CN108046331B - Molybdenum sulfide-ferrite nanoenzyme, preparation and application - Google Patents
Molybdenum sulfide-ferrite nanoenzyme, preparation and application Download PDFInfo
- Publication number
- CN108046331B CN108046331B CN201810024964.8A CN201810024964A CN108046331B CN 108046331 B CN108046331 B CN 108046331B CN 201810024964 A CN201810024964 A CN 201810024964A CN 108046331 B CN108046331 B CN 108046331B
- Authority
- CN
- China
- Prior art keywords
- ferrite
- molybdenum sulfide
- nanoenzyme
- magnesium
- reaction
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910000859 α-Fe Inorganic materials 0.000 title claims abstract description 72
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910052750 molybdenum Inorganic materials 0.000 title claims abstract description 47
- 239000011733 molybdenum Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 9
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 54
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 41
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 41
- 239000011777 magnesium Substances 0.000 claims abstract description 41
- 238000006243 chemical reaction Methods 0.000 claims abstract description 30
- 239000000243 solution Substances 0.000 claims abstract description 19
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims abstract description 15
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 11
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 9
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 9
- ZKKLPDLKUGTPME-UHFFFAOYSA-N diazanium;bis(sulfanylidene)molybdenum;sulfanide Chemical compound [NH4+].[NH4+].[SH-].[SH-].S=[Mo]=S ZKKLPDLKUGTPME-UHFFFAOYSA-N 0.000 claims abstract description 8
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 claims abstract description 8
- 238000001514 detection method Methods 0.000 claims abstract description 7
- 239000011259 mixed solution Substances 0.000 claims abstract description 7
- JRBPAEWTRLWTQC-UHFFFAOYSA-N dodecylamine Chemical compound CCCCCCCCCCCCN JRBPAEWTRLWTQC-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000007974 sodium acetate buffer Substances 0.000 claims abstract description 5
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 claims abstract description 4
- VITRLXDSBBVNCZ-UHFFFAOYSA-K trichloroiron;hydrate Chemical compound O.Cl[Fe](Cl)Cl VITRLXDSBBVNCZ-UHFFFAOYSA-K 0.000 claims abstract description 4
- 238000012258 culturing Methods 0.000 claims abstract description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000007795 chemical reaction product Substances 0.000 claims description 14
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 5
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 5
- 239000007788 liquid Substances 0.000 claims description 4
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 4
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000000376 reactant Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims 2
- 238000000034 method Methods 0.000 abstract description 10
- 230000035945 sensitivity Effects 0.000 abstract description 2
- 238000004140 cleaning Methods 0.000 abstract 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 abstract 1
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 10
- 239000000126 substance Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 6
- 102000004190 Enzymes Human genes 0.000 description 5
- 108090000790 Enzymes Proteins 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 238000004737 colorimetric analysis Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 235000002017 Zea mays subsp mays Nutrition 0.000 description 3
- 241000482268 Zea mays subsp. mays Species 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 3
- 150000002978 peroxides Chemical class 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 239000002028 Biomass Substances 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 229910017052 cobalt Inorganic materials 0.000 description 2
- 239000010941 cobalt Substances 0.000 description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- CXVCSRUYMINUSF-UHFFFAOYSA-N tetrathiomolybdate(2-) Chemical compound [S-][Mo]([S-])(=S)=S CXVCSRUYMINUSF-UHFFFAOYSA-N 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- PMJHNEFCWLUZBC-UHFFFAOYSA-N 4-(4-amino-3-methylphenyl)-2,6,6-trimethylcyclohexa-1,3-dien-1-amine Chemical compound CC1=C(N)C(C)(C)CC(C=2C=C(C)C(N)=CC=2)=C1 PMJHNEFCWLUZBC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 description 1
- 239000011609 ammonium molybdate Substances 0.000 description 1
- 235000018660 ammonium molybdate Nutrition 0.000 description 1
