CN113398957B - AgCl cube/porous carbon nanotube composite material and preparation method thereof - Google Patents
AgCl cube/porous carbon nanotube composite material and preparation method thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 106
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 102
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 102
- 229910021607 Silver chloride Inorganic materials 0.000 title claims abstract description 60
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Images
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/06—Halogens; Compounds thereof
- B01J27/08—Halides
- B01J27/10—Chlorides
-
- B01J35/39—
-
- B01J35/40—
-
- B01J35/60—
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The present invention belongs to photocatalysisThe technical field of composite material preparation, in particular to an AgCl cube/porous carbon nanotube composite material and a preparation method thereof. The invention utilizes Ag + Co-incubation with porous carbon nanotubes while impregnating with Ag + Introducing Cl into porous carbon nanotube ‑ (ii) a The AgCl cubic porous carbon nanotube composite material prepared by the preparation method of the invention has AgCl in a cubic shape and is uniformly distributed on the porous carbon nanotube. The preparation method disclosed by the invention is simple in process, does not introduce impurities, is complete in crystallization of the loaded active substance, is in a cubic shape, and has potential application value in the fields of clean energy conversion, environmental pollution remediation and the like.
Description
Technical Field
The invention belongs to the technical field of preparation of photocatalytic composite materials, and particularly relates to an AgCl cube/porous carbon nanotube composite material and a preparation method thereof.
Background
Environmental pollution and energy crisis have gradually endangered human survival, and photocatalytic technology is considered to be the most effective and promising approach to solve energy and environmental problems. In recent years, researchers find that AgCl has very high photocatalytic activity and has very wide application prospects in the fields of clean energy conversion, environmental pollution remediation and the like. However, in the course of photocatalytic degradation, AgCl is easily reduced to elemental silver by photoelectron under the action of light, so that the activity of the catalyst is gradually reduced, and the practical application of the catalyst is severely limited.
How to realize the practical and effective transfer of the photo-generated electrons and avoid the reduction of the content of AgCl is a key problem for improving the stability of the AgCl. The carbon nano tube can rapidly receive and transfer photo-generated electrons, so that photo-generated carriers are efficiently separated, and further the performance stability and activity of the photocatalyst are improved. Therefore, the AgCl/carbon nanotube composite material is suitable for degrading sewage and wastewater under the sun and has good safety.
The prior art mostly adopts complexation and charge action, orDirect utilization of Ag + With Cl - For example, patent document 1 discloses that a multiwalled carbon nanotube material is added to a silver nitrate solution, HCl is added, and then the mixture is washed, centrifuged, dispersed, and dried to obtain a multiwalled carbon nanotube-AgCl complex. However, the applicant finds that the AgCl crystals prepared by the method are easy to agglomerate, and the AgCl is easy to agglomerate in a large area, so that the AgCl is not uniformly distributed.
Patent document 1: publication No. CN108940324A and publication No. 2018.12.07, a photocatalytic multi-walled carbon nanotube-Ag @ AgCl composite nano material and a preparation method thereof.
Disclosure of Invention
1. Problems to be solved
Aiming at the problems that impurity ions are easy to introduce and the AgCl crystal structure is easy to damage in the preparation method in the prior art, the invention provides a preparation method of an AgCl cube/porous carbon nanotube composite material, which is characterized in that Cl is firstly introduced to a porous carbon nanotube - Obtaining intermediate carrier, and reusing Ag + Impregnating the intermediate carrier with the solution to obtain an AgCl cube/porous carbon nanotube; the preparation method has the advantages of simple preparation process, very few impurities in the product, no damage to the AgCl crystal structure and good photocatalytic performance under the action of visible light.
The invention further provides an AgCl cube/porous carbon nanotube composite material, wherein AgCl is uniformly loaded on the porous carbon nanotube, is completely crystallized, presents a cube shape and is uniformly loaded.
2. Technical scheme
In order to solve the problems, the technical scheme adopted by the invention is as follows:
the invention provides a preparation method of an AgCl cube/porous carbon nanotube composite material, which comprises the following steps,
s100, preparing a porous carbon nanotube, wherein the porous carbon nanotube is provided with a plurality of pore channels to form a porous structure; and
s200, providing an active ingredient, and loading the active ingredient on part or all of the pore channels, wherein the active ingredient is AgCl;
in S200, the manner of loading the active ingredient is:
s201, immersing the porous carbon nanotube in Cl - In a solution of (2), e.g. an aqueous solution of a soluble chlorine salt, etc., to make Cl - Loaded on partial or all pore channels to obtain Cl adsorbed - The intermediate carrier of (1); the Cl-containing compound used in the present invention - The solution of (A) is preferably an HCl solution, and not only Cl may be introduced - And impurities such as carbonate and the like introduced in the process of preparing the porous carbon nanotube can be removed;
s202, removing part or all of the unloaded Cl - Removing excess Cl - The method includes but is not limited to at least one rinsing of the intermediate carrier, wherein the rinsing solution used for rinsing includes but is not limited to high-purity water, deionized water and other solvents commonly used for cleaning; further impregnating the intermediate carrier with Ag + After the solution is obtained, the AgCl cube/porous carbon nanotube can be obtained.
The invention adopts a preparation route different from the prior art, and compounds the surface carbon by virtue of the adsorption effect of the porous carbon nanotube so as to activate the surface carbon and adsorb a large amount of Cl - Reintroducing Ag + (e.g., using a soluble salt such as silver nitrate solution, etc.) to make Cl on the surface - With Ag + And carrying out reaction to generate AgCl, and then loading the AgCl on the porous carbon nanotube. The AgCl cube/porous carbon nanotube prepared by the invention has large AgCl loading capacity, uniform loading, no damage to the crystal structure of AgCl and excellent photocatalysis performance.
Preferably, Cl - Is 0.5 to 1.8mol/L, for example, an HCl solution is used as the impregnation solution, the mass fraction of which is 2% to 6%.
Preferably, Ag + The concentration of (2) is 0.005-0.015mol/L, and AgCl structure is damaged when the concentration is too high, and AgCl loaded on the porous carbon nanotube is too little when the concentration is too low.
Preferably, the intermediate carrier contains Ag + The dipping time in the solution is 10-15 h.
Preferably, in an intermediate carrier containing Ag + After the solution is soaked, the ultrasonic treatment is also carried out, and the treatment time of the ultrasonic treatment isThe concentration time is 15-20min, so that ions can be better enriched, and meanwhile, the material has better dispersibility, and the synthesis of subsequent composite materials is facilitated. After ultrasonic treatment, the product can be fully dried, so that the content of residual solvent is lower than 3%, and the service performance of the final product is further improved.
The porous carbon nanotube can be a commercially available product, preferably a self-made porous carbon nanotube, and is etched by strong acid or strong base or other corrosive substances, so that the surface of the carbon nanotube has a porous structure. Further preferred is a method for producing a porous carbon nanotube, which comprises:
i) dipping the carbon nano tube by using an alkaline solution to change the inertia of the surface of the carbon nano tube; after etching by alkaline solution, a plurality of pore channels are generated on the surface of the carbon nano tube, carbon around the pore channels is activated, the surface of the carbon nano tube is rough from smooth, and a pretreatment body is formed;
ii) calcining the pretreatment body in the absence of gas or in the presence of non-active gas, and after high-temperature calcination, the wound carbon nanotubes are broken, so that the roughness and the activated carbon quantity are further increased, the adsorption quantity of active ingredients is improved, and the porous carbon nanotubes are formed. Further, the inert gas used in the present invention during the calcination process includes, but is not limited to, inert gases such as argon, helium, etc., and inert gases such as nitrogen, etc. The porous carbon nanotube prepared by the method has large loading capacity of the loaded active substances, and meanwhile, the loaded active substances are in a cubic shape and are uniformly loaded.
Preferably, in alkaline solution, OH - The concentration of (2) is 3 to 9mol/L, and if the concentration of the alkaline solution is too high or too low, the size and the number of pores are affected. It is worth noting that the alkaline solution of the present invention is preferably KOH, which produces product properties superior to other alkaline solutions (e.g., NaOH solution).
Preferably, in the calcination, the calcination temperature is 700-800 ℃, and the calcination time is 2-3 h.
Preferably, the impregnation with the alkaline solution comprises stirring and standing in an alkaline solution environment, wherein the stirring time is 10-15 hours, and the standing time is 20-25 hours, so that the total time of the impregnation treatment of the alkaline solution is controlled to be 30-40 hours.
The invention further provides the AgCl cube/porous carbon nanotube composite material prepared by the preparation method.
3. Advantageous effects
Compared with the prior art, the AgCl cube/porous carbon nanotube composite material prepared by the method has the advantages of simple preparation process and very few impurities in the product; in the prepared final product, AgCl is uniformly loaded on the porous carbon nanotube, and the AgCl crystal structure is not damaged, so that the photocatalytic performance is good under the action of visible light; meanwhile, the preparation method does not use an organic reagent, is green and environment-friendly, does not produce additional pollution, and has potential application value in the fields of clean energy conversion, environmental pollution remediation and the like.
Drawings
FIG. 1 is an SEM photograph of various materials of example 1;
fig. 2 is an XRD photograph in example 1, in which: a-carbon nanotubes; b-carbon nano tube dipped by alkali liquor; c, impregnating the carbon nano tube by alkali liquor and calcining the carbon nano tube; d-carbon nano tube loaded with active substance after alkali liquor impregnation and calcination;
FIG. 3 is an SEM photograph of various composites of comparative example 1;
FIG. 4 is an SEM photograph of a different composite material of comparative example 2;
FIG. 5 is an SEM photograph of a different composite material of comparative example 3;
FIG. 6 is an SEM photograph of a different composite material of comparative example 4;
fig. 7 is an SEM photograph of the different composite materials in comparative example 5.
Detailed Description
The following detailed description of exemplary embodiments of the invention refers to the accompanying drawings, which form a part hereof, and in which are shown by way of illustration exemplary embodiments in which the invention may be practiced, and in which features of the invention are identified by reference numerals. The following more detailed description of the embodiments of the invention is not intended to limit the scope of the invention, as claimed, but is presented for purposes of illustration only and not limitation to describe the features and characteristics of the invention, to set forth the best mode of carrying out the invention, and to sufficiently enable one skilled in the art to practice the invention. It will, however, be understood that various modifications and changes may be made without departing from the scope of the invention as defined in the appended claims. The detailed description and drawings are to be regarded in an illustrative rather than a restrictive sense, and any such modifications and variations, if any, are intended to fall within the scope of the invention as described herein. Furthermore, the background is intended to be illustrative of the present development and significance of the technology and is not intended to limit the invention or the application and field of application of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs; the terminology used herein in the description of the invention is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention; as used herein, the term "and/or" includes any and all combinations of one or more of the associated listed items.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products available commercially. The main instruments or devices used in the examples of the present invention are shown in table 1 below, and the main reagents used are shown in table 2 below. Furthermore, the particular instruments or devices or reagents set forth in tables 1 or 2 are intended to be illustrative of one of the instruments or devices or reagents that may be used in embodiments of the present invention and are not intended to limit the invention or the applications and uses of the invention.
TABLE 1 Experimental instrumentation and equipment
TABLE 2 Main reagents used in the experiment
Example 1
In this embodiment, the preparation of the porous carbon nanotube is performed first, and then the preparation of the AgCl cube/porous carbon nanotube is performed, specifically, the preparation method is as follows:
preparing a porous carbon nanotube: weighing 0.1g of carbon nanotube, putting the carbon nanotube into a 50mL beaker, adding 30mL of 6mol/L KOH solution, magnetically stirring the mixture at room temperature for 10 hours, and standing the mixture for 20 hours; centrifuging by a high-speed centrifuge, putting the treated carbon nano tube into a porcelain boat, placing the porcelain boat in the middle of a tube furnace, and calcining for 2 hours at about 700 ℃ in an argon atmosphere; and 6mL of HCl (5%) is added into the calcined sample, and then the sample is subjected to ultrasonic centrifugation for 10min and then washed for 3 times to obtain the porous carbon nanotube.
Preparing the AgCl cube/porous carbon nanotube: 0.015g of porous carbon nanotube is weighed into a 20mL beaker, and 0.05mol/L of AgNO is added 3 And (3) stirring the solution by magnetic force for 10 hours at room temperature, then carrying out ultrasonic reaction for 20 minutes, centrifuging after the ultrasonic reaction is finished, washing the solid product obtained by centrifuging for 3 times, and finally carrying out vacuum drying for 24 hours to obtain the AgCl cube/porous carbon nanotube.
Deionized water was added to the sample, and the mixture was sonicated for 20min, then dropped onto a clean copper sheet polished with sand paper, air dried naturally, and observed with SEM. The structure is shown in fig. 1, wherein: (a) SEM photographs of carbon nanotubes, (b) SEM photographs of porous carbon nanotubes, and (c) SEM photographs of AgCl cubes/porous carbon nanotubes. As can be seen from fig. 1(a), the carbon nanotubes are long and intertwined, and have a flat surface. As can be seen from FIG. 1(b), the porous carbon nanotubes are randomly dispersed and disordered, have small diameters and are intertwined with each other; furthermore, as is clear from fig. 1(b), the porous carbon nanotube has a porous structure, and the surface thereof is uneven and has a certain roughness. As can be seen from fig. 1(c), a large amount of AgCl is cubic and uniformly distributed on the porous carbon nanotube.
The sample prepared in this example was dried and then characterized by XRD. Wherein (a) is a carbon nanotube; (b) is carbon nano-tube dipped by alkali liquor; (c) is carbon nano-tube dipped and calcined by alkali liquor; (d) is a carbon nano tube loaded with active substances after being dipped and calcined by alkali liquor. As can be seen from fig. 2, the four curves show distinct and sharp diffraction peaks at 2 θ ═ 26.4 ° and 42 °, and the diffraction peaks were found to be (002) type and (100) type diffraction peaks of the porous carbon nanotube. Further, according to the d-curve observation, the sample shows obvious and sharp diffraction peaks at positions of 2 theta, 27.8 degrees, 32.22 degrees, 46.22 degrees, 54.81 degrees, 57.56 degrees, 67.4 degrees, 74.5 degrees and 76.6 degrees, and the diffraction peaks are respectively diffraction peaks of crystal faces of (111), (200), (220), (311), (222), (400), (331) and (420) of the silver chloride crystal with a cubic structure, and no other obvious impurity diffraction peaks are found except diffraction peaks of AgCl nano-materials and the diffraction peaks outside the carbon nano-tubes, and the positions indicate that the substance is a relatively pure AgCl cubic porous carbon nano-tube composite material. Furthermore, the sharp peak shape of the sample can be seen from the figure, which indicates that the composite material is completely crystallized, and the crystal structure of AgCl is not damaged in the process of compounding the AgCl cube and the carbon nano tube. Therefore, the feasibility of preparing the AgCl cube/porous carbon nanotube composite material is known, and the characterization analysis by XRD also proves that the substance loaded on the porous carbon nanotube is AgCl.
Example 2
The basic contents of this embodiment are different from those of embodiment 1 in that: in this example, the concentrations of KOH used in the production of the porous carbon nanotubes were 3mol/L and 9 mol/L. The morphological characteristics of the AgCl cubic/porous carbon nanotube prepared by the embodiment are similar to those of the embodiment 1.
Example 3
The basic contents of this embodiment are different from those of embodiment 1 in that: in this example, the calcination temperature was 750 ℃ and 800 ℃ and the calcination time was 3 hours. The morphology characteristics of the AgCl cubic/porous carbon nanotube prepared by the method are similar to those of the AgCl cubic/porous carbon nanotube prepared by the method in example 1.
Comparative example 1
The comparative example is basically the same as example 1, except that: in this example, after etching the carbon nanotubes with KOH, 5% HCl solution and AgNO with different concentrations were directly used without calcination 3 The solution was impregnated and the SEM image of the sample examination is shown in fig. 3. Wherein (a) is AgNO with the utilization concentration of 0.05mol/L 3 SEM photographs of the solution for immersion; (b) to utilize the concentration of 5X 10 -3 mol/L AgNO 3 SEM photographs of the solution for immersion; (c) to use the concentration of 5X 10 -4 mol/L AgNO 3 SEM photographs of the solution for immersion; (d) to use the concentration of 5X 10 -5 mol/L AgNO 3 SEM photographs of the solution for immersion; (e) to utilize the concentration of 5X 10 -6 mol/L AgNO 3 SEM photograph of the solution impregnated.
As can be seen from a comparison of the SEM images of fig. 3, the carbon nanotubes in fig. 2(a), (b), (c), and (d) have a supported material, but the supported material is not uniformly distributed. Furthermore, the load in fig. 2(a) and (b) showed aggregation, and the load in fig. 3(b) and (c) was small. Meanwhile, fig. 3(a) and (b) show that the active material loaded on the carbon nanotube is in a cubic state, but still has a small part of the material loaded in small particles. With AgNO 3 The solution is reduced, and the loading amount of the active substances on the carbon nano tubes is gradually reduced.
Comparative example 2
The basic contents of this comparative example are the same as example 1, except that: in this example, 0.1g of carbon nanotubes were weighed out and treated with 6mL of HCl (5%) and then with AgNO at various concentrations 3 Samples were prepared after dipping. The SEM image of sample detection is shown in FIG. 4, in which (a) is AgNO with concentration of 0.05mol/L 3 SEM photographs of the solution for immersion; (b) to use the concentration of 5X 10 -3 mol/L AgNO 3 SEM photographs of the solution for immersion; (c) to utilize the concentration of 5X 10 -4 mol/L AgNO 3 SEM photograph of the solution impregnated; (d) to utilize the concentration of 5X 10 -5 mol/L AgNO 3 SEM photographs of the solution for immersion; (e) to use the concentration of 5X 10 -6 mol/L AgNO 3 SEM photograph of the solution impregnated.
As can be seen from a comparison of the SEM pictures of fig. 4, only fig. 4(a) and (b) are loaded with a small amount of substance, probably because the active substance is difficult to be loaded due to the chemical inertness of the surface of the carbon nanotube; c. the d and e samples had little active loading, probably due to AgNO 3 The solution concentration is too low, making the carbon nanotube surface more difficult to load.
Comparative example 3
The basic contents of this comparative example are the same as example 1, except that: in this example, 0.1g of carbon nanotubes were weighed out and calcined at 800 ℃ followed by 6mL of HCl (5%) and then treated with AgNO at different concentrations 3 The solution was impregnated into the prepared sample, and the SEM image of the sample examination is shown in fig. 5. Wherein (a) is AgNO with the utilization concentration of 0.05mol/L 3 SEM photographs of the solution for immersion; (b) to utilize the concentration of 5X 10 -3 mol/L AgNO 3 SEM photographs of the solution for immersion; (c) to use the concentration of 5X 10 -4 mol/L AgNO 3 SEM photograph of the solution impregnated; (d) to use the concentration of 5X 10 -5 mol/L AgNO 3 SEM photographs of the solution for immersion; (e) to utilize the concentration of 5X 10 -6 mol/L AgNO 3 SEM photograph of the solution impregnated.
As can be seen from a comparison of the SEM images of fig. 5, active material was supported in fig. 5(a), (b), and (c), and no active material was supported in fig. 5(d) and (e); while the active material loading amounts in fig. 5(b) and (c) are small and unevenly distributed, the active material loading amounts in fig. 5(a) are large but unevenly distributed, and the loaded active materials have different shapes and are agglomerated.
Comparative example 4
The basic contents of this comparative example are the same as example 1, except that: in this example, AgNO at various concentrations was utilized 3 The solution was impregnated to prepare a sample, and the SEM image of the sample was shown in fig. 6. Wherein (a) is AgNO with the concentration of 5mol/L 3 SEM photographs of the solution for immersion; (b) to use AgNO with a concentration of 0.5mol/L 3 SEM photographs of the solution for immersion; (c) to use AgNO with a concentration of 0.05mol/L 3 The solution is soakedSEM photograph of the stain; (d) to utilize the concentration of 5X 10 -3 mol/L AgNO 3 SEM photographs of the solution for immersion; (e) to utilize the concentration of 5X 10 -4 mol/L AgNO 3 SEM photograph of the solution impregnated; (f) to utilize the concentration of 5X 10 -5 mol/L AgNO 3 SEM photograph of the solution impregnated.
As can be seen from a comparison of the SEM images of fig. 6, although a large amount of the active material is supported in fig. 6(a) and (b), the active material is highly unevenly distributed and is agglomerated; the active material loading on fig. 6(c) is large and uniformly distributed, and the loaded active material is in a cubic shape; the active loading on fig. 6(d) is small and all are small particles; fig. 6(e) and (f) show little active material loading or supporting amount.
Comparative example 5
The comparative example is basically the same as example 1, except that: in this example, the sample preparation method of the experimental group (a) is: 5% HCl solution and 0.05mol/L AgNO are sequentially used for the carbon nano tube 3 Carrying out dipping treatment on the solution; the sample preparation method of experimental group (b) was: using KOH solution, 5% HCl solution and 0.05mol/L AgNO in sequence for carbon nano tube 3 Carrying out dipping treatment on the solution; the sample preparation method of experimental group (c) was: calcining the carbon nano tube at 800 ℃, and then sequentially utilizing 5 percent HCl solution and 0.05mol/L AgNO 3 Carrying out dipping treatment on the solution; the sample preparation method of experimental group (d) was: etching the carbon nano tube by using KOH solution, calcining at 800 ℃, and finally sequentially using 5% HCl solution and 0.05mol/L AgNO 3 The solution is subjected to an impregnation treatment. SEM images of the samples prepared in experimental groups (a), (b), (c) and (d) are shown in FIG. 7.
As can be seen from the SEM comparison of fig. 7, the active materials of fig. 6(a) and (b) are less loaded, and the loaded active materials are in the form of finely divided particles; the active material of fig. 6(c) is loaded in large amounts and has cubic particles, but there are still a large number of finely divided particles and the distribution is not uniform; the active material loading amount of fig. 6(d) is large, the loaded active materials all have a cubic shape, and the loading is uniform.
More specifically, although exemplary embodiments of the invention have been described herein, the invention is not limited to these embodiments, but includes any and all embodiments modified, omitted, combined, e.g., between various embodiments, adapted and/or substituted, as would be recognized by those skilled in the art from the foregoing detailed description. The limitations in the claims are to be interpreted broadly based the language employed in the claims and not limited to examples described in the foregoing detailed description or during the prosecution of the application, which examples are to be construed as non-exclusive. Any steps recited in any method or process claims may be executed in any order and are not limited to the order presented in the claims. The scope of the invention should, therefore, be determined only by the appended claims and their legal equivalents, rather than by the descriptions and examples given above.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In case of conflict, the present specification, including definitions, will control. When a quality, concentration, temperature, time, or other value or parameter is expressed as a range, preferred range, or as a range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. For example, a range of 1 to 50 should be understood to include any number, combination of numbers, or subrange selected from 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, or 50, and all fractional values between the above integers, e.g., 1.1, 1.2, 1.3, 1.4, 1.5, 1.6, 1.7, 1.8, and 1.9. With respect to sub-ranges, specifically consider "nested sub-ranges" that extend from any endpoint within the range. For example, nested sub-ranges of exemplary ranges 1-50 may include 1-10, 1-20, 1-30, and 1-40 in one direction, or 50-40, 50-30, 50-20, and 50-10 in another direction.
Claims (8)
1. A preparation method of AgCl cube/porous carbon nanotube composite material comprises the following steps,
s100, preparing a porous carbon nanotube, wherein the porous carbon nanotube is provided with a plurality of pore channels to form a porous structure; and
s200, providing an active ingredient, and loading the active ingredient on part or all of the pore channels, wherein the active ingredient is AgCl;
the method is characterized in that in S200, the active ingredients are loaded in the following modes:
immersing porous carbon nanotube in solution containing Cl - In solution of (2), adding Cl - Loading part or all of the pore channels to obtain an intermediate carrier;
partial or complete removal of unsupported Cl - Immersing the intermediate carrier in the solution containing Ag + Obtaining AgCl cube/porous carbon nanotube after the solution is prepared, wherein the Ag is + The concentration of (A) is 0.005-0.015 mol/L;
the preparation method of the porous carbon nanotube comprises the following steps:
i) impregnating the carbon nano tube with an alkaline solution to obtain a pretreatment body; and
ii) calcining the pretreatment body in the absence of gas or in the presence of non-active gas to form the porous carbon nanotube, wherein the calcination temperature is 700-800 ℃ and the calcination time is 1-3 h.
2. The method for preparing an AgCl cube/porous carbon nanotube composite material according to claim 1, characterized in that: the Cl - The concentration of (B) is 0.5-1.8 mol/L.
3. The method for preparing the AgCl cube/porous carbon nanotube composite material according to claim 1, characterized in that: intermediate carrier in the presence of Ag + The dipping time in the solution of (2) is 10-15 h.
4. The method for preparing the AgCl cube/porous carbon nanotube composite material according to claim 3, characterized in that: in an intermediate carrier containing Ag + The solution of (2) is soaked, and then ultrasonic treatment is carried out, wherein the treatment time of the ultrasonic treatment is 15-20 min.
5. The method for preparing an AgCl cube/porous carbon nanotube composite material according to claim 1, characterized in that: in the alkaline solution, OH - The concentration of (b) is 3-9 mol/L.
6. The method for preparing the AgCl cube/porous carbon nanotube composite material according to claim 5, wherein the method comprises the following steps: the alkaline solution is a KOH solution.
7. The method for preparing an AgCl cube/porous carbon nanotube composite material according to claim 5, characterized in that: the impregnation by using the alkaline solution comprises stirring and standing in the alkaline solution environment, wherein the stirring time is 10-15 hours, and the standing time is 20-25 hours.
8. The AgCl cube/porous carbon nanotube composite material prepared by the preparation method according to any one of claims 1 to 7.
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