CN110540984B - 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
- CN110540984B CN110540984B CN201910809943.1A CN201910809943A CN110540984B CN 110540984 B CN110540984 B CN 110540984B CN 201910809943 A CN201910809943 A CN 201910809943A CN 110540984 B CN110540984 B CN 110540984B
- Authority
- CN
- China
- Prior art keywords
- hrp
- zif
- deionized water
- composite catalyst
- nano particles
- 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
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 239000003054 catalyst Substances 0.000 title claims abstract description 31
- 239000002131 composite material Substances 0.000 title claims abstract description 25
- 238000002360 preparation method Methods 0.000 title abstract description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000002105 nanoparticle Substances 0.000 claims abstract description 36
- 239000008367 deionised water Substances 0.000 claims abstract description 35
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 35
- 238000006243 chemical reaction Methods 0.000 claims abstract description 27
- 239000007864 aqueous solution Substances 0.000 claims abstract description 20
- 239000000243 solution Substances 0.000 claims abstract description 19
- GEYOCULIXLDCMW-UHFFFAOYSA-N 1,2-phenylenediamine Chemical compound NC1=CC=CC=C1N GEYOCULIXLDCMW-UHFFFAOYSA-N 0.000 claims abstract description 18
- YSWBFLWKAIRHEI-UHFFFAOYSA-N 4,5-dimethyl-1h-imidazole Chemical compound CC=1N=CNC=1C YSWBFLWKAIRHEI-UHFFFAOYSA-N 0.000 claims abstract description 17
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 16
- YZYKBQUWMPUVEN-UHFFFAOYSA-N zafuleptine Chemical compound OC(=O)CCCCCC(C(C)C)NCC1=CC=C(F)C=C1 YZYKBQUWMPUVEN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- ZBYYWKJVSFHYJL-UHFFFAOYSA-L cobalt(2+);diacetate;tetrahydrate Chemical compound O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O ZBYYWKJVSFHYJL-UHFFFAOYSA-L 0.000 claims abstract description 10
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 9
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 9
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 9
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 8
- 239000006185 dispersion Substances 0.000 claims abstract description 7
- 230000003197 catalytic effect Effects 0.000 claims abstract description 4
- 239000007788 liquid Substances 0.000 claims abstract description 3
- 108010001336 Horseradish Peroxidase Proteins 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 21
- 238000001035 drying Methods 0.000 claims description 18
- 238000000034 method Methods 0.000 claims description 12
- 238000001291 vacuum drying Methods 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 6
- 239000012295 chemical reaction liquid Substances 0.000 claims description 5
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000004108 freeze drying Methods 0.000 claims description 2
- 240000003291 Armoracia rusticana Species 0.000 claims 1
- 235000011330 Armoracia rusticana Nutrition 0.000 claims 1
- 108090000790 Enzymes Proteins 0.000 description 24
- 102000004190 Enzymes Human genes 0.000 description 24
- 230000000694 effects Effects 0.000 description 8
- 239000012621 metal-organic framework Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 4
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 239000004246 zinc acetate Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000000839 emulsion Substances 0.000 description 2
- 238000002386 leaching Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000013154 zeolitic imidazolate framework-8 Substances 0.000 description 2
- MFLKDEMTKSVIBK-UHFFFAOYSA-N zinc;2-methylimidazol-3-ide Chemical compound [Zn+2].CC1=NC=C[N-]1.CC1=NC=C[N-]1 MFLKDEMTKSVIBK-UHFFFAOYSA-N 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000011942 biocatalyst Substances 0.000 description 1
- 230000002210 biocatalytic effect Effects 0.000 description 1
- 229960000074 biopharmaceutical Drugs 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 238000012824 chemical production Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000004925 denaturation Methods 0.000 description 1
- 230000036425 denaturation Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
Images
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 HRP/Co3O4The @ ZIF-8 composite catalyst and the preparation method thereof, the preparation method is as follows: dissolving cobalt acetate tetrahydrate in an ethanol solvent, adding ammonia water, placing in a high-pressure reaction kettle, and carrying out strip forming at 120-150 DEG CReacting for 3-6 h under the condition of a workpiece to obtain Co3O4Dispersing the nano particles into deionized water to obtain Co3O4Dispersion of nanoparticles and then Co3O4Adding polyvinylpyrrolidone into the dispersion liquid of the nano particles, and stirring for 6-12 h to obtain modified Co3O4Nanoparticles; 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; HRP and modified Co3O4Adding the nano particles into a dimethyl imidazole aqueous solution, adding a zinc acetate dihydrate aqueous solution, and reacting at the temperature of 0-4 ℃ for 12-h to obtain HRP/Co3O4@ ZIF-8 composite catalyst. The HRP/Co of the invention3O4The @ ZIF-8 composite catalyst can be applied to catalytic conversion of o-phenylenediamine.