- 229940010552 ammonium molybdate Drugs 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000003018 immunoassay Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 239000011684 sodium molybdate Substances 0.000 description 1
- 235000015393 sodium molybdate Nutrition 0.000 description 1
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 description 1
- 238000011895 specific detection Methods 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 description 1
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G49/00—Compounds of iron
- C01G49/0018—Mixed oxides or hydroxides
-
- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
- B01J27/0515—Molybdenum with iron group metals or platinum group metals
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/80—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70
- C01P2002/84—Crystal-structural characteristics defined by measured data other than those specified in group C01P2002/70 by UV- or VIS- data
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Compounds Of Iron (AREA)
- Measuring Or Testing Involving Enzymes Or Micro-Organisms (AREA)
Abstract
The invention relates to a preparation method and an application method of molybdenum sulfide-ferrite nanoenzyme. The method comprises the following steps: dissolving ferric chloride hydrate, magnesium chloride hydrate and dodecylamine in a proper amount of glycol and uniformly mixing; repeatedly cleaning the product after reaction in the high-pressure reaction kettle; drying to obtain ferrite magnesium; dissolving ammonium tetrathiomolybdate in dimethylformamide; slowly adding hydrazine hydrate and uniformly mixing; adding a proper amount of ferrite magnesium into the mixed solution; repeatedly cleaning the product after reaction in the high-pressure reaction kettle; drying to obtain molybdenum sulfide-ferrite magnesium; adding a proper amount of TMB and hydrogen peroxide with different concentrations into a molybdenum sulfide-ferrite magnesium solution in an acetic acid-sodium acetate buffer solution; and measuring the concentration of hydrogen peroxide after culturing. The results prove that the molybdenum sulfide-ferrite magnesium nanoenzyme is convenient and rapid to detect hydrogen peroxide, high in sensitivity and wide in detection concentration range.
Description
Technical Field
The invention relates to the technical field of preparation of molybdenum sulfide-ferrite magnesium nanoenzyme, and also relates to a method technology for detecting peroxide. A molybdenum sulfide-ferrite nanoenzyme, preparation and application.
Background
The colorimetric method is widely applied to the fields of biomass detection, immunoassay, environmental prediction and the like all the time due to the advantages of simplicity, convenience, visibility and the like. The traditional colorimetric method based on biological enzyme is used for measuring peroxide, and has the disadvantages of high sensitivity, accuracy and reliability, complex operation and high cost. Recently, colorimetric determination of peroxides based on nanomaterials is receiving more and more attention, because "nanoenzymes" are used instead of biological enzymes, which not only greatly saves cost and simplifies operation steps, but also has higher detection stability. The so-called "nanoenzyme", i.e. the nanomaterial as a catalyst, catalyzes the oxidation of hydrogen peroxide, during which the color-developing agent 3, 3, 5, 5' -Tetramethylbenzidine (TMB) is converted into an oxidized state and changes from colorless to blue.
Metal oxides, metal nanoparticles, are commonly used "nanoenzyme" materials. Recently, graphene oxide and molybdenum sulfide have also been reported to have good catalytic effects of "nanoenzymes". In order to make these materials have better catalytic effect, the preparation of nano enzyme is one of effective approaches. Ferrites are receiving more and more extensive attention due to their good stability, wave absorption and catalytic properties. Therefore, if the composition of molybdenum sulfide and ferrite can be realized and the structure of the obtained material can be effectively controlled, based on the existing research results, a novel and efficient 'nanoenzyme' is likely to be obtained.
Disclosure of Invention
The present invention has been made in view of the above and/or the problems occurring in the conventional process of compounding molybdenum sulfide with ferrite.
Therefore, the invention aims to overcome the defects of the prior art and provide the molybdenum sulfide-ferrite nanoenzyme, and preparation and application thereof.
In order to solve the technical problems, the invention provides the following technical scheme:
the invention aims to provide a molybdenum sulfide-ferrite nanoenzyme convenient to detect.
