CN110540984A - HRP/Co3O4@ ZIF-8 composite catalyst and preparation method thereof - Google Patents
HRP/Co3O4@ ZIF-8 composite catalyst and preparation method thereof Download PDFInfo
- Publication number
- CN110540984A CN110540984A CN201910809943.1A CN201910809943A CN110540984A CN 110540984 A CN110540984 A CN 110540984A CN 201910809943 A CN201910809943 A CN 201910809943A CN 110540984 A CN110540984 A CN 110540984A
- Authority
- CN
- China
- Prior art keywords
- co3o4
- hrp
- zif
- nanoparticles
- composite catalyst
- 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.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N11/00—Carrier-bound or immobilised enzymes; Carrier-bound or immobilised microbial cells; Preparation thereof
- C12N11/14—Enzymes or microbial cells immobilised on or in an inorganic carrier
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12N—MICROORGANISMS OR ENZYMES; COMPOSITIONS THEREOF; PROPAGATING, PRESERVING, OR MAINTAINING MICROORGANISMS; MUTATION OR GENETIC ENGINEERING; CULTURE MEDIA
- C12N9/00—Enzymes; Proenzymes; Compositions thereof; Processes for preparing, activating, inhibiting, separating or purifying enzymes
- C12N9/0004—Oxidoreductases (1.)
- C12N9/0065—Oxidoreductases (1.) acting on hydrogen peroxide as acceptor (1.11)
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12Y—ENZYMES
- C12Y111/00—Oxidoreductases acting on a peroxide as acceptor (1.11)
- C12Y111/01—Peroxidases (1.11.1)
- C12Y111/01007—Peroxidase (1.11.1.7), i.e. horseradish-peroxidase
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Bioinformatics & Cheminformatics (AREA)
- Zoology (AREA)
- Wood Science & Technology (AREA)
- Genetics & Genomics (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Engineering & Computer Science (AREA)
- Biomedical Technology (AREA)
- Biotechnology (AREA)
- Microbiology (AREA)
- Medicinal Chemistry (AREA)
- Molecular Biology (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The invention discloses an HRP/Co3O4@ ZIF-8 composite catalyst and a preparation method thereof, wherein the preparation method comprises the following steps: dissolving cobalt acetate tetrahydrate in an ethanol solvent, adding ammonia water, placing the mixture in a high-pressure reaction kettle, reacting for 3-6 hours at 120-150 ℃ to obtain Co3O4 nanoparticles, dispersing the Co3O4 nanoparticles in deionized water to obtain a dispersion liquid of Co3O4 nanoparticles, adding polyvinylpyrrolidone into the dispersion liquid of the Co3O4 nanoparticles, and stirring for 6-12 hours to obtain modified Co3O4 nanoparticles; dissolving zinc acetate dihydrate in deionized water to obtain a zinc acetate dihydrate water solution with the concentration of 0.1-0.2 mol/L; dissolving dimethyl imidazole in deionized water to obtain a dimethyl imidazole aqueous solution with the concentration of 0.4-0.8 mol/L; adding HRP and modified Co3O4 nanoparticles into a dimethyl imidazole aqueous solution, adding a zinc acetate dihydrate aqueous solution, and reacting at 0-4 ℃ for 12-h to obtain the HRP/Co3O4@ ZIF-8 composite catalyst. The HRP/Co3O4@ ZIF-8 composite catalyst can be applied to catalytic conversion of O-phenylenediamine.
Description
(I) technical field
The invention relates to a simple, efficient, mild-condition and low-cost HRP/Co3O4@ ZIF-8 composite catalyst and a preparation method thereof, belonging to the technical field of biological catalytic materials.
