阅读说明：本技术 基于硅酸盐溶解动力学制备硅酸锰纳米酶的方法及应用 (Method for preparing manganese silicate nanoenzyme based on silicate dissolution kinetics and application ) 是由 吕路 王伟伟 魏蕾 张炜铭 潘丙才 于 2021-09-01 设计创作，主要内容包括：本发明公开了基于硅酸盐溶解动力学制备硅酸锰纳米酶的方法及应用,涉及材料化学与纳米酶催化技术领域,包括物理预处理、超声预处理、硅酸盐溶解和老化反应四个步骤,具体为：采用天然硅酸盐矿物作为模板,经研磨、过筛及超声分散预处理后,利用有机配体促进硅酸盐部分溶解并原位形成SiO4-4基团；最后,使用氨水/氯化铵缓冲液催化Mn～(2+)与SiO4-4基团结合,并老化反应制备得到硅酸锰纳米酶；将其作为模拟氧化酶,能够用于4-氨基氨替吡啉比色法检测苯酚类化合物以及催化氧化辣根过氧化物酶底物；本发明所制备得到的硅酸锰纳米酶结构完整,合成成本低、工艺简单,具有经济节约和规模化生产的优势,在环境、生物催化氧化和医学免疫方面具有广阔的应用前景。(The invention discloses a method for preparing manganese silicate nanoenzyme based on silicate dissolution kinetics and application, relates to the technical field of material chemistry and nanoenzyme catalysis, and comprises four steps of physical pretreatment, ultrasonic pretreatment, silicate dissolution and aging reaction, and specifically comprises the following steps: natural silicate minerals are used as templates, and after grinding, sieving and ultrasonic dispersion pretreatment, organic ligands are utilized to promote partial dissolution of silicate and in-situ formation of SiO4-4 groups; finally, Mn is catalyzed using an ammonia/ammonium chloride buffer 2+ Combining with SiO4-4 group, and aging to obtain manganese silicate nanometer enzyme; the analogue oxidase can be used for detecting phenols by 4-aminoimidacloprid colorimetric methodA compound and a catalytic oxidation horseradish peroxidase substrate; the manganese silicate nano enzyme prepared by the invention has the advantages of complete structure, low synthesis cost, simple process, economy, mass production and wide application prospect in the aspects of environment, biological catalytic oxidation and medical immunity.)

1. The method for preparing the manganese silicate nanoenzyme based on the silicate dissolution kinetics is characterized by comprising the following steps of:

s1: physical pretreatment

Grinding natural silicate minerals, sieving and removing impurities to obtain high-purity mineral powder;

s2: ultrasonic pretreatment

Dispersing the high-purity mineral powder obtained in the step S1 in water, and performing ultrasonic treatment under the condition of mechanical stirring to obtain a monodisperse silicate suspension;

s3: silicate dissolution

Adding an organic ligand into the monodisperse silicate suspension obtained in the step S2, wherein the organic ligand is used for complexing metal cations on the surface of the nano-structure of the silicate mineral, so that natural silicate is dissolved and SiO4-4 groups are formed in situ to obtain a solution containing SiO4-4 groups;

s4: aging reaction

Adding ammonia water/ammonium chloride buffer solution into the solution containing the SiO4-4 group obtained in the step S3 to catalyze Mn in the metal manganese salt²⁺Manganese silicate is formed in situ on the surface of the silicate nano structure and is subjected to aging reaction, and the product is centrifuged, washed by deionized water and dried in vacuum to obtain the manganese silicate nano enzyme.

2. The method for preparing manganese silicate nanoenzyme based on silicate dissolution kinetics of claim 1, wherein the natural silicate mineral in step S1 is any one or any combination of two or more of halloysite, attapulgite, vermiculite or volcanic rock.

3. The method for preparing manganese silicate nanoenzyme based on silicate dissolution kinetics as claimed in claim 1, wherein the grinding speed in step S1 is 80-120r/min, the grinding time is 1-2h, and the mesh number of the selected screen for sieving and removing impurities is 100-300 mesh.

4. The method for preparing manganese silicate nanoenzyme based on silicate dissolution kinetics as claimed in claim 1, wherein the ultrasonic pretreatment in step S2 comprises the following specific steps: 0.2-10g of the screened silicate mineral powder is dispersed in 1000mL of 100-plus deionized water, and ultrasonic dispersion treatment is carried out for 0.5-1h by using a 20-40KHz ultrasonic cleaner under the mechanical stirring of 100-plus 1000 r/min.

