BASE MATERIAL AND PREPARATION METHOD THEREOF

Abstract

A base material includes a base layer. The base layer includes a structured surface. The base layer includes a transition metal and a transition metal oxide, and a sum of the transition metal and a transition metal oxide accounts for at least 90 wt. % of the base layer. The transition metal oxide is concentratedly distributed on the structured surface. The base material is flexible in at least one direction, and has a bending angle of not less than 90° when being bent.

Claims

1. A base material, comprising a base layer, the base layer comprising a structured surface; wherein, the base layer comprises a transition metal and a transition metal oxide, and a sum of the transition metal and a transition metal oxide accounts for at least 90 wt. % of the base layer; the transition metal oxide is concentratedly distributed on the structured surface; the base material is flexible in at least one direction, and has a bending angle of not less than 90° when being bent.

2. The base material of claim 1, wherein the base material comprises transition metal flakes as raw materials; a plurality of concave and convex stripes is disposed on the transition metal flakes in a substantially uniform direction, and cross-sections of the concave and convex stripes have a mesoscopic scale; and a transition metal oxide film is formed on surfaces of the transition metal flakes, and has a hole array consistent with the direction of the concave and convex stripes, and the holes have an aperture of mesoscopic scale.

3. The base material of claim 2, wherein the transition metal oxide film and pores with an aperture of mesoscopic scale are formed by anodizing the transition metal flakes; and the structured surface is formed by performing an etching treatment on the transition metal flakes.

4. A base material, comprising a base layer having a structured surface, and the structured surface comprising: a) a first protrusion portion, wherein the first protrusion portion extends along one direction of the structured surface; b) a first structural channel extending substantially in the same direction as the first protrusion portion and being adjacent to the first protrusion portion; and c) a plurality of holes distributed in the first protrusion portion and/or the first structural channel; at least 0.05% of the holes distributed in the first protrusion portion communicate with an adjacent first structural channel to form a second structural channel; and the base material comprises at least one transition metal and a corresponding oxide of the transition metal; the base layer comprises a transition metal and a transition metal oxide, and a sum of the transition metal and a transition metal oxide accounts for at least 90 wt. % of the base layer; the transition metal oxide is concentratedly distributed on the structured surface.

5. The base material of claim 4, wherein the base material is flexible in at least one direction; the base material has a bending angle of not less than 90°, or not less than 120°, or reach 180°; and the base material has a bulk density not higher than 1 g/cm.sup.3.

6. The base material of claim 4, wherein the base material is prepared by using transition metal flakes as raw materials; a plurality of concave and convex stripes with a substantially uniform direction is disposed on the transition metal flakes, and cross-sections of the concave and convex stripes have a mesoscopic scale; a transition metal oxide film is formed on surfaces of the transition metal flakes, and has a hole array consistent with a direction of the concave and convex stripes, and the holes have an aperture of mesoscopic scale; and the structured surface is formed by performing an etching treatment on the transition metal flakes.

7. The base material of claim 6, wherein the transition metal oxide film and pores with an aperture of mesoscopic scale are formed by anodizing the transition metal flakes.

8. A base material, comprising: a first structural layer, a second structural layer located at least on one surface of the first structural layer; the second structural layer comprising: a) a first protrusion portion, wherein the first protrusion portion extends along one length direction of the second structural layer; b) a first concave portion that extends substantially in the same direction as the first protrusion portion and is adjacent to the first protrusion portion; and c) a plurality of holes distributed in the first protrusion portion; at least 0.05% of the holes communicate with adjacent first concave portions; and the base material comprises at least one transition metal and a corresponding oxide of the transition metal; a content of the transition metal in the first structural layer is at least 90%, and a content of the oxide of the transition metal in the second structural layer is at least 30%.

9. The base material of claim 8, wherein the base material is flexible in at least one direction; the base material has a bending angle of not less than 90°, or not less than 120°, or reach 180°; and the base material has a bulk density not higher than 1 g/cm.sup.3.

10. The base material of claim 8, wherein the base material is prepared by using transition metal flakes as raw materials; a plurality of concave and convex stripes with a substantially uniform direction is disposed on the transition metal flakes, and cross-sections of the concave and convex stripes have a mesoscopic scale; and a transition metal oxide film is formed on surfaces of the transition metal flakes, and has a hole array consistent with a direction of the concave and convex stripes; and the holes have an aperture of mesoscopic scale or an aperture of nanometer and/or micron scale.

11. The base material of claim 10, wherein the transition metal oxide film and the hole array thereon is formed by performing anodizing treatment on the transition metal flakes; and the second structural layer is formed by performing an etching treatment on the transition metal oxide film and the hole array thereon.

12. A method for preparing a base material, the method comprising: 1) performing treatment on transition metal flakes to form a hole array with an aperture of mesoscopic scale distributed along a stripe direction, or a hole array with a nanoscale and/or micron-scale aperture distributed along the stripe direction; 2) etching the material obtained in 1), so that the holes distributed at the convex stripes are connected to adjacent concave stripes to form a base material that is flexible in at least one direction.

13. The method of claim 12, wherein the concave and convex stripes on surfaces of the transition metal flakes comprise: a plurality of convex stripes with the same direction or substantially the same direction, and concave stripes formed between two adjacent convex stripes; and/or, a plurality of convex stripes parallel or substantially parallel to each other, and concave stripes formed between two adjacent convex stripes.

14. The method of claim 13, wherein a width of the convex stripes on the surfaces of the transition metal flakes is 0.01-50 μm; and/or, a concave stripe with a maximum depth of 0.001-10 nm is formed between the two adjacent convex stripes; and/or, a spacing between two adjacent convex stripes is 0.01-50 μm; and/or, a depth of the holes is 0.02-80 μm; and/or, an average aperture of the holes is at least 10-500 nm; and/or, a wall thickness of the holes is 5-100 nm.

15. The method of claim 12, wherein the material obtained in 1) is etched by using an acid solution; a pH value of the acid solution is 1-3.00, or a hydrogen ion concentration in the acid solution is 0.001 mol/L-0.65 mol/L, and a time for acid etching is 5-70 min.

16. A method for preparing a base material, the method comprising: 1) anodizing: anodizing transition metal flakes with convex stripes on the surface of the transition metal flakes, to form a hole array with an aperture of mesoscopic scale distributed along a stripe direction on the surfaces of the transition metal flakes, or, a hole array with a nanoscale and/or micron-scale aperture distributed along the stripe direction; and 2) etching control: performing surface etching treatment on the transition metal flakes, to form a base material that is flexible in at least one direction.

17. The method of claim 16, wherein when anodizing, an electrode spacing is 0.3-10 cm, a voltage is 10-200 V, and an oxidation time is 2-48 h.

18. The method of claim 16, wherein the etching control comprises performing acid etching control on the surface of the material obtained in 1) by using an acid solution; a pH value of the acid solution is 0.92-3.00; and/or, a hydrogen ion concentration in the acid solution is 0.001 mol/L-0.65 mol/L; a time for acid etching is 5-70 min; and the acid solution is a phosphoric acid solution having a concentration of 2-15 wt. %.