(II) background of the invention
The enzyme is used as an efficient biocatalyst, and is widely applied to various fields such as fine chemical production, biopharmaceuticals, renewable energy preparation, food processing and the like by virtue of the advantages of high chemical selectivity, regioselectivity, stereoselectivity and the like. However, the industrial application of enzymes is often limited by low operational stability, difficult recovery, and low reusability, and the enzyme immobilization is one of effective means for solving the above problems. Enzyme immobilization work has been developed to date, and the choice of immobilization support and method has a direct impact on the immobilization effect and may result in corresponding changes in the physical and chemical properties of the enzyme. In principle the immobilization method must keep the enzyme activity intact and not impede the diffusion of the substrate freely into and out of the enzyme active site. With the rapid development of material science, the diversity of carrier materials provides the possibility of meeting the immobilization work of enzymes with different sizes and properties. Conventional porous materials having a certain specific surface area and pore space, such as sol-gel matrix, hydrogel, organic microparticles, mesoporous silica, etc., have gained much attention as carriers for enzyme immobilization. However, there are adverse effects such as leaching, denaturation, and mass transfer limitation of the enzyme.
In contrast, due to the openness of the structure and the diversity of the material chemistry, the novel Metal Organic Frameworks (MOFs) can create stable micro-environments for different enzyme molecules through specific host/guest interactions and domain-limited effects, thereby being excellent in maintaining high enzyme loading rate and low enzyme loss rate, and even maintaining enzyme activity in extreme environments. These phenomena all indicate that MOFs can provide a very characteristic high-efficiency carrier for immobilization of different enzymes. However, since the synthesis of MOFs materials generally uses organic solvents and reacts at higher temperatures, which may have an effect on the activity of enzymes, it is necessary to synthesize the MOFs materials in advance. Although enzyme immobilization can be effectively achieved by simply attaching the enzyme to the MOFs carrier or by linking the enzyme and the MOFs carrier by peptide bonds, both of the two ways result in the enzyme on the surface of the complex being exposed to the environment without protection and easily losing activity. Therefore, if the enzyme can be fixed in the pores of the MOFs material and can be effectively prevented from being denatured in the synthesis process, the macromolecular enzyme can be effectively prevented from leaking and leaching from the fixed matrix, and the method is not influenced by environmental conditions, and has a great research significance for the application of enzyme immobilization in industry.
Disclosure of the invention
In order to overcome the defects in the prior art, the invention aims to provide an HRP/Co3O4@ ZIF-8 composite catalyst and a preparation method thereof, wherein Co3O4 nano particles are prepared and modified to improve the dispersibility, and then the nano particles and HRP are added into a precursor solution of ZIF-8 together to form the HRP/Co3O4@ ZIF-8 composite catalyst.
the technical scheme of the invention is as follows:
an HRP/Co3O4@ ZIF-8 composite catalyst is prepared by the following steps:
(1) Dissolving cobalt acetate tetrahydrate in an ethanol solvent, carrying out ultrasonic dissolution, adding 25% ammonia water by mass while carrying out vigorous stirring, fully stirring, placing in a high-pressure reaction kettle, reacting for 3-6 h at 120-150 ℃, washing and drying the obtained reaction solution to obtain Co3O4 nanoparticles; the volume dosage of the ethanol solvent is 50-60 mL/g calculated by the mass of cobalt acetate tetrahydrate; the volume usage of the ammonia water with the mass fraction of 25% is 5-15 mL/g based on the mass of the cobalt acetate tetrahydrate;
(2) dispersing the Co3O4 nanoparticles prepared in the step (1) into deionized water to obtain a dispersion liquid of Co3O4 nanoparticles, adding polyvinylpyrrolidone (PVP) into the dispersion liquid of the Co3O4 nanoparticles for ultrasonic dispersion, stirring for 6-12 h to obtain a reaction liquid B, and washing and drying to obtain modified Co3O4 nanoparticles; the mass ratio of the Co3O4 nanoparticles to the polyvinylpyrrolidone is 0.4-1.2: 1; the volume dosage of the deionized water is 50-100 mL/mg based on the mass of the Co3O4 nano particles;
(3) Dissolving zinc acetate dihydrate in deionized water, and uniformly mixing by ultrasonic waves to obtain a zinc acetate dihydrate water solution with the concentration of 0.1-0.2 mol/L; dissolving dimethyl imidazole in deionized water, and uniformly mixing by ultrasonic waves to obtain a dimethyl imidazole aqueous solution with the concentration of 0.4-0.8 mol/L; adding horseradish peroxidase (HRP) and the modified Co3O4 nano particles obtained in the step (2) into the dimethyl imidazole aqueous solution, adding the zinc acetate dihydrate aqueous solution, performing ultrasonic dispersion uniformly, and reacting at 0-4 ℃ for 12-h to obtain a reaction solution C, washing and drying to obtain an HRP/Co3O4@ ZIF-8 composite catalyst; the mass ratio of the horseradish peroxidase (HRP) to the modified Co3O4 nanoparticles is 1: 1-5; the volume dosage of the zinc acetate dihydrate aqueous solution is 2-10 mL/mg calculated by the mass of horseradish peroxidase (HRP); the volume consumption of the dimethyl imidazole aqueous solution is 2-10 mL/mg based on the mass of horseradish peroxidase (HRP).
