A preparation method and use of amidoxime-modified metal oxide array material

Abstract

The present invention discloses an amidoxime-modified metal oxide array material and a preparation method and application thereof, which belongs to the technical field of inorganic nanomaterial synthesis, and is a two-dimensional amidoxime-modified nanomaterial with uniform particle size and high catalytic activity obtained by hydrothermal synthesis. Specifically, the high-temperature and high-pressure water-enclosed environment provided by the hydrothermal reaction is conducive to the uniformity and yield of the reaction, and the localized growth of the metal hydroxide nanoarray is achieved. After calcination treatment under an inert atmosphere, a metal oxide with a regular structure is obtained. The present invention not only provides a new method for a completely new metal oxide nanoarray, but also obtains a reusable seawater uranium extraction material with stable physicochemical properties, high adsorption performance for uranyl ions, through amidoxime, providing theoretical support and a completely new material system for the industrialization of seawater uranium extraction.

Description

Technical Field

[0001] The invention belongs to the technical field of inorganic nano material synthesis, and particularly relates to a method for preparing a metal oxide nano array material and amidoximation thereof. Background Art

[0002] The preparation and application of new materials play an important role in human scientific and technological civilization, and have an irreplaceable role in industrial upgrading and social progress. With the growth of demand and the development of various fields, the dependence on new materials continues to increase. Nowadays, the preparation of inorganic nano materials mostly uses liquid phase hydrothermal method, which has a simple preparation process, short reaction time and good controllability. By adjusting the reaction temperature and time, the ratio of reactants in the solution and the pH value, it is expected to obtain a method for rapidly preparing new nano materials with high catalytic activity, intact crystallization and uniform particle size.

[0003] 2D nanomaterials such as metal oxides and layered double hydroxides can effectively promote charge transfer, adsorption and activation of reactive molecules, and thus enhance their catalytic activity due to their highly adjustable energy bands and electronic structures, highly exposed active sites, high specific surface areas, and high electrical conductivity. Compared with hydroxides, metal oxides have higher theoretical specific capacities and better stability. After amidoximation, metal oxides have high specific surface areas and good hydrophilicity, and have a particularly strong affinity for uranyl ions, which have great application potential in the extraction of uranium from seawater. Summary of the invention

[0004] The purpose of the present invention is to provide a preparation method and use of an amidoxime-modified metal oxide array material. The present invention not only provides a new method for metal oxide nanoarrays, solving the problems of difficult production and preparation of 2D nanomaterials, performance fluctuations easily caused by size effects, and difficulty in controlling material quality and purity, but also obtains a reusable seawater uranium extraction material with stable physicochemical properties, high uranyl ion adsorption performance, and high reusability through amidoximation, providing theoretical support and a new material system for the industrialization of seawater uranium extraction.

[0005] To achieve the above object, the present invention provides a method for preparing an amidoxime-modified metal oxide array material, wherein a metal hydroxide nanoarray material is prepared by a hydrothermal synthesis method under a high temperature and high pressure water environment, and then a metal oxide nanoarray material with a regular structure is obtained by calcination treatment under an inert atmosphere, and then a cyano group is introduced by a hydrothermal synthesis method for amidoximation to obtain an amidoxime-modified metal oxide nanoarray material, wherein the preparation of the metal oxide nanoarray material comprises the following steps:

[0006] (1) mixing a soluble metal nitrate solution, an ammonium fluoride solution and a urea solution to prepare a reaction solution I, immersing a conductive substrate in the reaction solution I to perform a hydrothermal reaction to obtain a metal hydroxide nanoarray material;

[0007] (2) placing the metal hydroxide nanoarray material in (1) in an atmosphere furnace, and calcining for 1-5 hours under the protection of an inert gas to obtain a metal oxide nanoarray material;

[0008] The amidoxime modification of the metal oxide nanoarray material comprises the following steps:

[0009] S1, mixing acrylic acid, acrylonitrile and N,N-dimethylformamide to prepare a reaction solution II, immersing the metal oxide nanoarray material in the reaction solution II, and performing a hydrothermal reaction;

[0010] S2. Prepare a mixed solution of a solvent, hydroxylamine hydrochloride and sodium hydroxide as reaction solution III, immerse the product in S1 in reaction solution III, and perform a hydrothermal reaction to obtain amidoxime-modified metal oxide nanoarray material.

