CN112958060A

CN112958060A - Two-dimensional catalytic material and preparation and application thereof

Info

Publication number: CN112958060A
Application number: CN202110172267.9A
Authority: CN
Inventors: 魏卡佳; 王陆; 韩卫清; 刘思琪; 刘润; 戴君诚
Original assignee: Nanjing University of Science and Technology
Current assignee: Nanjing University of Science and Technology
Priority date: 2021-02-08
Filing date: 2021-02-08
Publication date: 2021-06-15
Also published as: CN113648985A; CN113648985B

Abstract

The invention discloses a two-dimensional catalytic material and preparation and application thereof, wherein the two-dimensional material takes a transition metal foil with micron-sized thickness as a base material, and a two-dimensional matrix carrier with light flexibility, high specific surface area and roughness is prepared by pretreatment, anodic oxidation, acid etching regulation, hole breaking and thermal stabilization treatment; when the catalyst is applied to water treatment, the catalyst has the advantages of rapid interface mass transfer, excellent catalytic performance and the like; meanwhile, the preparation process of the two-dimensional catalytic material has the characteristics of simple method, easily adjustable process parameters, easy large-scale production, low preparation cost and the like.

Description

Two-dimensional catalytic material and preparation and application thereof

Technical Field

The invention belongs to the field of material preparation and application, and particularly relates to a two-dimensional catalytic material and preparation and application thereof.

Background

As one of advanced oxidation technologies, the heterogeneous ozone catalytic oxidation technology has the advantages of quick reaction, clean product, strong oxidation capacity, weak selectivity, no secondary pollution and the like, does not need to continuously add a catalyst, and is an effective wastewater treatment technology. However, the existing heterogeneous ozone catalytic oxidation technology still has the problems of insufficient catalytic performance of the catalyst, poor interface activity, low wastewater treatment efficiency and the like, and particularly has a significant bottleneck on the treatment efficiency of wastewater with low pollutant concentration and poor mass transfer. The heterogeneous ozone catalysts which are most widely used so far are granular catalysts (such as alumina-based granular catalysts, the particle size is more than millimeter) and powder catalysts (such as powdered activated carbon, the particle size is micron/nanometer), which respectively correspond to an ozone packed bed reaction process and a fluidized bed reaction process, but have defects respectively. Because the reaction site of the catalytic oxidation of ozone is mainly the surface of the catalyst, the internal structure of the particle catalyst can not directly participate in catalysis, and a large number of internal structures not only reduce the bulk density of active sites, but also lead to the waste of materials and the improvement of cost. Compared with a granular catalyst, the powder catalyst has the characteristics of high specific surface area, high mass transfer efficiency, light weight (easy fluidization), and the like, but in actual use, the powder catalyst is often used by combining a separation and recovery (magnetic/membrane separation and the like) process, and meanwhile, the actual problems of ozone resistance, service life and the like of an added unit need to be considered, so that extra energy consumption and cost are caused. How to improve the active specific surface area of the catalyst as much as possible, improve the interface mass transfer efficiency, and simultaneously avoid the powdering of the catalyst, thereby constructing a high-efficiency ozone catalytic oxidation reaction system independent of a separation and recovery unit, and being an important direction for breaking through the bottleneck of heterogeneous ozone catalytic oxidation technology.

Disclosure of Invention

1. Problems to be solved

Aiming at the problems of waste of an internal structure, low mass transfer efficiency, additional separation/recovery unit requirement of a powder type ozone catalyst and the like of a particle type carrier ozone catalyst in the existing ozone catalytic oxidation technology, the invention provides a novel two-dimensional catalytic material, which takes a two-dimensional transition metal foil with high specific surface area and light flexibility as a substrate material, and is loaded with an ozone catalytic active metal component and/or a non-metal active component, has the advantages of high specific surface area, high roughness, light weight, flexibility and the like, can solve the problems of difficult recovery and easy breakage of the existing material, and simultaneously has high mass transfer efficiency.

The invention carries out catalyst layer loading on the two-dimensional substrate material, and the prepared catalyst material has the characteristics of high mechanical strength, rapid interface mass transfer, excellent catalytic performance and the like.

2. Technical scheme

In order to solve the problems, the technical scheme adopted by the invention is as follows:

the invention provides a two-dimensional catalytic material, which comprises a two-dimensional material substrate material layer and a catalytic layer loaded on the substrate material, wherein the two-dimensional substrate material has the following structure:

comprises a first structural layer, a second structural layer at least positioned on one surface of the first structural layer, and a second structural layer which comprises

a) A first projection extending along one length direction of the second structural layer;

b) a first concave part which is basically consistent with the first convex part in the direction and is adjacent to the first convex part; and

c) a plurality of holes distributed in the first protrusion part;

wherein at least 0.05% of the holes communicate with the adjacent first recesses;

the base material comprises at least one transition metal and an oxide of the corresponding transition metal; wherein, the content of the transition metal of the first structural layer is at least 90%, and the content of the transition metal oxide of the second structural layer is at least 30%, preferably not less than 90%.

In addition, the first recess and its structure in the present invention are the main reason for the flexibility of the base material, and structures with higher porosity and smaller cross-section are generally more easily bent; the communication between the first concave portion (hereinafter, also referred to as a channel or a pore structure) and the plurality of pores on the first convex portion is a key for increasing the mass transfer rate of the substrate. Without being limited by theory, channel and/or pore structures with high connectivity generally have larger mass transfer rates, e.g., for two differences only: whether the holes on the first protruding part are communicated with the channel or not is characterized in that the mass transfer rate and the internal utilization rate of the material are higher with the communication characteristic than without the communication characteristic. Further not to be limited by theory, having a channel structure generally has a greater mass transfer rate, for example, for two differences only: the former one has a channel and a hole communicated with the channel, and the latter one has only mutually independent holes and no channel; the former mass transfer rate and the internal utilization rate of the material are higher in the application process, the material is flexible, water and pollutants can only diffuse through each hole port in the latter application process, the efficiency is low, and a large number of internal structures do not contribute to the reaction.

In one aspect of this embodiment, the substrate material satisfies one or more of the following conditions:

i) two adjacent channels of the second structure layer can be communicated through holes;

ii) a plurality of holes are distributed on the channel wall (comprising the channel side wall and the channel bottom) of the channel;

iii) wherein at least 0.05% of the pores are irregular pores.

In the case of i) and ii), it should be noted that the higher the connectivity and the higher the porosity, the higher the mass transfer rate of the matrix material and the internal utilization rate of the material. It should be noted that "irregular" of the holes may be formed by a material preparation method, or may be formed by crosslinking several relatively regular holes.

Preferably, the base material is flexible in at least one direction; when bending experiments are carried out, the bending angle is not less than 90 degrees.

It should be noted that, as shown in fig. 19B, the base material has a first protrusion and a first depression extending in the direction indicated by the arrow a, and at this time, the base material has flexibility at least in the direction indicated by the arrow B, and has a bending angle of not less than 90 °, or 120 °, or 150 °, or 180 ° when subjected to the bending test.

In certain embodiments, the bend angle is no less than 120 °;

in certain embodiments, the bend angle is no less than 150 °;

in some embodiments, the bend angle may be up to 180 °.

It should be noted that, for the substrate material, the flexible property is important in the use process, such as the preparation of water treatment catalyst/adsorbent by using the substrate material as a carrier. The integrity of the material can be well maintained in the using process, the catalyst is ensured to have good mechanical property and structural stability, the catalyst is prevented from being powdered, and the separation and recovery are more convenient; without being limited by theory, a flexible material has better toughness and lower brittleness, and has lower possibility of breaking during use, for example, most typical traditional porous anodic oxidation transition metal templates have regular array arrangement of pores on the surface, and the material has extremely high brittleness, and if the material is used as a carrier to prepare a catalyst, the material is fragile and has extremely high loss during use.

Preferably, the bulk density of the substrate material is less than 1g/cm³(ii) a Preferably, the bulk density of the base material is 0.1 to 0.5g/cm³。

It should be noted that, for the substrate material, it is important to have light weight property during the use process, such as the preparation of water treatment catalyst/adsorbent by using the substrate material as a carrier. The prepared catalyst is used in an environment with a certain water flow velocity, and the catalyst can generate dynamic relative motion along with the water, so that the problem of low utilization rate caused by catalyst accumulation can be avoided on one hand, and a certain void ratio is formed between the catalysts on the other hand, so that the mass transfer rate is further improved. It should be mentioned again that the powdering of the catalyst in the process can be avoided due to the flexibility of the catalyst.

Further, the base material is prepared by taking a transition metal foil as a raw material, and the thickness of the transition metal foil is not more than 500 μm; preferably 100-300 μm thick.

Further, the second structural layer is obtained after etching the pore layer with the nanometer and/or micron-sized pore diameter.

The base material satisfies one or more of the following conditions:

i) at least one surface of the first structural layer is provided with a pore layer with nano-scale pore size, and then the second structural layer is formed after the corrosion treatment is carried out on the pore layer;

ii) at least one surface of the first structural layer is provided with a pore layer with micron-sized pores, and then the pore layer is subjected to etching treatment to form the second structural layer;

iii) at least one surface of the first structural layer is provided with a pore layer with nano-scale and micro-scale apertures, and then the pore layer is subjected to corrosion treatment to form the second structural layer;

iiii) the pores of the pore layer, distributed in an array;

iiii) the pore layer is an oxide layer formed after anodic oxidation treatment;

the transition metal includes, but is not limited to, one or more of aluminum, tin, nickel, and titanium; the transition metal oxides include, but are not limited to, one or more of the oxides of aluminum, tin, nickel, and titanium.