Further, in the step (1), the post-treatment method of the reaction solution A comprises the following steps: and centrifugally washing the obtained reaction solution A with deionized water for three times, and drying in a vacuum drying oven at 60 ℃ for 4 hours to obtain the Co3O4 nanoparticles.
Further, in the step (2), the post-treatment method of the reaction solution B comprises the following steps: and centrifugally washing the obtained reaction solution B with deionized water for three times, and drying in a vacuum drying oven at 60 ℃ for 4 hours to obtain the modified Co3O4 nanoparticles.
Further, in the step (3), the post-treatment method of the reaction solution C comprises: and centrifugally washing the obtained reaction solution C with deionized water for three times, and drying at room temperature or by freeze drying (about 20 ℃) to obtain the HRP/Co3O4@ ZIF-8 composite catalyst.
the HRP/Co3O4@ ZIF-8 composite catalyst can be applied to catalytic conversion of O-phenylenediamine.
compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method is simple and the operation condition is mild;
(2) HRP and Co3O4 nanoparticles are embedded in ZIF-8 together, so that the catalytic activity and stability are improved;
(3) Can effectively reduce secondary pollution and improve the reusability of the catalyst.
(IV) description of the drawings
FIG. 1 shows the results of an o-phenylenediamine catalysis experiment using the catalyst of example 1 of the present invention;
FIG. 2 shows the results of an o-phenylenediamine catalysis experiment with the catalyst of example 2 of the present invention;
FIG. 3 shows the results of an o-phenylenediamine catalysis experiment using the catalyst of example 3 of the present invention.
(V) detailed description of the preferred embodiments
The present invention will be described in detail below with reference to specific examples, but the present invention is not limited to the following examples, and various modifications and implementations are included within the technical scope of the present invention without departing from the content and scope of the present invention.
the analysis and evaluation method of each embodiment of the invention comprises the following steps:
O-phenylenediamine catalysis experiment procedure: weighing 1.0mg of HRP/Co3O4@ ZIF-8 composite catalyst, adding the HRP/Co3O4@ ZIF-8 composite catalyst into 1mL of 50mmol/L NaCl aqueous solution, performing ultrasonic dispersion uniformly, adding 1mL of toluene, and performing shaking dispersion for 30s to obtain Pickering emulsion. 1mL of 10mmol/L o-phenylenediamine substrate solution is added into the prepared Pickering emulsion and uniformly shaken. 100 μ L of 5% H2O2 solution was added and samples were taken immediately at 20s,40s,1min,2min,3min,5min,10min,15min,20min,30min intervals. 50. mu.L of each sample was added to 2.45ml of toluene (corresponding to 50-fold dilution). Then, the absorbance value is measured at the wavelength of 450nm, and the conversion rate of o-phenylenediamine is obtained.
Example 1:
first, 0.5g of cobalt acetate tetrahydrate was dissolved in 25mL of an ethanol solvent, 2.5mL of 25% aqueous ammonia was added with vigorous stirring, stirred for 10min, and placed in a high-pressure reaction vessel to react at 150 ℃ for 3 hours. Centrifugally washing with deionized water for three times, and vacuum drying at 60 ℃ for 4 h. Then 0.2g of the nano particles prepared above is added into 10mL of deionized water, 0.4g of polyvinylpyrrolidone is added, ultrasonic dispersion is carried out, centrifugal washing is carried out for three times by deionized water after 12h of stirring, and drying is carried out for 4h in a vacuum drying oven at 60 ℃.