A molybdenum sulfide-ferrite nanoenzyme is provided, which has a popcorn-shaped structure, and is prepared by dissolving ammonium tetrathiomolybdate in dimethylformamide, slowly adding hydrazine hydrate for stirring, then dispersing ferrite magnesium in the mixed solution, reacting in a high-pressure reaction kettle, after the reaction is finished, centrifuging the reaction product to remove water, washing with deionized water for repeated washing until the pH value of the solution is close to 7.0, and drying the washed reaction product to obtain the molybdenum sulfide-ferrite magnesium nanoenzyme.
As a preferable aspect of the present invention, wherein: the preparation method of the ferrite magnesium comprises the steps of dissolving ferric chloride hydrate, magnesium chloride hydrate and dodecylamine in ethylene glycol, stirring uniformly at room temperature, transferring into a high-pressure reaction kettle for reaction, after the reaction is finished, centrifuging the reaction product to remove water, washing with deionized water repeatedly until the pH value of the solution is close to 7.0, and drying the washed reaction product to obtain the ferrite magnesium.
It should be emphasized that the magnesium ferrite in the molybdenum sulfide-ferrite nanoenzyme of the present invention may also be ferrite (zinc, nickel, cobalt), which is prepared by reacting hydrated ferric chloride and hydrated chloride (zinc, nickel, cobalt), and those skilled in the art can easily think of corresponding alternatives based on reading the present application, which should be included in the scope of the present invention.
As a preferable scheme of the invention, the ratio of the reactants is controlled during the reaction, the ratio of the amount of the hydrated ferric chloride to the amount of the hydrated magnesium chloride is kept between 3: 1 ~ 1: 3, and the ratio of the amount of the dodecylamine to the sum of the amounts of the hydrated ferric chloride and the hydrated magnesium chloride is kept between 0.8: 1 ~ 1: 1.
As a preferable scheme of the invention, the reaction temperature and time are controlled in the reaction process, the high-pressure reaction temperature is 190 ~ 220 ℃, and the time is 15 ~ 25 hours.
The invention is a preferable scheme, wherein the rotation speed of centrifugation in the reaction process is 3000 ~ 6000 rpm, the drying temperature is 50 ~ 65 ℃, and the time is 10 ~ 18 hours.
As a preferable scheme of the invention, the amount of the ferrite magnesium substance and the amount of the tetrathiomolybdate substance are kept between 0.3: 1 ~ 1.2.2: 1, so that the obtained molybdenum sulfide-ferrite magnesium nano enzyme can keep a popcorn-shaped structure.
The invention has been carried out through a great deal of research to obtain that the amount of the ferrite magnesium substance and the amount of the ammonium tetrathiomolybdate substance are kept between 0.3: 1 ~ 1.2.2: 1, which is a key technical scheme of the invention.
In a preferred embodiment of the present invention, the volume of hydrazine hydrate added is 1 ~ 2.5.5 ml, and the stirring time is 0.5 ~ 1 hours.
The preferable scheme of the invention is that the high-pressure reaction temperature in the reaction process is 160 ~ 250 ℃, the time is 8 ~ 15 hours, the centrifugal rate is 4000 ~ 8000 rpm, the drying temperature is 60 ~ 80 ℃, and the time is 6 ~ 15 hours.
The innovation of the invention is that the application of the molybdenum sulfide-ferrite nanoenzyme in the detection of the hydrogen peroxide in the water body is provided for the first time, and the specific detection operation process is as follows:
a) dispersing the molybdenum sulfide-ferrite nanoenzyme in water;
b) adding TMB with fixed concentration and hydrogen peroxide with different concentrations into acetic acid-sodium acetate buffer solution, and culturing;
c) measuring the concentration of hydrogen peroxide in the mixed liquid obtained in the step b) by using a spectrophotometer.