Description
(I) technical field
The invention relates to HRP/Co with the advantages of simplicity, high efficiency, mild condition and low cost3O4A @ ZIF-8 composite catalyst and a preparation method thereof, belonging to the technical field of biocatalytic 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/Co3O4The @ ZIF-8 composite catalyst is prepared through preparing Co3O4The nano particles are modified to improve the dispersibility, and then the nano particles and HRP are added into a precursor solution of ZIF-8 together to form HRP/Co3O4@ ZIF-8 composite catalyst.
The technical scheme of the invention is as follows:
HRP/Co3O4The @ 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 percentage while carrying out vigorous stirring, fully stirring, placing in a high-pressure reaction kettle, reacting for 3-6 h at the temperature of 120-150 ℃,washing and drying the obtained reaction liquid to obtain Co3O4Nanoparticles; 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) the Co prepared in the step (1) is added3O4Dispersing the nano particles into deionized water to obtain Co3O4Dispersion of nanoparticles and then to said Co3O4Adding polyvinylpyrrolidone (PVP) into the dispersion liquid of the nano particles, performing ultrasonic dispersion, stirring for 6-12 h to obtain reaction liquid B, washing and drying to obtain modified Co3O4Nanoparticles; the Co3O4The mass ratio of the nano particles to the polyvinylpyrrolidone is 0.4-1.2: 1; the volume dosage of the deionized water is Co3O4The mass of the nano particles is 50-100 mL/mg;
(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; horse Radish Peroxidase (HRP) and the modified Co obtained in the step (2)3O4Adding the nano particles into the dimethyl imidazole aqueous solution together, adding the zinc acetate dihydrate aqueous solution, performing ultrasonic dispersion uniformly, reacting for 12-h at 0-4 ℃, washing and drying the obtained reaction solution C to obtain HRP/Co3O4@ ZIF-8 complex catalyst; the horseradish peroxidase (HRP) and modified Co3O4The mass ratio of the nano particles 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: centrifugally washing the obtained reaction solution A with deionized water for three times, and drying in a vacuum drying oven at 60 ℃ for 4hTo obtain Co3O4Nanoparticles.
Further, in the step (2), the post-treatment method of the reaction solution B comprises the following steps: 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 modified Co3O4Nanoparticles.
Further, in the step (3), the post-treatment method of the reaction solution C comprises: 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 HRP/Co3O4@ ZIF-8 composite catalyst.
The HRP/Co of the invention3O4The @ 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 Co3O4The nano particles are embedded in the ZIF-8 together, so that the catalytic activity and the 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: weigh 1.0mg of HRP/Co3O4And adding the @ 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 a Pickering emulsion. 1mL of 10mmol/L o-phenylenediamine substrate solution is added into the prepared Pickering emulsion and uniformly shaken. Add 100. mu.L of 5% H2O2The solution was sampled 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; 1mg of HRP and 1mg of Co3O4Adding the nano particles into 2mL of dimethyl imidazole aqueous solution, adding 2mL of zinc acetate aqueous solution, uniformly dispersing by ultrasonic, and reacting for 12h at 4 ℃. Centrifugally washing with deionized water for three times, and drying at room temperature to obtain HRP/Co3O4@ ZIF-8 composite catalyst.
