CN108816286B - Cu-Ag/g-C3N4Preparation method of/ZIF (zinc-ferrum-potassium) ternary composite mimic enzyme - Google Patents

Cu-Ag/g-C3N4Preparation method of/ZIF (zinc-ferrum-potassium) ternary composite mimic enzyme Download PDF

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CN108816286B
CN108816286B CN201810325839.0A CN201810325839A CN108816286B CN 108816286 B CN108816286 B CN 108816286B CN 201810325839 A CN201810325839 A CN 201810325839A CN 108816286 B CN108816286 B CN 108816286B
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宋功武
杨美玲
何瑜
毛蜜
周建刚
葛伊莉
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Hubei University
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Abstract

The invention provides a Cu-Ag/g-C3N4The preparation method of the/ZIF ternary complex mimic enzyme comprises the following steps: a) synthesizing bulk carbon nitride by directly heating melamine; b) modifying the bulk carbon nitride according to a Hummers method; c) synthesizing ZIF-8; d) reducing the mixture in one step to obtain Cu @ Ag/g-C3N4the/ZIF ternary complex mimic enzyme. The nano mimic enzyme consists of copper silver nano particles and carbon nitride nano sheets (g-C)3N4) Compounded with a ZIF-8 ternary material, the carrier ZIF-8 has high specific surface area and high stability and promotes the catalytic activity to be more excellent, and the catalyst is used in the process of H2O2And good response is obtained in the application of glucose colorimetric detection, and meanwhile, the catalytic activity of the composite material is proved to be obviously superior to that of a pure material.

Description

Cu-Ag/g-C3N4Preparation method of/ZIF (zinc-ferrum-potassium) ternary composite mimic enzyme
Technical Field
The invention relates to the technical field of water quality analysis, in particular to Cu-Ag/g-C3N4A preparation method of a/ZIF ternary complex mimic enzyme.
Background
Graphite phase carbon nitride (g-C)3N4) Has a sheet structure similar to graphene, is an excellent raw material for preparing composite materials, and is g-C compared with graphene3N4The material is simple to prepare, is cheap and easy to obtain, can be prepared from precursors such as cyanamide, dicyandiamide, melamine, urea, thiourea and the like through thermal polymerization, and is easy to realize large-scale application. g-C as n-type semiconductor3N4Is a polymer formed by a triazabenzene unit, has the band gap energy of about 2.7ev, has the advantages of excellent thermal stability, higher electron transfer rate and the like, arouses more and more interest in the scientific field, and has the advantages of water decomposition, carbon dioxide reduction, organic pollutant degradation and organic synthesis reaction in the field of catalytic applicationHas great potential. However, studies have shown that g-C3N4Has the defects of low specific surface, high photoproduction electron-hole recombination rate and the like, and still can not meet the requirements of people. To this end, scientists have made many efforts to solve the above problems, such as: doping elements, introducing pore channels, preparing heterojunction materials and the like. Wherein the catalyst is combined or coupled with oxides, metals, noble metal nanoparticles, sulfides and carbon materials is an effective method for improving catalytic activity.
Metal organic framework Materials (MOFs) are porous crystal materials of supramolecular network structures assembled by polydentate organic ligands (mostly aromatic polyacid and polyacid) containing oxygen, nitrogen and the like and transition metal ions, have various advantages as a novel functional polymer material, such as diverse topological structures, excellent physical and chemical properties, easy design and assembly, become hot spots of research in the field of microporous materials, and are widely applied to the fields of adsorption separation, magnetic materials, gas storage, drug transportation and the like. At present, the novel MOFs porous material can combine the high stability of inorganic zeolite materials and the high porosity and organic function of MOFs, and is mostly applied to high-efficiency catalysis and separation processes.
Disclosure of Invention
In view of the above, the present invention provides a Cu-Ag/g-C3N4The preparation method of the/ZIF ternary composite mimic enzyme is used for preparing a novel composite material with excellent catalytic performance.
