WO2018113384A1

WO2018113384A1 - One-step method for synthesizing cyclodextrin-modified transition metal oxide material

Info

Publication number: WO2018113384A1
Application number: PCT/CN2017/104877
Authority: WO
Inventors: 占金华; 孔令帅; 孔娅; 张锦文; 李元培; 陈玉峰
Original assignee: 山东大学
Priority date: 2016-12-19
Filing date: 2017-09-30
Publication date: 2018-06-28

Abstract

A one-step method for synthesizing a cyclodextrin-modified transition metal oxide material comprises steps of: adding a transition metal oxide salt and a cyclodextrin to a solvent; stirring and reacting for 1-72 h; washing the resulting solid with an absolute ethanol and a deionized water respectively; after drying, the cyclodextrin-modified transition metal oxide material is obtained. The composite material is not only used for catalyzing hydrogen peroxide and photocatalysis, etc., but also has the effect of host-guest clathration of cyclodextrin supramolecules. The excellent catalytic performance and the supramolecule clathration effect thereof can improve the treatment of environmental pollution.

Description

Method for synthesizing cyclodextrin modified transition metal oxide material by one-step method

Technical field

The invention relates to a method for synthesizing a cyclodextrin-modified transition metal oxide material by one-step method, and belongs to the technical field of material synthesis.

Background technique

In the past few decades, oxide nanomaterials have been applied to many different fields, such as traditional photocatalysis, Fenton reaction, etc., and applications in new fields include photocatalytic hydrogen production and enzyme-like catalysis. In addition, oxide nanomaterials have broad application prospects in biomedical fields such as medical imaging, diagnostic treatment, and mimic enzymes. The use of oxide nanoparticles has become one of the most compelling and dynamic research areas.

It is well known that β-cyclodextrin (β-CDs), which is represented by the second-generation supramolecules, is a cyclic oligosaccharide produced by seven D-glucopyranose units, each of which has a 1,4-glycoside The bonds are combined into a ring. Since the glycosidic linkage to the glucose unit is not free to rotate, the cyclodextrin is not a cylindrical molecule but a slightly conical ring. The central cavity is hydrophobic and lipophilic, so cyclodextrin can selectively identify guest molecules and combine with some organic and inorganic guest molecules of appropriate size to form a supramolecular system, in biological probes, environmental management, Enzyme-catalyzed and other fields have been widely used, and the application prospect is huge.

Physiological hormones and pesticides in human life cause a certain degree of pollution to water quality. Because pesticide residues and physiological hormones are the most common pollutants in environmental water resources. Therefore, methods for removing physiological hormones and pesticides in water are facing major challenges, such as photocatalysis, physical adsorption, and biodegradation.

Summary of the invention

In view of the deficiencies of the prior art, the present invention provides a method for synthesizing a cyclodextrin-modified transition metal oxide material in a one-step process, and the obtained composite material not only has catalytic hydrogen peroxide, photocatalysis, enzyme-like catalysis, but also has a ring. The host-guest of dextrin supramolecular is used in combination, and its excellent catalytic performance and supramolecular cooperation will play an important role in environmental pollution control.

The invention is achieved by the following technical solutions:

A one-step method for synthesizing a cyclodextrin-modified transition metal oxide material comprises the following steps:

The transition metal oxide salt and the cyclodextrin are added to the solvent, and the reaction is stirred for 1 to 72 hours. The solid obtained by the reaction is washed with anhydrous ethanol and deionized water, respectively, and dried to obtain a cyclodextrin-modified transition metal oxide material. Metal oxide The mass ratio of salt to cyclodextrin is: (0.1-200): (0.1-50), the mass-to-volume ratio of transition metal oxide salt to solvent is: (0.1-10): (100-2000), unit: g /mL.

Preferably, the transition metal oxide salt is a copper salt or an iron salt.

Preferably, the copper salt is cuprous chloride, cuprous bromide, cuprous iodide, cuprous sulfate, cuprous carbonate or cuprous nitride.

Further preferably, the copper salt is cuprous chloride.

Preferably, the cyclodextrin is α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin.

Further preferably, the cyclodextrin is β-cyclodextrin.

Preferably, the iron salt is ferric chloride or ferrous chloride.

Further preferably, the iron salt is ferrous chloride.

Preferably, the solvent is water or an alcohol solvent.