Preferably, the catalytic layer comprises a metal active component and/or a non-metal active component, and/or the specific surface area of the two-dimensional catalytic material is 2-200m²/g。

It is noted that the supported metal active component forms Lewis point (M) with high valence metalⁿ⁺) Adsorbs hydroxyl radicals in water to catalyze ozone to generate adsorption type hydroxyl radicals (OH)_ads) (ii) a Or based on lattice defects, e.g. alpha-MnO₂Mn in (1)⁴⁺/Mn³⁺The presence of a metal in a lower valence state will generate a corresponding positively charged oxygen hole (V)_o) The catalyst is used for capturing ozone molecules (O ═ O-O) to realize catalysis. Nonmetal is mostly reacted in the form of functional groups, such as-C ═ O, pyrrole nitrogen, graphitized nitrogen, halogenated structure on the surface of carbon material, to generate adsorbability. O^2-Or OH, or to generate H₂O₂Wait for the intermediate product, further pass H₂O₂/O₃Excitation of free radical (. OH)_free). The metal supported catalyst is mainly surface reaction, while the non-metal supported catalyst can generate adsorbed or free radicals through surface and non-surface reaction. The generated hydroxyl free radicals attack organic matters non-selectively, and the aim of efficiently treating wastewater is fulfilled. Meanwhile, the introduction of metal and/or nonmetal active components regulates and controls the hydrophilic/hydrophobic performance of the catalyst, and greatly improves the mass transfer performance and the catalytic activity of the catalyst.

Preferably, for the two-dimensional catalytic material, the metal active component or the nonmetal active component can be loaded at the same time or different times, and when the two active components are not loaded at the same time, the loading amount of the two active components is 10-30 wt%, and the total loading amount when the two active components are loaded at the same time is 15-45 wt%.

In a preferred scheme, for the two-dimensional catalytic material, the metal active component comprises one or more of copper, iron, cobalt, cerium, nickel, chromium, cadmium, zinc, silver and manganese; the non-metal active component comprises one or more of carbon, nitrogen, sulfur, boron and silicon.

In a preferable scheme, the particle size of the metal and/or nonmetal active component loading material is nano-scale (in the form of nanorod or nanorod fiber), and the diameter of the nanorod/fiber is 1-20 nm.

The invention also provides a preparation method of the two-dimensional catalytic material, which comprises the following steps:

1) processing at least one transition metal foil with concave-convex stripes on the surface to form an array of holes with nano-scale and/or micro-scale apertures distributed along the stripe direction on the surface;

2) subjecting the material obtained in 1) to an etching treatment to form a base material having orientation flexibility in at least one direction;

3) and taking the two-dimensional substrate material as a substrate, and loading a catalytic layer on the surface of the substrate.

Preferably, the concave and convex stripes on the surface of the transition metal foil comprise: a plurality of convex stripes with consistent or basically consistent trend are arranged, and a concave stripe is formed between every two adjacent convex stripes; and/or a plurality of mutually parallel or basically parallel convex stripes, and concave stripes are formed between two adjacent convex stripes.

Preferably, the width of the protruding stripes on the surface of the metal foil is 0.01-50 μm; and/or concave stripes with the maximum depth of 0.001-10 nm are formed between the two adjacent convex stripes; and/or the distance between two adjacent protruding stripes is 0.01-50 μm.

Preferably, the depth of the pores is at least 20 nm; and/or the pores have an average pore diameter of at least 10 nm; and/or the walls of the pores have a thickness of at least 5 nm.

Preferably, the depth of the pores is 0.02 to 80 μm; and/or the pores have an average pore diameter of at least 10-500 nm; and/or the wall thickness of the pore is 5-100 nm.

It should be noted that, especially, there is a certain restriction relationship between the aperture size of the hole and the distance between two adjacent protruding stripes, and the aperture size of the hole cannot exceed the distance between two adjacent protruding stripes, otherwise, an effective microstructure cannot be formed.

Preferably, the corrosion control is surface acid corrosion control of the material obtained in the step 1) by using acid liquor.

Preferably, the pH value of the acid solution is 0.92-3.00, and the acid etching time is 5-70min when the acid etching is regulated.

And/or the concentration of hydrogen ions in the acid solution is 0.001-0.65 mol/L; when the acid etching is regulated, the acid etching time is 5-70 min.

It should be noted that, after anodic oxidation, a hard template structure with porous holes is formed on the surface of the transition metal foil, and the etching process can corrode and thin the hole wall between adjacent holes until the hole wall is broken and replaced, especially the etching effect on the hole wall between two adjacent holes distributed along the concave and convex stripes on the surface of the transition metal foil is more obvious, and a second structure layer structure can be effectively formed by limiting the time for adjusting and controlling the etching and simultaneously limiting the pH of the acid solution or the hydrogen ion concentration in the acid solution; if the acid etching control time is too long, or the pH of the acid solution is too low, or the hydrogen ion concentration in the acid solution is too high, the acid etching will be transited, so that the second structural layer structure of the substrate material is at risk of being completely peeled off, and finally the channel, the first protrusion and the corresponding hole structure can no longer be retained on the surface of the substrate material, thereby forming a surface structure having only mutually independent holes as shown in fig. 6 b; if the acid etching control time is insufficient, or the pH of the acid solution is too high, or the hydrogen ion concentration in the acid solution is too low, the acid etching is insufficient, so that the holes on the second structure layer structure of the substrate material cannot be effectively communicated with the channels, and finally the surface of the substrate material does not have effective channels, first protrusions and corresponding hole structures.

Preferably, the invention provides a preparation method of the two-dimensional catalytic material, which comprises the following steps:

1) anodic oxidation: carrying out anodic oxidation treatment on the metal foil with the convex stripes on the surface, so that an array of holes which are distributed along the stripe direction and have nano-scale and/or micro-scale apertures is formed on the surface of the metal foil;

2) corrosion regulation and control: carrying out surface corrosion treatment on the metal foil subjected to the anodic oxidation treatment to form a base material which is flexible in at least one direction;

3) the metal and/or non-metal components are supported on the base material.

Here, the surface of the transition metal foil subjected to the anodic oxidation treatment needs to have the characteristics of "concave and convex stripes", which is a basic condition for forming a flexible base material after the corrosion control treatment. The inventors of the present invention have tried to perform an anodic oxidation treatment on a transition metal foil having a smooth surface or a random texture and then perform corrosion control, and as a result, found that a flexible base material cannot be obtained regardless of the limitations of experimental parameters, and accordingly, the "concave and convex stripes" on the surface of the transition metal foil not only have a guiding effect on the formation of a pore array during anodic oxidation, but also have a guiding effect on the corrosion effect.

Preferably, during the anodic oxidation, the electrode distance is 0.3-10cm, the voltage is 10-200V, and the oxidation time is 2-48 hours.

Preferably, during the anodic oxidation, the electrode spacing is 0.5-3cm, the voltage is 40-80V, and the oxidation time is 6-24 hours, and the transition metal foil after the anodic oxidation is finished is cleaned and then placed in clean water for storage.

Preferably, the anodizing electrolyte comprises at least one acid selected from oxalic acid, sulfuric acid, phosphoric acid or hydrofluoric acid.

In one aspect of this embodiment, the anodized electrolyte meets one or more of the following conditions:

i) the concentration of acid in the anodic oxidation electrolyte is 10-80 g/L;

ii) during the anodic oxidation, the reaction vessel containing the anodic oxidation electrolyte is placed in an ice water bath so that the temperature of the anodic oxidation electrolyte in the vessel is maintained between 0 ℃ and 15 ℃.

Preferably, the metallic and/or non-metallic loading of step 3) comprises:

A. dipping the two-dimensional substrate material in a solution containing an acetic acid precursor, and synchronously corroding the two-dimensional substrate material by precursor salt in the dipping process;

B. placing the two-dimensional substrate material subjected to the immersion corrosion loading at room temperature for standing to fully diffuse the precursor;

C. drying and pre-pyrolysis are carried out on the two-dimensional material after the precursor is fully diffused;

D. and (3) placing the dried and pre-pyrolyzed two-dimensional material in a nitrogen/argon protective furnace for roasting treatment.

Preferably, in the step A, the impregnation mode comprises vacuum impregnation/non-vacuum impregnation, the impregnation time is 5-60min, and the temperature is 10-50 ℃;

and/or in the step B, the standing time is 6-24 h;

and/or in the step C, drying and pre-pyrolyzing for 12-24 hours by using a common oven/vacuum oven; the temperature of the common oven is 20-100 ℃; the temperature of the vacuum oven is 20-90 ℃.

And/or in the step D, the temperature rising/reducing speed is 1-10 ℃/min, and the temperature is kept at 500-550 ℃ for 0.5-10 h.

Preferably, in the step A, the precursor solution contains inorganic metal salt and/or organic matter; the inorganic metal salt comprises one or more of inorganic metal salts of copper, iron, cobalt, cerium, nickel, chromium, cadmium, zinc, silver and manganese; the organic matter comprises one or more of carbon, nitrogen, sulfur, boron and silicon;

different from the traditional impregnation loading method of the catalyst, the precursor salt has certain corrosivity on the two-dimensional carrier, and the two-dimensional carrier is subjected to corrosion loading (invasive loading) in the loading process, so that the loading depth and strength are enhanced, and the precursor salt is generally loaded in an excessive mode.

It should be noted that, by adding acetic acid, the precursor solution is in an acidic environment, which is helpful to stabilize metal ions in the precursor and prevent the metal ions from being resolved. In addition, acetic acid can carry out secondary corrosion on the two-dimensional substrate, and is beneficial to improving the loading efficiency of the active component on the carrier. There are two ways of adding acetic acid, one is directly adding acetate precursor (such as nickel acetate, copper acetate, ammonium acetate), and the second is adding acetic acid separately. Acetic acid is added as a precursor, and the preparation method is the same as that of a common precursor; the acetic acid is independently added, and can be added at one time or added dropwise by stirring.

Preferably, in the step A, the concentration of the acetic acid is about 20% -50% of the total concentration of the precursor.

In some embodiments, the two-dimensional catalytic material may be used in catalytic oxidation treatment of wastewater and exhaust gas.

Preferably, the two-dimensional ozone catalytic material can be used for ozone oxidation treatment of wastewater and waste gas.

Preferably, the two-dimensional ozone catalytic material is used as a material of a dynamic packed bed ozone reactor, a fluidized bed reactor is combined with a two-dimensional light catalyst, and the interlayer intermittent expansion of the catalytic bed is realized by adjusting the gas/water condition, so that the anti-scaling performance of the reaction can be effectively improved, and the long-term operation stability of the system is kept. The method can effectively solve the problem that the service life of the catalyst is shortened because the catalyst bed layer is easy to harden and lose efficacy in the operation process of the dynamic reaction bed of the existing HCO process (heterogeneous ozone catalytic oxidation process).