The invention provides a Cu-Ag/g-C3N4The preparation method of the/ZIF ternary complex mimic enzyme comprises the following steps:
s1, synthetic carbon nitride: heating melamine, and cooling to obtain carbon nitride;
s2, Synthesis g-C3N4: under the condition of ice-water bath, adding C3N4And H2SO4Stirring, adding KMnO4Stirring was continued, and the mixture was transferred to ultrapure water and H was added2O2Standing and centrifuging to obtain g-C3N4；
S3, synthesis of ZIF-8: dissolving with dimethylformamideZn (NO) decomposition3)2·6H2Adding O and 2-methylimidazole into a reaction kettle after constant volume is determined, cooling after reaction, removing mother liquor, adding chloroform, obtaining a colorless crystal on the upper layer, namely ZIF-8, washing with dimethylformamide and drying; carrying out activation pretreatment on ZIF-8 before loading metal, soaking ZIF-8 in methanol, and then carrying out vacuum drying;
s4, synthesizing a ternary composite mimic enzyme: mixing ZIF-8 and g-C3N4Dispersing in a solvent, wherein 5-100 mg ZIF-8 and 5-50 mg g-C are dispersed in 5-200 mL of the solvent3N4Adding copper salt solution, silver nitrate solution, ionic liquid and surfactant under the protection of inert gas, and adding the NaBH prepared in situ while stirring4Adding 0.1-1 mL of copper salt solution, 0.1-1 mL of silver nitrate solution, 0.1-1 mL of ionic liquid, 0.5-5 g of surfactant and 0.2-5 mL of NaBH into every 5-200 mL of solvent4The solution is centrifugally washed and dried to obtain Cu-Ag/g-C3N4the/ZIF ternary complex mimic enzyme.
In a second aspect, the present invention provides a method of using the above Cu-Ag/g-C3N4The product is prepared by the preparation method of the ZIF ternary complex mimic enzyme.
The invention has the beneficial effects that: the invention simply synthesizes a novel composite material Cu-Ag/g-C by a one-step reduction method3N4ZIF nano mimic enzyme, which is prepared from copper silver nanoparticles and carbon nitride nanosheets (g-C)3N4) Compounded with a ZIF-8 ternary material, the carrier ZIF-8 has high specific surface area and high stability and promotes the catalytic activity to be more excellent, and the catalyst is used in the process of H2O2And good response is obtained in the application of glucose colorimetric detection, and meanwhile, the catalytic activity of the composite material is proved to be obviously superior to that of a pure material.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below, and it is obvious that the drawings in the following description are some embodiments of the present invention, and for those skilled in the art, other drawings can be obtained according to these drawings without creative efforts.
FIG. 1 shows Cu-Ag/g-C obtained in example one3N4A scanning electron micrograph of/ZIF;
FIG. 2 shows Cu-Ag/g-C3N4Ultraviolet spectrogram of the ZIF catalytic reaction along with the change of the concentration of the hydrogen peroxide;
FIG. 3 shows Cu-Ag/g-C3N4A linear fitting curve chart of hydrogen peroxide for ZIF detection;
FIG. 4 shows Cu-Ag/g-C3N4Ultraviolet spectrogram of/ZIF catalytic reaction along with change of glucose concentration;
FIG. 5 shows Cu-Ag/g-C3N4Linear fit plot of/ZIF detected glucose.
Detailed Description
The invention provides Cu-Ag/g-C3N4The preparation method of the/ZIF ternary complex mimic enzyme comprises the following steps:
s1, synthetic carbon nitride: heating melamine, and cooling to obtain carbon nitride;
s2, Synthesis g-C3N4: under the condition of ice-water bath, adding C3N4And H2SO4Stirring, adding KMnO4Stirring was continued, and the mixture was transferred to ultrapure water and H was added2O2Standing and centrifuging to obtain g-C3N4；
S3, synthesis of ZIF-8: dissolving Zn (NO) with dimethylformamide3)2·6H2Adding O and 2-methylimidazole into a reaction kettle after constant volume is determined, cooling after reaction, removing mother liquor, adding chloroform, obtaining a colorless crystal on the upper layer, namely ZIF-8, washing with dimethylformamide and drying; carrying out activation pretreatment on ZIF-8 before loading metal, soaking ZIF-8 in methanol, and then carrying out vacuum drying;
s4, synthesizing a ternary composite mimic enzyme: mixing ZIF-8 and g-C3N4Dispersing in a solvent, wherein 5-100 mg ZIF-8 and 5-50 mg g-C are dispersed in 5-200 mL of the solvent3N4Adding a copper salt solution, a silver nitrate solution, an ionic liquid and a watch in the presence of inert gasAdding the surfactant into the NaBH prepared in situ while stirring4Adding 0.1-1 mL of copper salt solution, 0.1-1 mL of silver nitrate solution, 0.1-1 mL of ionic liquid, 0.5-5 g of surfactant and 0.2-5 mL of NaBH into every 5-200 mL of solvent4The solution is centrifugally washed and dried to obtain Cu/Ag/g-C3N4the/ZIF ternary complex mimic enzyme.