[0011] Preferably, in step (1), in the reaction solution I, the concentration of the soluble metal nitrate is 0.05-0.5 g / mL, the concentration of ammonium fluoride is 0.001-0.05 g / mL, the concentration of urea is 0.01-0.5 g / mL, the molar ratio of the soluble metal nitrate to ammonium fluoride is (2:1)-(1:2), and the molar ratio of the soluble metal nitrate to urea is (2:1)-(1:2).

[0012] Preferably, the soluble metal nitrate is selected from one of Mg(NO3)2, Co(NO3)2, Ni(NO3)2, Ca(NO3)2, Cu(NO3)2, Fe(NO3)2, Mn(NO3)2, and LiNO3.

[0013] Preferably, the conductive substrate is selected from one of nickel foam, ITO, FTO, nickel sheet, titanium sheet, copper mesh, carbon fiber cloth and transparent conductive cloth.

[0014] Preferably, the conductive substrate is cleaned before immersion, and the cleaning method of the conductive substrate is: ultrasonically cleaning the conductive substrate with anhydrous ethanol, acetone and deionized water in sequence, and the ultrasonic cleaning time of each time is 10-20 minutes.

[0015] Preferably, in step (1), the hydrothermal reaction time is 3-10h, and the reaction temperature is 80-200°C; in step (2), the calcination temperature is 350-900°C, the heating rate is 1-10°C / min, and the inert gas is nitrogen or argon; in step S1, the hydrothermal reaction time is 3-10h, and the reaction temperature is 50-100°C; in step S2, the hydrothermal reaction time is 3-10h, and the reaction temperature is 50-100°C.

[0016] Preferably, the volume ratio of acrylic acid to acrylonitrile is (4:1)-(1:4), and the volume ratio of acrylic acid to N,N-dimethylformamide is (4:1)-(1:4).

[0017] Preferably, the solvent is selected from one of methanol, formaldehyde, ethanol, acetaldehyde, and dimethyl sulfoxide, the volume ratio of the solvent to water is (1:5)-(1:15), the concentration of hydroxylamine hydrochloride is 0.005-0.05 g / mL, the concentration of sodium hydroxide is 0.01-0.1 g / mL, and the volume ratio of hydroxylamine hydrochloride to sodium hydroxide is (4:1)-(1:4).

[0018] The invention also discloses an amidoxime modified metal oxide array material, which is prepared by a method for preparing the amidoxime modified metal oxide array material.

[0019] The invention also discloses an amidoxime-modified metal oxide array material for use in the field of uranium extraction from seawater.

[0020] Therefore, the present invention adopts the above-mentioned method for preparing the amidoxime-modified metal oxide array material and its use, and its beneficial effects are:

[0021] 1. This invention uses a simple and fast hydrothermal synthesis method for the first time to prepare different types of metal oxide nanowire arrays on a variety of conductive substrates, providing a relatively universal method for the simple and fast preparation of metal oxides. By regulating the hydrothermal synthesis temperature and time, the size and density of the nanoarray are well regulated to achieve optimal performance;

[0022] 2. The present invention also provides a new and more universal method for the amidoximation of metal oxide nanowire arrays. A new, low-cost, high-catalytic-activity, stable-physicochemical-properties, high-adsorption-performance-for-uranyl-ions seawater uranium extraction material is prepared through amidoximation reaction, which expands the application field of metal oxide nanowire materials and provides theoretical support and a new material system for the industrialization of seawater uranium extraction.

[0023] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0024] Figure 1 This is a scanning electron microscope image of the FTO-loaded amidoxime-modified cobalt tetroxide nanowire array prepared in Example 1 of the present invention;

[0025] Figure 2 This is a scanning electron microscope image of the FTO-loaded amidoxime-modified cobalt tetroxide nanowire array prepared in Example 1 of the present invention after adsorbing uranium in seawater;

[0026] Figure 3 This is the XRD image of the FTO-loaded amidoxime-modified cobalt oxide nanowire array before and after adsorption prepared in Example 1 of the present invention. DETAILED DESCRIPTION

[0027] The technical solution of the present invention is further described below through the accompanying drawings and embodiments.