3. Advantageous effects

Compared with the prior art, the invention has the beneficial effects that:

(1) the two-dimensional catalytic material has higher mass transfer efficiency and separation recovery efficiency, the existing anodic oxidation (preparation and application research of curved surface anodic alumina template, Xueheng, Shandong building university, Master's academic paper) adopts polishing, primary anodic oxidation, acid corrosion to remove oxide layer and secondary anodic oxidation, the holes are regularly arrayed, and all the nanopores are mutually independent, when the two-dimensional catalytic material is applied to a semi-continuous flow ozone catalytic oxidation experiment, water and pollutants can only diffuse through the ports of all the nanopores, and the efficiency is low; the method is based on the aluminum, tin, nickel or titanium and other metals with the thickness reduced to the micron level and the length and width maintained to the level above millimeters as basic materials, realizes the two-dimension of the three-dimensional catalyst, obtains a two-dimensional substrate with concave-convex stripes on the surface by means of pretreatment in the steps of degreasing, polishing, wire drawing and water washing, and forms a nano porous array with high specific area and roughness on the two-dimensional substrate along the concave-convex stripes by adopting an anodic oxidation process; through acid etching regulation and control, a mass transfer channel of the hard template formed after the original anode oxidation is opened, and the carrier has orientation flexibility. Because the catalytic oxidation reaction of ozone is a surface reaction, and a large number of internal structures do not contribute to the reaction, the two-dimension effectively solves the waste of a large number of internal structures, reduces the cost, greatly improves the active specific surface area of the catalyst, improves the interface mass transfer efficiency and the catalytic performance, simultaneously the two-dimension catalyst has good mechanical performance and structural stability, avoids the catalyst from being powdered, and is more convenient to separate and recover;

(2) the two-dimensional ozone catalytic material for wastewater treatment is different from the traditional millimeter-scale granular ozone catalytic material and the micron/nanometer-scale powder catalytic material, is micron/nanometer in thickness dimension and more than millimeter-scale in length and width dimensions, and has the characteristics of light weight and flexibility; different from the traditional preparation mode of an impregnation-loading or granulation method, the two-dimensional ozone catalytic material can carry out nanoscale functional design on a carrier; different from the traditional anodic oxidation process, the nanoscale functionalized design of the two-dimensional ozone catalytic material is different from the hard template (which is fragile and inflexible) obtained by the traditional anodic oxidation technology, and the material with the functionalized design also has the flexible characteristic.

(3) The preparation method of the carrier of the two-dimensional ozone catalytic material and the active component loading method are easy to popularize, have strong applicability and can be used for preparing solid-phase catalytic materials such as heterogeneous Fenton, photocatalysis and the like. The catalytic material prepared by the invention has wide application field, and can be used in the fields of sewage treatment, organic waste gas treatment, ozonolysis and the like besides wastewater treatment. The material provided by the invention is used for carrying out ozone catalytic oxidation treatment on wastewater and waste gas, can effectively solve the problems of internal structure waste and difficult separation and recovery of powder catalysts in the use of the traditional three-dimensional catalyst (granular catalyst), and has the advantages of high catalytic activity ratio surface, high interface mass transfer efficiency, good mechanical property and structural stability.

Drawings

FIG. 1 is a polished surface topography of an aluminum foil (a), an enlarged surface topography of the aluminum foil after wire drawing (b), and an SEM (surface texture scanning electron microscope) of the aluminum foil after wire drawing (c);

FIGS. 2a and 2b are graphs showing the appearance of nano-pores on the surface of an aluminum foil prepared by anodic oxidation according to the present invention;

FIG. 3 is a cross-sectional view of an aluminum foil prepared by anodizing in accordance with the present invention;

FIG. 4 is a surface morphology of a material (4A) obtained by performing anodic oxidation, acid etching control and element loading on a transition metal aluminum foil as a base material in example 1 of the present invention; enlarged pore passage (4B); an enlarged view (4C) of the long and narrow part and the upper hole thereof damaged by the acid etching;

FIG. 5 is a cross-sectional view of a material obtained by performing anodic oxidation, acid etching control, and element loading on a base material of tin, which is a transition metal, in example 2 of the present invention;

FIG. 6 is the morphology of the metal and/or non-metal loaded two-dimensional catalytic material in example 2 of the present invention;

FIG. 7 is a side view of a two-dimensional ozone catalytic material prepared by using a transition metal tin as a base material in example 2 of the present invention;

FIG. 8 is a graph showing the effect of two-dimensional ozone catalytic material based on metallic aluminum (drawn and undrawn during pretreatment during preparation) prepared in example 1 and comparative example 1 on the removal of oxalic acid;

FIG. 9 is a graph showing the effect of the two-dimensional ozone catalytic material (too large, too small or proper acid etching control parameters during the preparation process) prepared in example 1 and comparative example 2 on removing phenol;

fig. 10 is a surface topography formed by the degree of acid etching not used due to acid etching after anodic oxidation and acid etching control are performed on an aluminum foil as a base material, fig. 10A is a surface topography formed by insufficient acid etching, and fig. 10B is a surface topography formed by excessive acid etching;

FIG. 11 is a graph comparing the removal effect of two-dimensional ozone catalytic material based on aluminum metal prepared in example 1 on phenol with ozone alone and a conventional particle-type three-dimensional catalyst;

FIG. 12 is a graph comparing the removal effect of the two-dimensional ozone catalytic material based on metallic tin prepared in example 2 on pyrazole with ozone alone and a conventional particle-type three-dimensional catalyst;

FIG. 13 is a graph comparing the effect of the two-dimensional ozone catalytic material based on metallic nickel prepared in example 3 on oxalic acid removal with ozone alone, a conventional particle type three-dimensional catalyst;

FIG. 14 is a diagram of oxalic acid degradation in a two-dimensional ozone catalytic material cycle test prepared in example 1;

FIG. 15 is a water flow velocity simulation calculation chart of the COMSOL finite element numerical simulation model at different heights of the nanopore; FIG. 15a is a non-etched pattern and FIG. 15b is an etched pattern;

FIG. 16 is a side cut water flow distribution simulation; FIG. 16a is a non-etched pattern and FIG. 16b is an etched pattern;

FIG. 17 is a perspective view of the manner in which flexibility tests (bending tests) are performed on a base material in accordance with the present invention;

FIG. 18 is a front view (a) of the platen of FIG. 17; side view (b).

FIG. 19 is a schematic view of the measurement of the bend angle β;

FIG. 20 is a schematic illustration of a bend in a two-dimensional catalytic material prepared according to the present invention;

in the figure: 1. testing the material; 2. a roller; 3. a pressing plate, 4 and a second structural layer; 410. a channel; 420. a first projecting portion; 421. a hole; 5. a first structural layer.

Detailed Description

The invention is further described with reference to specific examples.

Material

Transitional metal foil (or foil) with concave and convex stripes on surface | (non-conducting optical fibers)

In terms of the material of the transition metal foil (or foil) with concave and convex stripes on the surface, at least one surface of the transition metal foil is provided with convex stripes, and concave stripes with micro and/or nano level width and depth, especially micro level, are formed between two adjacent convex stripes; if a plurality of protruding stripes exist at the same time, the direction of each stripe is consistent or basically consistent, parallel or basically parallel; there is no particular limitation on the source thereof; such as commercially available "transition metal foil" with raised stripes on the surface; the metal foil can also be obtained by grinding, wire drawing and water washing (by using ethanol/acetone and deionized water) by taking the transition metal foil as a raw material in the embodiment, and can also be obtained by rolling.

If the transition metal foil (or foil) with raised stripes on the surface is obtained by grinding, wire drawing and water washing (with ethanol and deionized water) by taking the transition metal foil as a raw material as in the examples herein. The transition metal foil (before drawing) only needs to satisfy one of the following properties:

i) the content of transition metal in the transition metal foil is not less than 90 percent

ii) the transition metal foil has a thickness of not more than 500 μm.

(ii) substrate material | non-conducting phosphor

The base material comprises a first structural layer and a second structural layer positioned on the surface of the first structural layer, wherein the second structural layer comprises a) a first bulge, and the first bulge extends along one length direction of the second structural layer; b) a first concave part which is basically consistent with the first convex part in the direction and is adjacent to the first convex part; and c) a plurality of holes distributed in the first protrusion; wherein at least 0.05% of the holes communicate with the adjacent first recesses; the base material is flexible in at least one direction; the base material comprises at least one transition metal and an oxide of the corresponding transition metal; wherein the transition metal content of the first structural layer is at least 90%. The oxide content of the transition metal of the second structural layer is at least 30%, and preferably not less than 90%.

Method

Pretreatment

In some embodiments, the "transition metal foil (or foil) with concave-convex stripes on the surface" is obtained by using a transition metal foil as a raw material and performing wire drawing and water washing (with ethanol and deionized water) treatment as in the examples herein. In the process of daily storage and transportation, the transition metal foil has the problems of generating a natural oxidation film by oxidation on the surface, being polluted by pollutants such as grease, dust and the like, even having slight scratches and the like, and therefore, the transition metal foil needs to be pretreated before the preparation of the substrate material. This pretreatment is a known and conventional technique, and includes, for example, cutting, high-temperature annealing, degreasing, grinding, polishing, and the like.

In some embodiments, the transition metal foil is cut into a sample sheet with certain specifications for later use. In some embodiments, the high temperature annealing treatment is performed at a certain temperature under the protection of inert gas, and the annealing treatment is cooled along with the furnace, so that the internal stress of the transition metal foil can be eliminated. For example, in one embodiment, the transition metal foil is an aluminum foil, and the aluminum foil can be annealed at 450 ℃ for 5 hours under the protection of inert gas argon, and cooled along with the furnace to eliminate the internal stress of the aluminum foil.

In some embodiments, mechanical grinding is used to remove scratches that may be present on the surface of the transition metal foil, and a grinding tool is used to grind in a certain direction during grinding to form a grinding surface with consistent surface texture. After polishing, ensuring that the thickness of the transition metal foil is not more than 500 mu m; preferably 30-300 μm thick; further preferably, the thickness is 100 to 300 μm.

In some embodiments, the polishing can have a certain grinding effect on the aluminum alloy material, and can remove the defects of burrs, oxide scales and scratches on the surface of the product so as to reduce the roughness of the surface of the aluminum alloy material and obtain a bright appearance. Polishing methods are well known to those skilled in the art, such as mechanical lapping, chemical polishing, thermal chemical polishing or electropolishing, to ultimately obtain a mirror-finished wafer.