According to the preparation method, carbon nitride and a bimetallic material are compounded, a Cu-Ag alloy nano material is directly synthesized by taking ZIF as a template, the Cu-Ag alloy nano material is synchronously compounded with the carbon nitride to form the ternary compound mimic enzyme, and the carbon nitride and the Cu-Ag alloy material are cooperatively catalyzed to effectively improve the catalytic performance2O2And good response is obtained in the application of glucose colorimetric detection.
Preferably, in step S4, the copper salt solution has a concentration of 0.15M, the silver nitrate solution has a concentration of 0.15M, and NaBH is added4The solution concentration was 1M.
More preferably, the copper salt solution is one or more of copper nitrate, copper chloride and copper sulfate.
More preferably, the surfactant is one or more of sodium benzenesulfonate, sodium fatty alcohol-polyoxyethylene ether sulfate, and lauroyl glutamic acid.
Preferably, the ionic liquid is one or more of 1- (4-sulfonic group) butyl pyridine ionic liquid, 1-butyl-3-methylimidazole Lin tetrahydroborate ionic liquid and 1-allyl-3-methylimidazolium chloride ionic liquid.
Preferably, the step of synthesizing carbon nitride in step S1 includes: heating melamine to 200-700 ℃ and keeping for 1-8 hours, naturally cooling and grinding, and collecting powder to obtain the carbon nitride.
Preferably, in step S2, each 0.2-2gC3N4Correspondingly adopts 5-50mLH2SO4、0.5-5gKMnO450-500mL of ultrapure water and 5-50mLH2O2(ii) a Said H2SO4The mass concentration is 98 percent, and the content of H is2O2The mass concentration is 30 percent, the stirring time is 0.2 to 2 hours, theThe standing time is 2-24 h.
Preferably, in step S3, 0.1-1.0g of Zn (NO) is dissolved per 100mL of dimethylformamide3)2·6H2O and 0.05-0.2g of 2-methylimidazole, heating the mixed solution to 100-180 ℃ at the speed of 5 ℃/min in a reaction kettle, reacting at the high temperature for 2-48h, naturally cooling to 10-30 ℃, removing the mother solution, adding chloroform, removing the upper colorless crystal which is ZIF-8, washing the colorless crystal with dimethylformamide for three times, and naturally drying; ZIF-8 needs to be subjected to activation pretreatment before metal loading, and the ZIF-8 is soaked in methanol for 12-48h and then dried in vacuum for 3-12 h.
In a second aspect, the present invention provides a method of using the above Cu-Ag/g-C3N4The product is prepared by the preparation method of the ZIF ternary complex mimic enzyme.
In order to facilitate understanding of the present invention, the present invention will be described more fully and in detail below with reference to the accompanying drawings and examples, but the scope of the present invention is not limited to the following specific examples.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically stated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
Example 1
This example provides a Cu-Ag/g-C3N4The preparation method of the/ZIF ternary complex mimic enzyme comprises the following steps:
(1) synthesis of bulk carbon nitride by direct heating of melamine: 3g of melamine were placed in an alumina crucible with a lid, heated to 400 ℃ and held for 3 hours, and then cooled naturally. The resulting yellow, lumpy solid was then ground with a quartz mortar and the powder was collected.
(2) Bulk carbon nitride was modified according to Hummers method: under the condition of ice-water bath, 0.8gC3N4And 10mLH2SO4(98%) was stirred well and 0.8g KMnO was slowly added4Stirring was continued for 0.6 hour, and the mixture was transferred to 100mL of ultrapure water, and 70mLH was added2O2(30%). Standing for 12h, and centrifuging to obtain g-C3N4。
(3) Synthesis of ZIF-8: dissolving 0.3g Zn (NO) with dimethylformamide3)2·6H2O and 0.1g of 2-methylimidazole, transferring the mixture into a 100mL volumetric flask, and adding a certain amount of the mixture into a 50mL stainless steel reaction kettle. Transferring the reaction kettle to an oven, heating the oven to 120 ℃ at the speed of 5 ℃/min, reacting at the high temperature for 20h, and naturally cooling to room temperature. And removing the mother liquor, adding 20mL of chloroform, washing the upper layer with dimethylformamide for three times, and naturally drying to obtain a colorless crystal, namely ZIF-8. ZIF-8 needs to be subjected to activation pretreatment before metal loading, and is dried for 9 hours in vacuum after being soaked in methanol for 18 hours under natural conditions.