19. The method of claim 18, wherein the concave and convex stripes on the surfaces of the transition metal flakes comprise a plurality of convex stripes with the same direction or substantially the same direction, and concave stripes formed between two adjacent convex stripes; and/or, a plurality of convex stripes parallel or substantially parallel to each other, and concave stripes formed between two adjacent convex stripes; and/or convex stripes on the surface, which are formed by drawing or rolling the transition metal flakes as a basic material.

20. The method of claim 19, wherein the transition metal flakes are one or more of aluminum-containing flakes, tin-containing flakes, nickel-containing flakes and titanium-containing flakes; the thickness of the transition metal flakes is not greater than 500 μm.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

[0124] FIG. 1A shows a surface topography of a polished aluminum foil, FIG. 1B shows an enlarged view of the surface topography of the aluminum foil after wire drawing, and FIG. 1C shows a SEM image of the aluminum foil surface after wire drawing;

[0125] FIG. 2A shows a SEM image of a pore structure on the surface of transition metal aluminum foils after the element loading of Example 1 of the disclosure after anodization, and FIG. 2B shows a SEM image of the change process of the hole walls of transition metal aluminum foils after the element loading during the etching treatment process (not completed);

[0126] FIG. 3 shows a SEM image of the pore layer of the cross section of transition metal aluminum foils of Example 1 of the disclosure after anodization;

[0127] FIG. 4A shows an overall topography of a surface of material in Example 1 obtained through anodization, acid etching control and element loading by using transition metal aluminum foils as base materials; FIG. 4B shows an enlarge view of the first structure channel and the second structural channel; and FIG. 4C shows an enlarge view of the first protrusion portion and the holes thereon after being damaged by acid etching;

[0128] FIG. 5 shows a cross-sectional topography of a material in Example 2 obtained through anodization, acid etching control and element loading by using transition metal tin as the base material;

[0129] FIG. 6A shows a topography of a material obtained after element loading is carried out on the base material prepared by insufficient acid etching of transition metal nickel as the basic material in Comparative Example 2 of the disclosure; and FIG. 6B shows a topography of a material obtained after element loading is carried out on the base material prepared by excessive acid etching of transition metal nickel as the basic material in Comparative Example 2 of the disclosure;

[0130] FIG. 7 shows a pictorial diagram of a base material with orientation flexibility prepared in Example 1 of the disclosure;

[0131] FIG. 8 shows a comparison diagram of the oxalic acid removal effect of the two-dimensional ozone catalytic material prepared by using the base material prepared in Example 1 and Comparative Example 1 as the matrix;

[0132] FIG. 9 shows a comparison diagram of the phenol removal effect of the two-dimensional ozone catalytic material prepared by using the base material prepared in Example 1 and Comparative Example 2 as the matrix;

[0133] FIG. 10 shows a comparison diagram of the phenol removal effect of two-dimensional ozone catalytic material, single ozone, and traditional granular three-dimensional catalyst prepared by using the base material prepared in Example 1 as the matrix;

[0134] FIG. 11 shows a comparison diagram of the pyrazole removal effect of two-dimensional ozone catalytic material, single ozone, and traditional granular three-dimensional catalyst prepared by using the base material prepared in Example 2 as the matrix;

[0135] FIG. 12 shows a comparison diagram of the oxalic acid removal effect of two-dimensional ozone catalytic material, single ozone, and traditional granular three-dimensional catalyst prepared by using the base material prepared in Example 3 as the matrix;

[0136] FIG. 13A shows a mass transfer schematic diagram of the material after element loading of the transition metal aluminum foil after anodization in Example 1 of the disclosure during the water treatment; and FIG. 13B shows a mass transfer schematic diagram of the material after anodization, acid etching control and element loading during the water treatment;

[0137] FIG. 14A shows a reactor for packing a catalyst in the semi-continuous flow ozone catalytic oxidation experiment and a reactor for packing the traditional three-dimensional particle catalyst (20 g); and FIG. 14B shows a reactor for packing the catalyst (4 g) formed by using the base material prepared by the disclosure as a matrix;

[0138] FIG. 15 shows a perspective view of the method of the flexibility test (bending test) on the base material in the disclosure;

[0139] FIG. 16A shows a front view and FIG. 16B shows a side view of the pressing plate of FIG. 15;

[0140] FIG. 17A shows a schematic view of the measurement of the bending angle (3; and FIG. 17B shows a schematic view of the flexible orientation direction B of the base material and the extension direction A of the concave and convex stripes;

[0141] FIG. 18 shows a two-dimensional ozone catalytic material prepared by using the base material obtained in Example 1 as a matrix; and

[0142] FIG. 19 shows a schematic view of a cross-sectional shape of convex stripes (concave stripes) on the surface of transition metal flakes;

[0143] Reference numerals: 1, base material to be tested; 2, roller; 3, pressing plate, 4, structured surface (or may also be referred to as second structured layer); 410, first structural channel (or may also be called be referred to as first concave portion); 420, first protrusion portion; 421, hole; 422, second structural channel 5, base layer (or may also be referred to as first structural layer).

DETAILED DESCRIPTION

[0144] Materials

[0145] Transition metal flakes (or foils) with convex stripes (concave and convex stripes) on the surface

[0146] As far as the sampling of the “transition metal flakes (or foils) with convex stripes (concave and convex stripes) on the surface” is concerned, at least one surface of the “transition metal flakes” has convex stripes, and concave stripes with a cross-section of mesoscopic scale in width and depth are formed between two adjacent convex stripes, especially at the micron level (10.sup.−6-10.sup.−4 m); and if there are a plurality of convex stripes simultaneously, the direction of each stripe is identical or substantially identical, parallel or substantially parallel; there is no particular limitation on the source of stripes; for example, the source of source of stripes may be commercially available “transition metal flakes” with convex stripes on the surface; or may be obtained through grinding, wire drawing, and washing (with ethanol/acetone and deionized water) by using transition metal flakes as raw materials as shown in the embodiments herein, or obtained by rolling.

[0147] If the “transition metal flakes (or foils) with convex stripes on the surface” are obtained through grinding, wire drawing, and washing (with ethanol/acetone and deionized water) by using transition metal flakes as raw materials as shown in the embodiments herein, the transition metal flakes (before wire drawing treatment) only needs to meet one of the following properties: i) the transition metal content in the transition metal flakes is not less than 90%; ii) the thickness of the transition metal flakes is not more than 500 μm; preferably the thickness is 30-300 μm; more preferably, the thickness is 50-200 μm.

[0148] It should be noted herein that, i) as shown in FIG. 19, the mesoscopic level size of the cross section mainly means that the width (or the maximum width) L1 of the convex stripes, the width L2 (or the maximum width or the maximum spacing between two adjacent stripes) of concave stripes, the height H of the convex stripes (or the maximum height or the maximum depth of the concave stripes) are in a mesoscopic level; ii) the characteristic scale of the mesoscopic level (mesoscopic scale) described herein is 10.sup.−9-10.sup.−4 m, namely, from nanometer to micron scale.

