CN103285874B - Inorganic nano composite catalyst with peroxidase property and application of catalyst for performing catalytic decomposition on TMB thereof - Google Patents
Inorganic nano composite catalyst with peroxidase property and application of catalyst for performing catalytic decomposition on TMB thereof Download PDFInfo
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- CN103285874B CN103285874B CN201310233239.9A CN201310233239A CN103285874B CN 103285874 B CN103285874 B CN 103285874B CN 201310233239 A CN201310233239 A CN 201310233239A CN 103285874 B CN103285874 B CN 103285874B
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Abstract
The invention discloses an inorganic nano composite catalyst with peroxidase property. The inorganic nano composite catalyst is characterized in that oxidized graphene and Fe3O4(at)MnO2 nano particles are mixed and are ultrasonically dispersed to obtain a composite nanosheet with the size being 40-70nm, wherein the concentration of the oxidized graphene is 1-4mg.mL<-1>, the concentration of Fe3O4(at)MnO2 is 2-8mg.mL<-1>, and the ratio of the concentration of the oxidized graphene to the concentration of Fe3O4(at)MnO2 is 1:2. The capacity of performing catalytic decomposition on TMB for the obtained composite catalyst is superior to that of the oxidized graphene or the Fe3O4(at)MnO2 nano particles, and the composite catalyst is wide in application range and can be applied to sewage treatment.
Description
Technical field
The invention belongs to nanometer material science and quasi-enzyme catalytic technical field, a kind of inorganic nano combined catalyzer with peroxidase property specifically, can at normal temperature, weakly acidic pH environment, without the need to catalyzing hydrogen peroxide (H effectively under special external energy (referring to electric current, voltage, ultraviolet irradiation etc.) environment
2o
2) decompose the hydroxy radical qiao producing strong oxidizing property.
Background technology
Along with the fast development of China's industry, environmental pollution especially water pollution problems is day by day serious, and starts the development restricting China's economy and society, becomes one of problem that 21 century people are concerned about the most.In the numerous source of pollution causing water pollutions, the organic contamination source of high toxicity, difficult degradation accounts for larger ratio.At present, the conventional sewage water treatment method caused for organic contamination source comprises physical method, as extraction process, absorption method, ultrasonic degradation and method of enrichment etc.; Chemical process, as Ozonation, electrochemical oxidation process and burning method etc.; Biological method, as Anaerobic biotreatment method, activated sludge method and aerobe membrane processing method etc., but these method facility investments are larger, running expense is high, when using biological method, organic pollutant also likely causes microorganism cannot normal growth, reduces sewage treating efficiency.
Peroxidase can decompose the hydroxy radical qiao producing Strong oxdiative ability by catalyzing hydrogen peroxide, and the strong oxidizing property hydroxy radical qiao produced can oxidation of organic compounds, make organic substance decomposing, therefore peroxidase has been widely used in the fields such as biochemical analysis, biosensor, clinical medicine and environmental chemistry.After the eighties in 20th century, people start peroxidase to be used for sewage disposal, mainly for the treatment of the organism of the phenol in trade effluent, aniline, p-diaminodiphenyl and the high toxicity such as isomer and polynuclear aromatics thereof, difficult degradation.Compared to the catalyzed reaction of routine, Catalyzed Synthesis By Peroxidase reaction has high efficiency, specificity and higher selectivity, and reaction conditions is also gentleer.But peroxidase is the deactivation by the change (as the rising of temperature, the increase of pH value or reduction etc.) of environment easily, under therefore can not being applied to comparatively harsh envrionment conditions, and can by proteases for decomposing; In addition, peroxidase extraction process is complicated, expensive, storage condition is harsh, can not be recovered and recycle.
Summary of the invention
For the problems referred to above, the object of this aspect is to provide a kind of inorganic nano combined catalyzer with hydrogen peroxide enzymatic property, has strong
For achieving the above object, the present invention takes following technical scheme:
There is an inorganic nano combined catalyzer for peroxidase property, by graphene oxide (GO) and Fe
3o
4@MnO
2after nano particle mixing, ultrasonic disperse obtains composite nano plate, is of a size of 40 ~ 70nm.