(4) Sonicating 20mg ZIF-8 and 10mg g-C for 5min3N4Dispersed in 100mL of methanol in N2Adding 0.05mL of copper nitrate solution (0.0906g, 0.15M) and 0.05mL of silver nitrate solution (0.0378g, 0.15M) under protection, adding 0.3mL of 1- (4-sulfonic acid group) butylpyridine ionic liquid, adding 0.8g of sodium benzenesulfonate, and injecting 0.8mL of freshly prepared NaBH during vigorous stirring4Solution (0.0743g, 1M). The catalyst is obtained by centrifugal washing of methanol for three times. Finally, vacuum drying is carried out for 5h, and the frozen storage is carried out. The scanning electron microscope result of the obtained product is shown in the attached figure 1.
Example 2
This example provides a Cu-Ag/g-C3N4The preparation method of the/ZIF ternary complex mimic enzyme comprises the following steps:
(1) synthesis of bulk carbon nitride by direct heating of melamine: 7g of melamine were placed in an alumina crucible with a lid, heated to 470 ℃ and held for 1-8 hours, and then cooled naturally. The resulting yellow, lumpy solid was then ground with a quartz mortar and the powder was collected.
(2) Bulk carbon nitride was modified according to Hummers method: under the condition of ice-water bath, 0.7gC3N4And 19mLH2SO4(98%) was stirred well and 3.7g KMnO was slowly added4Stirring was continued for 1.7 hours, and the mixture was transferred to 370mL of ultrapure water and 37mLH was added2O2(30%). Standing for 17h, and centrifuging to obtain g-C3N4。
(3) Synthesis of ZIF-8: dissolving 0.7g Zn (NO) with dimethylformamide3)2·6H2O and 0.07g of 2-methylimidazole, transferring the mixture into a 100mL volumetric flask, and adding a certain amount of the mixture into a 50mL stainless steel reaction kettle. Transferring the reaction kettle to an oven, heating the oven to 150 ℃ at the speed of 5 ℃/min, reacting at high temperature for 2-48h, and naturally cooling to room temperature. And removing the mother liquor, adding 20mL of chloroform, washing the upper layer with dimethylformamide for three times, and naturally drying to obtain a colorless crystal, namely ZIF-8. ZIF-8 needs to be subjected to activation pretreatment before metal loading, and is dried in vacuum for 3-12 hours after being soaked in methanol for 17 hours under natural conditions.
(4) Sonicating 70mg ZIF-8 and 17mg g-C for 5min3N4Dispersed in 70mL of N-hexane2Adding 0.7mL of copper sulfate solution (0.15M) and 0.7mL of silver nitrate solution (0.15M) under protection, adding 0.7mL of 1-allyl-3-methylimidazolium chloride ionic liquid, adding 0.7g of lauroyl glutamic acid, and injecting 0.7mL of freshly prepared NaBH during vigorous stirring4Solution (0.0743g, 1M). The catalyst was obtained by three centrifugal washes of methanol. Finally, vacuum drying is carried out for 5h, and the frozen storage is carried out.
Example 3
This example provides a Cu-Ag/g-C3N4The preparation method of the/ZIF ternary complex mimic enzyme comprises the following steps:
(1) synthesis of bulk carbon nitride by direct heating of melamine: 6g of melamine were placed in an alumina crucible with a lid, heated to 600 ℃ and held for 6 hours, and then cooled naturally. The resulting yellow, lumpy solid was then ground with a quartz mortar and the powder was collected.
(2) Bulk carbon nitride was modified according to Hummers method: under the condition of ice-water bath, 0.16gC3N4And 36mLH2SO4(98%) was stirred well and 3.6g KMnO was slowly added4Stirring is continued for 1.4 hours, thenThe mixture was transferred to 366mL of ultrapure water and 46mLH was added2O2(30%). Standing for 20h, and centrifuging to obtain g-C3N4。
(3) Synthesis of ZIF-8: dissolving 0.6g Zn (NO) with dimethylformamide3)2·6H2O and 0.06g of 2-methylimidazole are transferred to a 100mL volumetric flask to a constant volume and then quantitatively added to a 50mL stainless steel reaction kettle. Transferring the reaction kettle to an oven, heating the oven to 160 ℃ at the speed of 5 ℃/min, reacting at the high temperature for 26h, and naturally cooling to room temperature. And removing the mother liquor, adding 20mL of chloroform, washing the upper layer with dimethylformamide for three times, and naturally drying to obtain a colorless crystal, namely ZIF-8. ZIF-8 needs to be subjected to activation pretreatment before metal loading, and is dried in vacuum for 6 hours after being soaked in methanol for 16 hours under natural conditions.