Dissolving 0.439g of zinc acetate dihydrate in 20mL of deionized water, and uniformly mixing by ultrasonic; 0.6568g of dimethyl imidazole is dissolved in 20mL of deionized water, and the mixture is ultrasonically mixed uniformly; adding 1mg of HRP and 1mg of Co3O4 nano particles into 2mL of dimethyl imidazole aqueous solution, adding 2mL of zinc acetate aqueous solution, performing uniform ultrasonic dispersion, and reacting at 4 ℃ for 12 h. And centrifugally washing the catalyst for three times by using deionized water, and drying the catalyst at room temperature to obtain the HRP/Co3O4@ ZIF-8 composite catalyst.
the conversion rate of O-phenylenediamine can reach 97% in 30min and still can reach 90% when the O-phenylenediamine is repeatedly used for 3 times by performing O-phenylenediamine catalytic experiment test analysis on the HRP/Co3O4@ ZIF-8 composite catalyst.
Example 2:
First, 0.5g of cobalt acetate tetrahydrate was dissolved in 25mL of an ethanol solvent, 2.5mL of 25% aqueous ammonia was added with vigorous stirring, stirred for 10min, and placed in a high-pressure reaction vessel to react at 150 ℃ for 3 hours. Centrifugally washing with deionized water for three times, and vacuum drying at 60 ℃ for 4 h. Then 0.2g of the nano particles prepared above is added into 10mL of deionized water, 0.4g of polyvinylpyrrolidone is added, ultrasonic dispersion is carried out, centrifugal washing is carried out for three times by deionized water after 12h of stirring, and drying is carried out for 4h in a vacuum drying oven at 60 ℃.
0.6585g of zinc acetate dihydrate is dissolved in 20mL of deionized water and is uniformly mixed by ultrasonic; 0.9852g of dimethyl imidazole is dissolved in 20mL of deionized water, and the mixture is ultrasonically mixed uniformly; adding 1mg of HRP and 1mg of Co3O4 nano particles into 2mL of dimethyl imidazole aqueous solution, adding 2mL of zinc acetate aqueous solution, performing uniform ultrasonic dispersion, and reacting at 4 ℃ for 12 h. And centrifugally washing the catalyst for three times by using deionized water, and drying the catalyst at room temperature to obtain the HRP/Co3O4@ ZIF-8 composite catalyst.
The conversion rate of O-phenylenediamine can reach 98% in 30min and still can reach 90% when the O-phenylenediamine is repeatedly used for 3 times by performing O-phenylenediamine catalytic experiment test analysis on the HRP/Co3O4@ ZIF-8 composite catalyst.
Example 3:
first, 0.5g of cobalt acetate tetrahydrate was dissolved in 25mL of an ethanol solvent, 2.5mL of 25% aqueous ammonia was added with vigorous stirring, stirred for 10min, and placed in a high-pressure reaction vessel to react at 150 ℃ for 3 hours. Centrifugally washing with deionized water for three times, and vacuum drying at 60 ℃ for 4 h. Then 0.2g of the nano particles prepared above is added into 10mL of deionized water, 0.4g of polyvinylpyrrolidone is added, ultrasonic dispersion is carried out, centrifugal washing is carried out for three times by deionized water after 12h of stirring, and drying is carried out for 4h in a vacuum drying oven at 60 ℃.
dissolving 0.439g of zinc acetate dihydrate in 20mL of deionized water, and uniformly mixing by ultrasonic; 0.6568g of dimethyl imidazole is dissolved in 20mL of deionized water, and the mixture is ultrasonically mixed uniformly; adding 0.5mg of HRP and 1.5mg of Co3O4 nanoparticles into 2mL of dimethyl imidazole aqueous solution, adding 2mL of zinc acetate aqueous solution, performing uniform ultrasonic dispersion, and reacting at 4 ℃ for 12 h. And centrifugally washing the catalyst for three times by using deionized water, and drying the catalyst at room temperature to obtain the HRP/Co3O4@ ZIF-8 composite catalyst.