[0028] Unless otherwise defined, technical or scientific terms used in the present invention shall have the common meanings understood by one having ordinary skills in the field to which the present invention belongs.

[0029] In addition, it should be understood that although this specification is described according to the implementation modes, not every implementation mode includes only one independent technical solution. This description of the specification is only for the sake of clarity. Those skilled in the art should regard the specification as a whole. The technical solutions in each embodiment can also be appropriately combined to form other implementation modes that can be understood by those skilled in the art. These other implementation modes are also covered within the protection scope of the present invention.

[0030] The present invention provides a method for preparing an amidoxime-modified metal oxide array material. The method comprises the following steps: preparing a metal hydroxide nanoarray material under a high temperature and high pressure water environment by a hydrothermal synthesis method, and then calcining the material under an inert atmosphere to obtain a metal oxide nanoarray material with a regular structure. Then, a cyano group is introduced by a hydrothermal synthesis method to perform amidoximation to obtain an amidoxime-modified metal oxide nanoarray material. The method comprises the following steps:

[0031] (1) mixing a soluble metal nitrate solution, an ammonium fluoride solution and a urea solution to prepare a reaction solution I, immersing a conductive substrate in the reaction solution I, and performing a hydrothermal reaction for 3-10 hours at a reaction temperature of 80-200° C.; obtaining a metal hydroxide nanoarray material;

[0032] The soluble metal nitrate is selected from one of Mg(NO3)2, Co(NO3)2, Ni(NO3)2, Ca(NO3)2, Cu(NO3)2, Fe(NO3)2, Mn(NO3)2, and LiNO3.

[0033] The concentration of the soluble metal nitrate is 0.05-0.5 g / mL, the concentration of ammonium fluoride is 0.001-0.05 g / mL, the concentration of urea is 0.01-0.5 g / mL, the molar ratio of the soluble metal nitrate to ammonium fluoride is (2:1)-(1:2), and the molar ratio of the soluble metal nitrate to urea is (2:1)-(1:2);

[0034] The conductive substrate is selected from one of nickel foam, ITO, FTO, nickel sheet, titanium sheet, copper mesh, carbon fiber cloth and transparent conductive cloth;

[0035] (2) placing the metal hydroxide nanoarray material in (1) in an atmosphere furnace, under the protection of an inert gas such as nitrogen or argon, at 350-900° C., at a heating rate of 1-10° C. / min, for 1-5 h to obtain a metal oxide nanoarray material;

[0036] (3) Mixing acrylic acid, acrylonitrile and N,N-dimethylformamide to prepare a reaction solution II, wherein the volume ratio of acrylic acid to acrylonitrile is (4:1)-(1:4), and the volume ratio of acrylic acid to N,N-dimethylformamide is (4:1)-(1:4), and immersing the metal oxide nanoarray material in (2) in the reaction solution II to perform a hydrothermal reaction, wherein the hydrothermal reaction time is 3-10 hours and the reaction temperature is 50-100° C.;

[0037] (4) preparing a mixed solution of a solvent, hydroxylamine hydrochloride and sodium hydroxide as reaction solution III, immersing the product in (3) in reaction solution III, and performing a hydrothermal reaction at a reaction time of 3-10 hours and a reaction temperature of 50-100° C. to obtain amidoxime-modified metal oxide nanoarray materials.

[0038] The conductive substrate is cleaned before immersion. The cleaning method of the conductive substrate is: ultrasonically clean the conductive substrate with anhydrous ethanol, acetone and deionized water in sequence, and the ultrasonic cleaning time of each time is 10-20 minutes.

