performance is higher；
(3) further doped graphene in the present invention, effectively improves CoOxThe catalytic performance of/GO nano-complex and its
Stability on ito glass surface, the nano catalytic material have outstanding reusable property；
(4) with above-mentioned load C oOxThe ito glass of/GO catalyst is the sample cell of element building, in conjunction with ultraviolet-visible point
Light photometer can realize the optimization of degradation process according to degradation efficiency, it can be achieved that monitoring to real sample degradation process, for
Realize that assessment and process control in During Industrial Wastewater Treatment Process are of great significance.
Detailed description of the invention
Fig. 1 is CoOx(A)、CoOxThe preparation of/GO nano-catalyst material (B) and utilization load C oOxThe sample of/GO catalyst
The schematic diagram (C) of the product pond realization real-time degrading monitoring of waste water from dyestuff.
Fig. 2 is the CoO after the scanning electron microscope image (SEM) (A) of Co ICPs presoma, activation polarizationxNanometer
The transmission electron microscope image (TEM) (B) of particle, Co ICP and CoOxElectrochemistry cyclic voltammogram (C).
Fig. 3 is CoOxThe transmission electron microscope image (TEM) of/GO.
Fig. 4 CoOx、GO、CoOxComparison of/GO the nano-catalyst material in PMS reaction system to the degradation efficiency of MB.
Fig. 5 CoOx、GO、CoOxThe electrochemistry cyclic voltammogram (A) and infrared figure (B) of/GO nano-catalyst material.
Fig. 6 is CoO in the case of different Co ICPs and GO mass ratiox/ GO nano-catalyst material is to colored dyes waste water
Degradation situation.
Fig. 7 is to use CoOx/ GO nano-catalyst material degrades colorful wastewater in the process to reaction condition catalyst amount
(A), the optimization of oxidizer (B), pH (C), temperature (D).
Fig. 8 is CoOxWith CoOx/ GO's recycles performance.
Fig. 9 is using load 0.5mg CoOxDegrade MB (A), dyeing waste water -1 in the portable example pond of/GO catalyst
(B), the ultraviolet spectrogram of dyeing waste water -2 (C), cosmetics waste water (D), photo are palliating degradation degree (the PMS concentration of corresponding time
It is 0.5mmol L-1)。
Figure 10 is to use load 0.5mg CoO after adjusting PMS content according to TOC contentxThe portable style of/GO catalyst
Product pond is degraded dyeing waste water -1 (A), (PMS concentration is successively to the ultraviolet spectrogram of dyeing waste water -2 (B), cosmetics waste water (C)
For 9.3mmol L-1、3.5mmol L-1、4.2mmol L-1)。
Specific embodiment
The present invention is further elaborated combined with specific embodiments below, but the present invention is not limited to following embodiments.Institute
State method is conventional method unless otherwise instructed.The raw material can be gotten from open business unless otherwise instructed.
Co-ICP presoma as used in the following examples, i.e. { Co (3,5-dbsq) (3,5-dbcat) (bix) } ICPs,
It is (Angew.Chem.Int.Ed.2009,48,2325-2329) that the method for reference literature report is prepared, it is specific to prepare
Method is as follows:.
It will after 18h (temperature 70 C) by being heated to reflux in 3.16g imidazoles and 0.78g xylene dichloride addition 50mL methanol
Product rotates (40 DEG C of temperature), and the product after revolving is added in wet chemical (6.13g, 100mL), solution is put into ice
Solution is filtered after freezing 12h in case, drying (40 DEG C) obtains product bix.
Claim prepared bix (12.1mg, 0.05mmol), 3,5- ditertiarybutyl catechols (11.0mg, 0.05mmol) are molten
In 1mL ethyl alcohol, oscillation is made it completely dissolved, and four hydrations cobalt acetate (12.0mg, 0.05mmol) is then added, what is be stirred continuously
5mL water is added dropwise in the process, the synthesis of { Co (3,5-dbsq) (3,5-dbcat) (bix) } ICPs particle finishes.According to SEM table
It levies (see Fig. 2A), it can be seen that ICPs particle is the nano spherical particle being evenly distributed, and average grain diameter is 56.19 ± 6.73nm, interior
Embedding picture shows that pewter is presented in the material of synthesis.