5. The method for preparing manganese silicate nanoenzyme based on silicate dissolution kinetics of claim 1, wherein the organic ligand of step S3 is any one or any combination of two or more of citric acid, sodium citrate, tannic acid, oxalic acid, sodium oxalate, tartaric acid, sodium tartrate, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, and humus.

6. The method for preparing manganese silicate nanoenzyme based on silicate dissolution kinetics of claim 1, wherein the catalytic metal manganese salt in step S4 is any one or any combination of two or more of manganese chloride, manganese acetate and manganese sulfate.

7. The method for preparing manganese silicate nanoenzyme based on silicate dissolution kinetics of claim 1, wherein the step S4 comprises adding ammonia/ammonium chloride buffer solution to the solution containing SiO4 "4 group, and then adding ammonia, ammonium chloride, Mn²⁺And the mass ratio of the organic ligand is 15:10:1:0.1-150:100:10: 10.

8. The method for preparing manganese silicate nanoenzyme based on silicate dissolution kinetics as set forth in claim 1, wherein the aging reaction temperature is 10-40 ℃, the reaction time is 6-24 hours, and the magnetic stirring speed is 300-700 r/min.

9. The use of the manganese silicate nanoenzyme prepared according to any one of claims 1 to 8, wherein the manganese silicate nanoenzyme is used for colorimetric detection of phenolic compounds and catalytic oxidation of horseradish peroxidase substrates in 4-aminoimidacloprid.

10. The use of the manganese silicate nanoenzyme prepared by the method of any one of claims 1 to 8, wherein the manganese silicate nanoenzyme is used for the colorimetric detection of phenolic compounds by 4-aminoimidacloprid.

Technical Field

The invention relates to the technical field of material chemistry and nano-enzyme catalysis, in particular to a method for preparing manganese silicate nano-enzyme based on silicate dissolution kinetics and application thereof.

Background

The natural oxidase in organisms is the main enzyme in peroxisome, which accounts for about half of the total amount of peroxisome enzymes, and comprises glucose oxidase, urate oxidase, laccase, and neuraminidase. In essence, various oxidases effect the catalytic oxidation of different substrates (such as phenol, TMB or ABTS) by producing water with molecular oxygen as an electron acceptor. However, natural oxidases are not reusable, sensitive to the environment, poorly stable and costly to synthesize, greatly limiting their application in biotechnology and industrialization.

The nano enzyme is regarded as an excellent substitute of natural enzyme as a nano material with enzymatic activity and a unique nano structure. The catalyst has high stability, high catalytic efficiency, low cost and easy synthesis, and has great application potential in biological and environmental catalysis. A large number of nanomaterials with enzyme-like activity, including metals, metal oxides, metal organic frameworks, carbon-based materials, and transition metal silicate materials, have been discovered and designed, and successfully applied to environmental detection and immunoassays. The oxidase nanoenzyme with high specificity can directly catalyze a substrate (such as phenol, TMB or ABTS) by using molecular oxygen as an oxidant without relying on peroxides such as hydrogen peroxide with low stability. Therefore, the development of the oxidase nanoenzyme with high specificity is more potential and attractive.

The phenol compounds are organic matters with high toxicity, and the trace amount of phenol compounds in water can cause great harm to the environment and human health. The 4-aminoantipyrine colorimetric method based on natural oxidase catalytic oxidation is a common determination method for phenol compounds, and essentially catalyzes phenol and 4-aminoantipyrine to generate oxidation coupling reaction to form a strong coloring product so as to realize the visual detection of the concentration of the coloring product. However, the natural oxidase in this method has many disadvantages in practical application, such as sensitivity to pH and temperature, poor stability, high cost, and harsh reaction conditions. The advent of inorganic nanoenzymes, while compensating for the above deficiencies, relied on the use of hydrogen peroxide. Therefore, there is a great challenge to develop oxidase-like nanoenzymes that are not dependent on hydrogen peroxide.