The conversion rate of O-phenylenediamine can reach 95% in 30min and still reach 90% when the O-phenylenediamine is repeatedly used for 3 times by performing O-phenylenediamine catalytic experiment test analysis on the HRP/Co3O4@ ZIF-8 composite catalyst.
Claims (5)
1. An HRP/Co3O4@ ZIF-8 composite catalyst is characterized in that: the composite catalyst is prepared by the following method:
(1) Dissolving cobalt acetate tetrahydrate in an ethanol solvent, carrying out ultrasonic dissolution, adding 25% ammonia water by mass while carrying out vigorous stirring, fully stirring, placing in a high-pressure reaction kettle, reacting for 3-6 h at 120-150 ℃, washing and drying the obtained reaction solution to obtain Co3O4 nanoparticles; the volume dosage of the ethanol solvent is 50-60 mL/g calculated by the mass of cobalt acetate tetrahydrate; the volume usage of the ammonia water with the mass fraction of 25% is 5-15 mL/g based on the mass of the cobalt acetate tetrahydrate;
(2) Dispersing the Co3O4 nanoparticles prepared in the step (1) into deionized water to obtain a dispersion liquid of Co3O4 nanoparticles, adding polyvinylpyrrolidone into the dispersion liquid of the Co3O4 nanoparticles for ultrasonic dispersion, stirring for 6-12 h to obtain a reaction liquid B, and washing and drying to obtain modified Co3O4 nanoparticles; the mass ratio of the Co3O4 nanoparticles to the polyvinylpyrrolidone is 0.4-1.2: 1; the volume dosage of the deionized water is 50-100 mL/mg based on the mass of the Co3O4 nano particles;
(3) Dissolving zinc acetate dihydrate in deionized water, and uniformly mixing by ultrasonic waves to obtain a zinc acetate dihydrate water solution with the concentration of 0.1-0.2 mol/L; dissolving dimethyl imidazole in deionized water, and uniformly mixing by ultrasonic waves to obtain a dimethyl imidazole aqueous solution with the concentration of 0.4-0.8 mol/L; adding horseradish peroxidase and the modified Co3O4 nano particles obtained in the step (2) into the dimethyl imidazole aqueous solution, adding the zinc acetate dihydrate aqueous solution, performing ultrasonic dispersion uniformly, and reacting at 0-4 ℃ for 12-h to obtain a reaction solution C, and washing and drying to obtain an HRP/Co3O4@ ZIF-8 composite catalyst; the mass ratio of the horseradish peroxidase to the modified Co3O4 nanoparticles is 1: 1-5; the volume dosage of the zinc acetate dihydrate aqueous solution is 2-10 mL/mg based on the mass of the horseradish peroxidase; the volume dosage of the dimethyl imidazole aqueous solution is 2-10 mL/mg based on the mass of the horseradish peroxidase.
2. The HRP/Co3O4@ ZIF-8 composite catalyst of claim 1, wherein: in the step (1), the post-treatment method of the reaction solution A comprises the following steps: and centrifugally washing the obtained reaction solution A with deionized water for three times, and drying in a vacuum drying oven at 60 ℃ for 4 hours to obtain the Co3O4 nanoparticles.
3. The HRP/Co3O4@ ZIF-8 composite catalyst of claim 1, wherein: in the step (2), the post-treatment method of the reaction solution B comprises the following steps: and centrifugally washing the obtained reaction solution B with deionized water for three times, and drying in a vacuum drying oven at 60 ℃ for 4 hours to obtain the modified Co3O4 nanoparticles.
4. The HRP/Co3O4@ ZIF-8 composite catalyst of claim 1, wherein: in the step (3), the post-treatment method of the reaction solution C comprises the following steps: and centrifugally washing the obtained reaction solution C with deionized water for three times, and drying at room temperature or by freeze drying to obtain the HRP/Co3O4@ ZIF-8 composite catalyst.