Further, in the above-mentioned case,
the concentration of the molybdenum sulfide-ferrite nanoenzyme in the step a) is kept at 0.8 ~ 1.5.5 mg/ml;
the volume of the molybdenum sulfide-ferrite nanoenzyme in the step a) adopted in the step b) is 5 ~ 20 microliters, the concentration of TMB is 1 ~ 2.5.5 millimoles/liter, the volume is 100 ~ 300 microliters, the volume of hydrogen peroxide is 80 ~ 100 microliters, the pH of the acetic acid-sodium acetate solution is 3.5 ~ 5.0.0, and the concentration is 0.1 ~ 0.2.2 moles/liter;
the culture temperature in the step b) is 40 ~ 48 ℃, and the culture time is 10 ~ 20 minutes.
The fixed concentration of TMB is relative, i.e., TMB determines a certain concentration and then changes the hydrogen peroxide concentration, but the concentration of TMB itself also varies.
Compared with the prior art, the invention has the following beneficial effects:
1. the method for synthesizing the molybdenum disulfide is different, common molybdate such as ammonium molybdate, sodium molybdate and the like is generally used in the prior art, hydrazine hydrate is not added, thiourea, thioacetamide and other reagents are used, the obtained molybdenum disulfide is generally in a layered structure, the molybdenum disulfide obtained by adding tetrathiomolybdate and hydrazine hydrate in the invention is reduced to be in a three-dimensional structure, and a foundation is laid for obtaining a popcorn-shaped compound subsequently. The change of the structure also has an influence on the performance, a larger specific surface area is generated, more active sites are generated, and finally higher catalytic activity is generated.
2. According to the invention, the amount of substances of ferrite magnesium and ammonium tetrathiomolybdate is controlled to be kept between 0.3: 1 ~ 1.2.2: 1, so that the obtained molybdenum sulfide-ferrite magnesium can keep a popcorn-shaped structure, the popcorn has a three-dimensional structure and a higher specific surface area, so that stronger catalytic activity is generated, the single molybdenum sulfide is flaky or petal-shaped, and the special structure is obtained by regulating and controlling the shape through the coordination effect between the ferrite and the molybdenum sulfide according to different proportions.
3. The mixed solution is sealed in a high-pressure reaction kettle, high pressure is generated in the reaction kettle along with the temperature rise to 160 ~ 250 ℃, ammonium tetrathiomolybdate, dimethylformamide and hydrazine hydrate can be fully dispersed in an aqueous solution under the physical and chemical environment of high temperature and high pressure, and the obtained molybdenum sulfide and ferrite magnesium generate higher catalytic performance through synergistic effect, so that a product with a popcorn-shaped structure is obtained.
4. During the application and operation, the volume of the molybdenum sulfide-ferrite magnesium is controlled to be 5 ~ 20 microliter, the concentration of TMB is controlled to be 1 ~ 2.5.5 millimole/liter, the volume is 100 ~ 300 microliter, the volume of hydrogen peroxide is controlled to be 80 ~ 100 microliter, the pH of the acetic acid-sodium acetate solution is 3.5 ~ 5.0.0, and the concentration is 0.1 ~ 0.2.2 millimole/liter, so that the most economical and efficient effects can be ensured.
5. The molybdenum sulfide-ferrite magnesium prepared by the invention has a popcorn structure, the mass ratio of the ferrite magnesium to the molybdenum sulfide is about (0.5 ~ 1.0.0): 1, the molybdenum sulfide-ferrite magnesium has excellent performance of catalyzing hydrogen peroxide, the cost is low, the detection limit is low, and the concentration range of the hydrogen peroxide which can be detected in 0.1 mol dm-3 acetic acid-sodium acetate buffer solution is 2.5 ~ 300 mu mol dm-3.
6. The invention overcomes the problems in the prior art and provides a method for detecting hydrogen peroxide by a colorimetric method in real time, accurately and efficiently.