Para HRP/Co3O4The test and analysis of o-phenylenediamine catalysis experiments carried out by the @ ZIF-8 composite catalyst show that the conversion rate of the o-phenylenediamine can reach 97% in 30min, and the conversion rate can still reach 90% when the o-phenylenediamine is repeatedly used for 3 times.
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; 1mg of HRP and 1mg of Co3O4Adding the nano particles into 2mL of dimethyl imidazole aqueous solution, adding 2mL of zinc acetate aqueous solution, uniformly dispersing by ultrasonic, and reacting for 12h at 4 ℃. Centrifugally washing with deionized water for three times, and drying at room temperature to obtain HRP/Co3O4@ ZIF-8 composite catalyst.
Para HRP/Co3O4The test and analysis of o-phenylenediamine catalysis experiments carried out by the @ ZIF-8 composite catalyst show that the conversion rate of the o-phenylenediamine can reach 98% in 30min and still can reach 90% when the o-phenylenediamine is repeatedly used for 3 times.
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; 0.5mg of HRP and 1.5mg of Co3O4Adding the nano particles into 2mL of dimethyl imidazole aqueous solution, adding 2mL of zinc acetate aqueous solution, uniformly dispersing by ultrasonic, and reacting for 12h at 4 ℃. Centrifugally washing with deionized water for three times, and drying at room temperature to obtain HRP/Co3O4@ ZIF-8 composite catalyst.
Para HRP/Co3O4The test and analysis of o-phenylenediamine catalysis experiments carried out by the @ ZIF-8 composite catalyst show that the conversion rate of the o-phenylenediamine can reach 95% in 30min and still can reach 90% when the o-phenylenediamine is repeatedly used for 3 times.
Claims (5)
1. HRP/Co3O4@ ZIF-8 composite catalyst, 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 percentage while carrying out vigorous stirring, fully stirring, placing in a high-pressure reaction kettle, reacting for 3-6 h at the temperature of 120-150 ℃, washing and drying reaction liquid A to obtain Co3O4Nanoparticles; 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) the Co prepared in the step (1) is added3O4Dispersing the nano particles into deionized water to obtain Co3O4Dispersion of nanoparticles and then to said Co3O4Adding polyvinylpyrrolidone into the dispersion liquid of the nano particles, performing ultrasonic dispersion, stirring for 6-12 h to obtain a reaction liquid B, washing and drying to obtain modified Co3O4Nanoparticles; the Co3O4The mass ratio of the nano particles to the polyvinylpyrrolidone is 0.4-1.2: 1; the volume dosage of the deionized water is Co3O4The mass of the nano particles is 50-100 mL/mg;
(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; horse radish peroxideEnzyme and modified Co obtained in step (2)3O4Adding the nanoparticles into the dimethyl imidazole aqueous solution, adding the zinc acetate dihydrate aqueous solution, performing ultrasonic dispersion uniformly, reacting at 0-4 ℃ for 12h to obtain a reaction solution C, washing and drying to obtain HRP/Co3O4@ ZIF-8 complex catalyst; the horseradish peroxidase and the modified Co3O4The mass ratio of the nano particles 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/Co of claim 13O4@ ZIF-8 composite catalyst, characterized in that: in the step (1), the post-treatment method of the reaction solution A comprises the following steps: 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 Co3O4Nanoparticles.
3. The HRP/Co of claim 13O4@ ZIF-8 composite catalyst, characterized in that: in the step (2), the post-treatment method of the reaction solution B comprises the following steps: 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 modified Co3O4Nanoparticles.