In some embodiments, wax removal is used to remove polishing wax from the product. The dewaxing method is well known to those skilled in the art, and can be carried out at 70-80 deg.C by using dewaxing water, such as commercially available zinc alloy dewaxing water (e.g. zinc alloy dewaxing water). In a preferred case, ultrasound may be used to enhance the wax removal effect.

In some embodiments, the transition metal foil is polished and then degreased, wherein the degreasing is to remove surface grease, dirt and uncleaned polishing wax, and the degreasing method can adopt various existing and mature degreasing processes, such as organic solvent degreasing, chemical degreasing, electrolytic degreasing, emulsion degreasing, ultrasonic degreasing and the like, as long as the purpose of removing the oil stain on the surface of the transition metal foil can be achieved;

in some embodiments, the mechanical friction method is used to draw at least one surface of the transition metal foil to form straight lines and continuous drawing as shown in fig. 1. Forming a transition metal foil with concave-convex stripes on the surface after wire drawing. In some embodiments, after drawing, the transition metal foil surface forms a plurality of concave-convex stripes with uniform or approximately uniform directions. In some embodiments, after drawing, the transition metal foil surface forms a plurality of concave-convex stripes which are parallel or basically parallel to each other. In some embodiments, after drawing, the maximum width of the relief stripes on the surface of the transition metal foil is at least 10nm, and may range from 0.01 to 50 μm. In some embodiments, the maximum depth of the relief stripes on the surface of the transition metal foil after drawing is at least 3nm, and may range from 0.01 to 10 μm in range. In some embodiments, after drawing, the maximum fringe spacing between two adjacent concave-convex fringes on the surface of the transition metal foil is at least 10nm, and can range from 0.01 μm to 50 μm.

In some embodiments, the drawn transition metal foil is subjected to an alcohol/ketone wash and a water wash for further cleaning.

Preparation of hole array on surface of transition metal foil

The transition metal foil surface may be formed with an array of holes (nano-scale and/or micro-scale pore size holes) using any of the existing techniques, such as, for example, published (bulletin) nos: CN103402908B publication (announcement) day: 2016.08.31 discloses a method for producing highly ordered nanopillar or nanopore structures over large areas, as well as anodization.

In some embodiments, after the "transition metal foil with concave-convex stripes on the surface" is processed by using a conventional anodic oxidation method, an array of holes with nanometer-scale and/or micrometer-scale apertures distributed along the stripe direction is formed on the surface of the transition metal foil.

In some embodiments, the transition metal foil is used as an anode and connected to a positive electrode of an external power supply and placed in an electrolyte solution, and the cathode can be made of materials which are not easy to react with acid, such as a Pt sheet, a titanium plate, stainless steel, a graphite rod and the like.

In some embodiments, the anodic oxidation electrolyte is an acid solution comprising at least one acid selected from oxalic acid, sulfuric acid, phosphoric acid or hydrofluoric acid, wherein the concentration of the acid is 10-80g/L, and during the anodic oxidation process, the reaction container containing the anodic oxidation electrolyte is placed in an ice-water bath, so that the temperature of the anodic oxidation electrolyte in the container is kept between 0 ℃ and 15 ℃;

it has been found that during the anodic oxidation of transition metals, the structure of the oxide film (i.e., the pore layer) is affected by the applied voltage, and that the higher the voltage is within a certain range, the more uniform and dense the oxide film layer is. In the preferred embodiment the voltage ranges from 10-200V, such as 20-30V, 30-50V, 40-80V, 100-120V.

In some embodiments, after anodization, an ordered porous anodized film is formed on the surface of the transition metal foil. In some embodiments, the depth of the pores is at least 20nm, and in range aspects, the depth of the pores is 0.02-80 μm. In some embodiments, the pores have a maximum pore diameter of at least 10nm and, in range aspects, a depth of 10-500 nm. In some embodiments, the walls of the pores (between two adjacent pores) have a thickness of at least 5nm, and in range aspects the walls of the pores have a thickness of 5-100 nm.

Corrosion regulation

Any of the existing techniques may be used to control corrosion of a transition metal foil surface having an array of pores (nanometer and/or micrometer sized pores), such as, for example, an alkaline etching process, and, for example, an acid etching process.

In some embodiments, the surface of the transition metal foil having an array of pores (pores with nanometer and/or micrometer pore sizes) is modified by etching using a conventional acid etching process, such that at least 5% of the pores on the surface of the transition metal foil are connected to adjacent pores to form irregular pores, and for example, at least 0.05% of the pores are connected to adjacent pores.

Example 1

In the embodiment, an aluminum foil with the thickness of 200 μm is selected as a base material to prepare a two-dimensional base material, and the surface before polishing is shown in figure 1 a; the method comprises the following specific steps:

1) pretreatment: the aluminum foil (upper and lower surfaces) is pretreated by degreasing, polishing, wire drawing and water washing, wherein acetone solution is used for degreasing, and ethanol and deionized water are respectively used for washing. Drying in a 50 ℃ oven for later use after completion, wherein a comparison graph after treatment is shown as 1 b;

2) anodic oxidation: taking a titanium plate and the like as cathodes, a pretreated aluminum foil as an anode, taking 50g/L oxalic acid solution (300 ml) as corrosive electrolyte, and putting a reaction container filled with the corrosive electrolyte in an ice-water bath all the time in the anodic oxidation treatment process, wherein the temperature is kept at 10 +/-1 ℃; during anodic oxidation treatment, the distance between a cathode and an anode is 2cm, the voltage is 60V, and the treatment time is 12 hours; cleaning the oxidized aluminum foil, and then placing the aluminum foil in deionized water for storage;

preparing a nano-pore array on an aluminum foil after anodic oxidation, wherein the surface microstructure is shown in figures 2a and 2 b; the microstructure of the cross section is as shown in fig. 3a, and it can be seen from fig. 2a and 2b that after anodic oxidation is performed on the aluminum foil with concave-convex stripes on the surface, a plurality of nanopores are distributed on the surface (upper and lower surfaces) of the two-dimensional material, and the nanopores are regularly arranged in a nanopore array manner in the direction of the stripes under the guidance of the concave-convex stripes;

3) acid etching regulation and control: drying the anodized aluminum foil in a 50 ℃ oven for 12 hours; 500ml of a 4 wt% phosphoric acid solution (molar concentration of hydrogen ions: 3.2X 10) was prepared at room temperature^-3mol/L and pH of 2.50); then, placing the dried aluminum foil in a phosphoric acid solution for soaking and softening for 60min, and placing the phosphoric acid solution in an oven for preserving at the constant temperature of 35 ℃; and cleaning the two-dimensional material by using deionized water after the acid etching regulation and control is finished, and drying in a 50 ℃ drying oven.

The substrate material prepared in this embodiment has a first structural layer 5, and the upper and lower surfaces of the first structural layer 5 have a second structural layer 4 (anodic oxide film layer) as shown in fig. 4a, the second structural layer 4 has a plurality of channels 410 with substantially uniform directions, a first concave portion formed thereon, and a first convex portion 420 located between two adjacent channels 410; meanwhile, it is apparent that a plurality of holes 421 are distributed on the first protrusion 420, wherein at least 0.05% of the holes 421 are communicated with the adjacent channels 410. Fig. 4b is a partial enlarged view, which clearly shows the channel 410, the first protrusion 420 and the hole 421 of the second structural layer 4. Further, fig. 4c is a partially enlarged view of the first protrusion 420, from which the wall surface morphology after etching and the change of the hole formed on the anodized film after etching can be clearly seen.

In the base material prepared in this embodiment, the aluminum content of the first structural layer 5 is not less than 90%, and the aluminum oxide content of the second structural layer 4 is more than 30%.

Taking the two-dimensional substrate material as a carrier; preparing precursor solutions of 60g/L glucose, 30g/L manganese sulfate, 20g/L copper nitrate, 30g/L cobalt chloride and 40g/L acetic acid (wherein the glucose, the manganese sulfate, the copper nitrate, the cobalt chloride and the acetic acid all belong to the precursor solutions), wherein the mass concentration of the acetic acid is about 22% of the total mass concentration of the precursor solutions, and preparing the two-dimensional ozone catalytic material, wherein the specific preparation steps are as follows:

A. placing the aluminum foil in the precursor solution for vacuum impregnation (the volume of the precursor solution measured in the step can be only required to be completely immersed in the foil), wherein the impregnation time is 20min, the temperature is constant at 20 +/-5 ℃, and precursor salt synchronously corrodes the two-dimensional carrier in the impregnation process;

B. placing the impregnated and loaded aluminum foil at room temperature and standing for 15 h;

C. putting the carrier with the fully diffused precursor into a vacuum oven at 70 ℃ for drying and pre-pyrolysis for 15 hours;

D. placing the dried and pre-pyrolyzed carrier in an argon protection furnace for high-temperature roasting treatment; heating to 550 ℃ at the speed of 3 ℃/min, preserving the heat for 1.5h, and then cooling to room temperature at the speed of 3 ℃/min to obtain a finished product, namely the aluminum-based two-dimensional ozone catalytic material;

the specific surface area of the two-dimensional ozone catalytic material prepared by taking the aluminum foil as the base material is 15.1352m²(ii)/g; the load amount was calculated with reference to: the loading amount is equal to the mass of the active component/(the mass of the active component + the mass of the carrier), wherein the mass of the active component is equal to the mass difference of the catalytic material before and after loading, and the amount of the loaded metal and the nonmetal obtained by calculation is 40 wt%;

in the embodiment, an aluminum foil is used as a base material, and single-side channels (the channels between adjacent nanopores in the direction of a drawing stripe are completely communicated, and the channels between the nanopores perpendicular to the drawing direction are not completely communicated) are generated on the surface of a two-dimensional ozone catalytic material formed after roasting through anodic oxidation, acid etching regulation and vacuum impregnation (precursor invasive load), so that the two-dimensional ozone catalytic material has orientation flexibility, the mechanical strength and the structural stability of the material are greatly improved, the mass transfer performance of the material in the use process is improved, and the pore structure diagram 4b is enlarged to obtain a pore structure with high mass transfer performance.