7. And (3) performing predictive analysis on market implementation possibility and economic benefit: the colorimetric method is one of the most common methods for measuring the concentration of a substance, and for biomass detection, good economic benefits can be obtained if cheap and efficient nano-enzyme can be used for replacing biological enzyme.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings needed to be used in the description of the embodiments will be briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without inventive exercise. Wherein:
FIG. 1 is a scanning electron micrograph of molybdenum sulfide-ferrite magnesium according to example 1 of the present invention;
FIG. 2 is a graph of the ultraviolet absorption spectrum of hydrogen peroxide detected by the molybdenum sulfide-ferrite magnesium nanoenzyme of example 2 of the present invention;
FIG. 3 is a graph showing the relationship between the hydrogen peroxide concentration and the absorbance according to the present invention.
Detailed Description
In order to make the aforementioned objects, features and advantages of the present invention comprehensible, embodiments accompanied with examples are described in detail below.
In the following description, numerous specific details are set forth in order to provide a thorough understanding of the present invention, but the present invention may be practiced in other ways than those specifically described and will be readily apparent to those of ordinary skill in the art without departing from the spirit of the present invention, and therefore the present invention is not limited to the specific embodiments disclosed below.
Example 1
(1) Weighing 5.8 mmol of ferric chloride hydrate, 2.9 mmol of magnesium chloride hydrate and 8.0 mmol of dodecylamine, dissolving in 75 ml of ethylene glycol, and stirring at room temperature;
(2) transferring the mixed solution obtained in the step (1) into a 100 ml high-pressure reaction kettle, and reacting for 20 hours at 220 ℃;
(3) after the reaction product in the step (2) is centrifuged to remove water (the rotating speed is 4500 rpm), the reaction product is washed by deionized water for 3 ~ 5 times repeatedly until the pH value of the solution is close to 7.0, and the washed reaction product is dried for 10 hours at 55 ℃ to obtain ferrite magnesium;
(4) 0.54 mmol of ammonium tetrathiomolybdate is weighed and dissolved in 65 ml of dimethylformamide;
(5) slowly adding 1.0 ml of hydrazine hydrate into the mixed solution obtained in the step (4), and stirring for 0.5 hour to ensure that the mixture is uniformly mixed;
(6) weighing 0.3 millimole of ferrite magnesium obtained in the step (3), and dispersing the ferrite magnesium in the mixed liquid obtained in the step (5);
(7) transferring the mixed solution obtained in the step (6) into a 100 ml high-pressure reaction kettle, and reacting for 10 hours at 200 ℃;
(8) and (3) after the reaction product obtained in the step (7) is centrifuged to remove water (the rotating speed is 600 rpm, 5 minutes), washing with deionized water repeatedly until the pH value of the solution is close to 7.0, and drying the washed reaction product at 60 ℃ for 10 hours to obtain the molybdenum sulfide-ferrite magnesium nanoenzyme.
FIG. 1 is a scanning electron micrograph of molybdenum sulfide-ferrite magnesium prepared according to the present invention, in which it can be seen that the resulting composite has a three-dimensional structure similar to popcorn.
The method for detecting hydrogen peroxide by using the molybdenum sulfide-ferrite magnesium nanoenzyme is further illustrated by combining specific examples.
Example 2
a) 1 mg of the molybdenum sulfide-ferrite magnesium nanoenzyme obtained in example 1 was dispersed in 1 ml of deionized water to obtain a molybdenum sulfide-ferrite magnesium dispersion solution of 1 mg/ml;
b) weighing 10. mu.l of the mixture of step a), 250. mu.l of 2 mmol/l TMB and 100. mu.l of 2.5 ~ 300. mu.l of hydrogen peroxide in 0.1 mol/l of pH 4.0 acetic acid-sodium acetate buffer;
c) incubating the mixture obtained in step b) at 45 ℃ for 15 minutes;
d) measuring the concentration of hydrogen peroxide in the mixed liquid obtained in the step c) by using a spectrophotometer.