[0149] Base Materials

[0150] A base material in the disclosure comprises a base layer, and a structured surface formed on the surface of the base layer; the structured surface comprises a) a first protrusion portion, and the first protrusion portion extends along a length direction of the structured surface; b) a first structural channel extending substantially in the same direction as the first protrusion portion and being adjacent to the first protrusion portion; and c) a plurality of holes distributed in the first protrusion portion and/or the first structural channel; at least 0.05% of the holes communicate with the adjacent first structural channel; the base material is flexible in at least one direction; the base material comprises at least one transition metal and the corresponding oxide of the transition metal; the base layer comprises transition metals and transition metal oxides, and the sum of contents thereof is at least 90% of the weight of the base layer; most of the transition metal oxides are concentratedly distributed on the structured surface.

[0151] Or, a base material in the disclosure comprises a first structural layer, and a second structural layer located on the surface of the first structural layer, and the second structural layer comprises a) a first protrusion portion, the first protruding portion extends along one length direction of the second structural layer; b) a first concave portion that extends substantially in the same direction as the first protrusion portion and is adjacent to the first protrusion portion; and c) a plurality of holes distributed in the first protrusion portion; at least 0.05% of the holes communicate with the adjacent first concave portions; the base material is flexible in at least one direction; the base material comprises at least one transition metal and the corresponding oxide of the transition metal; the content of the transition metal in the first structural layer is at least 90%, and the content of the oxide of the transition metal in the second structural layer is at least 30%, preferably not less than 90%.

[0152] Method

[0153] Pretreatment

[0154] In some embodiments, the “transition metal flakes (or foils) with concave and convex stripes on the surface” are obtained by using transition metal flakes as raw materials after wire drawing, washing treatment (with ethanol and deionized water) as shown in the embodiments herein. In the process of daily storage and transportation, the surface of the transition metal flakes is oxidized to form a natural oxide film, or is contaminated by contaminants such as grease and dust, or even has the problems of slight scratches, etc. Therefore, pretreatment should be performed before preparing the base material. The pretreatment is a well-known/existing technical means, for example, the steps of cutting, high temperature annealing, degreasing, grinding, polishing, etc.

[0155] In some embodiments, the transition metal flakes need to be cut into samples of a certain size for later use. In some embodiments, high temperature annealing treatment at a certain temperature is required under the protection of an inert gas, and cooling of the furnace is carried out, to eliminate the internal stress of the transition metal flakes. For example, in one embodiment, the transition metal flake is an aluminum foil, which can be annealed at 450° C. for 5 h under the protection of inert gas argon, and cooled with the furnace, to eliminate the internal stress of the aluminum foils.

[0156] In some embodiments, mechanical grinding is used to remove possible scratches on the surface of the transition metal flakes. During the grinding process, a grinding tool is used to grind in a certain direction to form a polished surface with a consistent surface texture. After grinding, the thickness of the transition metal flakes is ensured to be not more than 500 μm; preferably, the thickness is 30-300 μm; and more preferably, the thickness is 50-200 μm.

[0157] In some embodiments, polishing can be adopted to produce a certain grinding effect on the aluminum alloy material, and remove the defects of burrs, oxide scales and scratches on the surface of the product, so as to reduce the surface roughness of the aluminum alloy material and obtain a bright appearance. The methods of polishing are well known to those skilled in the art, for example, mechanical abrasive polishing, chemical polishing, thermochemical polishing or electrolytic polishing. For example, in one embodiment, in order to make the surface of the sample to be sufficiently flat, the sample needs to be polished. The polishing is performed at 0° C. by using perchloric acid and absolute ethanol at a volume ratio of 1:4. In one embodiment, a mixed solution of 15% (mass fraction) sodium carbonate and 5% (mass fraction) sodium phosphate is used as a polishing solution, and the polishing is performed at a temperature of 60° C. and a voltage of 5V for 10 min, to finally obtain samples with a mirror effect.

[0158] In some embodiments, wax removal is used to remove polishing wax from the product. The method for removing wax is well known to those skilled in the art, for example, a wax remover is used to remove wax at a temperature of 70-80° C., the wax remover can be selected from commercially available zinc alloy wax remover (for example, Shangma zinc alloy wax remover). Preferably, ultrasonic waves can be used to enhance the wax removal effect.

[0159] In some embodiments, degreasing is required after polishing the transition metal flakes. The purpose of degreasing is to remove surface grease, dirt and polishing wax that has not been removed. The degreasing method can adopt various existing mature degreasing processes, for example, organic solvent degreasing, chemical degreasing, electrolytic degreasing, emulsification degreasing, ultrasonic degreasing, etc., as long as the purpose of removing oil stains on the surface of the transition metal flakes can be achieved; for example, in one embodiment, cathodic electrolysis may be used to remove oil in the degreasing fluid, then ultrasonic oil removal may be used to enhance the oil removal effect, and the frequency of the ultrasonic wave is 20-28 kHz. The degreasing fluid can be zinc alloy degreasing powder of Macdermet, Shangma or International Chemical Company. For another example, in one embodiment, the acetone solution is used as the degreasing fluid to remove oil in ultrasonic waves for 6 min. For another example, in one embodiment, a mixed solution of 0.5% (mass fraction) sodium hydroxide, 0.8% (mass fraction) sodium carbonate and 2% (mass fraction) sodium phosphate is selected as the degreasing fluid, and the oil is removed in ultrasonic waves for 6 min.

[0160] In some embodiments, the method of mechanical friction is used to perform wire drawing on at least one surface of the transition metal flakes, to form straight lines as shown in FIGS. 1A-1B, and continuous wire drawing is performed. After drawing, the transition metal flakes with “concave and convex stripes” are formed on the surface. In some embodiments, after wire drawing, a plurality of convex stripes with the same direction or approximately the same direction is formed on the surface of the transition metal flakes, and concave stripes are formed between two adjacent convex stripes. In some embodiments, after the wire drawing, a plurality of convex stripes that are parallel or substantially parallel to each other are formed on the surface of the transition metal flakes, and concave stripes are formed between two adjacent convex stripes. In some embodiments, after wire drawing, the maximum width of the convex stripes on the surface of the transition metal flakes is at least 10 nm, and the range may be 0.01-50 μm.

[0161] In some embodiments, after the wire drawing, the maximum depth of the concave stripes formed between two adjacent convex stripes on the surface of the transition metal flakes is at least 3 nm, and the range may be 0.001-10 μm. In some embodiments, after wire drawing, the maximum stripe spacing between two adjacent convex stripes on the surface of the transition metal flakes is at least 10 nm, and the range may be 0.01-50 μm.

[0162] In some embodiments, the transition metal flakes should be washed with alcohol and/or ketone and/or water after wire drawing, for further cleaning.

[0163] Preparation of Surface Hole Arrays of Transition Metal Flakes

[0164] Hole arrays (holes with aperture of mesoscopic scale) can be formed on the surface of transition metal flakes by adopting any existing technologies, for example, the method for producing highly ordered nanopillars or nanoporous structures on large areas disclosed in the patent with publication number CN103402908B (publication date: 2016 Aug. 31), and for another example, anodization method.

[0165] In some embodiments, after the “transition metal flakes with concave and convex stripes on the surface” are treated by conventional anodization, an array of holes with aperture of mesoscopic scale distributed along the stripe direction is formed on the surface of the transition metal flakes.