Preferably, the alcohol solvent is an alcohol solvent having two or more hydroxyl groups, and more preferably, the alcohol is selected from the group consisting of ethylene glycol, diethylene glycol, 1,2-propylene glycol, 1, 3‐ One or more of propylene glycol, glycerin, 1,3-butanediol, 1,4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol or trimethylolpropane mixture.

Most preferably, the solvent is water.

When the transition metal oxide salt is a copper salt, a one-step synthesis of a cyclodextrin-modified cuprous oxide material is prepared, and the preparation method comprises the following steps:

The copper salt and the cyclodextrin are added to the solvent, and the reaction is stirred for 1 to 72 hours. The brick red solid obtained by the reaction is respectively washed with anhydrous ethanol and deionized water, and dried to obtain a cyclodextrin-modified cuprous oxide material, copper salt and The mass ratio of the cyclodextrin is: (0.1 to 10): (0.1 to 50), and the mass to volume ratio of the copper salt to the solvent is: (0.1 to 10): (100 to 2000), and the unit is g/mL.

Preferably, the mass ratio of the copper salt to the cyclodextrin is (0.1 to 8): (0.1 to 20).

Preferably, the mass to volume ratio of the copper salt to the solvent is: (0.1-10): (100-1000), unit: g/mL; preferably, the mass-volume ratio of the copper salt to the solvent is: (0.1-10) ): (100 to 600), unit: g / mL; most preferably, the mass ratio of copper salt to solvent is: (0.1 ~ 10): 200, unit: g / mL.

Preferably, the reaction time is from 10 to 48 h, more preferably, the reaction time is from 20 to 36 h, and most preferably, the reaction time is 24 h.

In the preferred embodiment of the present invention, the reaction environment is a reaction at a temperature of 40 ° C or less. Preferably, the reaction temperature is 20 to 40 ° C.

Preferably, the drying is carried out in a vacuum drying oven for drying at a temperature of 50 to 70 ° C and a drying time of 10 to 16 hours.

A preferred technical solution of the present invention, a method for synthesizing a cyclodextrin-modified cuprous oxide material in a one-step process, comprising the steps as follows:

The copper salt and the cyclodextrin are added to water or an alcohol solvent, and the reaction is stirred for 10 to 48 hours. The brick red solid obtained by the reaction is respectively washed with anhydrous ethanol and deionized water, and dried to obtain a cyclodextrin-modified cuprous oxide material. The mass ratio of copper salt to cyclodextrin is: (0.1～10): (0.1～50), the mass to volume ratio of copper salt to solvent is: (0.1～10): (100～1000), unit: g/ mL.

When the transition metal oxide salt is an iron salt, a one-step synthesis of a cyclodextrin-modified iron oxyhydroxide material is prepared, and a metal salt is doped during the preparation to obtain a metal-doped cyclodextrin-modified iron oxyhydroxide material, and the preparation method includes Proceed as follows:

The iron salt, the metal salt and the cyclodextrin are added to the water, and the reaction is stirred for 10 to 72 hours. The yellow-brown solid obtained by the reaction is washed with anhydrous ethanol and deionized water, respectively, and dried to obtain a metal-doped cyclodextrin-modified iron oxyhydroxide. The mass ratio of the material, iron salt and cyclodextrin is: (10 ~ 200): (1 ~ 50), the mass to volume ratio of iron salt to water is: (0.1 ~ 10): (10 ~ 200), unit: g /mL, the metal salt is added in an amount of 0.1-10% by mass of the iron salt.

Preferably, the metal salt is a transition metal salt or a noble metal salt, the transition metal salt is a carbonate, a sulfate, a nitrate, a chloride salt of copper, manganese, cobalt or nickel; the transition metal salt is gold, silver, Palladium or platinum salts.

Further preferably, the transition metal salt is a nitrate of copper, manganese, cobalt or nickel.

Further preferably, the salt of gold, silver, palladium or platinum is chloroauric acid, silver nitrate, palladium chloride or palladium acetate.

When the metal salt is a transition metal salt, the iron salt, the transition metal salt and the cyclodextrin are added to water, the reaction is stirred, the reaction is washed, and after drying, a metal-doped cyclodextrin-modified iron oxyhydroxide material is obtained.

When the metal salt is a noble metal salt, the iron salt, the noble metal salt and the cyclodextrin are added to water, the reaction is stirred, the reaction is washed, dried, and hydrogen-reduced to obtain a metal-doped cyclodextrin-modified iron oxyhydroxide material.