The concentration of graphene oxide is 1 ~ 4 mgmL
-1, Fe
3o
4@MnO
2concentration be 2 ~ 8 mgmL
-1, and graphene oxide concentration and Fe
3o
4@MnO
2the ratio of concentration is 1: 2.
Present invention process is simple, input cost is low, gained nano-composite catalyst can be applied to sewage treatment area as peroxidase, just effectively the hydroxy radical qiao producing Strong oxdiative ability can be decomposed by catalyzing hydrogen peroxide without the need to external energy (as electric current, voltage, ultraviolet irradiation etc.) at normal temperature, decomposing the strong oxidizing property hydroxy radical qiao produced can oxygenolysis 3,3', 5,5'-tetramethyl benzidine (TMB), make the color of solution be converted into dusty blue by colourless, realize the detection analysis to content of hydrogen peroxide in environment.This inorganic nano combined catalyst energy force rate is used alone graphene oxide or Fe
3o
4@MnO
2nano particle is stronger.
This composite catalyst is inorganic nano composite material, does not belong to enzyme, does not have strict requirement to the temperature of environment for use and pH value, and environmental resistance ability is strong, is easy to store and recyclablely recycles, the material oxidation Graphene, the Fe that adopt
3o
4and MnO
2material all has biocompatibility, can not work the mischief to environment and pollute after using.
accompanying drawing explanation
Fig. 1 is Fe in the embodiment of the present invention 1
3o
4@MnO
2the TEM electromicroscopic photograph of nanometer sheet catalyst fines.As seen from Figure 1, the composite catalyst prepared is the sheet structure of Nano grade, is of a size of 40 ~ 70nm, and MnO
2be distributed in the edge section of nanometer sheet.
Fig. 2 is Fe in the embodiment of the present invention 1
3o
4@MnO
2the XRD figure spectrum of nanometer sheet catalyst fines.As seen from Figure 2, there is significant Fe in XRD figure spectrum
3o
4face-centred cubic structure crystalline diffraction cutting edge of a knife or a sword, and there is not significant MnO
2crystal cutting edge of a knife or a sword, only has MnO
2amorphous peak exists, and describes MnO
2exist with amorphous state in composite particles, and Fe
3o
4existence be then face-centred cubic structure form, graphene oxide and Fe are described
3o
4@MnO
2nano particle is not simple physical mixed after ultrasonic, defines new compound substance.
Fig. 3 is GO-Fe in the embodiment of the present invention 1
3o
4@MnO
2nano-composite catalyst (a), Fe
3o
4@MnO
2ultraviolet absorptivity curve after nanometer sheet catalyzer (b), GO (c) and PBS damping fluid (d) background correction.As seen from Figure 3, GO-Fe is added
3o
4@MnO
2after nano-composite catalyst, the ultraviolet light absorption angle value of solution is maximum, illustrates that its colour-change is the darkest, stronger to the catalytic activity of superoxide, thus GO-Fe is described
3o
4@MnO
2nano-composite catalyst has extraordinary peroxidase property, and this compound action has significant lifting to its catalytic effect in addition, and catalytic effect is better than alone graphene oxide or Fe
3o
4@MnO
2nano particle.
Fig. 4 is GO-Fe in the embodiment of the present invention 1
3o
4@MnO
2nano-composite catalyst (1), Fe
3o
4@MnO
2nanometer sheet catalyzer (2), GO(3) and PBS damping fluid (4) catalysis TMB color developing effect comparison diagram.As seen from Figure 4, PBS damping fluid is colourless solution, adds GO-Fe
3o
4@MnO
2after nano-composite catalyst, the colour-change of solution is the darkest, and GO-Fe is described
3o
4@MnO
2nano combined have extraordinary peroxidase property.
Embodiment
Below in conjunction with accompanying drawing and embodiment, the present invention is described in detail.