5. the HRP/Co3O4@ ZIF-8 composite catalyst as defined in claim 1 is applied to catalytic conversion of O-phenylenediamine.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910809943.1A CN110540984B (en) | 2019-08-29 | 2019-08-29 | HRP/Co3O4@ ZIF-8 composite catalyst and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910809943.1A CN110540984B (en) | 2019-08-29 | 2019-08-29 | HRP/Co3O4@ ZIF-8 composite catalyst and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110540984A true CN110540984A (en) | 2019-12-06 |
| CN110540984B CN110540984B (en) | 2021-07-27 |
Family
ID=68712310
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910809943.1A Active CN110540984B (en) | 2019-08-29 | 2019-08-29 | HRP/Co3O4@ ZIF-8 composite catalyst and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110540984B (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484990A (en) * | 2020-04-21 | 2020-08-04 | 陕西师范大学 | Cobaltose peroxidase-loaded nanoreactor modified by polydopamine and prepared from cobalt hierarchical porous material and application of nanoreactor |
| CN111690637A (en) * | 2020-05-11 | 2020-09-22 | 河北工业大学 | Preparation method of organophosphorus degrading enzyme-based multifunctional catalyst, organophosphorus degrading enzyme-based multifunctional catalyst and application thereof |
| CN112063612A (en) * | 2020-08-12 | 2020-12-11 | 华南理工大学 | Separated type multienzyme-MOF (Metal organic framework) microcapsule and preparation method thereof |
| CN113097490A (en) * | 2021-04-02 | 2021-07-09 | 扬州大学 | Dodecahedral ZIF-67/Co3O4Composite material, preparation method and application thereof |
| CN113651970A (en) * | 2021-08-24 | 2021-11-16 | 合肥工业大学 | Universal method for preparing multi-shell hollow metal organic framework |
| CN115920971A (en) * | 2022-12-27 | 2023-04-07 | 辽宁大学 | ZIF-8 pickering emulsion based on metal organic framework and preparation method and application thereof |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962462A (en) * | 2006-11-23 | 2007-05-16 | 南京大学 | Process for preparing nanometer cobalt oxide |
| CN104087572A (en) * | 2014-07-01 | 2014-10-08 | 清华大学 | Protein and metal organic skeleton compound composite material and preparation method thereof |
| CN105734038A (en) * | 2016-01-22 | 2016-07-06 | 南京工业大学 | Enzyme-GO-MOFs nano composite catalyst and preparation method thereof |
| CN107267494A (en) * | 2017-05-23 | 2017-10-20 | 陕西师范大学 | The@Fe of enzyme@ZIF 83O4Magnetic Nano enzyme reactor and preparation method thereof |
-
2019
- 2019-08-29 CN CN201910809943.1A patent/CN110540984B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1962462A (en) * | 2006-11-23 | 2007-05-16 | 南京大学 | Process for preparing nanometer cobalt oxide |
| CN104087572A (en) * | 2014-07-01 | 2014-10-08 | 清华大学 | Protein and metal organic skeleton compound composite material and preparation method thereof |
| CN105734038A (en) * | 2016-01-22 | 2016-07-06 | 南京工业大学 | Enzyme-GO-MOFs nano composite catalyst and preparation method thereof |
| CN107267494A (en) * | 2017-05-23 | 2017-10-20 | 陕西师范大学 | The@Fe of enzyme@ZIF 83O4Magnetic Nano enzyme reactor and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| JIANSHUAI MU等: ""Intrinsic peroxidase-like activity and catalase-like activity of Co3O4 nanoparticles"", 《CHEM. COMMUN.》 * |
| WENFEI DONG等: ""High peroxidase-like activity of metallic cobalt nanoparticles encapsulated in metal–organic frameworks derived carbon for biosensing"", 《SENSORS AND ACTUATORS B: CHEMICAL》 * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111484990A (en) * | 2020-04-21 | 2020-08-04 | 陕西师范大学 | Cobaltose peroxidase-loaded nanoreactor modified by polydopamine and prepared from cobalt hierarchical porous material and application of nanoreactor |
| CN111484990B (en) * | 2020-04-21 | 2023-04-07 | 陕西师范大学 | Cobaltose peroxidase-loaded nanoreactor modified by polydopamine and prepared from cobalt hierarchical porous material and application of nanoreactor |
| CN111690637A (en) * | 2020-05-11 | 2020-09-22 | 河北工业大学 | Preparation method of organophosphorus degrading enzyme-based multifunctional catalyst, organophosphorus degrading enzyme-based multifunctional catalyst and application thereof |