[0166] In some embodiments, the transition metal flakes are used as the anode to connect to the positive pole of the external power supply, and is placed in the electrolyte solution, and the cathode can be made of materials that are not easy to react with acid, such as Pt sheet, titanium plate, stainless steel, and stone grinding rod, etc.

[0167] In some embodiments, the anodizing electrolyte is at least one acid solution selected from oxalic acid, sulfuric acid, phosphoric acid or hydrofluoric acid, and the concentration of the acid is 10-150 g/L. During the anodizing process, it is required to place a reaction vessel containing the anodizing electrolyte in an ice-water bath, and keep the temperature of the anodizing electrolyte in the vessel between 0 and 15° C.;

[0168] It has been found that the applied voltage will affect the structure of the oxide film (i.e. the hole layer) during the anodization of transition metals. Under a voltage within a certain range, the higher the voltage, the more uniform and denser the obtained oxide film will be. In a preferred embodiment, the voltage is in the range of 10-200 V, for example, 10-30 V, 20-30 V, 30-50 V, 30-80 V, 40-80 V, 100-120 V.

[0169] In some embodiments, the anodizing electrolyte is an oxalic acid solution, the oxalic acid concentration is 10-80 g/L, the oxidation time during anodization is 6-12 hours, and the voltage is 30-80 V; in some embodiments, the anodizing electrolyte is a sulfuric acid solution, the concentration of sulfuric acid is 10-100 g/L, the oxidation time during anodization is 2-16 hours, and the voltage is 10-30 V; in some embodiments, the anodizing electrolyte is a phosphoric acid solution, the concentration of phosphoric acid is 30-150 g/L, the oxidation time during anodization is 1-10 hours, and the voltage is 100-120 V; in some embodiments, the anodizing electrolyte is a hydrofluoric acid solution, and the concentration of hydrofluoric acid is 10-20 g/L, the oxidation time during anodization is 2-6 hours, and the voltage is 20-30 V.

[0170] In some embodiments, after anodization, an ordered porous anodic oxide film as shown in FIG. 2A and FIG. 3 is formed on the surface of the transition metal flakes. In some embodiments, the depth of the holes is at least 20 nm, and is in the range of 0.02-80 μm. In some embodiments, the average aperture of the holes is at least 10 nm, and is in the range of 10-500 nm. In some embodiments, the wall thickness of holes (between two adjacent holes) is at least 5 nm, and is in the range of 5-100 nm.

[0171] Etching Control

[0172] The surface of transition metal flakes having a hole array (holes with an aperture of mesoscopic scale) can be etch-controlled by using any prior art, for example, alkaline etching, or acid etching.

[0173] In some embodiments, the surface of transition metal flakes having a hole array (holes with an aperture of mesoscopic scale) can be etch-controlled by using a conventional acid etching method, so that the holes on the surface of the transition metal flakes are changed, for example, at least 5% of the holes are in communication with adjacent holes to form irregular holes, and for another example, at least 0.05% of the holes are in communication with the adjacent first structural channels thereof.

[0174] In some embodiments, the hydrogen ion concentration in the acid solution for the acid etching control is 0.001-0.65 mol/L; when the acid etching control is performed, the time of acid etching is 5-70 min. In some embodiments, the pH of the electrolyte in the acid etching control may be 0.92-3.00; when the acid etching control is performed, the acid etching is 5-70 min.

[0175] In some embodiments, the ordered porous anodic oxide film obtained by anodization is subjected to acid etching, to obtain a base material as shown in FIG. 4A.

[0176] In some embodiments, the final prepared base material has a bulk density of not higher than 1 g/cm.sup.3; in some embodiments, the bulk density of the base material is 0.1-0.5 g/cm.sup.3. In some embodiments, the base material has an apparent density of not less than 1 g/cm.sup.3 and a porosity of not less than 5%; in some embodiments, the porosity is 5-30%.

[0177] Test

[0178] Bending Test

[0179] The bending angle β of the base material can be tested by the following method. As shown in FIG. 15, it is a perspective view of a bending test. FIG. 16A and FIG. 16B show a front view and a side view of a pressing plate 3 as a plate-shaped bending fixture respectively.

[0180] The method is as follows. First, in 2 rollers 2 arranged in parallel and provided with a roll opening L, a base material 1 to be tested is horizontally placed on the positions relative to the rollers 2 with equal distance on the left and right, as shown in the dotted lines in FIG. 15.

[0181] Next, above the base material 1 to be tested, a pressing plate 3 serving as a bending fixture for the base material 1 to be tested is placed in a manner of standing vertically relative to the base material 1 to be tested. Specifically, the edge of the front end of the pressing plate 3 is placed at the center of the roll opening L, and the rolling direction of the base material 1 to be tested and the extending direction of the pressing plate 3 of the base material 1 to be tested are orthogonal to each other. The roller 2, the base material 1 to be tested and the pressing plate 3 are placed in this way.

[0182] Then, the pressing plate 3 is pushed to the center of the base material 1 to be tested from above, and a load F is applied, so that the base material 1 to be tested is bent (punched) toward the aforementioned narrow roll opening L, and the central portion of the base material to be tested that is bent and deformed is pressed into the narrow roll opening.

[0183] At this time, the angle of the outer side of the curve of the central portion of the base material 1 to be tested (angle formed by the extended line of the outer tangent of the base material 1 to be tested) when the load F applied from the upper pressing plate 3 reaches the maximum is taken as the bending angle β(°) and is measured. The flexibility is evaluated by the bending angle. Namely, the larger the bending angle, the better the flexibility of the base material 1 to be tested.

[0184] As the test conditions of the bending test, the size of the base material 1 to be tested is 5 cm×5 cm×0.01 mm (length×width×thickness), the diameters D of the two rolls 2 are 20 mm, and the roll opening L is 2.0 times the thickness of the base material 1 to be tested. S is the pressing depth of the central portion of the base material to be tested into the roll opening when the load F reaches the maximum.

[0185] As shown in FIG. 16B, the length of the side of the pressing plate 3 that is in contact with the base material 1 to be tested is 600 mm, and the lower end side (tip) in contact with the central portion of the base material 1 to be tested is as shown in FIG. 17A when viewed from the front, which is a sharp cone with a radius r of 0.2 mmφ.

[0186] As shown in FIG. 16B on the opposite side of the tip of the pressing plate 3, two recesses with a width of 9 mm and a depth of 12 mm are formed, and the recesses are embedded into an overload device (not shown in the figure), and are configured so that the pressure plate 3 applies a load to the base material 1 to be tested.

[0187] Or, a test can be conducted with reference to the national standard GB3356-1982.

[0188] Apparent Density Test

[0189] The testing is conducted in accordance with GBT6343-2009 Cellular plastics and rubbers—Determination of apparent density.

[0190] Bulk Density Test

[0191] Bulk density (ρb, g/cm.sup.3) refers to the mass per unit volume of the material to be tested in the bulk state. Before conducting a bulk density test, a base material is cut into a size of 0.1 mm×0.5 mm×0.5 mm; for the specific method, refer to ASTM D7481-2009 Standard Test Methods for Determining Loose and Tapped Bulk Densities of Powders using a Graduated Cylinder.

[0192] Bulk density: ρb=m/V.