CoO as used in the following examplesx、CoOx/ GO nano-catalyst material is according to following electrochemistry post processing mode
It realizes:
By { Co (3,5-dbsq) (3,5-dbcat) (bix) } ICPs solution drop coating to ITO conductive glass surface, 60 DEG C of bakings
It is dry.Using the ITO electro-conductive glass as working electrode, Ag/AgCl (saturation potassium chloride) is reference electrode, platinum filament is to carry out electricity to electrode
Chemical polarization process, electrolyte are 0.10mol L-1Klorvess Liquid (VEthyl alcohol: VWater=1:9), the constant polarization potential applied
For -1.1V, polarization time 1000s.Polarization process whole process carries out at room temperature, and naturally dry after polarization can be obtained
The CoO being supported on ITO electro-conductive glassxNanoparticle.SEM chart is bright (see Fig. 2 B), and activation polarization acts on extra small
The average grain diameter of the CoOx nano particle of size is 1.42 ± 0.34nm.Before the polarization of cyclic voltammetry scan-type electrochemical
Substance afterwards observes that its electro-chemical activity changes, and the oxidation of a pair of Co (III)/Co (II) occurs also in 0.222V
Parent peak (Fig. 2 C), it was demonstrated that successfully synthesize CoOx。
GO is (J.Am.Chem.Soc.1958,80,1339-1339) being prepared according to method reported in the literature.Tool
Body are as follows: graphite powder (0.5g), sodium nitrate (0.5g), mixed liquor stirring in ice-water bath (being lower than 4 DEG C) of the concentrated sulfuric acid (23mL)
5min.3g potassium permanganate is then slowly added in 10min, after gained mixed liquor stirs 2h at 35 DEG C, at room temperature dropwise
40mL water is added, mixed liquor is then stirred into 30min at 90 DEG C.Finally, the hydrogen peroxide that 100mL water and 3mL 30% is added is whole
It only reacts, obtains the mixed liquor of glassy yellow.Then, gained mixed liquor is successively used into 400mL dilute hydrochloric acid (1mol L-1) and 400mL
Water filtration washing.Final product ultrasonic disperse 3h in ultrapure water obtains the graphene oxide suspension (5mgmL of brown-1)。
When adulterating graphene oxide into ICPs, the mass ratio of control ICPs and GO is that 7:5 is made into mixing suspension, and ultrasonic disperse is about
30min is stirred after 15min can be obtained CoOx/GO。
By CoOxTo ITO conductive glass surface, 60 DEG C dry/GO solution drop coating.Using the ITO electro-conductive glass as work electricity
Pole, Ag/AgCl (saturation potassium chloride) is reference electrode, platinum filament is to carry out activation polarization process to electrode, and electrolyte is
0.10mol L-1Klorvess Liquid (VEthyl alcohol: VWater=1:9), the constant polarization potential applied is -1.1V, and the polarization time is
1000s.Polarization process whole process carries out at room temperature, and naturally dry after polarization can be obtained and be supported on ITO electro-conductive glass
CoOx/ GO nanoparticle.
From the figure 3, it may be seen that obtaining the CoO of size distribution ranges smaller (1.21 ± 0.28nm) under the conditions of identical polarizationxMaterial
It is evenly dispersed to be grown on GO lamella.Since the surface functional group of GO lamella and its defect sites abundant are capable of function as nanometer
The growth site of particle, therefore nanoparticle is able to maintain fully dispersed, CoOxGrowth in situ on GO can obtain smaller
Size distribution, and avoid aggregation to a greater extent.
Embodiment 1, CoOx、CoOxComparison of/GO the nano-catalyst material in PMS reaction system to the degradation efficiency of MB
It selects MB as the model dyestuff in catalytic oxidation process, selects PMS as oxidant, assess the catalyst of preparation
Activate the ability of PMS degradation of dye.As shown in figure 4, CoO ought be added individuallyx、GO、CoOxWhen/GO, MB is de- in 6.7 minutes
Colour efficiency is almost the same, and without substantially changeing, shows that MB will not decolourize because of the suction-operated of catalyst.Continue to exist to dyestuff
In the case where PMS individualism and CoOxOr CoOxIn the case that/GO activates PMS, degradation effect is compared.Such as Fig. 4
It is shown, when PMS is used alone, after 6.7 minutes, the C of MB solutiont/C0It is only down to 81.12%, is shown without activation of catalyst
PMS is very limited to the degradation of MB.When use CoOxWhen catalyst and PMS are acted on simultaneously, the degradation efficiency of MB reaches after 6.7 minutes
To 92.33%, illustrate the super-small CoO of preparation early periodxNano material can activate PMS, be a kind of more efficient nanometer
Catalysis material.When use CoOxWhen/GO composite Nano catalysis material and PMS are acted on simultaneously, in 6.7 minutes, MB degradation (C completelyt/
C0=0%), the above result of study shows after being doped with graphene, CoOxThe catalytic performance of nano material has great promotion.