The preparation (Hummers S, Offeman R, J. Am. Chem. Soc., 1958,80 (6), 1339.) of graphene oxide: by 1 g natural graphite, 1 g NaNO
3be blended in ice-water bath with the 46 mL vitriol oils (98%) and react 4 ~ 5 h.Then by 6 g KMnO
4join in mixture solution and temperature risen to 35 DEG C simultaneously and keep temperature of reaction, after 2 ~ 3 h are carried out in reaction, add 90 ~ 95 mL H
2temperature is also risen to 98 DEG C by O, adds 200 mL warm water, the H of 20 mL 30% after reaction carries out two hours
2o
2, and at room temperature continue reaction 1 ~ 2 h.Stirring will be remained in whole reaction process.The product for preparing is filtered, after use distilled water wash in the baking oven of 60 DEG C dry 24 ~ 48 h, obtain oxide yellow Graphene solid.
Fe
3o
4@MnO
2the preparation (Z. Zhao, J. Liu, F. Cui, H. Feng and L. Zhang, J. Mater. Chem., 2012,22,9052.) of composite nano materials:
The beaker filling 100 mL ultrapure waters is placed in the water-bath of 90 DEG C, logical N
2discharge the O in water
2, in solution, add the FeSO of 2.5 mmol
47H
2add the NaOH of 1 mL 5.0 M after O and 1 g polyvinylpyrrolidone (K-30) react 1 ~ 2 hour, solution turns green immediately.After 5 ~ 10 minutes, dropwise add 2.5 mmol KMnO
4, generate dark brown deposit.React after 10 ~ 14 hours, by pelleting centrifugation, washing, dry at being placed in 50 DEG C.
Embodiment 1
Graphene oxide is ground broken after, take 0.1 g and join ultrasonic 1 ~ 2 h in the PBS damping fluid of 100 mL, obtain homogeneous graphene oxide solution; Get 0.2 gFe
3o
4@MnO
2composite Nano is scattered in 100 mL graphene oxide solution, ultrasonic 10min, and dispersion obtains composite nano plate.
The peroxidase activity test of inorganic nano combined particle
1) at room temperature, by GO-Fe
3o
4@MnO
2after inorganic composite nano particle ultrasonic disperse, get 20 these solution of μ L, join in 1.8 mL PBS damping fluids, measure its absorbancy within the scope of 500 ~ 700 nm as a setting.Add 100 μ L nitrite ion A liquid and 200 μ L nitrite ion B liquid in upper solution successively, react and after 5 ~ 6 minutes, to measure its absorbing state within the scope of 500 ~ 700 nm.
2) at room temperature, by Fe
3o
4@MnO
2after inorganic composite nano particle ultrasonic disperse, get 20 these solution of μ L, join in 1.8 mL PBS damping fluids, measure its absorbancy within the scope of 500 ~ 700 nm as a setting.Add 100 μ L nitrite ion A liquid and 200 μ L nitrite ion B liquid in upper solution successively, react and after 5 ~ 6 minutes, to measure its absorbing state within the scope of 500 ~ 700 nm.
3) at room temperature, after GO nanometer sheet ultrasonic disperse, get 20 these solution of μ L, join in 1.8 mL PBS damping fluids, measure its absorbancy within the scope of 500 ~ 700 nm as a setting.Add 100 μ L nitrite ion A liquid and 200 μ L nitrite ion B liquid in upper solution successively, react and after 5 ~ 6 minutes, to measure its absorbing state within the scope of 500 ~ 700 nm.
4) at room temperature, get 2 mL PBS damping fluids, measure its absorbancy within the scope of 500 ~ 700 nm as a setting.Add 100 μ L nitrite ion A liquid and 200 μ L nitrite ion B liquid in above-mentioned solution successively, react and after 5 ~ 6 minutes, to measure its absorbing state within the scope of 500 ~ 700 nm.
Result illustrates GO-Fe
3o
4@MnO
2nano combined have extraordinary peroxidase property, and catalytic effect is better than any one component alone.
Embodiment 2
Graphene oxide is ground broken after, take 0.4 g and join ultrasonic 1 ~ 2 h in the PBS damping fluid of 100 mL, obtain homogeneous graphene oxide solution; Get 0.8gFe
3o
4@MnO
2composite Nano is scattered in 100 mL graphene oxide solution, ultrasonic 10min, and dispersion obtains composite nano plate, and the length of side is 40 ~ 70nm, can effective catalysis TMB, and catalytic activity is better than graphene oxide or Fe
3o
4@MnO
2nano particle.
Embodiment 3
Graphene oxide is ground broken after, take 0.3g and join ultrasonic 1 ~ 2 h in the PBS damping fluid of 100 mL, obtain homogeneous graphene oxide solution; Get 0.6gFe
3o
4@MnO
2composite Nano is scattered in 100 mL graphene oxide solution, ultrasonic 10min, and dispersion obtains composite nano plate, and the length of side is 40 ~ 70nm, can effective catalysis TMB, and catalytic activity is better than graphene oxide or Fe
3o
4@MnO
2nano particle.
Embodiment 4
Graphene oxide is ground broken after, take 0.2g and join ultrasonic 1 ~ 2 h in the PBS damping fluid of 100 mL, obtain homogeneous graphene oxide solution; Get 0.4gFe
3o
4@MnO
2composite Nano is scattered in 100 mL graphene oxide solution, ultrasonic 10min, and dispersion obtains composite nano plate, and the length of side is 40 ~ 70nm, can effective catalysis TMB, and catalytic activity is better than graphene oxide or Fe
3o
4@MnO
2nano particle.
Claims (2)
1. there is an inorganic nano combined catalyzer for peroxidase property, it is characterized in that by graphene oxide and Fe
3o
4@MnO
2nano particle is dissolved in PBS damping fluid, mixes, obtains composite nano plate through ultrasonic disperse, be of a size of 40 ~ 70nm; The concentration of graphene oxide is 1 ~ 4mgmL
-1, Fe
3o
4@MnO
2the concentration of nano particle is 2 ~ 8mgmL
-1, and graphene oxide concentration and Fe
3o
4@MnO
2the ratio of concentrations of nanoparticles is 1: 2;
Wherein Fe
3o
4@MnO
2the preparation method of nano particle is as follows:
The beaker filling 100mL ultrapure water is placed in the water-bath of 90 DEG C, logical N
2discharge the O in water
2, in solution, add the FeSO of 2.5mmol
47H
2the reaction of O and 1g polyvinylpyrrolidone adds the NaOH of 1mL 5.0M after 1 ~ 2 hour, solution turns green immediately, after 5 ~ 10 minutes, dropwise adds 2.5mmol KMnO
4, generate dark brown deposit, react after 10 ~ 14 hours, by pelleting centrifugation, washing, dry at being placed in 50 DEG C.
2. claim 1 gained has the application of the inorganic nano combined catalyst decomposition TMB of peroxidase property.
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| CN105388145A (en) * | 2015-10-16 | 2016-03-09 | 上海纳米技术及应用国家工程研究中心有限公司 | Method for catalyzing TMB and ABTS with nanocrystalline metal oxides serving as oxidation mimic enzyme |
| CN106093272B (en) * | 2016-06-01 | 2018-08-07 | 西安交通大学 | A kind of method of manganese dioxide nano-plates simulation oxide enzyme detection reproducibility biomolecule |
| CN106927418A (en) * | 2017-03-29 | 2017-07-07 | 广东工业大学 | A kind of micro-nano engine and preparation method thereof |
| CN107913667B (en) * | 2017-10-25 | 2020-10-13 | 浙江工商大学 | Magnetic graphene/ferroferric oxide/manganese dioxide nanocomposite and preparation and application thereof |
| CN107913668B (en) * | 2017-10-25 | 2020-10-13 | 浙江工商大学 | Nano composite material with adsorption and catalytic degradation functions and preparation method and application thereof |
| CN108329470B (en) * | 2018-02-12 | 2020-10-20 | 吉林大学 | Method for preparing inorganic nano particles in conductive polymer nanotube and application of inorganic nano particles in peroxidase-like enzyme catalysis |
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