FIG. 2 is a diagram of the ultraviolet absorption spectrum of the molybdenum sulfide-ferrite magnesium nanoenzyme of the invention for detecting hydrogen peroxide with different concentrations.
The method for detecting hydrogen peroxide by using the molybdenum sulfide-ferrite magnesium nanoenzyme is further illustrated by combining specific examples.
Example 3
A linear plot was obtained by plotting the absorbance at 652 nm versus the hydrogen peroxide concentration in example 2 (FIG. 3).
As can be seen in fig. 3: the molybdenum sulfide-ferrite magnesium nanoenzyme maintains good linear relation to hydrogen peroxide in the range of 2.5 to 300 micromoles/liter.
It should be noted that the above-mentioned embodiments are only for illustrating the technical solutions of the present invention and not for limiting, and although the present invention has been described in detail with reference to the preferred embodiments, it should be understood by those skilled in the art that modifications or equivalent substitutions may be made on the technical solutions of the present invention without departing from the spirit and scope of the technical solutions of the present invention, which should be covered by the claims of the present invention.
Claims (9)
1. A molybdenum sulfide-ferrite nanoenzyme is characterized in that the molybdenum sulfide-ferrite nanoenzyme has a popcorn-shaped structure and is prepared by dissolving ammonium tetrathiomolybdate in dimethylformamide, slowly adding hydrazine hydrate, stirring, then dispersing ferrite magnesium in the mixed solution, reacting in a high-pressure reaction kettle, after the reaction is finished, centrifugally removing water from a reaction product, washing and repeatedly washing the reaction product with deionized water until the pH value of the solution is close to 7.0, and drying the washed reaction product to obtain the molybdenum sulfide-ferrite magnesium nanoenzyme, wherein the amount of the ferrite magnesium and the amount of the ammonium tetrathiomolybdate are kept between 0.3: 1 ~ 1.2.2: 1, so that the obtained molybdenum sulfide-ferrite nanoenzyme can keep the popcorn-shaped structure.
2. The molybdenum sulfide-ferrite nanoenzyme of claim 1, wherein the ferrite magnesium is prepared by dissolving ferric chloride hydrate, magnesium chloride hydrate and dodecylamine in ethylene glycol, stirring uniformly at room temperature, transferring into a high-pressure reaction kettle for reaction, centrifuging the reaction product after the reaction is finished to remove water, washing with deionized water repeatedly until the pH value of the solution is close to 7.0, and drying the washed reaction product to obtain the ferrite magnesium.
3. The molybdenum sulfide-ferrite nanoenzyme of claim 2, wherein the ratio of reactants is controlled during the reaction, the ratio of the amount of the hydrated ferric chloride to the amount of the hydrated magnesium chloride is maintained between 3: 1 ~ 1: 3, and the ratio of the amount of the dodecylamine to the sum of the amounts of the hydrated ferric chloride and the hydrated magnesium chloride is maintained between 0.8: 1 ~ 1: 1.
4. The molybdenum sulfide-ferrite nanoenzyme of claim 2, wherein the reaction temperature and time are controlled during the preparation of the ferrite magnesium, the reaction temperature under high pressure is 190 ~ 220 ℃ and the time is 15 ~ 25 hours.
5. The molybdenum sulfide-ferrite nanoenzyme of claim 2, wherein the ferrite magnesium is prepared at a centrifugal rotation speed of 3000 ~ 6000 rpm during the reaction, a drying temperature of 50 ~ 65 ℃ and a time of 10 ~ 18 hours.
6. The molybdenum sulfide-ferrite nanoenzyme of claim 1, wherein the hydrazine hydrate is added in a volume of 1 ~ 2.5.5 ml and the stirring time is 0.5 ~ 1 hours.
7. The molybdenum sulfide-ferrite nanoenzyme of claim 1, wherein the reaction temperature is 160 ~ 250 ℃ and the reaction time is 8 ~ 15 hours, the centrifugation rate is 4000 ~ 8000 rpm, the drying temperature is 60 ~ 80 ℃ and the reaction time is 6 ~ 15 hours.