(reaction condition: CMB=20mg L-1, VMB=2mL, CoOx=0.3mg, GO=0.2mg, CoOx/ GO=0.5mg, PMS=
0.5mmol L-1, pH=7.0, T=60 DEG C)
For definitely CoOxThe catalytic performance of/GO nanocomposite brilliance, the present invention pass through cyclic voltammetry scan
And infrared spectroscopy is to CoOx、CoOx/ GO nano-catalyst material is characterized.As shown in Figure 5A, compared to CoOx, CoOxThe peak /GO
Electric current is remarkably reinforced, and illustrates CoOx/ GO has higher electron-transport efficiency.In addition, being observed that from FI-IR characterization
(Fig. 5 B), works as CoOxWhen/GO formation, stretching vibration absworption peak of the hydrone on GO is from 3386cm-1It is displaced to 3398cm-1, and
And the C-OH on GO is in 1055cm-1The bending vibration at place is weakened, and shows that the surface of GO is likely to form hydroxy cobalt oxide (Co-
OH), the generation of free radical is particularly critical in this activation heterogeneous for PMS.The above result of study shows the doping of graphene,
On the one hand it effectively accelerates the electron transfer rate in degradation process as electron transmission carrier, on the other hand, graphene table
The formation of face hydroxy cobalt oxide (Co-OH) is for CoOxHeterocatalysis PMS generates SO4 -Play facilitation.
In order to enable CoOx/ GO nanocomposite has a highest degradation speed and degree to colored dyes, the present invention into
Series of parameters in one-step optimization experimentation.The final mass ratio for determining Co ICPs and GO is 7:5 (Fig. 6), catalyst
CoOxThe dosage of/GO nanocomposite is 0.5mg, and the concentration of oxidant PMS is 0.5mmol L-1, the initial pH value of solution is
7.0, reaction constant temperature under the conditions of 60 DEG C carries out (Fig. 7).
Embodiment 2, load C oOxWith CoOxThe repeat performance of the reaction tank of/GO catalyst
With load C oOxWith CoOxThe ITO electro-conductive glass of/GO nanocatalyst is element, prepares catalytic device.By one piece
(1.0cm × 1.0cm × 0.1cm) loads 0.10mg CoOx, two pieces (1.2cm × 4.5cm × 0.1cm) load 0.10mg respectively
CoOxUltraviolet sample detection pond is spliced into the ito glass of two panels (1.0cm × 4.5cm × 0.1cm) unsupported catalyst.By one
Block (1.0cm × 1.0cm × 0.1cm) loads 0.10mg CoOx/ GO, two pieces (1.2cm × 4.5cm × 0.1cm) load respectively
0.20mg CoOxThe ito glass of/GO and two panels (1.0cm × 4.5cm × 0.1cm) unsupported catalyst is spliced into ultraviolet sample
Detection cell.Due to CoOx/ GO can activate PMS for organic dyestuff degradation, therefore study its whether can reuse for
The decoloration of colorful wastewater is particularly important.CoO is assessed respectively with 5 recycling processesxAnd CoOxThe repeat performance of/GO,
As shown in Figure 8, for load C oOxSample cell, by 5 times circulation after, the degradation efficiency of MB is reduced to
74.7%, and for load C oOxThe sample cell of/GO catalyst, the degradation efficiency of MB still can achieve 100%, show graphene
Doping, effectively promoted CoOxIts mechanical strength in ito glass substrate is increased while nano particle catalysis performance.
CoO is loadedxThe reaction tank of/GO nano catalytic material has good reusable performance.(reaction condition: CMB=20mg
L-1, VMB=2mL, CoOx=0.3mg, GO=0.2mg, CoOx/ GO=0.5mg, PMS=0.5mmol L-1, pH=7.0, T=60
℃)
Embodiment 3 degrades to actual industrial colorful wastewater
In the above-mentioned catalyzing oxidizing degrading process study using MB as model dyestuff, CoOx/ GO composite catalyst is shown
Excellent catalytic activity utilizes ito glass supported catalyst CoOxThe portable example pond of/GO building has good repeatable
Utility.Using the above-mentioned sample cell of building, further carry out for colorful wastewater degradation real-time monitoring and process optimization
Research.By 2.0mL 20mg L-1Supported catalyst CoO is added in MBxThe sample cell of/GO, is then added PMS thereto, 60
Under the conditions of DEG C isothermal reaction, at interval of the UV-vis spectrogram of 0.5min recording solution, as shown in Figure 9 A, above-mentioned reaction tank is available
In the real-time monitoring of MB degradation.Similarly, under the same conditions, above-mentioned reaction tank can be used for monitoring actual industrial colorful wastewater
The degradation of (waste water from dyestuff -1, waste water from dyestuff -2, cosmetics waste water).As shown in Fig. 9 B, C, D, two kinds of dyeing waste waters and cosmetics
Waste water decolourizes as time went on and significantly, the major absorbance peak A of dyeing waste water -1614, the major absorbance peak of dyeing waste water -2
A546, the major absorbance peak A of cosmetics waste water418It significantly reduces, which can be light by spectrum change
Realize on-line monitoring.However, since actual industrial waste component is complex, total organic carbon (total organic carbon,
TOC) content is respectively 725.5mg L-1, 278.1mg L-1With 324.5mg L-1(table 1), much higher than model dyestuff MB solution
TOC content (32.55mg L-1), therefore, wherein the degree of colored dyes degradation is by the insufficient influence of oxidant.Further,
According to the TOC of actual sample, the present invention increases separately the concentration of oxidant to 9.3mmol L-1, 3.5mmol L-1,
4.2mmol L-1Afterwards, as a result as shown in table 1, the TOC removal rate of three samples is up to 70-80%, and can be in 2min
It degrades (Figure 10).This shows to can get the real time information in colorful wastewater degradation process, root using sample cell constructed by the present invention
According to the dosage of above- mentioned information adjustment oxidant, the efficient oxidation degradation to the organic dye waste water of high TOC content can be realized easily.