The manganese-based oxide and silicate nano material thereof show various enzyme activities such as peroxidase, oxidase, superoxide dismutase, glucose oxidase and the like due to rich oxidation states. In particular, the manganese silicate nanomaterial has the dual characteristics of the multi-valence state of the metal oxide and the structural stability of the silicate. In addition, the manganese silicate also has higher specific surface area, abundant active sites and multilevel structural characteristics, and is widely applied to the fields of adsorption, catalysis, energy storage, drug delivery and the like. Particularly, the manganese silicate used as a substrate for simulating the catalytic oxidation of the oxidase has the characteristics of rapid pH response and remarkable oxidation effect, and has great application prospect in the aspects of biological catalytic oxidation and medical immunodetection.

However, the preparation method of manganese silicate reported at present mostly needs to form silicate groups by means of alkali etching with the aid of silicon dioxide as a template. For example, the carbon nanotubes are used as templates to synthesize silica nanotube templates by the songwort team of the chemical institute of the chinese academy of sciences in 2012 (j. mater.chem.,2012,22, 17222-. Chinese patent document (CN201711134136.1) discloses a synthesis method of double-layer hollow nano-manganese silicate based on a bell-shaped template, which utilizes ZIF-8 nano-composite particles coated by mesoporous silica with a bell-shaped core-shell structure as a template to prepare the double-layer hollow nano-manganese silicate particles. The method is mainly based on a Stober method, takes TEOS as a raw material, obtains silicon dioxide microspheres with different particle sizes as hard templates through hydrolytic polycondensation under the catalysis of an organic solvent, a surfactant and alkali, and then obtains the silicon dioxide microspheres in soluble manganese salt through a hydrothermal method. The synthesis process of the methods is complicated, the cost is high, and the method is not beneficial to batch production; and the use of organic solvent in the preparation process does not meet the requirements of environment-friendly and green process, thereby preventing the wide application of the manganese silicate.

The natural silicate is widely distributed in nature, and accounts for about 95 percent of the crust content and 25 percent of the total amount of minerals. The silicate is composed of Si-O tetrahedral anion basic structural units with four negative charges, Si atoms occupy the center, four O atoms occupy four corners and are connected in different modes to form different structures, such as island-shaped olivine, layered halloysite or attapulgite, cyclic montmorillonite and the like. The layered adjustable structure of the silicate endows the silicate with excellent chemical stability and natural nano-structure appearance, and is a main raw material of silicate industry. For example, halloysite is assembled into a natural nanotube-like morphology in a coiled form, with inner and outer surfaces consisting of Al-OH octahedrons and Si-O tetrahedrons, respectively, having a high specific surface area and rich reactivity. The attapulgite is formed by connecting an indirect reverse arranged Si-O tetrahedral layer and a discontinuous arranged octahedral layer, has unique layer chain structure and pore channel structure characteristics, and has needle-shaped, fibrous or fiber aggregation crystals. These unique morphologies make natural silicates an ideal matrix for the construction of composite materials. Chinese patent document (CN202011224423.3) discloses a green one-step hydrothermal synthesis method of manganese silicate microspheres, which is to prepare the manganese silicate microspheres by carrying out hydrothermal reaction on soluble metal manganese salt, soluble silicate and ammonium salt under an alkaline condition. However, the natural layered silicate mineral is not easy to form Si-O tetrahedral anions under acid-base conditions, so that the manganese silicate is difficult to form on the surface of the silicate nano structure by in-situ growth of metal manganese ions.

Under the epigenetic condition, the dissolution of silicate minerals is ubiquitous, however, the bulk dissolution rate is unstable and linear, and the dissolution rate under the acidic condition is positively correlated with the proton activity. The organic ligand of the soluble organic matter can complex metal ions on the solution and a solid-liquid interface, reduce the saturation index of a exchange phase and promote the reaction to move towards the silicate dissolution direction, thereby obviously improving the dissolution rate of silicate minerals. D.E.Grandstaff research shows that under the normal temperature and under the catalysis of organic matters in organic solution, the silicate structure has the dissolution rate sequence of EDTA, citrate, oxalate, tannic acid and succinate. However, there has been no report in the prior art of the preparation of manganese silicates based on natural silicates. Therefore, the development of the method for preparing the manganese silicate nanoenzyme based on the natural silicate dissolution power has important significance for the mass production and further application of the manganese silicate material.

Disclosure of Invention

In order to solve the technical problems, the invention provides a method for preparing manganese silicate nanoenzyme based on silicate dissolution kinetics and application thereof.