(4) Ultrasonic treating 60mg ZIF-8 and 26mg g-C for 5min3N4Dispersed in 150mL of acetone in N2Adding 0.6mL of copper chloride (0.15M) and 0.6mL of silver nitrate solution (0.15M) under protection, adding 0.6mL of 1-butyl-3-methylimidazole -forest tetrahydroborate ionic liquid, adding 2.1g of sodium fatty alcohol-polyoxyethylene ether sulfate, and injecting 2.6mL of freshly prepared NaBH in the process of vigorous stirring4Solution (0.0743g, 1M). The catalyst was obtained by three centrifugal washes of methanol. Finally, vacuum drying is carried out for 5h, and the frozen storage is carried out.
Example 4
The seed Cu-Ag/g-C obtained in the first example3N4Application of/ZIF (zinc-ferrum-phosphate) ternary composite mimic enzyme in detection of H2O2。
Because TMB and hydrogen peroxide are subjected to oxidation reaction in the presence of a catalyst, the absorbance of the solution at 652nm is changed. Based on this, different concentrations of H were separately added2O2And a catalytic amount of Cu-Ag/g-C3N4the/ZIF was added to a solution containing 0.5mM TMB, the pH was adjusted to 3.8 with acetate buffer solution, and the absorbance at 652nm was measured and recorded, respectively, with an ultraviolet spectrophotometer. At H2O2When the catalyst and the solution are simultaneously present, the solution is blue, and has obvious ultraviolet absorption at 652nm, which indicates that the ternary composite material is feasible to detect the hydrogen peroxide. It can be seen in FIG. 2 that with catalysisThe solution color changes obviously (from colorless to dark blue) when the hydrogen peroxide concentration rises in the reaction, and the absorbance gradually increases, which shows that Cu-Ag/g-C3N4the/ZIF catalyst has the potential of detecting hydrogen peroxide by naked eye sensing. Under optimal conditions, the absorbance at 652nm with H between 0.05mM and 1mM2O2The concentration is linear, as shown in fig. 3, the calibration function is a, 1.0389C +0.0078, the correlation coefficient is 0.993, the linear range is wide, and the detection limit is low.
Example 5
The seed Cu-Ag/g-C obtained in the first example3N4the/ZIF ternary complex mimic enzyme is used for detecting glucose.
The solution has ultraviolet absorption at 652nm because the reaction between glucose and glucose oxidase can not occur under the condition of a catalyst. Based on the method, glucose with different concentrations and Cu-Ag/g-C with catalytic amount are respectively added3N4the/ZIF was added to the solution containing glucose oxidase and its absorbance at 652nm was measured and recorded separately with an ultraviolet spectrophotometer. When glucose and a catalyst exist at the same time, the solution is blue, and has obvious ultraviolet absorption at 652nm, which indicates that the ternary composite material is feasible to detect the glucose. As can be seen in FIG. 4, as the concentration of glucose increased during the catalytic reaction, the color of the solution changed significantly (from colorless to blue), and the absorbance gradually increased, indicating that Cu-Ag/g-C3N4the/ZIF catalyst has the potential of detecting glucose by naked eye sensing. Under optimal conditions, the absorbance at 652nm is linear with glucose concentration from 5 μ M to 1000 μ M, as shown in fig. 5, the calibration function is a 0.0004C +0.02886, the correlation coefficient is 0.991, the linear range is wide, and the detection limit is low.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents, improvements and the like that fall within the spirit and principle of the present invention are intended to be included therein.