8. The use of the molybdenum sulfide-ferrite nanoenzyme of any one of claims 1 ~ 7 in detecting hydrogen peroxide in a water body, wherein the detection is performed by the following steps:
a) dispersing the molybdenum sulfide-ferrite nanoenzyme in water;
b) adding TMB with fixed concentration and hydrogen peroxide with different concentrations into acetic acid-sodium acetate buffer solution, and culturing;
c) measuring the concentration of hydrogen peroxide in the mixed liquid obtained in the step b) by using a spectrophotometer.
9. The use of the molybdenum sulfide-ferrite nanoenzyme of claim 8 for detecting hydrogen peroxide in a body of water,
the concentration of the molybdenum sulfide-ferrite nanoenzyme in the step a) is kept at 0.8 ~ 1.5.5 mg/ml;
the volume of the molybdenum sulfide-ferrite nanoenzyme in the step a) adopted in the step b) is 5 ~ 20 microliters, the concentration of TMB is 1 ~ 2.5.5 millimoles/liter, the volume is 100 ~ 300 microliters, the volume of hydrogen peroxide is 80 ~ 100 microliters, the pH of the acetic acid-sodium acetate solution is 3.5 ~ 5.0.0, and the concentration is 0.1 ~ 0.2.2 moles/liter;
the culture temperature in the step b) is 40 ~ 48 ℃, and the culture time is 10 ~ 20 minutes.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810024964.8A CN108046331B (en) | 2018-01-11 | 2018-01-11 | Molybdenum sulfide-ferrite nanoenzyme, preparation and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810024964.8A CN108046331B (en) | 2018-01-11 | 2018-01-11 | Molybdenum sulfide-ferrite nanoenzyme, preparation and application |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108046331A CN108046331A (en) | 2018-05-18 |
| CN108046331B true CN108046331B (en) | 2020-01-21 |
Family
ID=62127167
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810024964.8A Active CN108046331B (en) | 2018-01-11 | 2018-01-11 | Molybdenum sulfide-ferrite nanoenzyme, preparation and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108046331B (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108872216A (en) * | 2018-05-24 | 2018-11-23 | 首都师范大学 | A kind of cobalt nickel nano-wire array and the preparation method and application thereof |
| CN109387508B (en) * | 2018-11-18 | 2021-06-04 | 扬州大学 | Preparation method of magnetic carbon tube-molybdenum disulfide nanoenzyme and method for detecting hydrogen peroxide and glucose by using magnetic carbon tube-molybdenum disulfide nanoenzyme |
| CN111001423B (en) * | 2019-12-25 | 2022-07-01 | 扬州大学 | Preparation of semiconductor bismuth ferrite-titanium dioxide-nickel phosphide nanoenzyme and method for detecting hydrogen peroxide |
| CN111001410B (en) * | 2019-12-25 | 2022-07-26 | 扬州大学 | Preparation of semiconductor bismuth vanadate-iron oxyhydroxide nanoenzyme and method for detecting hydrogen peroxide |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413921A (en) * | 2013-08-26 | 2013-11-27 | 中国科学技术大学 | Spinel magnetic ferrite/molybdenum disulfide nanometer composite material as well as preparation method and application thereof |
| CN105289660A (en) * | 2015-10-27 | 2016-02-03 | 江苏大学 | Synthesis method and application of magnesium ferrite/molybdenum sulfide heterostructure nanowires |
-
2018
- 2018-01-11 CN CN201810024964.8A patent/CN108046331B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103413921A (en) * | 2013-08-26 | 2013-11-27 | 中国科学技术大学 | Spinel magnetic ferrite/molybdenum disulfide nanometer composite material as well as preparation method and application thereof |
| CN105289660A (en) * | 2015-10-27 | 2016-02-03 | 江苏大学 | Synthesis method and application of magnesium ferrite/molybdenum sulfide heterostructure nanowires |
Non-Patent Citations (1)
| Title |
|---|