[0193] m—the mass of the material to be tested in the graduated cylinder, in grams (g);

[0194] V—the bulk volume of the material to be tested, in milliliters (mL), including the volume of the material itself and the volume of voids between the materials (the voids within the material can be ignored).

[0195] It should be noted that the mass m can be measured by a balance;

[0196] The volume V can be measured by the following way:

[0197] By naturally filling a container with a certain volume until it is full, the volume of the container is the bulk volume of the material to be tested. The natural filling is specifically as follows: the material to be tested falls into the container naturally until the container is filled from a place with a vertical height of not more than 10 cm form the container inlet, without any tapping and pressing operations.

[0198] SEM Topography

[0199] The surface morphology is characterized by JSM-IT500HR scanning electron microscope, and the SEM image is obtained.

[0200] It should be noted that in the disclosure, when the scanning electron microscope is used to observe the morphology of the base material, the surface of the base material is loaded with active components, to improve the observation effect. The loading of active components can effectively improve the electron response of the surface of the base material, which is conducive to SEM imaging. In addition, after the active components are loaded, the morphology of the base material will not be changed. For the loading method, please refer to the following part: Preparation of Two-Dimensional Ozone Catalytic Materials.

[0201] Application

[0202] The base materials described above can have many applications. Such applications can include, but are not limited to: catalysts, directly using a carrier for a catalytic process in a specific situation (for example, a nickel catalyst); adsorbents, directly using a carrier for an adsorption process in a specific situation (for example, alumina defluorination); carrier materials, for example, catalyst carriers, absorbent carriers.

[0203] Particularly, in some embodiments, the above base materials can be used as a carrier to prepare a two-dimensional ozone catalytic material. The prepared catalyst material has the physical properties of light weight and flexibility, and the chemical properties of high interfacial mass transfer efficiency and good catalytic performance, and can be used in many fields such as waste water and waste gas.

[0204] Preparation of Two-Dimensional Ozone Catalytic Materials

[0205] Pre-treatment: The base material stored in clean water after the acid etching control is dried in a 50° C. drying oven for future use;

[0206] Preparation of a precursor solution: the solution consists of 50 g/L glucose, 50 g/L manganese sulfate (5 g), 20 g/L copper nitrate, 50 g/L cobalt chloride and 80 g/L acetic acid.

[0207] Two-dimensional ozone catalytic materials are prepared. The specific steps are as follows: A. placing the above base material into the above precursor solution for vacuum impregnation (the volume of the precursor solution measured in this step can completely immerse the foils), the immersion time is 20 min, the temperature is constant at 20±5° C., and the precursor salt synchronously corrodes the two-dimensional base material during the immersion process;

[0208] B. placing the base material after dipping and loading at room temperature for 15 h;

[0209] C. placing the base material after the precursor is fully diffused in a vacuum oven at 70° C. for drying and pre-pyrolysis for 15 h;

[0210] D. placing the base material after drying and pre-pyrolysis in an argon protective furnace for high-temperature calcination treatment; heating to 550° C. at a rate of 3° C./min, and holding for 1.5 h, then cooling to room temperature at a rate of 3° C./min, to obtain a corresponding two-dimensional ozone catalytic material (hereinafter referred to as two-dimensional ozone catalytic material).

[0211] Semi-Continuous Flow Ozone Catalytic Oxidation Test

[0212] A semi-continuous flow ozone catalytic oxidation test is conducted according to the following conditions. As shown in FIG. 14, a catalyst material is loaded into a reaction reactor, and the filling height should be identical when different types of catalysts are used for the loading of the reactor; in the disclosure, when conventional granular catalysts are used for loading, the dosage is 20 g, and the dosage of other types of catalysts is 4 g.

[0213] Test group: catalyst+ozone, including conventional granular catalysts, catalysts prepared in the disclosure (it needs to be cut into a size with a side length of 1-3 mm);

[0214] Blank control: no catalyst, only ozone;

[0215] Water body to be treated: three types according to different types of simulated contaminants (phenol, pyrazole, oxalic acid) in the water body to be treated; specifically: water body to be treated with simulated contaminants of phenol and pyrazole with a volume of 500 mL; water body to be treated with simulated contaminant of oxalic acid with a volume of 200 mL; and simulated contaminant with a concentration of 100 mg/L;

[0216] Sampling time: the water samples at different time points are tested during the catalytic ozone oxidation reaction; of which, phenol (water samples at the time points of 0, 2.5, 5, 7.5, 10, 15 min), pyrazole (water samples at the time points of 0, 2.5, 5, 7.5, 10, 15, 20, 30, 45 and 60 min), oxalic acid (water samples at the time points of 0, 2.5, 5, 7.5, 10 and 15 min).

[0217] Steps/Methods of Semi-Continuous Flow Ozone Catalytic Oxidation Test

[0218] 1) performing ozone aeration in a simulated water body containing contaminants, where the inflow rate of ozone is 0.5 L/min, and the inflow concentration is 5 mg/L;

[0219] 2) feeding the ozone-dissolved solution into a reactor, and returning the effluent to the solution, where the recycling time for the treatment of the water body to be treated with a simulated contaminant of phenol is 15 min, the recycling time for the treatment of the water body to be treated with a simulated contaminant of pyrazole is 60 min, and the recycling time for the treatment of the water body to be treated with a simulated contaminant of oxalic acid is 15 min.

[0220] The following examples are intended to illustrate certain embodiments but not to illustrate the full scope of the invention. The term “structured surface” mentioned in the whole text of the disclosure can also be referred to as the “second structural layer”, and both have the same meaning; similarly, the term “first structural channel” mentioned in the whole text of the disclosure can also be referred to as the “first concave portion”, and both have the same meaning; the “base layer” mentioned in the whole text of the disclosure can also be referred to as the “first structural layer”, and both have the same meaning.

Example 1

[0221] In this example, a transition metal aluminum foil with a thickness of 200 μm was selected as the basic material to prepare a base material; the specific steps were as follows: 1) wire drawing: As shown in FIG. 1A, aluminum foils (upper and lower surfaces) were subjected to high temperature annealing, degreasing, grinding and polishing pretreatment, then subjected to wire drawing treatment, so that a plurality of basically parallel convex stripes with a width of about 50±10 nm were formed on the upper and lower surfaces of the transition metal aluminum foils, and concave stripes with a depth of 1 nm and a width of 50±10 nm were formed, and then washing was performed using ethanol and deionized water respectively, after washing, drying was performed in a drying oven at 50° C. for later use. The obtained materials after wire drawing had a surface as shown in FIG. 1B;

[0222] 2) Anodizing: Anodizing was carried out by taking a titanium plate as a cathode, a pretreated aluminum foil as an anode, and 50 g/L of oxalic acid solution (300 ml) as a corrosion electrolyte. During the anodizing process, the reaction vessel containing the corrosion electrolyte was always placed in an ice-water bath, with a temperature kept at 10±1° C.; during the anodization, the spacing between the anode and cathode electrodes was 2 cm, the voltage was 60 V, and the treatment time was 12 hours; the aluminum foils after oxidation were cleaned and placed in deionized water for preservation;

[0223] A nanopore array was prepared on the anodized aluminum foil (hereinafter referred to as 0.5A), and its surface microstructure was shown in FIG. 2A, and its cross-sectional microstructure was shown in FIG. 3. As shown from FIG. 2A, after the aluminum foil with concave and convex stripes on the surface was anodized, there was a plurality of nanopores distributed on the surface (upper and lower surfaces) of the two-dimensional material, and these nanopores were distributed in a regular form of nanopore arrays according to the direction of the stripes under the guidance of the concave and convex stripes;

[0224] 3) Acid etching control: the anodized aluminum foil was dried in a drying oven at 50° C. for 12 h; under room temperature, 500 ml of 4 wt. % phosphoric acid solution (the molar concentration of hydrogen ions of 3.2×10.sup.1 mol/L, and the pH of 2.50) was prepared; subsequently, the dried aluminum foil was soaked in phosphoric acid solution for softening for 60 min; during which, the phosphoric acid solution was placed in a drying oven at a constant temperature of 35° C. for preservation; after the acid etching control was completed, the base material (hereinafter referred to as 1A) was cleaned with deionized water, and stored in clean water.