Preferably, the mass ratio of the iron salt to the cyclodextrin is (10 to 100): (5 to 20).

Preferably, the mass to volume ratio of iron salt to water is: (0.5-10): (10-100), unit: g/mL;

Preferably, the mass to volume ratio of iron salt to water is: (0.5-10): (10-80), unit: g/mL; most preferably, the mass-volume ratio of iron salt to water is: (0.5-10) : 50, unit: g / mL.

Preferably, the reaction time is from 10 to 36 h, more preferably, the reaction time is from 20 to 36 h, and most preferably, the reaction time is 24 h.

In the preferred embodiment of the present invention, the reaction environment is a reaction at a temperature of 50 ° C or less. Preferably, the reaction temperature is 25 ° C.

Preferably, the drying is carried out in an electric blast drying oven for drying at a temperature of 60 to 80 ° C and a drying time of 10 to 16 hours.

In the metal doped cyclodextrin-modified iron oxyhydroxide material of the invention, the metal ion is supported in the channel of the iron oxyhydroxide, and the hydroxyl group of the iron oxyhydroxide forms an H bond with the hydroxyl group of the cyclodextrin, and the bonding structure is on the one hand The cyclodextrin is encapsulated on the outside of the iron oxyhydroxide to increase the stability of the iron oxyhydroxide, and on the other hand to promote the stable loading of the metal ions in the hydroxy oxidation In the channel of iron, the stability of the material is further increased, and the doping of the metal and the inclusion of the cyclodextrin synergistically improve the catalytic degradation performance of the material. Precious metal doping can achieve strong interaction of metal carriers, synergistic with multiple functions, and achieve efficient combined catalysis. It can also achieve surface interaction with atoms based on cyclodextrin-modified carriers at the atomic level to achieve internal electronic surface enrichment. Collecting, thus improving the original nature. The doping width of the iron oxyhydroxide can be changed by the doping of the transition metal, thereby making the optical response range adjustable, and finally achieving a better catalytic effect. In the Fenton reaction, the doping of the transition metal of the transition metal contributes to the circulation of the ferrous iron and the ferric iron, and improves the stability of the material; the doping can also achieve efficient degradation of organic pollutants in a wide pH environment.

The materials and equipment used in the present invention are all prior art.

The advantages of the invention are as follows:

1. The composite material prepared by the invention not only has the catalytic hydrogen peroxide, photocatalysis, enzyme-like catalysis, but also has the host-guest inclusion of cyclodextrin supramolecular, with its excellent catalytic performance and supramolecular package. Cooperation will play an important role in environmental pollution control.

2. The composite material of the invention is doped by noble metal or transition metal, and the modification of cyclodextrin greatly improves the catalytic effect of iron oxyhydroxide, and has the characteristics of catalytic hydrogen peroxide, photocatalysis, enzyme-like catalysis, etc. The host-guest of cyclodextrin supramolecules is used in combination, and its excellent catalytic performance and supramolecular cooperation play a very important role in the catalytic degradation of pollutants such as pesticides and physiological hormones in water.

3. The doping of the noble metal or transition metal of the composite material of the invention improves the catalytic effect of the cyclodextrin-modified iron oxyhydroxide, and the catalytic degradation effect of the iron oxyhydroxide modified by the undoped cyclodextrin is from 0 to 1. The breakthrough; at the same time, after the metal doping, the ultraviolet spectrum changes, resulting in the change of the band gap of the iron oxyhydroxide, and the photocatalytic performance changes.

DRAWINGS

1 is a Fourier transform infrared spectroscopy (FTIR) spectrum of a cyclodextrin-modified cuprous oxide composite prepared in Example 1. The German Bruker ALPHA-T Fourier transform infrared spectrometer was used, and the detector was RT-DLATGS.

2 is a comparison diagram of the degradation effect of cuprous oxide and cyclodextrin-modified cuprous oxide material on hydrogen peroxide degradation of bisphenol;

Figure 3. Degradation kinetics of bisphenol catalyzed by hydrogen peroxide degradation by cuprous oxide and cyclodextrin-modified cuprous oxide materials.

4 is a Fourier transform infrared spectroscopy (FTIR) spectrum of a cyclodextrin-modified iron oxyhydroxide composite prepared in Example 20. The German Bruker ALPHA-T Fourier transform infrared spectrometer was used, and the detector was RT-DLATGS.

