CN103285874A - 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 PDF

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CN103285874A
CN103285874A CN2013102332399A CN201310233239A CN103285874A CN 103285874 A CN103285874 A CN 103285874A CN 2013102332399 A CN2013102332399 A CN 2013102332399A CN 201310233239 A CN201310233239 A CN 201310233239A CN 103285874 A CN103285874 A CN 103285874A
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catalyst
graphene oxide
nano
concentration
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CN103285874B (en
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杜向前
穆立文
张岗
巴换粉
张立刚
徐晓明
乔风笙
吴显斌
徐枫
刘维佳
沈建锋
李明波
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CHINA NUCLEAR HUAWEI ENGINEERING DESIGN AND RESEARCH Co.,Ltd.
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Jiangsu China Nuclear Industry Huawei Engineering Design And Research Co Ltd
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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

A kind of application with inorganic nano combined catalyst and catalytic decomposition TMB thereof of peroxide enzymatic property
Technical field
The invention belongs to nanometer material science and quasi-enzyme catalytic technical field, a kind of inorganic nano combined catalyst with peroxide enzymatic property specifically, can be at normal temperature, nearly neutral environment, need not under special external energy (referring to electric current, voltage, the ultraviolet irradiation etc.) environment catalyzing hydrogen peroxide (H effectively 2O 2) decompose to produce the hydroxy radical of strong oxidizing property.
Background technology
Along with the fast development of China's industry, environmental pollution especially water pollution problems is serious day by day, and begins to restrict the development of China's economy and society, becomes one of problem that the 21 century people are concerned about the most.In causing numerous pollution sources that water pollutes, the organic contamination source of high toxicity, difficult degradation accounts for bigger ratio.At present, the sewage water treatment method that causes at the organic contamination source commonly used comprises physical method, as extraction, absorption method, ultrasonic degradation and concentration method etc.; Chemical method is as ozone oxidation method, electrochemical oxidation process and burning method etc.; Biological method, as anaerobic bio-treated method, activated sludge process and aerobe membrane processing method etc., but these method equipment investments are bigger, the running expense height, when using biological method, organic pollution also might cause the microorganism can't normal growth, reduces sewage treating efficiency.
Peroxide endonuclease capable catalyzing hydrogen peroxide decomposes the hydroxy radical that produces strong oxidability, and the strong oxidizing property hydroxy radical that produces can oxidation of organic compounds, organic matter is decomposed, so peroxidase has been widely used in fields such as biochemical analysis, biology sensor, clinical medicine and Environmental Chemistry.After the eighties in 20th century, people begin peroxidase is used for sewage disposal, mainly for the treatment of the organic matter of the phenol in the industrial wastewater, aniline, benzidine and high toxicities such as isomers and polycyclic aromatic hydrocarbons (PAH) thereof, difficult degradation.Than the catalytic reaction of routine, the peroxide enzymic catalytic reaction has high efficiency, selectivity and higher selective, and reaction condition is also relatively gentleer.But peroxidase is subjected to the change (as the increase of the rising of temperature, pH value or reduce etc.) of environment and the sex change inactivation easily, therefore can not be applied to comparatively under the rigorous environment condition, and can be decomposed by protease; In addition, peroxidase extraction process complexity, expensive, storage condition is harsh, can not be recovered and recycle etc.
Summary of the invention
At the problems referred to above, the purpose of this aspect provides a kind of inorganic nano combined catalyst with hydrogen peroxide enzymatic property, has strong
For achieving the above object, the present invention takes following technical scheme:
A kind of inorganic nano combined catalyst with peroxide enzymatic property is by graphene oxide (GO) and Fe 3O 4@MnO 2Nano particle mixes the ultrasonic dispersion in back and 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.
Technology of the present invention is simple, input cost is low, the gained nano-composite catalyst can be applied to sewage treatment area as peroxidase, normal temperature and need not external energy (as electric current, voltage, ultraviolet irradiation etc.) just effectively catalyzing hydrogen peroxide decompose to produce the hydroxy radical of strong oxidability, the strong oxidizing property hydroxy radical that decompose to produce can oxidation Decomposition 3,3', 5,5'-tetramethyl benzidine (TMB), make the color of solution by the colourless dusty blue that is converted into, realize the detection analysis to content of hydrogen peroxide in the environment.This inorganic nano combined catalyst can force rate use graphene oxide or Fe separately 3O 4@MnO 2Nano particle is stronger.
This composite catalyst is inorganic nano composite material, does not belong to enzyme, and the temperature of environment for use and pH value are not had strict requirement, and the environment tolerance is strong, is easy to storage and recyclable recycling, the raw material graphene oxide, the Fe that adopt 3O 4And MnO 2Material all has biocompatibility, can not work the mischief and pollutes environment after the use.
Description of drawings
Fig. 1 is Fe in the embodiment of the invention 1 3O 4@MnO 2The TEM electromicroscopic photograph of nanometer sheet catalyst fines.From Fig. 1 as seen, the composite catalyst for preparing is the laminated structure of Nano grade, is of a size of 40～70nm, and MnO 2Be distributed in the marginal portion of nanometer sheet.
Fig. 2 is Fe in the embodiment of the invention 1 3O 4@MnO 2The XRD collection of illustrative plates of nanometer sheet catalyst fines.From Fig. 2 as seen, there is significant Fe in the XRD collection of illustrative plates 3O 4Face-centred cubic structure crystal diffraction cutting edge of a knife or a sword, and do not have significant MnO 2The crystal cutting edge of a knife or a sword only has MnO 2The amorphous peak exists, and MnO has been described 2In composite particles, exist with amorphous state, and Fe 3O 4Existence then be the face-centred cubic structure form, graphene oxide and Fe are described 3O 4@MnO 2Nano particle is not that simple physics is mixed after ultrasonic, has formed new compound substance.