Importantly, above-mentioned load C oOxThe ito glass of/GO nanocatalyst can construct according to actual needs adapts to detector
Sample cell, facilitate a variety of multidate informations during obtaining coloured organic wastewater degraded, to reasonably be adjusted and be optimized
Degradation process.
Table 1
To sum up, the present invention provides utilize activation polarization to handle ICPs presoma, one-step synthesis super-small at room temperature
The method of metal oxide nanoparticles, and be working electrode using the ITO electro-conductive glass for being modified with ICPs/GO, polarization obtains
Load has CoOxThe ITO electro-conductive glass of/GO nano material is that element is assembled into catalytic device using the electro-conductive glass, is used
Real-time monitoring and process adjustment during colored dyes wastewater degradation.This realizes industry for developing on-line monitoring equipment
Assessment and process control in wastewater treatment process are of great significance, and have certain industrial applications prospect.
Protection content of the invention is not limited to above embodiments.Without departing from the spirit and scope of the invention, originally
Field technical staff it is conceivable that variation and advantage be all included in the present invention, and with appended claims be protect
Protect range.
Claims (10)
1. a kind of CoO of super-smallx、CoOxThe preparation method of/GO nanocatalyst, which is characterized in that received with conductivity type ICPs
Rice material is as presoma, doped or undoped graphene oxide GO, after dry, by activation polarization, in ITO electro-conductive glass
Surface in situ prepares the nanocatalyst.
2. preparation method as described in claim 1, which is characterized in that the ICPs is a kind of organic coordination polymer nanoparticle
Son, including ligand and central metallic ions.
3. preparation method as claimed in claim 2, which is characterized in that the ligand is that (Isosorbide-5-Nitrae-is bis- (imidazoles -1- methyl) by bix
Benzene) and the 3,5- ditertiarybutyl catechol with redox active and the catechol with coordination ability in one
Kind is a variety of；The central metallic ions are one of metal ion, including cobalt ions, copper ion of variable valence or two
Kind；The ligand and central metal ion molar ratio are 2:1.
4. preparation method as described in claim 1, which is characterized in that the concentration of the ICPs is 1-4mg/mL；The oxidation
The concentration of graphene is 3-20mg/mL；When the ICPs is with graphene oxide doped, the mass ratio of ICPs and GO are (2:1)-
(1:1)；The temperature of the drying is 30-70 DEG C.
5. preparation method as described in claim 1, which is characterized in that the system used in the polarization process is three electrode bodies
System, reference electrode: Ag/AgCl；To electrode: platinum filament；Working electrode: the ITO electro-conductive glass of drop coating ICPs/GO；Wherein, the pole
The electrolyte of change is 0.10mol L-1Klorvess Liquid, polarization potential be -1.1V, polarization time 1000s.
6. such as the CoO for the super-small that any one the method for claim 1-5 is preparedx、CoOx/ GO nanocatalyst.
7. a kind of preparation method for loading super-small nano catalytic material device, which is characterized in that with load such as claim 6
The super-small CoOxOr CoOxThe ITO electro-conductive glass of the nanocatalyst of/GO is element, prepares the catalysis material device
Part.
8. the method for claim 7, which is characterized in that the catalysis material device is by one piece of load C oOx/ GO nanometers is urged
The ito glass of agent, two pieces of difference load C oOxThe ito glass of/GO nanocatalyst and the unsupported nanocatalyst of two panels
Ito glass is spliced；Or the catalysis material device is by one piece of load C oOxThe ito glass of nanocatalyst, two pieces of difference
Load C oOxThe ito glass of the unsupported nanocatalyst of ito glass and two panels of nanocatalyst is spliced.
9. the load super-small nano catalytic material device being prepared such as claim 7 or 8 the methods.
10. the CoO of super-small as claimed in claim 6x、CoOx/ GO nanocatalyst is as claimed in claim 9 negative
Carry application of the super-small nano catalytic material device in dye wastewater degradation.
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