[0039] Preferably, the solvent is selected from one of methanol, formaldehyde, ethanol, acetaldehyde, and dimethyl sulfoxide, the volume ratio of the solvent to water is (1:5)-(1:15), the concentration of hydroxylamine hydrochloride is 0.005-0.05 g / mL, the concentration of sodium hydroxide is 0.01-0.1 g / mL, and the volume ratio of hydroxylamine hydrochloride to sodium hydroxide is (4:1)-(1:4).

[0040] The invention also discloses an amidoxime-modified metal oxide array material, which is prepared by a method for preparing the amidoxime-modified metal oxide array material.

[0041] The invention also discloses an amidoxime-modified metal oxide array material for use in the field of uranium extraction from seawater.

[0042] [Example 1]

[0043] This embodiment discloses a amidoxime-modified metal oxide array material: the synthesis of FTO-loaded cobalt oxide nanowire arrays, comprising the following steps:

[0044] (1) The FTO conductive glass was ultrasonically treated with hydrochloric acid, anhydrous ethanol and deionized water for 10 min each to remove surface impurities. A mixed solution of 0.1 g / mL cobalt nitrate, 0.007 g / mL ammonium fluoride and 0.03 g / mL urea was prepared, and the FTO conductive glass was immersed in the above reaction solution for a hydrothermal reaction at a reaction time of 5 h and a reaction temperature of 120°C to obtain a metal hydroxide nanoarray material.

[0045] (2) The metal hydroxide nanoarray material in (1) is placed in an atmosphere furnace, protected by nitrogen gas, at 350° C., with a heating rate of 2° C. / min, and calcined for 2 h to obtain a metal oxide nanoarray material.

[0046] (3) A mixed solution of acrylic acid, acrylonitrile and N,N-dimethylformamide is prepared as a reaction solution, wherein the volume ratio of acrylic acid to acrylonitrile is (1:4), and the volume ratio of acrylic acid to N,N-dimethylformamide is (1:4). The metal oxide nanoarray material in (2) is immersed in the reaction solution to carry out a hydrothermal reaction. The reaction time is 10 hours and the reaction temperature is 75°C.

[0047] (4) A mixed solution of dimethyl sulfoxide, hydroxylamine hydrochloride and sodium hydroxide was prepared as a reaction solution, wherein the volume ratio of the solvent to water was 1:10, the concentration of hydroxylamine hydrochloride was 0.035 g / mL, and the concentration of sodium hydroxide was 0.02 g / mL. The product of (3) was immersed in the reaction solution for a hydrothermal reaction. The reaction time was 10 h and the reaction temperature was 75° C. to obtain an amidoxime-modified metal oxide nanoarray material.

[0048] Instructions attached Figure 1 And the instruction manual Figure 2 This is a scanning electron microscope picture of this embodiment. The cobalt tetroxide nanowires are successfully loaded on the FTO conductive glass, and the crystallization is intact, the particle size is uniform, the particle dispersion is good, and the agglomeration of the cobalt tetroxide particles is avoided.

[0049] Instructions attached Figure 3 This is the XRD picture of this example. By comparing it before and after adsorption, it is shown that the material has a stable structure and can be reused.

[0050] [Example 2]

[0051] This embodiment discloses an amidoxime-modified metal oxide array material: the synthesis of a carbon fiber cloth-supported cobalt oxide nanowire array, which specifically includes the following steps:

[0052] (1) After soaking the carbon fiber cloth in potassium permanganate solution for 10 hours, the carbon fiber cloth was ultrasonically treated with deionized water for 20 minutes each to remove surface impurities. A mixed solution of 0.1 g / mL cobalt nitrate, 0.007 g / mL ammonium fluoride and 0.03 g / mL urea was prepared, and the carbon fiber cloth was soaked in the above reaction solution for hydrothermal reaction at a reaction time of 5 hours and a reaction temperature of 120°C to obtain a metal hydroxide nanoarray material.

[0053] (2) The metal hydroxide nanoarray material in (1) is placed in an atmosphere furnace, protected by nitrogen gas, at 550° C., with a heating rate of 2° C. / min, and calcined for 2 h to obtain a metal oxide nanoarray material.