Figure 5 is a kinetic diagram of the degradation of 4-chlorophenol by hydrogen peroxide catalyzed by iron oxyhydroxide and a cyclodextrin-modified iron oxyhydroxide material.

Figure 6 is a comparison diagram of the effect of iron oxyhydroxide and cyclodextrin-modified iron oxyhydroxide material on the degradation of 4-chlorophenol by hydrogen peroxide;

Figure 7 is a graph showing the relationship of αhv∝hv function of iron oxyhydroxide;

8 is an αhv∝hv function of a cyclodextrin-coated composite material of iron oxyhydroxide and cobalt ions prepared in Example 22. Number relationship diagram;

Figure 9 is a graph showing the αhv∝hv function of a composite of a cyclodextrin-coated iron oxyhydroxide and a nickel ion prepared in Example 24.

detailed description

The invention is further illustrated by the following specific examples, but is not limited thereto.

The raw materials used in the following examples are all commercially available and analytically pure.

Example 1

A one-step method for synthesizing a cyclodextrin-modified cuprous oxide material is as follows:

First, weigh 0.1-10 grams of cuprous chloride and 0.1-50 grams of β-cyclodextrin in a conical flask, pour 200mL of water, dissolve at room temperature, stir, react for 24h, respectively, the prepared brick red solids The mixture is washed with absolute ethanol, deionized water, and dried to obtain a cyclodextrin-modified cuprous oxide material.

Example 2: A one-step method for synthesizing a cyclodextrin-modified cuprous oxide material as described in Example 1, except that cuprous bromide was substituted for cuprous chloride.

Example 3: A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that cuprous iodide was substituted for cuprous chloride.

Example 4: A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that cuprous sulfate was substituted for cuprous chloride.

Example 5: A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that cuprous carbonate was substituted for cuprous chloride.

Example 6: A one-step method for synthesizing a cyclodextrin-modified cuprous oxide material as described in Example 1, except that cuprous nitride was substituted for cuprous chloride.

Example 7: A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that α-cyclodextrin was substituted for β-cyclodextrin.

Example 8: A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that γ-cyclodextrin was substituted for β-cyclodextrin.

Example 9: A one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the reaction time was 12 h.

Example 10: A one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the reaction time was 36 h.

Example 11: A one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the reaction time was 72 h.

Example 12: A one-step process for the synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that ethylene glycol was used instead of water.

Example 13: A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that glycerin was used instead of water.

Example 14: A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the reaction temperature was 40 °C.

Example 15: A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the reaction temperature was 30 °C.

Example 15: A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the amount of water added was 400 mL.

Example 16: A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the amount of water added was 800 mL.

Example 17: A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the amount of water added was 1000 mL.

Example 18: A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the amount of water added was 1500 mL.

Example 19: A method for the one-step synthesis of a cyclodextrin-modified cuprous oxide material as described in Example 1, except that the amount of water added was 2000 mL.

Experimental Example 1: Catalytic degradation

The cyclodextrin-modified cuprous oxide material prepared by the invention catalyzes the degradation of bisphenol A (BPA) by hydrogen peroxide, and simultaneously compares the catalytic degradation performance with unmodified cuprous oxide.

Experimental equipment: high performance liquid chromatography (HPLC), model ELITE P1201, instrument assembled diode array detector and C18 reverse phase column (5μm, 4.6mm * 150mm), mobile phase is methanol / water (70:30, v / v) The flow rate was 1 mL/min, the column temperature was 40 ° C, and the BPA detection wavelength was 278 nm.

Experimental formulation: Cu ₂ O at a concentration of 0.01 g/L and Cu ₂ O@β-CD, 30 mM H ₂ O ₂ , 10 ppm bisphenol A, stirred at room temperature.

The bisphenol A content in the reaction solution was measured by high performance liquid chromatography (HPLC) at different time points. The comparative degradation effect is shown in Fig. 2, and the degradation kinetics obtained is shown in Fig. 3.

The kinetic analysis by Fig. 3 shows that the apparent rate constant (Kobs) of Cu ₂ O@β-CD is 0.0064 min-1, which is significantly higher than the value of Cu ₂ O degradation of bisphenol A (kobs=0.0036min-1). .