[0225] The microstructure of the aluminum foil surface was observed during the acid etching control. As shown in FIG. 2B, the hole wall along the extension direction of the concave and convex stripes (or the length direction of the nanopore array) has become thinner obviously.

[0226] The base material prepared in this example had a base layer 5, and the upper and lower surfaces of the base layer 5 had a structured surface 4 as shown in FIG. 4A. There is a plurality of obvious first structural channels 410 with a substantially consistent direction and a first protrusion portion 420 located between two adjacent first structural channels 410 on the structured surface 4; meanwhile, obviously, a large number of holes 421 are distributed on the first protrusion portion 420, at least 0.05% of the holes 421 communicate with the adjacent first structure channels 410 to form second structural channels 422. FIG. 4B showed a partial enlarged view. As shown from the figure, the first structure channel 410, the first protrusion portion 420, the hole 421 and the second structure channel 422 could be clearly seen for the structured surface 4. Further, FIG. 4C was a partial enlarged view of the first protruding portion 420. From the figure, the wall surface morphology and the change of the holes formed on the anodic oxide film after corroding could be clearly seen.

[0227] In this example, for the prepared base material, the aluminum content of the base layer 5 (or the first structural layer) was not less than 90%, the aluminum oxide content of the structured surface 4 (or the second structural layer) was higher than 30%, the bulk density was about 0.5 g/cm.sup.3, and the apparent density was about 2 g/cm.sup.3.

Example 2

[0228] In this example, a two-dimensional transition metal tin foil with a thickness of 300 μm and convex stripes (the width of the convex stripes of about 60 nm, the depth of the concave stripes of 4 nm, and the spacing between two adjacent concave stripes of 60 nm (namely, the width of the concave stripes)) was used as a basic material to prepare the base material; the specific steps were as follows:

[0229] 1) Pretreatment: the two sides of the tin foil were pretreated by degreasing and washing with water. The degreasing was performed using acetone solution, and the washing was performed using ethanol and deionized water respectively. After washing, drying was performed in a drying oven at 50° C. for later use;

[0230] 2) Anodizing: Anodizing was carried out by taking a titanium plate as a cathode, a pretreated tin foil as an anode, and 70 g/L of sulfuric acid solution (300 ml) as a corrosion electrolyte. During the anodizing process, the reaction vessel containing the corrosion electrolyte was always placed in an ice-water bath, with a temperature kept at 10±1° C.; during the anodization, the spacing between the anode and cathode electrodes was 1 cm, the voltage was 15V, and the treatment time was 12 hours; the tin foil after oxidation was cleaned and placed in deionized water for preservation;

[0231] 3) Acid etching control: the anodized tin foil was dried in a drying oven at 50° C. for 12 h; under room temperature, 500 ml of 7 wt. % phosphoric acid solution (the molar concentration of hydrogen ions of 5.60×10.sup.−3 mol/L, and the pH of 2.25) was prepared; subsequently, the dried tin foil was soaked in phosphoric acid solution for softening for 30 min; during which, the phosphoric acid solution was placed in a drying oven at a constant temperature of 35° C. for preservation; after the acid etching control was completed, the base material (hereinafter referred to as 2A) was cleaned with deionized water, and dried in a drying oven at 50° C.

[0232] As shown in FIG. 5, the base material prepared in this example has a base layer 5, and the upper and lower surfaces of the base layer 5 both have a structured surface 4.

Example 3

[0233] In this example, a two-dimensional transition metal nickel foil with a thickness of 100 μm and concave and convex stripes (the width of the convex stripes of about 100 nm, the depth of the concave stripes of 4 nm, and the width of 100 nm) was used as a basic material to prepare the base material; the specific steps were as follows:

[0234] 1) Pretreatment: the two sides of the nickel foil were pretreated by degreasing and washing with water. The degreasing was performed using acetone solution, and the washing was performed using ethanol and deionized water respectively. After washing, drying was performed in a drying oven at 40° C. for later use;

[0235] 2) Anodizing: Anodizing was carried out by taking a titanium plate as a cathode, a pretreated nickel foil as an anode, and 120 g/L of phosphoric acid solution (300 ml) as a corrosion electrolyte. During the anodizing process, the reaction vessel containing the corrosion electrolyte was always placed in an ice-water bath, with a temperature kept at 10±1° C.; during the anodization, the spacing between the anode and cathode electrodes was 1.5 cm, the voltage was 100 V, and the treatment time was 9 hours; the nickel foil after oxidation was cleaned and placed in deionized water for preservation;

[0236] 3) Acid etching control: the anodized nickel foil was dried in a drying oven at 50° C. for 12 h; under room temperature, 500 ml of 10 wt. % phosphoric acid solution (the molar concentration of hydrogen ions of 8.1×10.sup.−3 mol/L, and the pH of 2.09) was prepared; subsequently, the dried nickel foil was soaked in phosphoric acid solution for softening for 20 min; during which, the phosphoric acid solution was placed in a drying oven at a constant temperature of 35° C. for preservation; after the acid etching control was completed, the base material (hereinafter referred to as 3A) was cleaned with deionized water, and dried in a drying oven at 50° C.

Example 4

[0237] In this example, a two-dimensional transition metal titanium foil with a thickness of 100 μm and convex stripes (the width of the stripes of about 60 nm, the depth of the stripes of 4 nm, and the spacing between stripes of 60 nm) was used as a basic material to prepare the base material; the specific steps were as follows:

[0238] 1) Pretreatment: the two sides of the titanium foil were pretreated by degreasing and washing with water. The degreasing was performed using acetone solution, and the washing was performed using ethanol and deionized water respectively. After washing, drying was performed in a drying oven at 40° C. for later use;

[0239] 2) Anodizing: Anodizing was carried out by taking a stainless steel plate as a cathode, a pretreated titanium foil as an anode, and 10 g/L of hydrofluoric acid solution (300 ml) as a corrosion electrolyte. During the anodizing process, the reaction vessel containing the corrosion electrolyte was always placed in an ice-water bath, with a temperature kept at 10±1° C.; during the anodization, the spacing between the anode and cathode electrodes was 1.5 cm, the voltage was 25 V, and the treatment time was 6 hours; the titanium foil after oxidation was cleaned and placed in deionized water for preservation;

[0240] 3) Acid etching control: the anodized titanium foil was dried in a drying oven at 50° C. for 12 h; under room temperature, 500 ml of 7 wt. % chromic acid solution (the molar concentration of hydrogen ions of 0.63 mol/L, and the pH of 0.94) was prepared; subsequently, the dried titanium foil was soaked in chromic acid solution for softening for 25 min; during which, the chromic acid solution was placed in a drying oven at a constant temperature of 35° C. for preservation; after the acid etching control was completed, the base material (hereinafter referred to as 4A) was cleaned with deionized water, and dried in a drying oven at 50° C.