After the loading is finished, the shape of the metal and/or nonmetal is rod-shaped fiber with the nanometer scale, as shown in fig. 6, and the metal active component and/or the nonmetal active component are distributed on the surface of the base material layer in a cluster shape.

Example 2

In this example, a two-dimensional transition metal tin foil with a thickness of 300 μm and concave-convex stripes (stripe width of about 60nm, stripe depth of 4nm, and stripe pitch of 60nm) was selected as a base material to prepare a base material, and the steps were as follows:

1) pretreatment: the method comprises the following steps of degreasing, polishing, wire drawing and water washing on two sides of a tin foil, wherein an acetone solution is adopted for degreasing, and ethanol and deionized water are respectively adopted for washing. Drying in a 50 ℃ oven for later use after completion;

2) anodic oxidation: taking a titanium plate and the like as cathodes, a pretreated tin foil as an anode, taking 150g/L sulfuric acid solution (300 ml) as corrosive electrolyte, and putting a reaction container filled with the corrosive electrolyte in an ice-water bath all the time in the anodic oxidation treatment process, wherein the temperature is kept at 10 +/-1 ℃; during anodic oxidation treatment, the distance between a cathode and an anode is 1cm, the voltage is 15V, and the treatment time is 0.5 hour; cleaning the oxidized tin foil, and then placing the tin foil in deionized water for storage;

3) acid etching regulation and control: placing the anodized tin foil in a 50 ℃ oven for drying for 12 hours; 500ml of a 7 wt% phosphoric acid solution (molar concentration of hydrogen ions: 5.60X 10) was prepared at room temperature^-3mol/L and pH of 2.25); subsequently, the dried tin foil is placed in a phosphoric acid solution for soaking and softening for 30min, during which the phosphoric acid solution is placed in a baking ovenPreserving at constant temperature of 35 deg.C; after the acid etching regulation and control are finished, the two-dimensional material is cleaned by deionized water and dried in a 50 ℃ oven;

taking the two-dimensional substrate material as a carrier; preparing a precursor solution of 70g/L glucose and 18g/L acetic acid to prepare a two-dimensional ozone catalytic material, wherein the mass concentration of the acetic acid accounts for 20% of the total mass concentration of the precursor solution, and the specific preparation steps are as follows:

A. the tin foil is placed in the precursor solution for vacuum impregnation (the volume of the precursor solution measured in the step can be only required to be completely immersed in the foil), the impregnation time is 20min, the temperature is constant at 20 +/-5 ℃, and precursor salt synchronously corrodes the two-dimensional carrier in the impregnation process;

B. placing the dipped and loaded tin foil at room temperature and standing for 15 h;

C. putting the carrier with the fully diffused precursor into a vacuum oven at 65 ℃ for drying and pre-pyrolysis for 15 hours;

D. placing the dried and pre-pyrolyzed carrier in an argon protection furnace for high-temperature roasting treatment; heating to 550 ℃ at the speed of 3 ℃/min, preserving the heat for 1.5h, and then cooling to room temperature at the speed of 3 ℃/min to obtain a finished product, namely the tin-based two-dimensional ozone catalytic material;

the microstructure of the cross section of the two-dimensional ozone catalytic material prepared by taking tin foil as a base material is shown in FIG. 7, and the specific surface area is 8.3953m²(ii)/g; the amount of non-metal loaded is 16 wt%;

the tin foil with concave-convex stripes is used as a base material, and the nano-pore arrays can be formed on the front surface and the back surface of a tin oxide matrix after anodic oxidation, acid etching regulation and control, vacuum impregnation and roasting.

Example 3

In this example, a two-dimensional transition metal nickel foil with a thickness of 100 μm and concave-convex stripes (stripe width of about 100nm, stripe depth of 4nm, and stripe pitch of 100nm) was selected as a base material to prepare a base material, and the steps were as follows:

1) pretreatment: the method comprises the following steps of degreasing, polishing, wire drawing and water washing on two sides of a nickel foil sheet, wherein an acetone solution is adopted for degreasing, and ethanol and deionized water are respectively adopted for washing. Drying in a drying oven at 40 ℃ for later use;

2) anodic oxidation: taking a titanium plate and the like as cathodes, a pretreated nickel foil as an anode, and 120g/L phosphoric acid solution (300 ml) as corrosive electrolyte, wherein a reaction container filled with the corrosive electrolyte is always placed in an ice-water bath during anodic oxidation treatment, and the temperature is kept at 10 +/-1 ℃; during anodic oxidation treatment, the distance between a cathode and an anode is 1.5cm, the voltage is 10V, and the treatment time is 1 hour; cleaning the oxidized nickel foil, and then placing the nickel foil in deionized water for storage;

3) acid etching regulation and control: placing the nickel foil subjected to anodic oxidation in a 50 ℃ oven for drying for 12 h; 500ml of a 10 wt% phosphoric acid solution (molar concentration of hydrogen ions: 8.1X 10) was prepared at room temperature^-3mol/L and pH of 2.09); then, placing the dried tin foil piece into a phosphoric acid solution for soaking and softening for 20min, and placing the phosphoric acid solution into an oven for preserving at the constant temperature of 35 ℃; after the acid etching regulation and control are finished, the two-dimensional material is cleaned by deionized water and dried in a 50 ℃ oven;

taking the two-dimensional substrate material as a carrier; before preparing a precursor solution of 20g/L copper nitrate, 50g/L cobalt chloride and 25g/L acetic acid, preparing the two-dimensional ozone catalytic material, wherein the specific preparation steps are as follows:

A. putting the nickel foil into the precursor solution for vacuum impregnation (the volume of the precursor solution measured in the step can be only required to be completely immersed in the foil), wherein the impregnation time is 20min, the temperature is constant at 20 +/-5 ℃, and precursor salt synchronously corrodes the two-dimensional carrier in the impregnation process;

B. placing the nickel foil subjected to impregnation loading at room temperature and standing for 15 hours;

the specific surface area of the two-dimensional ozone catalytic material prepared by taking the nickel foil as the base material is 10.1209m²(ii)/g; the amount of supported metal and nonmetal was 23 wt%; the material has orientation flexibility and excellent mechanical strength.

Example 4

In the embodiment, a two-dimensional transition metal titanium foil with the thickness of 100 μm and concave-convex stripes (the stripe width is about 60nm, the stripe depth is 4nm, and the stripe distance is 60nm) is selected as a base material to prepare a base material;

the method comprises the following specific steps: 1) pretreatment: the two sides of the titanium foil are pretreated by degreasing and water washing, wherein acetone solution is adopted for degreasing, and ethanol and deionized water are respectively adopted for washing. Drying in a drying oven at 40 ℃ for later use;

2) anodic oxidation: taking a stainless steel plate as a cathode, a pretreated titanium foil as an anode, taking 10g/L hydrofluoric acid solution (300 ml) as corrosive electrolyte, and putting a reaction container filled with the corrosive electrolyte in an ice-water bath all the time in the anodic oxidation treatment process, wherein the temperature is kept at 10 +/-1 ℃; during anodic oxidation treatment, the distance between a cathode and an anode is 1.5cm, the voltage is 25V, and the treatment time is 1 hour; cleaning the oxidized titanium foil, and then placing the titanium foil in deionized water for storage;

3) acid etching regulation and control: placing the anodized titanium foil in a 50 ℃ oven for drying for 12 hours; 500ml of a 7 wt% chromic acid solution (hydrogen ion molar concentration 0.63mol/L, pH 0.94) was prepared at room temperature; then, placing the dried titanium foil in chromic acid solution for soaking and softening for 6min, and placing the chromic acid solution in an oven for preservation at constant temperature of 35 ℃; after the acid etching regulation and control are finished, the two-dimensional material is cleaned by deionized water and dried in a 50 ℃ oven;

taking the two-dimensional substrate material as a carrier; preparing precursor solution of 70g/L copper nitrate and 25g/L acetic acid, and preparing the two-dimensional ozone catalytic material, wherein the preparation steps are as follows:

A. putting the titanium foil into the precursor solution for vacuum impregnation (the volume of the precursor solution measured in the step can be only required to be completely immersed in the foil), wherein the impregnation time is 20min, the temperature is constant at 20 +/-5 ℃, and precursor salt synchronously corrodes the two-dimensional carrier in the impregnation process;

B. placing the titanium foil subjected to the impregnation loading at room temperature and standing for 15 h;

D. placing the dried and pre-pyrolyzed carrier in an argon protection furnace for high-temperature roasting treatment; heating to 550 ℃ at the speed of 3 ℃/min, preserving the heat for 1.5h, and then cooling to room temperature at the speed of 3 ℃/min to obtain a finished product, namely the titanium-based two-dimensional ozone catalytic material;

the specific surface area of the two-dimensional ozone catalytic material prepared by using the titanium foil as the base material is 11.9151m²(ii) a metal and non-metal loading of 25 wt.%;

in the catalytic materials of examples 1-4, the diameter of the metallic and/or non-metallic nanofibers supported on the substrate surface was 1-20 nm.

Example 5

In this embodiment, an aluminum foil with a thickness of 200 μm is selected as a base material to prepare a two-dimensional base material, and the specific steps are as follows:

1) pretreatment: the aluminum foil (upper and lower surfaces) is pretreated by degreasing, polishing, wire drawing and water washing, wherein acetone solution is used for degreasing, and ethanol and deionized water are respectively used for washing. Drying in a 50 ℃ oven for later use after completion;

taking the two-dimensional substrate material as a carrier; preparing precursor solution of 60g/L glucose, 30g/L manganese sulfate, 20g/L copper nitrate, 30g/L cobalt chloride and 40g/L acetic acid, and preparing the two-dimensional ozone catalytic material, wherein the specific preparation steps are as follows:

A. placing the aluminum foil in the precursor solution for vacuum impregnation (the volume of the precursor solution measured in the step can be completely immersed in the foil), wherein the impregnation time is 5min, the temperature is constant at 45 +/-5 ℃, and precursor salt synchronously corrodes the two-dimensional carrier in the impregnation process;

B. placing the impregnated and loaded aluminum foil at room temperature and standing for 6 hours;

D. placing the dried and pre-pyrolyzed carrier in an argon protection furnace for high-temperature roasting treatment; heating to 500 deg.C at a speed of 1 deg.C/min, maintaining for 10h, and cooling to room temperature at 3 deg.C/min to obtain the final product;

the specific surface area of the two-dimensional ozone catalytic material prepared by taking the aluminum foil as a base material and not regulating and controlling the acid corrosion is 2.1575m²(ii)/g; the amount of supported metal and nonmetal was 39.5 wt%.