The technical scheme of the invention is as follows: the method for preparing the manganese silicate nanoenzyme based on the silicate dissolution kinetics comprises the following steps:

s1: physical pretreatment

Grinding natural silicate minerals, sieving and removing impurities to obtain high-purity mineral powder;

s2: ultrasonic pretreatment

Dispersing the high-purity mineral powder obtained in the step S1 in water, and performing ultrasonic treatment under the condition of mechanical stirring to obtain a monodisperse silicate suspension;

s3: silicate dissolution

Adding an organic ligand into the monodisperse silicate suspension obtained in the step S2, wherein the organic ligand is used for complexing metal cations on the surface of the nano-structure of the silicate mineral, so that natural silicate is dissolved and SiO4-4 groups are formed in situ to obtain a solution containing SiO4-4 groups;

s4: aging reaction

Adding ammonia water/ammonium chloride buffer solution into the solution containing the SiO4-4 group obtained in the step S3 to catalyze Mn in the metal manganese salt²⁺Manganese silicate is formed in situ on the surface of the silicate nano structure and is subjected to aging reaction, and the product is centrifuged, washed by deionized water and dried in vacuum to obtain the manganese silicate nano enzyme.

Further, the natural silicate mineral in the step S1 is any one or any combination of more than two of halloysite, attapulgite, vermiculite or vesuvianite, and the raw materials are selected widely.

Further, in the step S1, the grinding speed is 80-120r/min, the grinding time is 1-2h, and the mesh number of the screen used for sieving and removing impurities is 100-300 meshes, so that the powder has good dispersion effect in deionized water.

Further, the ultrasonic pretreatment in step S2 includes the specific steps of: 0.2-10g of the screened silicate mineral powder is dispersed in 1000mL of 100-plus-one deionized water, and under the mechanical stirring of 1000 r/min-100-plus-one, an ultrasonic cleaning machine of 20-40KHz is used for ultrasonic dispersion treatment for 0.5-1h, and under the ultrasonic treatment parameters, the ultrasonic treatment effect is good and the efficiency is high.

Further, the organic ligand in step S3 is any one or any combination of two or more of citric acid, sodium citrate, tannic acid, oxalic acid, sodium oxalate, tartaric acid, sodium tartrate, ethylenediaminetetraacetic acid, disodium ethylenediaminetetraacetate, and humus, and the raw materials of the organic ligand are widely selected.

Further, the catalytic metal manganese salt in step S4 is any one or any combination of more than two of manganese chloride, manganese acetate and manganese sulfate, and the manganese salt has a good catalytic effect.

Further, in step S4, after adding an aqueous ammonia/ammonium chloride buffer solution to the solution containing SiO4-4 groups, aqueous ammonia, ammonium chloride, and Mn²⁺And the mass ratio of the organic ligand is 15:10:1:0.1-150:100:10: 10.

Furthermore, the aging reaction temperature is 10-40 ℃, the reaction time is 6-24 hours, the magnetic stirring speed is 300-700r/min, and the efficiency of the aging reaction is high under the aging reaction parameters.

The invention also puts forward the application of the manganese silicate nanoenzyme prepared by the method in the colorimetric detection of phenol compounds and the catalytic oxidation of horseradish peroxidase substrates by 4-aminoiminoimidacloprid.

Further, the catalytic oxidation horseradish peroxidase substrate comprises TMB: 3,3',5,5' -tetramethylbenzidine and ABTS: 2, 2' -hydrazine-bis- [ 3-ethylbenzothiazoline-6-sulfonic acid ] -diammine salt.

The invention has the beneficial effects that:

compared with the prior art, the invention has the following remarkable advantages:

(1) the nano-structure characteristics of natural silicate minerals are fully utilized to replace the use of a silicon dioxide template with a complex synthesis process;

(2) organic solvent and surfactant are not needed in the synthesis process, and the process is green and environment-friendly;

(3) the cost of the natural silicate is low, and the in-situ coprecipitation synthesis method is easy for batch production;

(4) the prepared manganese silicate nano material has a unique nano structure and reaction active sites with rich metal active sites with variable valence states, endows the nano enzyme with excellent oxidase-like activity, and has higher performance and wider applicability in the process of catalyzing phenol compounds to generate phenol oxygen free radical intermediates.