Comparative Example 1 about Concave and Convex Stripes

[0241] This comparative example was basically the same as Example 1, with the only difference as follows: in the step 1), the aluminum foil (upper and lower surfaces) was subjected to high temperature annealing, degreasing, grinding, and pre-polishing treatment, and then washed with ethanol and deionized water respectively, and after washing, drying was performed in a drying oven at 50° C. for later use; there was no wire drawing during the whole process, namely, the upper and lower surfaces of the transition metal aluminum foil had a smooth mirror structure, and basically had no a plurality of convex stripes with a width of about 50±10 nm and concave stripes with a depth of 3±1 nm and a width of 50±10 nm that were basically parallel. The rest were the same as those in Example 1. The base material prepared in this comparative example was named as 1C.

Comparative Example 2 about Etching Parameter Control

[0242] This comparative example was basically the same as Example 1, with the only difference as follows: the acid solution concentration and acid etching time parameters in the step 3) were changed in the preparation process of the base material, to obtain two groups of base materials, which were named as 2C-1; 2C-2 respectively; specifically:

[0243] Base material 2C-1: the acid concentration was 12 wt. %, the hydrogen ion concentration in the phosphoric acid solution was 9.8×mol/L, the pH was 2.01, and the acid etching time was 90 min;

[0244] Base material 2C-2: the acid concentration was 0.05 wt. %, the hydrogen ion concentration in the phosphoric acid solution was 3.9×10.sup.−4 mol/L, the pH was 3.41, and the etching time was 20 min; the rest were the same as those in Example 1;

[0245] As shown in FIG. 6A, the base material 2C-2 was not sufficiently etched to cross-link the nanopore array formed along the convex stripes, and the structured surface of the base material did not form the basic first structural channel and the first protrusion portion. As shown in FIG. 6B, the base material 2C-1 had obviously excessive acid etching, resulting in only a part of the pore structure remaining on the surface of the material and almost no structured surface any longer.

Example 5

[0246] In this example, an ozone oxidation catalyst was prepared using a base material according to the aforementioned part of Preparation of Two-Dimensional Ozone Catalytic Materials. The base material 1A was used to prepare an ozone oxidation catalyst in Example 1, which was named as 1A-catalyst;

[0247] The base material 2A was used to prepare an ozone oxidation catalyst, in Example 2, which was named as 2A-catalyst;

[0248] The base material 3A was used to prepare an ozone oxidation catalyst in Example 3, which was named as 3A-catalyst;

[0249] The base material 4A was used to prepare an ozone oxidation catalyst in Example 4, which was named as 4A-catalyst;

[0250] The aluminum base-base material 1C was used to prepare an ozone oxidation catalyst in Comparative Example 1, which was named as 1C-catalyst;

[0251] The aluminum base-base materials 2C-1, 2C-2 were used to prepare ozone oxidation catalysts in Comparative Example 2, which were named as 2C-1-catalyst and 2C-1-catalyst respectively;

[0252] At the same time, as a comparison, the corresponding two-dimensional ozone catalytic material was prepared based on the aluminum foil 0.5A without acid etching control after anodization, which was named as 0.5A-catalyst.

[0253] The two-dimensional ozone catalytic material of 1A-catalyst prepared by the above method was based on an aluminum foil, and was subjected to anodization, acid etching control, and vacuum impregnation (precursor intrusive loading). The above preparation method not only made the two-dimensional ozone catalytic material to be flexible, but also greatly improved the mechanical strength and structural stability of the material. Compared with the catalyst prepared from the base material (FIG. 13A) only after anodizing, the catalyst prepared from the base material (FIG. 13B) after acid etching control had better mass transfer performance during use. Therefore, when the two-dimensional ozone catalytic material prepared by the invention was applied to the semi-continuous flow ozone catalytic oxidation wastewater, mass transfer could be carried out along a structural channel interconnected with a certain hole, which greatly improved the mass transfer efficiency.

Example 6

[0254] In this example, the anodized hard template 0.5A after anodizing, cleaning and drying, the base material 1A after acid etching control and cleaning and drying in Example 1, and the product base material 1C in Comparative Example 1 were selected to perform a bending test respectively. The results were shown in Table 1.

TABLE-US-00001 TABLE 1 Comparison of β values of mechanical properties of base materials in different preparation stages Preparation stage of base material Angleβ(°) Anodized hard template 0.5 A in Example 1 Below 10 Finished base material 1A in Example 1 Approaching 180 Undrawn base material 1C in Comparative Example 1 Approaching 90 Excessively acid-etched base material 2C-1 in Approaching 180 Comparative Example 2 Insufficiently acid-etched base material 2C-2 in Approaching 30 Comparative Example 2

[0255] It should be noted that, for the anodized hard template 0.5A as shown in the above table, after the aluminum foil was anodized, a dense porous oxide film would be formed on its surface, and the obtained material was extremely brittle, dense and fragile, without any flexibility; for the finished base material 1A in Example 1 and the undrawn base material 1C in Comparative Example 1 in above table, the flexibility of the material would be improved to a certain extent after acid etching; the base material 1C in Comparative Example 1 that was not drawn had improved flexibility due to the existence of the oxide film and its pore structure, but the ability to bend was limited; while for the finished base material 1A in Example 1 provided by the disclosure, due to the effect of the concave and convex stripes on the surface, a structure shown in FIG. 4A-4C was formed after acid etching control, so the flexibility was greatly improved, and the ability to bend became stronger.

Comparative Example 3 Preparation of Conventional Granular Three-Dimensional Catalysts

[0256] In this comparative example, three conventional granular three-dimensional catalysts were prepared, which were named as 1B-catalyst, 2B-catalyst, and 3B-catalyst respectively; the preparation method of conventional granular three-dimensional catalysts was as follows:

[0257] 1) Three groups of γ-alumina particles with the same mass and a size of 3-5 mm were taken and washed clean with deionized water, dried in a drying oven at 50° C.;

[0258] 2) The following three groups of substances were weighed at room temperature and prepared into precursor solutions:

[0259] Group 1 (1 B-catalyst): the precursor solution was the same as that in Example 1;

[0260] Group 2 (2 B-catalyst): the precursor solution was the same as that in Example 2;

[0261] Group 3 (3 B-catalyst): the precursor solution was the same as that in Example 3;

[0262] 3) The weighed three groups of γ-alumina were subjected to vacuum impregnation in the three groups of precursor solutions in step 2), respectively (a certain amount of precursor solution was measured, and the selected three groups of γ-alumina could just be immersed in the precursor solutions); the immersion time and temperature of group 1 were the same as those in Example 1; the immersion time and temperature of group 2 were the same as those in Example 2; and the immersion time and temperature of group 3 were the same as those in Example 3;

[0263] 4) After immersion, the γ-alumina placed at room temperature, standing for 15 h, to fully diffuse the precursor; then placed in a 70° C. vacuum oven for drying and pre-pyrolysis for 15 h;

[0264] 5) The base material after drying and pre-pyrolysis was placed in an argon protective furnace for high-temperature calcination treatment; heated to 550° C. at a rate of 3° C./min, holding for 1.5 h, then cooled to room temperature at a rate of 3° C./min, to obtain a finished product.