| CN112063612A (en) * | 2020-08-12 | 2020-12-11 | 华南理工大学 | Separated type multienzyme-MOF (Metal organic framework) microcapsule and preparation method thereof |
| CN113097490A (en) * | 2021-04-02 | 2021-07-09 | 扬州大学 | Dodecahedral ZIF-67/Co3O4Composite material, preparation method and application thereof |
| CN113651970A (en) * | 2021-08-24 | 2021-11-16 | 合肥工业大学 | Universal method for preparing multi-shell hollow metal organic framework |
| CN115920971A (en) * | 2022-12-27 | 2023-04-07 | 辽宁大学 | ZIF-8 pickering emulsion based on metal organic framework and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110540984B (en) | 2021-07-27 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110540984B (en) | HRP/Co3O4@ ZIF-8 composite catalyst and preparation method thereof | |
| US10737240B2 (en) | 3D ruthenium / graphene aerogel composite loaded with metal-organic frameworks, preparation method thereof, and its application in continuous treatment of CO | |
| US11198112B2 (en) | Dinuclear rhodium complex-doped platinum/hollow mesoporous silica sphere composite material, and preparation method and application thereof | |
| CN110592064B (en) | Horseradish peroxidase @ MOF composite catalyst and preparation method thereof | |
| CN107233924B (en) | The preparation and application of mercapto-modified metal organic framework compound catalyst | |
| CN104525264A (en) | Amino metal organic framework material containing active metal component as well as preparation method and application of amino metal organic framework material | |
| CN105149006B (en) | Part amination metal organic framework loaded catalyst and preparation method and application | |
| CN110484527A (en) | A kind of deficiency metal organic framework-multienzyme complex and preparation method thereof and its application | |
| CN106111198B (en) | The preparation method and applications of the catalyst of metal organic gel materials loaded Ag of the one kind based on MIL 100 (Al) | |
| CN108212217B (en) | Catalyst for degrading chlorophenol pollutants, preparation method and application | |
| CN112403519B (en) | Preparation method and application of COF-300/PPy/Au (G) nanoenzyme catalyst | |
| CN108404987A (en) | A method of improving nano particle@MOFs material catalytic efficiencies | |
| CN108554416B (en) | Modified cobalt-based catalyst and preparation method and application thereof | |
| CN106582719A (en) | Preparation method for CdS/MIL-53 (Fe) visible light catalyst | |
| CN107774246A (en) | The preparation method and applications of loaded palladium catalyst in a kind of hollow nanometer capsule core | |
| CN109433190A (en) | Mesoporous zircite nanometer tube composite materials of supported platinum nano particle and preparation method thereof and the application in lasting processing organic exhaust gas | |
| CN108097315A (en) | A kind of support type NH2The synthetic method of-UiO-66 hydrogenation catalysts and application | |
| CN105445477A (en) | Preparation method and application of environment estrogen sensor marked by nitrogen-doped graphene | |
| CN110592065B (en) | Horseradish peroxidase @ metal organic framework spherical particle catalyst and preparation method thereof | |
| CN108948366A (en) | A kind of preparation and its desulfurization application of the Fe-MOF catalyst with abundant Lewis acidic site | |
| CN105622985B (en) | A kind of magnetic cellulose/2-methylimidazole zinc salt and preparation method and application | |
| CN108236954A (en) | A kind of method of low temperature removing formaldehyde | |
| CN113731486A (en) | Preparation method of hydrophilic MOF and application of prepared MOF as catalyst carrier | |
| CN106179452A (en) | A kind of preparation method of porous nitrogenous charcoal load palladium catalysis material | |
| CN108273557B (en) | A kind of iron schiff bases compound photochemical catalyst and preparation method thereof |
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 |