Claims (9)

1. Cu-Ag/g-C3N4ZIF ternary compound dieThe preparation method of the mimic enzyme is characterized by comprising the following steps: the method comprises the following steps:
s1, synthetic carbon nitride: heating melamine, and cooling to obtain carbon nitride;
s2, Synthesis g-C3N4: under the condition of ice-water bath, adding C3N4And H2SO4Stirring, adding KMnO4Stirring was continued, and the mixture was transferred to ultrapure water and H was added2O2Standing and centrifuging to obtain g-C3N4；
S3, synthesis of ZIF-8: dissolving Zn (NO) with dimethylformamide3)2·6H2Adding O and 2-methylimidazole into a reaction kettle after constant volume is determined, cooling after reaction, removing mother liquor, adding chloroform, obtaining a colorless crystal on the upper layer, namely ZIF-8, washing with dimethylformamide and drying; carrying out activation pretreatment on ZIF-8 before loading metal, soaking ZIF-8 in methanol, and then carrying out vacuum drying;
s4, synthesizing a ternary composite mimic enzyme: mixing ZIF-8 and g-C3N4Dispersing in a solvent, wherein 5-100 mg ZIF-8 and 5-50 mg g-C are dispersed in 5-200 mL of the solvent3N4Adding copper salt solution, silver nitrate solution, ionic liquid and surfactant under the protection of inert gas, and adding the NaBH prepared in situ while stirring4Adding 0.1-1 mL of copper salt solution, 0.1-1 mL of silver nitrate solution, 0.1-1 mL of ionic liquid, 0.5-5 g of surfactant and 0.2-5 mL of NaBH into every 5-200 mL of solvent4 The solution is centrifugally washed and dried to obtain Cu-Ag/g-C3N4the/ZIF ternary complex mimic enzyme.
2. The Cu-Ag/g-C of claim 13N4The preparation method of the/ZIF ternary composite mimic enzyme is characterized by comprising the following steps: step S4, the concentration of the copper salt solution is 0.15M, the concentration of the silver nitrate solution is 0.15M, and the NaBH is added4The solution concentration was 1M.
3. The Cu-Ag/g-C of claim 23N4The preparation method of the/ZIF ternary composite mimic enzyme is characterized by comprising the following steps: the above-mentionedThe copper salt is one or more of copper nitrate, copper chloride and copper sulfate.
4. The Cu-Ag/g-C of claim 23N4The preparation method of the/ZIF ternary composite mimic enzyme is characterized by comprising the following steps: the surfactant is one or more of sodium benzenesulfonate, sodium fatty alcohol-polyoxyethylene ether sulfate, and lauroyl glutamic acid.
5. The Cu-Ag/g-C of claim 13N4The preparation method of the/ZIF ternary composite mimic enzyme is characterized by comprising the following steps: the ionic liquid is 1-allyl-3-methylimidazole chloride ionic liquid.
6. The Cu-Ag/g-C of claim 13N4The preparation method of the/ZIF ternary composite mimic enzyme is characterized by comprising the following steps: step S1 the step of synthesizing carbon nitride includes: heating melamine to 200-700 ℃ and keeping for 1-8 hours, naturally cooling and grinding, and collecting powder to obtain the carbon nitride.
7. The Cu-Ag/g-C of claim 13N4The preparation method of the/ZIF ternary composite mimic enzyme is characterized by comprising the following steps: in step S2, every 0.2-2g C3N4Correspondingly adopts 5-50mLH2SO4、0.5-5gKMnO450-500mL of ultrapure water and 5-50mLH2O2(ii) a Said H2SO4The mass concentration is 98 percent, and the content of H is2O2The mass concentration is 30%, the stirring time is 0.2-2 hours, and the standing time is 2-24 hours.
8. The Cu-Ag/g-C of claim 13N4The preparation method of the/ZIF ternary composite mimic enzyme is characterized by comprising the following steps: in step S3, 0.1-1.0g of Zn (NO) is dissolved per 100mL of dimethylformamide3)2·6H2O and 0.05-0.2g 2-methylimidazole, the mixed solution is put in a reaction kettle and heated to 180 ℃ at the speed of 5 ℃/min, the temperature is raised to 10-30 ℃ after the high-temperature reaction for 2-48h, and the mixture is removedAdding chloroform into the mother liquor, wherein a colorless crystal appearing on the upper layer is ZIF-8, washing the colorless crystal with dimethylformamide for three times, and naturally drying; ZIF-8 needs to be subjected to activation pretreatment before metal loading, and the ZIF-8 is soaked in methanol for 12-48h and then dried in vacuum for 3-12 h.
9. Use of the Cu-Ag/g-C of claim 13N4The product is prepared by the preparation method of the ZIF ternary complex mimic enzyme.
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