Example 7 Semi-Continuous Flow Ozone Catalytic Oxidation Test

[0265] In this example, a semi-continuous flow ozone catalytic oxidation test was carried out for each catalyst prepared above, specifically:

[0266] Group 1—catalyst types: 1A-catalyst, 1C-catalyst;

[0267] Type of water body to be treated: the water body to be treated with simulated contaminant of oxalic acid;

[0268] Conclusion: As shown in FIG. 8, apparently, the aluminum-based two-dimensional ozone catalytic material prepared by wire drawing during the degradation process was significantly better than that prepared without wire drawing; at 15 min, the removal rate of oxalic acid by the aluminum-based two-dimensional ozone catalytic material prepared by wire drawing reached more than 80%, while the removal rate of oxalic acid by the aluminum-based two-dimensional ozone catalytic material prepared without wire drawing treatment was only about 60%.

[0269] As shown in FIGS. 13A-13B, the holes of the base material prepared in Comparative Example 1 were still distributed in a regular array, and various nanopores were independent of each other. When applied to the semi-continuous flow ozone catalytic oxidation test, the water and contaminants could only diffuse through each nanopore port, and the efficiency was low; moreover, because the ozone catalytic oxidation reaction was a surface reaction, its large number of internal structures had no contribution to the reactions.

[0270] Group 2—catalyst types: 1A-catalyst, 2C-1-catalyst, 2C-2-catalyst;

[0271] Type of water body to be treated: the water body to be treated with simulated contaminant of phenol;

[0272] Conclusion: As shown in FIG. 9, apparently, the aluminum-based two-dimensional ozone catalytic material prepared by appropriate acid etching control of parameters during the degradation process was significantly better than that prepared with too large or too small parameters in the acid etching control process; at 15 min, the removal rate of phenol by the aluminum-based two-dimensional ozone catalytic material prepared by appropriate acid etching control of parameters reached more than 80%, while the removal rate of phenol by the aluminum-based two-dimensional ozone catalytic material prepared with too large or too small parameters in the acid etching control process were 20% and 60%, respectively.

[0273] Description for 1A-catalyst: in the process of acid etching control, the base material would gradually open the hole wall barrier between the hard template nanopores formed after anodization under the action of appropriate acid solution, and cracks would be formed between nanopore arrays in the direction of the convex stripes. In the direction perpendicular to the convex stripes, alternately arranged nanopore array-fault channel-nanopore array morphology composed of single or multiple rows of nanopores would be gradually generated.

[0274] Description for 2C-1-catalyst: if the surface nanopores were not sufficiently corroded in the process of acid etching control, the nanopores could not be fully interconnected, forming an effective structured surface.

[0275] Description for 2C-2-catalyst: If the corrosion was excessive in the process of acid etching control, the surface part of the material would return to a smooth structure, and an effective structured surface would also not be formed.

[0276] Group 3—catalyst types: 0.5A-catalyst, 1A-catalyst.

[0277] Type of water body to be treated: the water body to be treated with simulated contaminant of oxalic acid;

[0278] Conclusion: In order to understand the degradation of oxalic acid during the test, the water samples at 0, 2.5, 5, 7.5, 10, 15, 25, 35, and 60 min in the catalytic ozone oxidation reaction process were tested. The final removal rate of oxalic acid by 1A-catalyst was higher than 80%; and the final removal rate of oxalic acid by 0.5A-catalyst was only 25%. In addition, after the water treatment was completed, the damage rate of 0.5A-catalyst was as high as about 20%, while 1A-catalyst maintained nearly 100% integrity.

[0279] Group 4—Catalyst types: 1A-catalyst, 2A-catalyst, 3A-catalyst, conventional granular three-dimensional catalysts (1B-catalyst, 2B-catalyst, 3B-catalyst) of Comparative Example 3.

[0280] Type of water body to be treated: three types of water bodies to be treated, namely, water body to be treated with simulated contaminant of phenol; water body to be treated with simulated contaminant of pyrazol; water body to be treated with simulated contaminant of oxalic acid;

[0281] Conclusion: with reference to FIG. 10, for the catalyst with the same loading volume in the reactor, the loading mass of 1A-catalyst was only ⅕ of the granular three-dimensional catalyst 1B. It was obvious that the removal effect of phenol by 1A-catalyst was obviously better than that of the granular three-dimensional catalyst 1B during the degradation process; at 15 min, the removal effect of phenol by the aluminum-based two-dimensional ozone catalyst material was more than 80%, while the removal effect of phenol by the granular three-dimensional catalyst 1B was about 70%, and the removal effect of phenol by ozone oxidation alone was only 30%.

[0282] Conclusion: with reference to FIG. 11, for the catalyst with the same loading volume in the reactor, the loading mass of 2A-catalyst was only ⅕ of the granular three-dimensional catalyst 2B. It was obvious that the removal effect of pyrazol by 2A-catalyst was slightly better than that of the granular three-dimensional catalyst 2B during the degradation process; and with reference to Table 1, at 60 min, the removal rate of pyrazole by the granular three-dimensional catalyst 1B was about 80%, while the removal rate of pyrazole by the 2A-catalyst was slightly higher than 80%, and the removal rate of pyrazole by ozone oxidation alone was only 50%.

[0283] With reference to FIG. 12, for the catalyst with the same loading volume in the reactor, the loading mass of 3A-catalyst was only ⅕ of the granular three-dimensional catalyst 3B. It was obvious that the removal effect of oxalic acid by 3A-catalyst was obviously better than that of the granular three-dimensional catalyst 3B during the degradation process; and with reference to Table 1, at 15 min, the removal rate of oxalic acid by the 3A-catalyst was more than 90%, while the removal rate of oxalic acid by the granular three-dimensional catalyst 3B was only 60%, and the removal rate of oxalic acid by ozone oxidation alone was only 8%.

[0284] In addition, FIG. 18 was a schematic diagram of the effect of recycling 1A-catalyst prepared in Example 1 for oxalic acid degradation; as shown in the figure, in the process of recycling, 1A-catalyst maintained an efficient removal rate of oxalic acid, and after 20 times of recycling, the integrity was still as high as 99%, nearly 100%.

[0285] All of the above showed that, for the removal of different target contaminants, the two-dimensional ozone catalytic material provided by the disclosure had obvious advantages for the removal of target contaminants when the dosage was only ⅕ of the conventional granular three-dimensional catalyst, indicating that the ozone oxidation catalytic performance of the two-dimensional ozone catalytic material provided by the disclosure was obviously superior to the conventional granular three-dimensional catalyst.

[0286] It will be obvious to those skilled in the art that changes and modifications may be made, and therefore, the aim in the appended claims is to cover all such changes and modifications.