Example 20

A one-step synthesis method of metal doped cyclodextrin-modified iron oxyhydroxide material, the steps are as follows:

Weigh 10 to 100 grams of ferrous chloride, 5 to 20 grams of β-cyclodextrin, copper nitrate in a conical flask, pour 250mL of water, sonicate, stir in a 25 ° C water bath, reaction time 30h, reaction The obtained solids are respectively washed with anhydrous ethanol and deionized water, and dried to obtain a metal-doped cyclodextrin-modified iron oxyhydroxide material, which is a composite material in which cyclodextrin is coated with iron oxyhydroxide and copper ions.

Example 21:

The one-step synthesis method described in Example 1 was different except that ferric chloride was used instead of ferrous chloride.

Example 22

The one-step synthesis method described in Example 1 is different in that cobalt nitrate is used instead of copper nitrate to obtain a composite material in which cyclodextrin is coated with iron oxyhydroxide and cobalt ions.

Example 23

The one-step synthesis method described in Example 1 is different in that manganese nitrate is used instead of copper nitrate to obtain a composite material in which cyclodextrin is coated with iron oxyhydroxide and manganese ions.

Example 24:

The one-step synthesis method described in Example 1 is different in that nickel nitrate is used instead of copper nitrate to obtain a composite material in which cyclodextrin is coated with iron oxyhydroxide and nickel ions.

Example 25

The one-step synthesis method described in Example 1 was different in that α-cyclodextrin was substituted for β-cyclodextrin.

Example 26:

The one-step synthesis method described in Example 1 was different in that γ-cyclodextrin was substituted for β-cyclodextrin.

Example 27:

The one-step synthesis method described in Example 1 was different in that the reaction time was 12 h.

Example 28

The one-step synthesis method described in Example 1 was different in that the reaction time was 36 h.

Example 29

The one-step synthesis method described in Example 1 was different in that the reaction time was 72 h.

Example 30:

The one-step synthesis method described in Example 1 was different in that the amount of water added was 400 mL.

Example 31:

The one-step synthesis method described in Example 1 was different in that the amount of water added was 800 mL.

Example 32:

The one-step synthesis method described in Example 1 was different in that the amount of water added was 1000 mL.

Example 33:

The one-step synthesis method described in Example 1 was different in that the amount of water added was 1500 mL.

Example 34:

The one-step synthesis method described in Example 1 was different in that the amount of water added was 2000 mL.

Example 35:

The one-step synthesis method described in the first embodiment is different from: replacing the cobalt nitrate with gold chlorate, stirring the reaction, washing, drying, and then performing hydrogen reduction to obtain a composite of cyclodextrin-coated iron oxyhydroxide and gold. material.

Example 36:

The one-step synthesis method described in the first embodiment is different from: replacing silver nitrate with silver nitrate, stirring the reaction, washing, drying, and then performing hydrogen reduction to obtain a composite material of cyclodextrin-coated iron oxyhydroxide and silver. .

Example 37:

The one-step synthesis method described in the first embodiment is different from: replacing the cobalt nitrate with palladium acetate, stirring the reaction, washing, drying, and then performing hydrogen reduction to obtain a composite material of cyclodextrin-coated iron oxyhydroxide and palladium. .

Example 38:

The one-step synthesis method described in the first embodiment is different from: replacing the cobalt nitrate with platinum chloride, stirring the reaction, washing, drying, and then performing hydrogen reduction to obtain a composite of cyclodextrin-coated iron oxyhydroxide and platinum. material.

Experimental Example 2: Catalytic degradation

1. The cyclodextrin-modified iron oxyhydroxide material prepared by the invention catalyzes the degradation of p-chlorophenol (4-cp) by hydrogen peroxide, and simultaneously with hydrogen peroxide, hydrogen peroxide-cyclodextrin, iron oxyhydroxide- Hydrogen peroxide and metal doped cyclodextrin-modified iron oxyhydroxide were compared for catalytic degradation performance.

Experimental equipment: high performance liquid chromatography (HPLC), model ELITE P1201, instrument assembled diode array detector and C18 reverse phase column (5μm, 4.6mm * 150mm), mobile phase is methanol / water (70:30, v / v) The flow rate was 1 mL/min, the column temperature was 30 ° C, and the 4-CP detection wavelength was 280 nm.

Experimental formulation: FeOOH at a concentration of 0.1 g/L and FeOOH@β-CD, 20 mM H2O2, 100 ppm p-chlorophenol, 100 ppm β-CD, stirred at room temperature.