[0054] (3) Prepare a mixed solution of acrylic acid, acrylonitrile and N,N-dimethylformamide as a reaction solution, wherein the volume ratio of acrylic acid to acrylonitrile is (1:4), and the volume ratio of acrylic acid to N,N-dimethylformamide is (1:4). Soak the metal oxide nanoarray material in (2) in the reaction solution and perform a hydrothermal reaction, the reaction time is 8 hours, and the reaction temperature is 65°C.

[0055] (4) A mixed solution of ethanol, hydroxylamine hydrochloride and sodium hydroxide was prepared as a reaction solution, wherein the volume ratio of the solvent to water was 1:8, the concentration of hydroxylamine hydrochloride was 0.035 g / mL, and the concentration of sodium hydroxide was 0.02 g / mL. The product of (3) was immersed in the reaction solution for a hydrothermal reaction. The reaction time was 5 h and the reaction temperature was 70° C. to obtain an amidoxime-modified metal oxide nanoarray material.

[0056] [Example 3]

[0057] This embodiment discloses a amidoxime-modified metal oxide array material: the synthesis of FTO-loaded nickel oxide nanowire array, which specifically includes the following steps:

[0058] (1) The FTO conductive glass was ultrasonically treated with hydrochloric acid, anhydrous ethanol, and deionized water for 10 min each to remove surface impurities. A mixed solution of 0.02 g / mL nickel nitrate, 0.007 g / mL ammonium fluoride, and 0.03 g / mL urea was prepared, and the FTO conductive glass was immersed in the above reaction solution for a hydrothermal reaction at a reaction time of 8 h and a reaction temperature of 150°C to obtain a metal hydroxide nanoarray material.

[0059] (2) The metal hydroxide nanoarray material in (1) was placed in an atmosphere furnace, and calcined at 500°C for 2 h at a heating rate of 2°C / min under nitrogen gas protection to obtain a metal oxide nanoarray material.

[0060] (3) Prepare a mixed solution of acrylic acid, acrylonitrile and N,N-dimethylformamide as a reaction solution, wherein the volume ratio of acrylic acid to acrylonitrile is (1:4), and the volume ratio of acrylic acid to N,N-dimethylformamide is (1:4). Soak the metal oxide nanoarray material in (2) in the reaction solution and perform a hydrothermal reaction for 8 hours at a reaction temperature of 75°C.

[0061] (4) A mixed solution of dimethyl sulfoxide, hydroxylamine hydrochloride and sodium hydroxide was prepared as a reaction solution, wherein the volume ratio of the solvent to water was 1:5, the concentration of hydroxylamine hydrochloride was 0.035 g / mL, and the concentration of sodium hydroxide was 0.02 g / mL. The product of (3) was immersed in the reaction solution for a hydrothermal reaction. The reaction time was 6 h and the reaction temperature was 75° C. to obtain an amidoxime-modified metal oxide nanoarray material.

[0062] Therefore, the present invention provides a preparation method and use of an amidoxime-modified metal oxide array material. The present invention not only provides a new method for metal oxide nanoarrays, solving the problems of difficult production and preparation of 2D nanomaterials, performance fluctuations easily caused by size effects, and difficulty in controlling material quality and purity, but also obtains a reusable seawater uranium extraction material with stable physicochemical properties, high uranyl ion adsorption performance, and through amidoximation, providing theoretical support and a new material system for the industrialization of seawater uranium extraction.

[0063] Finally, it should be noted that the above embodiments are only used to illustrate the technical solution of the present invention rather than to limit it. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solution of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solution to deviate from the spirit and scope of the technical solution of the present invention.