Example 6

3) acid etching regulation and control: drying the anodized aluminum foil in a 50 ℃ oven for 12 hours; 500ml of 6 wt% phosphoric acid solution was prepared at room temperature; then, placing the dried aluminum foil in a phosphoric acid solution for soaking and softening for 60min, and placing the phosphoric acid solution in an oven for preserving at the constant temperature of 35 ℃; after the acid etching regulation and control are finished, the two-dimensional material is cleaned by deionized water and dried in a 50 ℃ oven;

before the BET (specific surface area) test, a sample is peeled off from an Al substrate, and then is pretreated at 150 ℃ for 4 hours to remove adsorbed moisture, so that the specific surface area of the two-dimensional ozone catalytic material prepared by taking an aluminum foil as a base material is 190.1792m²(ii)/g; the amount of supported metal and nonmetal was 41 wt%.

Example 7

taking the two-dimensional substrate material as a carrier; preparing a precursor solution of 35g/L glucose and 35g/L acetic acid, wherein the mass concentration of the acetic acid solution accounts for 50% of the total mass concentration of the precursor, and preparing the two-dimensional ozone catalytic material, wherein the preparation steps are as follows:

A. placing the aluminum foil in the precursor solution for vacuum impregnation (the volume of the precursor solution measured in the step can be completely immersed in the foil), wherein the impregnation time is 60min, the temperature is constant at 5 +/-5 ℃, and precursor salt synchronously corrodes the two-dimensional carrier in the impregnation process;

B. placing the impregnated and loaded aluminum foil at room temperature and standing for 24 hours;

D. placing the dried and pre-pyrolyzed carrier in an argon protection furnace for high-temperature roasting treatment; heating to 550 ℃ at the speed of 10 ℃/min, preserving the heat for 0.5h, and then cooling to room temperature at the speed of 3 ℃/min to obtain a finished product, namely the aluminum-based two-dimensional ozone catalytic material;

testing to obtain the two-dimensional ozone prepared by taking the aluminum foil as the base materialThe specific surface area of the catalytic material is 7.1525m²(ii)/g; the amount of non-metal loaded was 10 wt%.

Example 8

taking the two-dimensional substrate material as a carrier; preparing a precursor solution of 120g/L glucose and 40g/L acetic acid, and preparing the two-dimensional ozone catalytic material, wherein the preparation steps are as follows:

the specific surface area of the two-dimensional ozone catalytic material prepared by using the aluminum foil as the base material is 13.3984m²(ii)/g; the amount of non-metal loaded was 30 wt%.

Example 9

taking the two-dimensional substrate material as a carrier; preparing 0.1g/L cobalt acetate and 40g/L copper nitrate precursor solution for preparing the two-dimensional ozone catalytic material, wherein the preparation steps are as follows:

the specific surface area of the two-dimensional ozone catalytic material prepared by using the aluminum foil as the base material is 7.6986m²(ii)/g; the amount of the supported metal was 10 wt%.

Example 10

taking the two-dimensional substrate material as a carrier; preparing 0.1g/L cobalt acetate and 100g/L copper nitrate precursor solution for preparing the two-dimensional ozone catalytic material, wherein the preparation steps are as follows:

the specific surface area of the two-dimensional ozone catalytic material prepared by using the aluminum foil as the base material is 11.1912m²(ii)/g; the amount of the supported metal was 30 wt%.

Example 11

taking the two-dimensional substrate material as a carrier; preparing precursor solution of 60g/L glucose, 30g/L manganese sulfate, 30g/L copper nitrate, 30g/L cobalt chloride and 50g/L acetic acid, and preparing the two-dimensional ozone catalytic material, wherein the specific preparation steps are as follows:

the specific surface area of the two-dimensional ozone catalytic material prepared by using the aluminum foil as the base material is 15.9512m²(ii)/g; the amount of supported metal and nonmetal was 45 wt%.

Example 12

taking the two-dimensional substrate material as a carrier; preparing 30g/L copper nitrate, 20g/L manganese sulfate and 20g/L acetic acid precursor solution, and preparing the two-dimensional ozone catalytic material, wherein the preparation steps are as follows:

the specific surface area of the two-dimensional ozone catalytic material prepared by using the aluminum foil as the base material is 9.5692m²(ii)/g; the amount of supported metal and nonmetal was 15 wt%.

Comparative example 1

This comparative example is substantially the same as example 1 except that: step 1) carrying out high-temperature annealing, degreasing, grinding and polishing pretreatment on aluminum foils (upper and lower surfaces), then respectively washing with ethanol and deionized water, and drying in a 50 ℃ oven for later use; the whole process is not subjected to wire drawing treatment, namely the upper surface and the lower surface of the transition metal aluminum foil are of smooth mirror surface structures, and basically, the transition metal aluminum foil does not have a plurality of basically parallel stripes with the width of about 50 +/-10 nm, the depth of 3 +/-1 nm and the distance of 50 +/-10 nm, and the rest is the same as that of the embodiment 1;

in the comparative example, a semi-continuous flow ozone catalytic oxidation degradation experiment was performed on the two-dimensional ozone catalytic material prepared in example 1 and the two-dimensional ozone catalytic material (4 g of the two-dimensional ozone catalytic material was used for each group) which was not subjected to wire drawing treatment in comparative example 1.

In order to know the degradation condition of the oxalic acid in the experimental process, water samples of 0min, 2.5 min, 5min, 7.5 min, 10 min and 15min in the catalytic ozonation reaction process are detected. Specifically, the method comprises the following steps:

1. semi-continuous flow ozone catalytic oxidation experiment step/mode

In the semi-continuous flow ozone catalytic oxidation experiment, ozone is aerated in an oxalic acid solution, then the solution dissolved with the ozone is introduced into a reactor, and effluent returns to the solution and circulates for 15 min. The two-dimensional ozone catalytic material of example 1 and comparative example 1 filled in the reactor was cut to fill the reactor, cut to 3-5 parts in the same direction as the direction in which the alternating nanopore arrays were formed, and cut to a strip having a width of 1-3mm in the direction perpendicular to the direction in which the alternating nanopore arrays were formed.

2. Conclusion

As shown in fig. 8, it is clearly seen that the aluminum-based two-dimensional ozone catalytic material prepared by wire drawing treatment in the degradation process has a significantly better oxalic acid removal effect than the aluminum-based two-dimensional ozone catalytic material prepared without wire drawing treatment; at 15min, the oxalic acid removal rate of the aluminum-based two-dimensional ozone catalytic material prepared by wire drawing treatment reaches over 80 percent, while the oxalic acid removal rate of the aluminum-based two-dimensional ozone catalytic material prepared without wire drawing treatment is only about 60 percent.

Comparative example 2

The comparative example is basically the same as example 1, and is different in that the acid solution concentration and the acid etching time parameter regulated and controlled by the acid etching in the step 3) in the preparation process of the substrate material are changed to obtain two groups of substrate materials which are respectively named as 2C-1; 2C-2; specifically, the method comprises the following steps:

base material 2C-1: the acid solution concentration is 12 wt%, and the hydrogen ion concentration in the phosphoric acid solution is 9.8X 10^-3mol/L, pH of 2.01, and acid etching time of 90 min;

base material 2C-2: the acid solution concentration is 0.05 wt%, and the hydrogen ion concentration in the phosphoric acid solution is 3.9X 10^-4Acid etching time is 20min with pH of 3.41;

the rest is the same as the embodiment 1;

in the acid corrosive liquid soaking process, under the action of phosphoric acid, the pore wall separation between hard template nano-pores formed after anodic oxidation can be gradually and directionally opened, cracks can be formed between nano-pore arrays along the direction of concave-convex stripes, and the appearance of the alternative arrangement of nano-pore arrays, fault channels and nano-pore arrays consisting of single-row or multi-row nano-pores is gradually generated in the direction vertical to the concave-convex stripes. Results of this comparative example: as shown in fig. 10a, the base material 2C-1 is significantly under acid-etched, and the nanopore arrays formed along the concave-convex stripes are not cross-linked, and the second structural layer of the base material does not form the basic pore portion and the long and narrow portion. As shown in fig. 10b, the base material 2C-2 is significantly over-etched, resulting in a material surface that tends to be smooth and almost no surface structure layer exists.

In the comparative example, a semi-continuous flow ozone catalytic oxidation degradation experiment was performed using the two-dimensional ozone catalytic material prepared in example 1 (4 g of the two-dimensional ozone catalytic material was used for each group). In order to know the degradation condition of phenol in the experimental process, water samples of 0min, 2.5 min, 5min, 7.5 min, 10 min and 15min in the catalytic ozonation reaction process are detected. Specifically, the method comprises the following steps:

1. semi-continuous flow ozone catalytic oxidation experiment step/mode

In the semi-continuous flow ozone catalytic oxidation experiment, ozone is aerated in a phenol solution, then the solution dissolved with the ozone is introduced into a reactor, and effluent returns to the solution and circulates for 15 min. The two-dimensional ozone catalytic material, which was filled in the reactor and had excessive and insufficient acid etching as in example 1 and comparative example 2, was cut to fill the reactor, cut into 3-5 parts in the same direction as the direction in which the alternating nanopore arrays were formed, and cut into strips having a width of 1-3mm in the direction perpendicular to the direction in which the alternating nanopore arrays were formed.

2. Conclusion

As shown in fig. 9, it is clearly seen that the aluminum-based two-dimensional ozone catalytic material prepared with appropriate parameters for controlling acid etching during the degradation process has a significantly better phenol removal effect than the aluminum-based two-dimensional ozone catalytic material prepared with excessive or insufficient parameters for controlling acid etching; when 15min, the removal rate of the aluminum-based two-dimensional ozone catalytic material prepared by properly adjusting and controlling the parameters of acid etching to phenol reaches more than 80%, and the removal rates of the aluminum-based two-dimensional ozone catalytic material prepared by excessively large and excessively small parameters of the acid etching adjusting and controlling process to phenol are respectively 20% and 60%.