Fig. 3 is GO-Fe in the embodiment of the invention 1 3O 4@MnO 2Nano-composite catalyst (a), Fe 3O 4@MnO 2Ultraviolet absorptivity curve after nanometer sheet catalyst (b), GO (c) and PBS buffer solution (d) background correction.From Fig. 3 as seen, add GO-Fe 3O 4@MnO 2The ultraviolet absorptivity value maximum of solution illustrates that its change color is the darkest behind the nano-composite catalyst, and is stronger to the catalytic activity of peroxide, thus explanation GO-Fe 3O 4@MnO 2Nano-composite catalyst has extraordinary peroxide enzymatic property, and this compound action has significant lifting to its catalytic effect in addition, and catalytic effect is better than single with graphene oxide or Fe 3O 4@MnO 2Nano particle.
Fig. 4 is GO-Fe in the embodiment of the invention 1 3O 4@MnO 2Nano-composite catalyst (1), Fe 3O 4@MnO 2Nanometer sheet catalyst (2), GO(3) and PBS buffer solution (4) catalysis TMB color developing effect comparison diagram.From Fig. 4 as seen, the PBS buffer solution is colourless solution, adds GO-Fe 3O 4@MnO 2The change color of solution is the darkest behind the nano-composite catalyst, and GO-Fe is described 3O 4@MnO 2Nano combined have an extraordinary peroxide enzymatic property.
The specific embodiment
Be described in detail below in conjunction with accompanying drawing and the present invention of embodiment.
The preparation of graphene oxide (Hummers S, Offeman R, J. Am. Chem. Soc., 1958,80 (6), 1339.): with 1 g native graphite, 1 g NaNO 3Be blended in the 46 mL concentrated sulfuric acids (98%) and react 4～5 h in the ice-water bath.Then with 6 g KMnO 4Join and simultaneously temperature is risen to 35 ℃ and keep reaction temperature in the mixture solution, reaction is carried out adding 90～95 mL H behind 2～3 h 2O also rises to 98 ℃ with temperature, and reaction carries out adding after two hours 200 mL warm water, the H of 20 mL 30% 2O 2, and at room temperature continue reaction 1～2 h.To remain stirring in the entire reaction course.The product for preparing is filtered, after using the distilled water washing in 60 ℃ baking oven drying 24～48 h, obtain oxide yellow Graphene solid.
Fe 3O 4@MnO 2The preparation of composite nano materials (Z. Zhao, J. Liu, F. Cui, H. Feng and L. Zhang, J. Mater. Chem., 2012,22,9052.):
The beaker that fills 100 mL ultra-pure waters is placed in 90 ℃ the water-bath logical N 2O in the discharge water 2, add the FeSO of 2.5 mmol in the solution 47H 2O and the reaction of 1 g polyvinylpyrrolidone (K-30) add the NaOH of 1 mL, 5.0 M after 1～2 hour, it is green that solution turns immediately.After 5～10 minutes, dropwise add 2.5 mmol KMnO 4, generate the dark-brown precipitation.React after 10～14 hours, will precipitate centrifugal, washing, place 50 ℃ down dry.
Embodiment 1
With graphene oxide grind broken after, take by weighing 0.1 g and join ultrasonic 1～2 h in the PBS buffer solution of 100 mL, obtain the graphene oxide solution of homogeneous; Get 0.2 gFe 3O 4@MnO 2Composite Nano is scattered in the 100 mL graphene oxide solution, and ultrasonic 10min disperses to obtain composite nano plate.
The peroxidase activity test of inorganic nano combined particle
1) at room temperature, with GO-Fe 3O 4@MnO 2After the ultrasonic dispersion of inorganic composite nano particle, get 20 these solution of μ L, join in the 1.8 mL PBS buffer solutions, measure its absorbance in 500～700 nm scopes as a setting.Add 100 μ L colour developing liquid A liquid and 200 μ L colour developing liquid B liquid in the last solution successively, react and measure its absorbing state in 500～700 nm scopes after 5～6 minutes.
2) at room temperature, with Fe 3O 4@MnO 2After the ultrasonic dispersion of inorganic composite nano particle, get 20 these solution of μ L, join in the 1.8 mL PBS buffer solutions, measure its absorbance in 500～700 nm scopes as a setting.Add 100 μ L colour developing liquid A liquid and 200 μ L colour developing liquid B liquid in the last solution successively, react and measure its absorbing state in 500～700 nm scopes after 5～6 minutes.
3) at room temperature, after the ultrasonic dispersion of GO nanometer sheet, get 20 these solution of μ L, join in the 1.8 mL PBS buffer solutions, measure its absorbance in 500～700 nm scopes as a setting.Add 100 μ L colour developing liquid A liquid and 200 μ L colour developing liquid B liquid in the last solution successively, react and measure its absorbing state in 500～700 nm scopes after 5～6 minutes.
4) at room temperature, get 2 mL PBS buffer solutions, measure its absorbance in 500～700 nm scopes as a setting.Add 100 μ L colour developing liquid A liquid and 200 μ L colour developing liquid B liquid in the above-mentioned solution successively, react and measure its absorbing state in 500～700 nm scopes after 5～6 minutes.
Presentation of results GO-Fe 3O 4@MnO 2Nano combined have an extraordinary peroxide enzymatic property, and catalytic effect is better than single any component of using.
Embodiment 2
With graphene oxide grind broken after, take by weighing 0.4 g and join ultrasonic 1～2 h in the PBS buffer solution of 100 mL, obtain the graphene oxide solution of homogeneous; Get 0.8gFe 3O 4@MnO 2Composite Nano is scattered in the 100 mL graphene oxide solution, and ultrasonic 10min disperses to obtain composite nano plate, and the length of side is 40～70nm, and effectively catalysis TMB, and catalytic activity is better than graphene oxide or Fe 3O 4@MnO 2Nano particle.
Embodiment 3
With graphene oxide grind broken after, take by weighing 0.3g and join ultrasonic 1～2 h in the PBS buffer solution of 100 mL, obtain the graphene oxide solution of homogeneous; Get 0.6gFe 3O 4@MnO 2Composite Nano is scattered in the 100 mL graphene oxide solution, and ultrasonic 10min disperses to obtain composite nano plate, and the length of side is 40～70nm, and effectively catalysis TMB, and catalytic activity is better than graphene oxide or Fe 3O 4@MnO 2Nano particle.
Embodiment 4
With graphene oxide grind broken after, take by weighing 0.2g and join ultrasonic 1～2 h in the PBS buffer solution of 100 mL, obtain the graphene oxide solution of homogeneous; Get 0.4gFe 3O 4@MnO 2Composite Nano is scattered in the 100 mL graphene oxide solution, and ultrasonic 10min disperses to obtain composite nano plate, and the length of side is 40～70nm, and effectively catalysis TMB, and catalytic activity is better than graphene oxide or Fe 3O 4@MnO 2Nano particle.