Claims

1. A method for preparing an amidoxime-modified metal oxide array material, characterized in that: A metal hydroxide nanoarray material is prepared by a hydrothermal synthesis method under a high temperature and high pressure water environment, and then a metal oxide nanoarray material with a regular structure is obtained by calcination in an inert atmosphere. Subsequently, a cyano group is introduced by a hydrothermal synthesis method to perform amidoximation to obtain an amidoxime-modified metal oxide nanoarray material, wherein the preparation of the metal oxide nanoarray material comprises the following steps: (1) mixing a soluble metal nitrate solution, an ammonium fluoride solution and a urea solution to prepare a reaction solution I, immersing a conductive substrate in the reaction solution I to perform a hydrothermal reaction to obtain a metal hydroxide nanoarray material; (2) placing the metal hydroxide nanoarray material in (1) in an atmosphere furnace, and calcining for 1-5 hours under the protection of an inert atmosphere to obtain a metal oxide nanoarray material; The amidoxime modification of the metal oxide nanoarray material comprises the following steps: S1, mixing acrylic acid, acrylonitrile and N,N-dimethylformamide to prepare a reaction solution II, immersing the metal oxide nanoarray material in the reaction solution II, and performing a hydrothermal reaction; S2, preparing a mixed solution of a solvent, hydroxylamine hydrochloride and sodium hydroxide as a reaction solution III, immersing the product in S1 in the reaction solution III, and performing a hydrothermal reaction to obtain an amidoxime-modified metal oxide nanoarray material; The solvent is selected from one of methanol, formaldehyde, ethanol, acetaldehyde and dimethyl sulfoxide.

2. The method for preparing an amidoxime-modified metal oxide array material according to claim 1, characterized in that: In step (1), in the reaction solution I, the concentration of the soluble metal nitrate is 0.05-0.5 g / mL, the concentration of ammonium fluoride is 0.001-0.05 g / mL, the concentration of urea is 0.01-0.5 g / mL, the molar ratio of the soluble metal nitrate to the ammonium fluoride is (2:1)-(1:2), and the molar ratio of the soluble metal nitrate to the urea is (2:1)-(1:2).

3. The method for preparing an amidoxime-modified metal oxide array material according to claim 1, characterized in that: The soluble metal nitrate is selected from one of Mg(NO3)2, Co(NO3)2, Ni(NO3)2, Ca(NO3)2, Cu(NO3)2, Fe(NO3)2, Mn(NO3)2, and LiNO3.

4. The method for preparing an amidoxime-modified metal oxide array material according to claim 1, characterized in that: The conductive substrate is selected from one of foamed nickel, ITO, FTO, nickel sheet, titanium sheet, copper mesh, carbon fiber cloth and transparent conductive cloth.

5. The method for preparing an amidoxime-modified metal oxide array material according to claim 1, characterized in that: The conductive substrate is cleaned before immersion. The cleaning method of the conductive substrate is: ultrasonically cleaning the conductive substrate with anhydrous ethanol, acetone and deionized water in sequence, and the ultrasonic cleaning time of each time is 10-20 minutes.

6. The method for preparing an amidoxime-modified metal oxide array material according to claim 1, characterized in that: In step (1), the hydrothermal reaction time is 3-10 hours, and the reaction temperature is 80-200°C; in step (2), the calcination temperature is 350-900°C, the heating rate is 1-10°C / min, and the inert atmosphere is nitrogen or argon; in step S1, the hydrothermal reaction time is 3-10 hours, and the reaction temperature is 50-100°C; in step S2, the hydrothermal reaction time is 3-10 hours, and the reaction temperature is 50-100°C.

7. The method for preparing an amidoxime-modified metal oxide array material according to claim 1, characterized in that: The volume ratio of acrylic acid to acrylonitrile is (4:1)-(1:4), and the volume ratio of acrylic acid to N,N-dimethylformamide is (4:1)-(1:4).

8. The method for preparing an amidoxime-modified metal oxide array material according to claim 1, characterized in that: The volume ratio of the solvent to water is (1:5)-(1:15), the concentration of hydroxylamine hydrochloride is 0.005-0.05 g / mL, the concentration of sodium hydroxide is 0.01-0.1 g / mL, and the volume ratio of hydroxylamine hydrochloride to sodium hydroxide is (4:1)-(1:4).

9. An amidoxime-modified metal oxide array material, characterized in that: The amidoxime-modified metal oxide array material is prepared by the preparation method of the amidoxime-modified metal oxide array material according to any one of claims 1 to 8.

10. A use of the amidoxime-modified metal oxide array material as claimed in claim 9, characterized in that: An amidoxime-modified metal oxide array material is used in the field of uranium extraction from seawater.

Images