The content of p-chlorophenol in the reaction solution was measured by high performance liquid chromatography (HPLC) at different time points, and the comparative degradation effect is shown in Fig. 6. The kinetic analysis by Fig. 6 shows that the apparent rate constant (Kobs) of FeOOH@β-CD is 0.0064 min-1, which is significantly higher than the value of degrading 4-chlorophenol by FeOOH (kobs=0.0036 min-1).

From the comparison of FIG. 7-9, the doping of the noble metal or transition metal of the composite material of the invention improves the catalytic effect of the cyclodextrin-modified iron oxyhydroxide, and after the metal doping, the ultraviolet spectrum changes, resulting in oxidation of the hydroxyl group. The width of the forbidden band changes and the photocatalytic properties change.

Claims

A one-step method for synthesizing a cyclodextrin-modified transition metal oxide material comprises the following steps:

The transition metal oxide salt and the cyclodextrin are added to the solvent, and the reaction is stirred for 1 to 72 hours. The solid obtained by the reaction is washed with anhydrous ethanol and deionized water, respectively, and dried to obtain a cyclodextrin-modified transition metal oxide material. The mass ratio of the metal oxide salt to the cyclodextrin is: (0.1 to 200): (0.1 to 50), and the mass to volume ratio of the transition metal oxide salt to the solvent is: (0.1 to 10): (100 to 2000), Unit: g/mL.
The one-step synthesis of a cyclodextrin-modified transition metal oxide material according to claim 1, wherein the transition metal oxide salt is a copper salt or an iron salt.
The method for synthesizing a cyclodextrin-modified transition metal oxide material by the one-step method according to claim 2, wherein the copper salt is cuprous chloride, cuprous bromide, cuprous iodide or sulfuric acid Copper, cuprous carbonate or cuprous nitride; the copper salt is cuprous chloride.
The method for synthesizing a cyclodextrin-modified transition metal oxide material by the one-step method according to claim 1, wherein the cyclodextrin is α-cyclodextrin, β-cyclodextrin or γ-cyclodextrin Preferably, the cyclodextrin is β-cyclodextrin.
The method for synthesizing a cyclodextrin-modified transition metal oxide material by the one-step method according to claim 1, wherein the iron salt is ferric chloride or ferrous chloride; preferably, the iron salt It is ferrous chloride.
The method for synthesizing a cyclodextrin-modified transition metal oxide material by the one-step method according to claim 1, wherein the solvent is water or an alcohol solvent; preferably, the alcohol solvent is two More preferably, the alcoholic substance is a hydroxyl group or higher, and the alcohol is selected from the group consisting of ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, glycerin, 1,3-butanediol, a mixture of one or more of 1,4-butanediol, neopentyl glycol, diethylene glycol, dipropylene glycol or trimethylolpropane; the solvent is water.
The method for synthesizing a cyclodextrin-modified transition metal oxide material by the one-step method according to claim 1, wherein the transition metal oxide salt is a copper salt, and the one-step synthesis of a cyclodextrin-modified cuprous oxide material is prepared, and the preparation method thereof , including the steps below:

The copper salt and the cyclodextrin are added to the solvent, and the reaction is stirred for 1 to 72 hours. The brick red solid obtained by the reaction is respectively washed with anhydrous ethanol and deionized water, and dried to obtain a cyclodextrin-modified cuprous oxide material, copper salt and The mass ratio of the cyclodextrin is: (0.1 to 10): (0.1 to 50), and the mass to volume ratio of the copper salt to the solvent is: (0.1 to 10): (100 to 2000), and the unit is g/mL.
The one-step synthesis of a cyclodextrin-modified transition metal oxide material according to claim 7, wherein the mass ratio of the copper salt to the cyclodextrin is (0.1 to 8): (0.1 to 20).
A method for synthesizing a cyclodextrin-modified transition metal oxide material by a one-step method according to claim 7, The mass-volume ratio of copper salt to solvent is: (0.1-10): (100-1000), unit: g/mL;
The method for synthesizing a cyclodextrin-modified transition metal oxide material according to claim 9, wherein the mass ratio of the copper salt to the solvent is: (0.1 to 10): (100 to 600), the unit : g / mL; most preferably, the mass ratio of copper salt to solvent is: (0.1 ~ 10): 200, unit: g / mL.
A method for synthesizing a cyclodextrin-modified transition metal oxide material by a one-step method according to claim 7, wherein the reaction time is from 10 to 48 hours, and more preferably, the reaction time is from 20 to 36 hours, most preferably, the reaction The time is 24h.
The method for synthesizing a cyclodextrin-modified transition metal oxide material according to claim 7, wherein the reaction environment is a reaction at a temperature of 40 ° C or lower, preferably, the reaction temperature is 20 to 40 ° C; The drying is carried out in a vacuum drying oven for drying at a temperature of 50 to 70 ° C and a drying time of 10 to 16 hours.
A one-step method for synthesizing a cyclodextrin-modified cuprous oxide material comprises the following steps:

The copper salt and the cyclodextrin are added to water or an alcohol solvent, and the reaction is stirred for 10 to 48 hours. The brick red solid obtained by the reaction is respectively washed with anhydrous ethanol and deionized water, and dried to obtain a cyclodextrin-modified cuprous oxide material. The mass ratio of copper salt to cyclodextrin is: (0.1～10): (0.1～50), the mass to volume ratio of copper salt to solvent is: (0.1～10): (100～1000), unit: g/ mL.
The method for synthesizing a cyclodextrin-modified transition metal oxide material by the one-step method according to claim 1, wherein when the transition metal oxide salt is an iron salt, a one-step synthesis of a cyclodextrin-modified iron oxyhydroxide material is prepared, and the preparation process The metal salt is doped to obtain a metal-doped cyclodextrin-modified iron oxyhydroxide material, and the preparation method comprises the following steps:

The iron salt, the metal salt and the cyclodextrin are added to the water, and the reaction is stirred for 10 to 72 hours. The yellow-brown solid obtained by the reaction is washed with anhydrous ethanol and deionized water, respectively, and dried to obtain a metal-doped cyclodextrin-modified iron oxyhydroxide. The mass ratio of the material, iron salt and cyclodextrin is: (10 ~ 200): (1 ~ 50), the mass to volume ratio of iron salt to water is: (0.1 ~ 10): (10 ~ 200), unit: g /mL, the metal salt is added in an amount of 0.1-10% by mass of the iron salt.
The method for synthesizing a cyclodextrin-modified transition metal oxide material by the one-step method according to claim 14, wherein the metal salt is a transition metal salt or a noble metal salt, and the transition metal salt is carbon of copper, manganese, cobalt or nickel. Acid salts, sulfates, nitrates, chloride salts; transition metal salts are salts of gold, silver, palladium or platinum.
A one-step synthesis of a cyclodextrin-modified transition metal oxide material according to claim 14, wherein the transition metal salt is a nitrate of copper, manganese, cobalt or nickel.
The method for synthesizing a cyclodextrin-modified transition metal oxide material by the one-step method according to claim 16, wherein the salt of gold, silver, palladium or platinum is chloroauric acid, silver nitrate, palladium chloride or acetic acid. palladium;

When the metal salt is a transition metal salt, the iron salt, the transition metal salt and the cyclodextrin are added to the water, the reaction is stirred, the reaction is washed, and after drying, the metal-doped cyclodextrin-modified iron oxyhydroxide material is obtained;

When the metal salt is a noble metal salt, the iron salt, the noble metal salt and the cyclodextrin are added to water, the reaction is stirred, the reaction is washed, dried, and hydrogen-reduced to obtain a metal-doped cyclodextrin-modified iron oxyhydroxide material.
The one-step synthesis of a cyclodextrin-modified transition metal oxide material according to claim 14, wherein the mass ratio of the iron salt to the cyclodextrin is (10 to 100): (5 to 20).
The method for synthesizing a cyclodextrin-modified transition metal oxide material by the one-step method according to claim 14, wherein the mass ratio of the iron salt to the water is: (0.5 to 10): (10 to 100), the unit :g/mL;

Preferably, the mass to volume ratio of iron salt to water is: (0.5-10): (10-80), unit: g/mL; most preferably, the mass-volume ratio of iron salt to water is: (0.5-10) : 50, unit: g / mL; reaction time is 10 to 36 h, further preferably, the reaction time is 20 to 36 h, and most preferably, the reaction time is 24 h.
The method for synthesizing a cyclodextrin-modified transition metal oxide material by a one-step method according to claim 14, wherein the reaction environment is a reaction at a temperature of 50 ° C or less, preferably, the reaction temperature is 25 ° C; The drying is carried out in an electric blast drying oven, and the drying temperature is 60 to 80 ° C, and the drying time is 10 to 16 hours.