Claims (3)

1. the inorganic nano combined catalyst with peroxide enzymatic property is characterized in that by graphene oxide (GO) and Fe 3O 4@MnO 2Nano particle is dissolved in the PBS buffer solution, mixes, obtains composite nano plate through ultrasonic dispersion, is of a size of 40～70nm.
2. the inorganic nano combined catalyst with peroxide enzymatic property according to claim 1, the concentration that it is characterized in that graphene oxide is 1～4 mgmL -1, Fe 3O 4@MnO 2The concentration of nano particle is 2～8 mgmL -1, and graphene oxide concentration and Fe 3O 4@MnO 2The ratio of concentrations of nanoparticles is 1: 2.
3. claim 1 gained has the application of the inorganic nano combined catalyst decomposition TMB of peroxide enzymatic property.
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Cited By (6)

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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
CN106093272A (en) * 2016-06-01 2016-11-09 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
CN107913668A (en) * 2017-10-25 2018-04-17 浙江工商大学 A kind of nanocomposite with absorption and catalytic degradation and its preparation method and application
CN107913667A (en) * 2017-10-25 2018-04-17 浙江工商大学 A kind of magnetic graphene/ferroso-ferric oxide/manganese dioxide nano-composite material and its preparation and application
CN108329470A (en) * 2018-02-12 2018-07-27 吉林大学 A kind of method preparing inorganic nano-particle in conducting polymer nanotube pipe and its application in class Catalyzed Synthesis By Peroxidase

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CN101941842A (en) * 2010-10-11 2011-01-12 东华大学 Method for preparing graphene loaded ferroferric oxide magnetic nanometer particle composite material
CN102553593A (en) * 2012-01-10 2012-07-11 常州大学 Method for preparing magnetic nanometer ferroferric oxide-graphene composite catalyst

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Cited By (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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
CN106093272A (en) * 2016-06-01 2016-11-09 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
CN107913668A (en) * 2017-10-25 2018-04-17 浙江工商大学 A kind of nanocomposite with absorption and catalytic degradation and its preparation method and application
CN107913667A (en) * 2017-10-25 2018-04-17 浙江工商大学 A kind of magnetic graphene/ferroso-ferric oxide/manganese dioxide nano-composite material and its preparation and application
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
CN108329470A (en) * 2018-02-12 2018-07-27 吉林大学 A kind of method preparing inorganic nano-particle in conducting polymer nanotube pipe and its application in class Catalyzed Synthesis By Peroxidase
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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