Drawings

FIG. 1 is an XRD pattern of a manganese silicate nanomaterial prepared in example 1;

FIG. 2 is a TEM image of halloysite-derived manganese silicate nanotubes prepared in example 5;

FIG. 3 is the absorption spectrum and the photograph of the manganese silicate nanomaterial prepared in example 5 for colorimetry of phenolic pollutants;

FIG. 4 is an absorption spectrum and a photograph of a manganese silicate nanomaterial prepared in example 5 catalyzing oxidation of a TMB substrate;

FIG. 5 is the absorption spectrum and photograph of the manganese silicate nanomaterial prepared in example 8 catalyzing the oxidation of ABTS substrate.

Detailed Description

Example 1

The method for preparing the manganese silicate nanoenzyme based on the silicate dissolution kinetics comprises the following steps:

s1: physical pretreatment

Grinding natural silicate minerals, sieving and removing impurities to obtain high-purity mineral powder;

s2: ultrasonic pretreatment

Dispersing the high-purity mineral powder obtained in the step S1 in water, and performing ultrasonic treatment under the condition of mechanical stirring to obtain a monodisperse silicate suspension;

s3: silicate dissolution

Adding an organic ligand into the monodisperse silicate suspension obtained in the step S2, wherein the organic ligand is used for complexing metal cations on the surface of the nano-structure of the silicate mineral, so that natural silicate is dissolved and SiO4-4 groups are formed in situ to obtain a solution containing SiO4-4 groups;

s4: aging reaction

Adding ammonia water/ammonium chloride buffer solution into the solution containing the SiO4-4 group obtained in the step S3 to catalyze Mn in the metal manganese salt²⁺Manganese silicate is formed in situ on the surface of the silicate nano structure and is subjected to aging reaction, and the product is centrifuged, washed by deionized water and dried in vacuum to obtain the manganese silicate nano enzyme.

The natural silicate mineral in step S1 is halloysite.

In the step S1, the grinding speed is 80r/min, the grinding time is 1h, and the mesh number of the screen used for sieving and removing impurities is 100 meshes, so that the powder has good dispersion effect in deionized water.

The ultrasonic pretreatment in step S2 includes the following steps: 0.2g of the screened silicate mineral powder is dispersed in 100mL of deionized water, and under the mechanical stirring of 100r/min, a 20KHz ultrasonic cleaner is used for ultrasonic dispersion treatment for 0.5h, and under the ultrasonic treatment parameters, the ultrasonic treatment effect is good and the efficiency is high.

The organic ligand of step S3 is oxalic acid.

The catalytic metal manganese salt in the step S4 is manganese chloride, and the manganese salt has good catalytic effect.

In step S4, after adding an aqueous ammonia/ammonium chloride buffer solution to the solution containing SiO4-4 group, aqueous ammonia, ammonium chloride, Mn²⁺And the mass ratio of the organic ligand is 15:10:1: 0.1.

The aging reaction temperature is 10 ℃, the reaction time is 6 hours, the magnetic stirring speed is 300r/min, and the efficiency of the aging reaction is high under the aging reaction parameters.

The manganese silicate nanoenzyme obtained in the step S4 can be applied to the colorimetric detection of phenol compounds by 4-aminoimidacloprid and the catalytic oxidation of horseradish peroxidase substrates.

Catalytic oxidation of horseradish peroxidase substrates included TMB: 3,3',5,5' -tetramethylbenzidine and ABTS: 2, 2' -hydrazine-bis- [ 3-ethylbenzothiazoline-6-sulfonic acid ] -diammine salt.

Example 2

This example differs from example 1 in that:

the natural silicate mineral in step S1 is attapulgite.

In the step S1, the grinding speed is 100r/min, the grinding time is 1.5h, and the mesh number of the screen used for sieving and removing impurities is 200 meshes, so that the powder has good dispersion effect in deionized water.

The ultrasonic pretreatment in step S2 includes the following steps: 0.2g of the screened silicate mineral powder is dispersed in 100mL of deionized water, and ultrasonic dispersion treatment is carried out for 0.5h by using a 30KHz ultrasonic cleaner under the mechanical stirring of 150r/min, wherein the ultrasonic treatment effect is good and the efficiency is high under the ultrasonic treatment parameters.

The organic ligand of step S3 is sodium oxalate.

The catalytic metal manganese salt in the step S4 is manganese acetate, and the manganese salt has good catalytic effect.