Comparative example 3

In the comparative example, three traditional granular three-dimensional catalysts are prepared and named as a granular three-dimensional catalyst 1B, a granular three-dimensional catalyst 2B and a granular three-dimensional catalyst 3B respectively;

the preparation method of the traditional granular three-dimensional catalyst comprises the following steps:

1) selecting three groups of gamma alumina particles with the same size of 3-5mm and mass, washing with deionized water, and drying in a 50 ℃ oven;

2) the following three groups of substances are respectively called at room temperature and are prepared into precursor solutions:

first group (particle type three-dimensional catalyst 1B): the precursor solution was the same as in example 1;

second group (particle type three-dimensional catalyst 2B): the precursor solution was the same as in example 2;

third group (particle type three-dimensional catalyst 3B): the precursor solution was the same as in example 3;

3) respectively placing the three groups of weighed gamma alumina into the three groups of precursor solutions in the step 2) for vacuum impregnation (measuring a certain amount of precursor solution, wherein the three groups of selected gamma alumina can be just immersed into the measured precursor solution); wherein

The first group of immersion time and temperature were the same as in example 1;

the second group of immersion time and temperature were the same as in example 2;

the immersion time and temperature of the third group were the same as those of example 3;

4) after impregnation, standing the impregnated gamma alumina at room temperature for 15h to fully diffuse the precursor; then placing the mixture in a vacuum oven at 70 ℃ for drying and pre-pyrolysis for 15 hours;

5) placing the dried and pre-pyrolyzed carrier in an argon protection furnace for high-temperature roasting treatment; heating to 550 ℃ at the speed of 3 ℃/min, preserving the heat for 1.5h, and then cooling to room temperature at the speed of 3 ℃/min to obtain finished products which are respectively named as a granular three-dimensional catalyst 1B, a granular three-dimensional catalyst 2B and a granular three-dimensional catalyst 3B.

Comparative example 4

Semi-continuous flow ozone catalytic oxidation experiment

In the comparative example, a semi-continuous flow ozone catalytic oxidation degradation experiment was carried out with the two-dimensional ozone catalytic material prepared in examples 1-3 and three groups of conventional particle-type three-dimensional catalysts (1B-3B) prepared in comparative example 3 (4 g of the two-dimensional ozone catalytic material and 20g of the conventional particle-type three-dimensional catalyst were used for each group of control to ensure that the filling heights of the catalytic materials in the reactor were the same), and a single ozone oxidation degradation experiment was used as a control to detect water samples of 0, 2.5, 5, 7.5, 10 and 15min in the catalytic ozone oxidation reaction process in order to solve the degradation condition of phenol in the experiment process; in order to know the degradation condition of pyrazole in the experimental process, water samples of 0min, 2.5 min, 5min, 7.5 min, 10 min, 15min, 20min, 30min, 45 min and 60min in the catalytic ozonation reaction process are detected; in order to know the degradation condition of oxalic acid in the experimental process, water samples of 0min, 2.5 min, 5min, 7.5 min, 10 min and 15min in the catalytic ozonation reaction process are specifically detected:

1. semi-continuous flow ozone catalytic oxidation experiment step/mode

In the semi-continuous flow ozone catalytic oxidation experiment, ozone is aerated in a phenol solution, a pyrazole solution or an oxalic acid solution respectively, then the solution dissolved with the ozone is introduced into a mini-reactor, and effluent returns to the solution and circulates for 15min, 60min and 15min respectively. The two-dimensional ozone catalytic material of examples 1 to 3 filled in the reactor was cut to fill the reactor, cut 3 to 5 parts in the same direction as the direction in which the alternating nanopore arrays were formed, and cut in the direction perpendicular to the direction in which the alternating nanopore arrays were formed to obtain strips having a width of 1 to 3 mm.

2. Experimental setup

TABLE 1

3. Conclusion

As can be seen from the above table in conjunction with fig. 11, 12, and 13:

as shown in fig. 11, in the case that the reactor filling volume is the same and the filling mass of the catalytic material of example 1 is only one fifth of that of the granular three-dimensional catalyst 1B, it is clearly seen that the catalytic material of example 1 has a significantly better phenol removal effect than the granular three-dimensional catalyst 1B during the degradation process; and as can be seen from table 1, at 15min, the removal rate of phenol by the catalytic material of example 1 reaches more than 80%, while the removal rate of phenol by the granular three-dimensional catalyst 1B is about 70%, and the removal effect of phenol by ozone oxidation alone is only 30%.

As shown in fig. 12, in the case that the reactor filling volume is the same and the filling mass of the catalytic material of example 2 is only one fifth of that of the granular three-dimensional catalyst 2B, it is clearly seen that the catalytic material of example 2 has slightly better removal effect on pyrazole than the granular three-dimensional catalyst 2B during degradation; and as can be seen by combining table 1, at 60min, the removal rate of pyrazole by the granular three-dimensional catalyst 1B is about 80%, while the removal rate of pyrazole by the catalytic material of example 2 is slightly higher than 80%, and the removal effect of pyrazole by ozone oxidation alone is only 50%.

As shown in fig. 13, in the case that the reactor filling volume is the same and the filling mass of the catalytic material of example 3 is only one fifth of that of the granular three-dimensional catalyst 3B, it is clearly seen that the catalytic material of example 3 has a significantly better oxalic acid removal effect than the granular three-dimensional catalyst 3B during the degradation process; and as can be seen from table 1, the removal rate of oxalic acid by the catalytic material of example 3 reaches over 90% at 15min, while the removal rate of oxalic acid by the granular three-dimensional catalyst 3B is only 60%, and the removal effect of oxalic acid by ozone oxidation alone is only 8%.

All the above shows that, aiming at the removal of different target pollutants, the two-dimensional ozone catalytic material provided by the invention has obvious advantages on the removal rate of the target pollutants under the condition that the dosage is only one fifth of that of the traditional particle type three-dimensional catalyst, and the ozone oxidation catalytic performance of the two-dimensional ozone catalytic material provided by the invention is obviously due to the traditional particle type three-dimensional catalyst. FIG. 14 is a diagram of oxalic acid degradation in a two-dimensional ozone catalytic material cycle test prepared in example 1; the method still has high removal rate within a certain time of recycling. And after 20 times of recycling, the integrity is still more than 99%.

Example 13

Simulation of Process-Mass transfer

The water and dilute matter transfer of matter on a two-dimensional material and the modeling of CFD (computational fluid dynamics) are represented by COMSOL Multiphysics 5.4 finite element numerical simulation, the software is used for generating geometric figures, dividing meshes, physically setting, solving and post-processing results, and an iterative matrix solver (GMRES) is used for solving a fluid dynamics control equation. The simulation modeling is optimized according to an actual two-dimensional material SEM image (pore canals of the non-corroded two-dimensional material are nano holes, the pore canals are amplified in equal proportion for the same size order of magnitude as the size order of the corroded two-dimensional material, the size order of magnitude of the corroded two-dimensional material is the same as the actual size order of the corroded two-dimensional material), and a non-corroded two-dimensional material modeling main body is composed of a cuboid and 120 cylinders.

The simulated fluid was liquid water at 20 ℃. In the non-corroded two-dimensional material model, a fluid inlet is arranged on the left surface of a cuboid, the constant flow rate of the inlet is kept to be 0.001m/s, a fluid outlet is arranged on the right surface of the cuboid, a zero-pressure boundary condition is applied to the outlet, and a non-slip condition is applied to other boundaries. When fluid flows in from the left side of the fluid channel (cuboid), the fluid can move rightwards and downwards, at the same time, substances can move downwards along with the fluid to convectively transfer mass to the inner surface of the pore channel of the two-dimensional material, but the flow velocity of the fluid is very slow and is almost zero, and the mass transfer can only depend on molecular diffusion. In the corroded two-dimensional material, the fluid inlet and the fluid flow rate are the same as those in the above, the fluid outlet is arranged on the right side of the cuboid and the right side of the newly added cuboid (namely, the right side of the corrosion channel, as shown in FIG. 15 b), and the zero-pressure boundary condition is also applied. When fluid flows from the left side of the fluid channel, the fluid flows downwards while flowing rightwards, and the difference is that the wall surface of the original pore channel is opened due to the channel formed by corrosion, and a water outlet is formed at the right side, so that the downward flowing speed of the fluid is far higher than that of the original two-dimensional material, more substances are transferred into the pore channel, and the probability of transferring the substances to the inner surface of the pore channel of the two-dimensional material is greatly increased.

On the basis of the CFD physical field, a dilute substance transfer physical field is newly added, and the two physical fields are coupled by adopting a flow coupling condition. The dilute mass transfer material diffusion coefficient was set to 10^-9m²S, initial value of model substance concentration is set to 0mol/L, concentration of influent substance is set to 0.1mol/m³The boundary imposes a concentration constraint.

When fluid flows through a fixed interface (wall surface) and is subjected to mass transfer with the fluid, the mass transfer is mainly divided into three layers from the fluid main body to the wall surface, namely a turbulent layer, a transition layer and a laminar layer.

The faster the fluid flow velocity, the stronger the vortex pulsation in the turbulent layer and the transition layer, the faster the mass transfer; in the laminar layer, the thickness of the laminar layer becomes thinner along with the increase of the flow velocity of the fluid, the molecular diffusion distance of the substance in the laminar layer becomes smaller, and the time for transferring the substance to the solid phase is greatly reduced. )

The CFD results are shown in fig. 15, which shows that when water flows through the top of the micropores, the water enters the inside of the micropores. The calculated water flow rate simulation plot at different heights of the micropores is shown in fig. 15 (the calculated mass transfer flow rate is only 2.28 x 10)^-5m/s), as can be seen from fig. 15, the simulated calculation graphs of the flow velocity distribution of the tangent water at different heights of the micron pores after the two-dimensional material is not corroded and is obviously different. The flow rates of the sections 1-5 of the non-corroded material are not obviously different, each section of the corroded two-dimensional material has higher flow rate distribution, and the flow rate advantage is more obvious towards the bottom of the nanopore compared with the non-corroded material (for example, the maximum flow rate is 7 orders of magnitude higher in section five). In the figure, the mass transfer efficiency of the corroded two-dimensional material is gradually reduced from the section 1 to the section 5, the mass transfer efficiency of the section 1 is the highest, the overall mass transfer efficiency is high, and the flow rate can reach 4.74 x 10 in total^-4m/s。

As shown in fig. 16, it can be known from fig. 16 that a substance moves along with the water flowing into the two-dimensional material, and because the flow rate of the water body not corroding the pore channel of the two-dimensional material is very low, the substance cannot transfer mass to the inner surface of the two-dimensional material through convection of the water body, and only can transfer mass to the inner surface of the two-dimensional material by the spontaneous diffusion behavior of the substance, so that the mass transfer effect is poor; the mass of the corroded two-dimensional material can be transferred not only through spontaneous diffusion but also through water flow convection, and the mass transfer effect is good.