4. The HRP/Co of claim 13O4@ ZIF-8 composite catalyst, characterized in that: in the step (3), the post-treatment method of the reaction solution C comprises the following steps: centrifugally washing the obtained reaction liquid C with deionized water for three times, and drying at room temperature or freeze drying to obtain HRP/Co3O4@ ZIF-8 composite catalyst.
5. An HRP/Co as defined in claim 13O4Application of @ ZIF-8 composite catalyst in 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 CN110540984A (en) | 2019-12-06 |
| CN110540984B true 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) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN111690637B (en) * | 2020-05-11 | 2021-11-30 | 河北工业大学 | Preparation method of organophosphorus degrading enzyme-based multifunctional catalyst, organophosphorus degrading enzyme-based multifunctional catalyst and application thereof |
| CN112063612B (en) * | 2020-08-12 | 2022-05-17 | 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 |
| CN113651970B (en) * | 2021-08-24 | 2022-12-06 | 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 |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100408483C (en) * | 2006-11-23 | 2008-08-06 | 南京大学 | Process for preparing nanometer cobalt oxide |
| 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
Also Published As
| Publication number | Publication date |
|---|---|
| CN110540984A (en) | 2019-12-06 |
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 | |
| CN107233924B (en) | The preparation and application of mercapto-modified metal organic framework compound catalyst | |
| CN104525264B (en) | Ammonobase organic framework material, its preparation method and application comprising active metal component | |
| CN110592064B (en) | Horseradish peroxidase @ MOF composite catalyst and preparation method thereof | |
| CN103920534B (en) | Immobilized alkaline ionic liquid catalyst of a kind of metal-organic framework materials and preparation method thereof | |
| CN105344368B (en) | A kind of preparation method and application of transition metal phosphide for hydrogenation-dechlorination reaction | |
| WO2023274269A1 (en) | Noble metal-loaded covalent organic framework composite material, and preparation method therefor | |
| CN105149006B (en) | Ligand aminated metal-organic framework supported catalyst and preparation method and application thereof | |
| CN106984312B (en) | A kind of composite photocatalyst and preparation method thereof | |
| CN109772463B (en) | Catalyst ZIF-67-Me/CuO for CO reduction and low-temperature denitrationxAnd preparation method and application thereof | |
| CN112403519B (en) | Preparation method and application of COF-300/PPy/Au (G) nanoenzyme catalyst | |
| CN108554416B (en) | Modified cobalt-based catalyst and preparation method and application thereof | |
| CN106111198A (en) | A kind of preparation method and applications of the catalyst of metal organic gel materials loaded Ag based on MIL 100 (Al) | |
| CN107774246A (en) | The preparation method and applications of loaded palladium catalyst in a kind of hollow nanometer capsule core | |
| CN108404987A (en) | Method for improving catalytic efficiency of nanoparticle @ MOFs material | |
| CN108097315A (en) | A kind of support type NH2The synthetic method of-UiO-66 hydrogenation catalysts and application | |
| CN106362736A (en) | Low-load palladium-platinum core-shell structure catalyst and preparation method and application thereof | |
| 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 | |
| Zhang et al. | Synthesis of high efficient and stable Au@ ZIF-8 with difference particle size for chemselective hydrogenation of nitro compounds | |
| CN110592065B (en) | Horseradish peroxidase @ metal organic framework spherical particle catalyst and preparation method thereof | |
| CN108404993B (en) | A method of nitryl aromatic hydrocarbons are handled using the carbonitride load type nano gold catalyst of poly-dopamine reduction | |
| CN108948366A (en) | A kind of preparation and its desulfurization application of the Fe-MOF catalyst with abundant Lewis acidic site | |
| CN108236954A (en) | A kind of method of low temperature removing formaldehyde | |
| CN115888683A (en) | Zinc monoatomic catalyst, preparation method thereof and application thereof in catalytic preparation of N-formyl compound |
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 |