In step S4, after adding an aqueous ammonia/ammonium chloride buffer solution to the solution containing SiO4-4 group, aqueous ammonia, ammonium chloride, Mn²⁺And the mass ratio of the organic ligand is 15:10:1: 0.1.

The aging reaction temperature is 20 ℃, the reaction time is 8 hours, the magnetic stirring speed is 300r/min, and the efficiency of the aging reaction is high under the aging reaction parameters.

Example 3

This example differs from example 1 in that:

the natural silicate mineral in step S1 is vermiculite.

In the step S1, the grinding speed is 110r/min, the grinding time is 1.5h, and the mesh number of the screen used for sieving and removing impurities is 300 meshes, so that the powder has good dispersion effect in deionized water.

The ultrasonic pretreatment in step S2 includes the following steps: 1g of the screened silicate mineral powder is dispersed in 100mL of deionized water, and under the mechanical stirring of 200r/min, a 30KHz ultrasonic cleaner is used for ultrasonic dispersion treatment for 1h, wherein under the ultrasonic treatment parameters, the ultrasonic treatment effect is good and the efficiency is high.

The organic ligand of step S3 is tartaric acid.

The catalytic metal manganese salt in the step S4 is manganese sulfate, and the manganese salt has good catalytic effect.

In step S4, after adding an aqueous ammonia/ammonium chloride buffer solution to the solution containing SiO4-4 group, aqueous ammonia, ammonium chloride, Mn²⁺And the mass ratio of the organic ligand is 15:10:1: 1.

The aging reaction temperature is 30 ℃, the reaction time is 10 hours, the magnetic stirring speed is 400r/min, and the efficiency of the aging reaction is high under the aging reaction parameters.

Example 4

This example differs from example 1 in that:

the natural silicate mineral in step S1 is volcanic rock.

In the step S1, the grinding speed is 120r/min, the grinding time is 2h, and the mesh number of the screen used for sieving and removing impurities is 300 meshes, so that the powder has good dispersion effect in deionized water.

The ultrasonic pretreatment in step S2 includes the following steps: 1g of the screened silicate mineral powder is dispersed in 100mL of deionized water, and under the mechanical stirring of 150r/min, a 40KHz ultrasonic cleaner is used for ultrasonic dispersion treatment for 1h, wherein under the ultrasonic treatment parameters, the ultrasonic treatment effect is good and the efficiency is high.

The organic ligand of step S3 is tannic acid.

The catalytic metal manganese salt in the step S4 is manganese chloride, and the manganese salt has good catalytic effect.

In step S4, after adding an aqueous ammonia/ammonium chloride buffer solution to the solution containing SiO4-4 group, aqueous ammonia, ammonium chloride, Mn²⁺And the mass ratio of the organic ligand is 15:10:1: 1.

The aging reaction temperature is 40 ℃, the reaction time is 12 hours, the magnetic stirring speed is 500r/min, and the efficiency of the aging reaction is high under the aging reaction parameters.

Example 5

This example differs from example 1 in that:

the natural silicate mineral in the step S1 is a mixture of halloysite and attapulgite.

In the step S1, the grinding speed is 120r/min, the grinding time is 2h, and the mesh number of the screen used for sieving and removing impurities is 300 meshes, so that the powder has good dispersion effect in deionized water.

The ultrasonic pretreatment in step S2 includes the following steps: 5g of the screened silicate mineral powder is dispersed in 500mL of deionized water, and under the mechanical stirring of 500r/min, a 40KHz ultrasonic cleaner is used for ultrasonic dispersion treatment for 1h, wherein under the ultrasonic treatment parameters, the ultrasonic treatment effect is good and the efficiency is high.

The organic ligand of step S3 is citric acid.

The catalytic metal manganese salt in the step S4 is manganese chloride, and the manganese salt has good catalytic effect.

In step S4, after adding an aqueous ammonia/ammonium chloride buffer solution to the solution containing SiO4-4 group, aqueous ammonia, ammonium chloride, Mn²⁺And the mass ratio of the organic ligand is 15:10:1: 1.

The aging reaction temperature is 40 ℃, the reaction time is 18 hours, the magnetic stirring speed is 700r/min, and the efficiency of the aging reaction is high under the aging reaction parameters.

Example 6

This example differs from example 1 in that:

the natural silicate mineral in the step S1 is a mixture of vermiculite and vesuvianite.

In the step S1, the grinding speed is 120r/min, the grinding time is 2h, and the mesh number of the screen used for sieving and removing impurities is 300 meshes, so that the powder has good dispersion effect in deionized water.

The ultrasonic pretreatment in step S2 includes the following steps: 10g of the screened silicate mineral powder is dispersed in 1000mL of deionized water, and under the mechanical stirring of 1000r/min, a 40KHz ultrasonic cleaner is used for ultrasonic dispersion treatment for 1h, wherein under the ultrasonic treatment parameters, the ultrasonic treatment effect is good and the efficiency is high.

The organic ligand of step S3 is disodium edetate.

The catalytic metal manganese salt in the step S4 is manganese chloride, and the manganese salt has good catalytic effect.

In step S4, after adding an aqueous ammonia/ammonium chloride buffer solution to the solution containing SiO4-4 group, aqueous ammonia, ammonium chloride, Mn²⁺And the mass ratio of the organic ligand is 15:10:1: 5.

The aging reaction temperature is 40 ℃, the reaction time is 24 hours, the magnetic stirring speed is 700r/min, and the efficiency of the aging reaction is high under the aging reaction parameters.

Example 7

This example differs from example 6 in that:

the organic ligand of step S3 is citric acid.

In step S4, after adding an aqueous ammonia/ammonium chloride buffer solution to the solution containing SiO4-4 group, aqueous ammonia, ammonium chloride, Mn²⁺And the mass ratio of the organic ligand is 15:10:1: 10.

Example 8

This example differs from example 6 in that:

the natural silicate mineral in step S1 is halloysite.

The organic ligand of step S3 is sodium tartrate.

In step S4, after adding an aqueous ammonia/ammonium chloride buffer solution to the solution containing SiO4-4 group, aqueous ammonia, ammonium chloride, Mn²⁺And the mass ratio of the organic ligand is 15:10:1: 8.

Example 9

This example differs from example 8 in that:

the organic ligand of step S3 is ethylenediaminetetraacetic acid.

In step S4, after adding an aqueous ammonia/ammonium chloride buffer solution to the solution containing SiO4-4 group, aqueous ammonia, ammonium chloride, Mn²⁺And the mass ratio of the organic ligand is 15:10:1: 10.

Example 10

This example differs from example 9 in that:

the organic ligand of step S3 is humus.

Application example:

(1) the manganese silicate nanoenzyme derived from natural silicate is prepared and used for colorimetric sensing of phenolic pollutants, and the method specifically comprises the following steps: firstly, 200 mu g/mL of manganese silicate nano enzyme suspension, 0.9-72ppm of phenol solution (phenolic compound is one or more of phenol, o-chlorophenol, p-bromophenol, p-chlorocatechol and p-bromocatechol), 1mg/mL of 4-aminoantipyrine and 30mM of MES buffer solution, namely 2- (N-morpholine) ethanesulfonic acid (pH is 6.8) are respectively prepared. Mixing the above solutions 100, 200, 600 and 100 μ L respectively, dispersing uniformly at room temperature in dark and shaking, standing for 30min, and testing the absorbance change of the solution system with ultraviolet spectrophotometer (scanning 510 nm).

(2) The manganese silicate nanoenzyme derived from natural silicate is prepared and used for catalyzing TMB substrate oxidation, and the specific steps comprise: first, 200. mu.g/mL of a manganese silicate nanoenzyme suspension, a 1.5mM TMB-dimethylsulfoxide solution, and a 56mM acetic acid-sodium acetate buffer solution (pH 4.5) were prepared, respectively. Mixing 100 μ L, 200 μ L and 700 μ L of the above solutions, standing for 30min in dark place, and testing absorbance change of the solution system with ultraviolet spectrophotometer (scanning at 652 nm).

(3) The manganese silicate nanoenzyme derived from natural silicate is prepared and used for catalyzing ABTS substrate oxidation, and the specific steps comprise: first, 200. mu.g/mL of a manganese silicate nanoenzyme suspension, a 1.5mM aqueous ABTS solution, and a 56mM acetic acid-sodium acetate buffer solution (pH 4.5) were prepared, respectively. Mixing 100 μ L, 200 μ L and 700 μ L of the above solutions, standing at room temperature in dark place, shaking to disperse uniformly, and testing the absorbance change of the solution system with an ultraviolet spectrophotometer (scanning 655 nm).