Example 14

Test-bending test

The test of the bending angle of the base material can be performed by the following method, and fig. 17 to 19 are bending experimental drawings showing a front view and a side view of the platen 3 as a plate-shaped press bending jig in fig. 18a and 18b, respectively.

Specifically, first, a sheet-like test material 1 is horizontally placed on 2 rolls 2 arranged in parallel with each other with a roll gap L set, at a position equal to the left and right of the rolls 2.

Next, a platen 3 as a press bending jig for the sheet-like base material is placed on the sheet-like test material 1 so as to stand vertically with respect to the sheet-like test material 1. Specifically, the roller 2, the sheet-like test material 1, and the platen 3 are placed such that the edge of the front end of the platen 3 is positioned at the center of the roll opening L and the rolling direction of the sheet-like test material 1 and the extending direction of the platen 3 of the sheet-like test material 1 are orthogonal to each other.

Then, the pressing plate 3 is pushed from above to the center of the sheet-like test material 1, and a load F is applied to the sheet-like test material 1, so that the sheet-like test material 1 is bent (impact-bent) toward the narrow roll gap L, and the center of the bent and deformed sheet-like test piece is pressed into the narrow roll gap.

At this time, the center of the plate-like test piece 1 is bent when the load F applied from the upper platen 3 is maximized

The angle outside the curve was measured as the bending angle (°), and the flexibility was evaluated by the magnitude of the bending angle. That is, the larger the bending angle, the better the flexibility of the sheet base material.

As test conditions of the bending test, the sheet-like test material 1 was 5cm × 5cm × 0.01mm (length × width × thickness), the diameters D of the 2 rolls 2 were 20mm, and the roll opening L was 2.0 times the thickness of the sheet-like test material 1. S is the depth of press-fitting of the central portion of the plate-like test piece into the roll opening when the load F reaches the maximum.

Further, as shown in FIG. 18b, the platen 3 has a side length of 600mm in contact with the sheet-like test material 1, and the lower end side (tip portion) in contact with the central portion of the sheet-like test material 1 is tapered with a radius r of 0.2mm φ as shown in a front view 18 a.

As shown in fig. 18b, a concave portion having a width of 9mm and a depth of 12mm is formed at 2 positions on the opposite side of the tip portion of the pressing plate 3, and the concave portion is fitted into an overload device (not shown) so that the pressing plate 3 applies a load to the sheet-like test material 1.

In this embodiment, 0.5A of the anodized hard template (defined as 0.5A) obtained in example 1 after anodization is completed and cleaning and drying, 1A of the substrate obtained after acid etching control is completed and cleaning and drying, and 1C of the product substrate obtained in comparative example 1 are selected and subjected to bending test, and the specific results are shown in table 2:

TABLE 2 comparison of the B values of the mechanical properties of the base materials at different stages of preparation

Stage of preparation of base material	Angle beta (°)
		Anodic oxidation hard template 0.5A in example 1	Less than 10
Base material 1A of example 1	Approaches to 180
		Base Material 1C without drawing in comparative example 1	Approach to 90
Comparative example 2 acid etching transition base Material 2C-1	Approaches to 180
		Comparative example 2 acid etching deficient base Material 2C-2	Approaches 30

It should be noted that, as shown in the above table of the hard anodic oxidation template 0.5A, a layer of dense porous oxide film is formed on the surface layer of the aluminum foil after anodic oxidation, and the obtained material is extremely brittle, dense and fragile, and has no flexibility; as shown in the above table of the base material 1A of example 1 and the base material 1C of comparative example 1, which is not drawn, the flexibility of the material after acid etching is improved to some extent; on the other hand, the base material 1C in comparative example 1, which was not drawn, had a limited ability to be bent although flexibility was improved because the oxide film and the pore structure thereof remained; in the base material 1A of example 1 provided by the present invention, the structure shown in fig. 4a-c is formed after the acid etching is controlled due to the concave and convex stripes on the surface, so that the flexibility is greatly improved, and the ability of bending is enhanced.

Bulk density test

Bulk density (. rho.)_b，g/cm³) Refers to the mass per unit volume of the material to be measured in a stacked state, also known as bulk density. Wherein, before the stacking density test of the substrate material, the substrate material is cut into the specification of 0.1mm multiplied by 0.5 mm; specific determination methods reference is made to ASTM D7481-2009, a standard test method for determining bulk and bulk powder density using a graduated cylinder.

Bulk density: rho_b＝m/V。

m is the mass of the material to be measured in the measuring cylinder, and the unit is gram (g);

v-the bulk volume of the material to be measured in milliliters (mL), including the volume of the material itself and the volume of the voids between the materials (the internal gaps of the materials are negligible).

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

the volume V can be measured by:

the method comprises the steps of naturally filling a container with a certain volume until the container is filled with the material, wherein the volume of the container is the stacking volume of the material to be detected, and naturally falling the material to be detected into the container until the container is filled with the material to be detected under the condition that the vertical height of the material to be detected from an inlet of the container is not higher than 10cm, without any jolt ramming and pressing operations.

Claims

1. A two-dimensional catalytic material, characterized by: the catalyst comprises a two-dimensional material substrate material layer and a catalyst layer loaded on the substrate material layer, wherein the two-dimensional material substrate material has the following structure:

c) a plurality of holes distributed in the first protrusion part;

at least 0.05% of the holes of the first convex part are communicated with the adjacent first concave part; the catalytic layer is loaded on the surface of the second structural layer;

the base material comprises at least one transition metal and an oxide of the corresponding transition metal; wherein the transition metal content of the first structural layer is at least 90%; the transition metal oxide content of the second structural layer is at least 30%.

2. The two-dimensional catalytic material of claim 1, wherein: the second structural layer is obtained by carrying out corrosion treatment on the pore layer with the nano and/or micron-sized pore diameter;

and/or the substrate material is prepared by taking a transition metal foil as a raw material, wherein the thickness of the transition metal foil is not more than 500 mu m;

and/or, the transition metal includes, but is not limited to, one or more of aluminum, tin, nickel, and titanium; the transition metal oxides include, but are not limited to, one or more of the oxides of aluminum, tin, nickel, and titanium.

3. Two-dimensional catalytic material according to claim 1 or 2, characterized in that: the base material is flexible in at least one direction: when a bending experiment is carried out, the bending angle is not less than 90 degrees; and/or the bulk density of the substrate material is less than 1g/cm³。

4. A two-dimensional catalytic material according to claim 3, characterized in that: the catalytic layer includes a metal active component and/or a non-metal active component.

5. A two-dimensional catalytic material according to claim 3, characterized in that: the specific surface area of the two-dimensional catalytic material is 2-200m²/g。

6. The two-dimensional catalytic material of claim 4, wherein: the metal active components or the nonmetal active components can be loaded simultaneously or independently, when the metal active components or the nonmetal active components are loaded independently, the loading amounts of the metal active components or the nonmetal active components are both 10-30 wt%, and the total loading amount when the metal active components or the nonmetal active components are loaded simultaneously is 15-45 wt%.

7. The two-dimensional catalytic material of claim 5, wherein: the metal active component comprises one or more of copper, iron, cobalt, cerium, nickel, chromium, cadmium, zinc, silver and manganese; the non-metal active component comprises one or more of carbon, nitrogen, sulfur, boron and silicon.

8. A preparation method of a two-dimensional catalytic material is characterized by comprising the following steps: the method comprises the following steps:

9. The method of preparing a two-dimensional catalytic material of claim 7, wherein: the surface of the transition metal foil is provided with a plurality of concave-convex stripes with consistent or approximately consistent directions;

and/or the surface of the transition metal foil is provided with a plurality of concave-convex stripes which are parallel or basically parallel to each other.

10. The method of preparing a two-dimensional catalytic material of claim 8, wherein:

the depth of the pores is at least 20 nm;

and/or the pores have an average pore diameter of at least 10 nm;

and/or the walls of the pores have a thickness of at least 5 nm.

11. The method of preparing a two-dimensional catalytic material of claim 9, wherein: regulating and controlling the surface acid etching of the material obtained in the step 1) by using acid liquor.

The pH value of the acid solution is 0.92-3.00;

and/or the concentration of hydrogen ions in the acid solution is 0.001-0.65 mol/L;

wherein, when the acid etching is regulated, the acid etching time is 5-70 min.

12. A method of preparing a two-dimensional catalytic material according to any of claims 8-11, characterized in that: the two-dimensional substrate material is prepared by the following steps:

s1, carrying out anodic oxidation treatment on the metal sheet with the concave-convex stripes on the surface, so that an array of holes with nano-scale apertures distributed along the stripe trend is formed on the surface of the metal sheet;

s2, corrosion regulation: and carrying out surface corrosion treatment on the metal foil subjected to the anodic oxidation treatment to form a base material which is flexible in at least one direction.

13. A method of preparing a two-dimensional catalytic material according to any of claims 8-11, characterized in that: the step 3) comprises the following steps:

14. The method of preparing a two-dimensional catalytic material of claim 12, wherein: in the step A, the impregnation mode comprises vacuum impregnation/non-vacuum impregnation, the impregnation time is 5-60min, and the temperature is 10-50 ℃;

and/or in the step B, the standing time is 6-24 h;

15. Use of the two-dimensional catalytic material according to claims 1-7 or the two-dimensional catalytic material prepared by the preparation method according to claims 8-14 in catalytic oxidation treatment of wastewater and exhaust gas.

16. Use according to claim 15, characterized in that: the catalytic oxidation treatment comprises ozone catalytic oxidation, Fenton oxidation, electrochemical oxidation and photocatalytic oxidation.