| Fabrication of MgFe2O4/MoS2 Heterostructure Nanowires for Photoelectrochemical Catalysis;Weiqiang Fan等;《Langmuir》;20160121;1629-1636页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108046331A (en) | 2018-05-18 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108046331B (en) | Molybdenum sulfide-ferrite nanoenzyme, preparation and application | |
| Shi et al. | Copper-based two-dimensional metal-organic framework nanosheets as horseradish peroxidase mimics for glucose fluorescence sensing | |
| Zhang et al. | A flower-like MoS2-decorated MgFe2O4 nanocomposite: Mimicking peroxidase and colorimetric detection of H2O2 and glucose | |
| Hosseini et al. | Enhancement of the peroxidase-like activity of cerium-doped ferrite nanoparticles for colorimetric detection of H 2 O 2 and glucose | |
| CN107356591B (en) | Enzyme-free one-pot glucose color development detection method based on enzyme-like nano material | |
| CN109092364B (en) | Copper metal organic framework mimic enzyme material and preparation and application thereof | |
| Hur et al. | Reagentless colorimetric biosensing platform based on nanoceria within an agarose gel matrix | |
| US20240066511A1 (en) | Mn-mof-based cold-adapted nanozyme and preparation method thereof | |
| CN114414514A (en) | Preparation method of manganese Prussian blue nano-enzyme and application of manganese Prussian blue nano-enzyme in alcohol concentration detection | |
| Kim et al. | Poly-γ-glutamic Acid/Chitosan hydrogel nanoparticles entrapping glucose oxidase and magnetic nanoparticles for glucose biosensing | |
| Wang et al. | Catalase active metal-organic framework synthesized by ligand regulation for the dual detection of glucose and cysteine | |
| CN110389125B (en) | Application of nano copper selenide as peroxide mimic enzyme to detection of hydrogen peroxide and L-cysteine | |
| CN112014336A (en) | Universal method for detecting activity of alpha-glucosidase based on cascade reaction | |
| Zhang et al. | Advances in the application of metal–organic framework nanozymes in colorimetric sensing of heavy metal ions | |
| CN113351220B (en) | CuNi/CoMoO serving as multifunctional laccase-like enzyme 4 Preparation method and application of | |
| Hong-Ying et al. | Colorimetric detection of hydrogen peroxide and glutathione based on peroxidase mimetic activity of Fe3O4-sodium lignosulfonate nanoparticles | |
| Rathinam et al. | TiO2 Nanoparticles Based Peroxidase Mimics for Colorimetric Sensing of Cholesterol and Hydrogen Peroxide | |
| CN109387508A (en) | A kind of preparation method of magnetic carbon tube-molybdenum disulfide nano enzyme and its method for detecting hydrogen peroxide, glucose | |
| Zhang et al. | Selective and sensitive colorimetric sensing of iodine ions based on porous MoS2 particles with excellent haloperoxidase-like activity | |
| Zou et al. | Stimuli-responsive colorimetric sensor based on bifunctional pyrophosphate-triggered controlled release and enhancing activity of CoOOH nanozyme | |
| CN105738447A (en) | Preparation method and application of electrochemical chloramphenicol biosensor | |
| CN116003818B (en) | Method for preparing functionalized multi-metal organic framework nano enzyme and application of peroxidase activity thereof | |
| Cheng et al. | Colorimetric and electrochemical integrated dual-mode detection of glucose by utilizing CoOOH@ Cu nanosheets as peroxidase mimetics | |
| CN111965136A (en) | Preparation method of peroxidase-like nanoenzyme beta-FeOOH and its application in H2O2Applications in assays | |
| CN104459154B (en) | A kind of synthesis of novel artificial analogue enztme and the structure to glycosyl detection method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |