CN111234245A - Ag nanowire/ZIF ultrathin nanosheet composite material, preparation method and application - Google Patents
Ag nanowire/ZIF ultrathin nanosheet composite material, preparation method and application Download PDFInfo
- Publication number
- CN111234245A CN111234245A CN202010042693.6A CN202010042693A CN111234245A CN 111234245 A CN111234245 A CN 111234245A CN 202010042693 A CN202010042693 A CN 202010042693A CN 111234245 A CN111234245 A CN 111234245A
- Authority
- CN
- China
- Prior art keywords
- nanowire
- zif
- soluble metal
- composite material
- nanosheet composite
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1691—Coordination polymers, e.g. metal-organic frameworks [MOF]
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/06—Elements
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K2201/00—Specific properties of additives
- C08K2201/011—Nanostructured additives
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Inorganic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
The invention provides an Ag nanowire/ZIF ultrathin nanosheet composite material, a preparation method and application thereof. The invention utilizes one-dimensional inorganic metal nanowire material as a template to prepare two-dimensional ultrathin metal organic framework nanosheets in an inducing manner, particularly adopts one-dimensional Ag nanowire as a template material, adopts an epitaxial growth method to obtain ultrathin ZIF nanosheets, has flat surfaces and uniform sizes, grows around the Ag nanowire, is simple to operate, does not need complex equipment, is mild in condition, easy to obtain template material, controllable in process, wide in raw material source and beneficial to industrial realization, and the prepared composite nanomaterial has a very wide application prospect in the fields of photoelectrocatalysis, electronic devices, energy storage, photoelectric detection and the like.
Description
Technical Field
The invention belongs to the field of metal organic framework materials, and particularly relates to an Ag nanowire/ZIF ultrathin nanosheet composite material, a preparation method and application thereof.
Background
Metal Organic Frameworks (MOFs) are a common class of porous crystalline materials that have received a great deal of attention since their discovery. Since the aperture in the MOFs is controllable, the comparative area thereof can also be controlled. The derived materials thereof are attracting wide interest in the fields of energy conversion and energy storage. To date, a variety of MOFs structures have been converted to microporous carbon materials via pyrolysis reactions in an inert gas. An article with the number of eaav6009, volume 5 in journal of scientific progress, reports that the MIL-88A is used as a precursor to obtain the Ni-doped FeP/C hollow nanorod structure, which shows good electrocatalytic hydrogen production performance.
However, the preparation process of the existing MOFs is difficult to control, and the obtained MOFs material is generally large in size, non-uniform, and even difficult to control in size, so that the performance of the obtained product is unstable, and the obtained product is not suitable for macro-preparation. Therefore, how to control the synthesis of MOFs materials and MOFs-based composite materials has become one of the hot spots of general interest in the industry.
Disclosure of Invention
In view of the above, the present invention provides an Ag nanowire/ZIF ultrathin nanosheet composite material and a preparation method thereof.
The invention provides an Ag nanowire/ZIF ultrathin nanosheet composite material and a preparation method thereof, and the preparation method comprises the following steps:
mixing a soluble metal source, an organic ligand, an Ag nanowire and a solvent to form a reaction solution, and stirring for a period of time to obtain the Ag nanowire/ZIF ultrathin nanosheet composite material.
Preferably, the specific steps are as follows: and mixing and stirring the soluble metal source, the dispersion liquid of the Ag nanowire and the dispersion liquid of the organic ligand for reaction to obtain the Ag nanowire/ZIF ultrathin nanosheet composite material.
More preferably, the specific steps are as follows:
s1) mixing a soluble metal source, Ag nanowires and a first solvent to obtain a first dispersion liquid; the concentration of the soluble metal salt in the first dispersion liquid is 0.001-10 mol/L;
mixing an organic ligand with a second solvent to obtain a second dispersion liquid, wherein the concentration of the organic ligand in the second dispersion liquid is 0.001-10 mol/L;
s2) mixing and stirring the first dispersion liquid and the second dispersion liquid for reaction to obtain the Ag nanowire/ZIF ultrathin nanosheet composite material.
Specifically, the solvent is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, pentanol, benzene, phenol, toluene, N-dimethylformamide and water.
Preferably, the soluble metal source is a soluble metal salt, and comprises one or more of soluble metal halide, soluble metal nitrate, soluble metal acetate and soluble metal sulfate, and the metal element comprises one or more of Co, Zn, Mn, Fe, Ni and Cu.
Preferably, the organic ligand is an imidazole compound, and comprises one or more of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-nitroimidazole, benzimidazole, 3, 4-dichloroimidazole, purine, 5, 6-dimethylbenzimidazole and 5-chlorobenzimidazole.
Preferably, the diameter of the Ag nanowire is 0.2-100 nm.
Preferably, the concentration of the Ag nanowires in the first dispersion liquid is 0.1-100 mg/mL.
Preferably, the molar ratio of the soluble metal source to the Ag nanowires is 1: (0.005-2).
Preferably, the stirring time is 0.5-100 h; the stirring temperature is 0-60 ℃.
Preferably, the thickness of the ZIF ultrathin nanosheet in the Ag nanowire/ZIF ultrathin nanosheet composite material is less than or equal to 10 nm.
The invention also provides application of the Ag nanowire/ZIF ultrathin nanosheet composite material prepared by any one of the technical schemes in the aspects of photoelectrocatalysis, electronic devices, energy storage or photoelectric detection.
Compared with the prior art, the preparation method has the advantages that the preparation method is simple to operate, complex equipment is not needed, the conditions are mild, the template material is easy to obtain, the process is controllable, the raw material source is wide, the industrialization is facilitated, and the size of the obtained Ag nanowire/ZIF ultrathin nanosheet composite material is uniform. Experiments show that the thickness of the nano-sheet of the Ag nano-wire/ZIF ultrathin nano-sheet composite material prepared by the invention is less than 10 nm.
Drawings
Fig. 1 is a transmission electron microscope photograph of Ag nanowires prepared in example 1 of the present invention.
Fig. 2 is an X-ray diffraction pattern of the Ag nanowire prepared in example 1 of the present invention.
Fig. 3 is a scanning electron microscope photograph of the Ag nanowire/ZIF-67 ultrathin nanosheet composite prepared in example 1 of the present invention.
Fig. 4 is a projection electron microscope photograph of the Ag nanowire/ZIF-67 ultrathin nanosheet composite prepared in example 1 of the present invention.
FIG. 5 is a SEM of a ZIF-67 material prepared in comparative example 1 of the present invention.
Fig. 6 is a scanning electron microscope photograph of the Ag nanowire/ZIF-67 ultrathin nanosheet composite prepared in example 2 of the present invention.
Fig. 7 is a projection electron microscope photograph of the Ag nanowire/ZIF-67 ultrathin nanosheet composite prepared in example 2 of the present invention.
Fig. 8 is a scanning electron microscope photograph of the Ag nanowire/ZIF-67 ultrathin nanosheet composite prepared in example 3 of the present invention.
Fig. 9 is a scanning electron microscope photograph of the Ag nanowire/ZIF-67 ultrathin nanosheet composite prepared in example 4 of the present invention.
Fig. 10 is a transmission electron microscope photograph of the Ag nanowire/ZIF-67 ultrathin nanosheet composite prepared in example 4 of the present invention.
Fig. 11 is a scanning electron microscope photograph of the Ag nanowire/ZIF-67 ultrathin nanosheet composite prepared in example 5 of the present invention.
Fig. 12 is a scanning electron microscope photograph of the Ag nanowire/ZIF-67 ultrathin nanosheet composite prepared in example 6 of the present invention.
Fig. 13 is a scanning electron microscope photograph of the Ag nanowire/ZIF-67 ultrathin nanosheet composite prepared in example 7 of the present invention.
Fig. 14 is a scanning electron microscope photograph of the Ag nanowire/ZIF-67 ultrathin nanosheet composite prepared in example 8 of the present invention.
Fig. 15 is a scanning electron microscope photograph of the Ag nanowire/ZIF-67 ultrathin nanosheet composite prepared in example 9 of the present invention.
Detailed Description
For a further understanding of the invention, preferred embodiments of the invention are described below in conjunction with the examples, but it should be understood that these descriptions are included merely to further illustrate the features and advantages of the invention and are not intended to limit the invention to the claims.
All of the starting materials of the present invention, without particular limitation as to their source, may be purchased commercially or prepared according to conventional methods well known to those skilled in the art.
All the raw materials of the present invention are not particularly limited in purity, and the present invention preferably employs purity which is conventional in the field of analytical purification or nanomaterials.
The invention provides a preparation method of an Ag nanowire/ZIF ultrathin nanosheet composite material, which comprises the following steps:
s) mixing a soluble metal source, an organic ligand, a silver nanowire and a solvent to form a reaction solution, and stirring for a period of time to obtain the Ag nanowire/ZIF ultrathin nanosheet composite material.
The stirring conditions are not particularly limited, and conventional stirring conditions known to those skilled in the art can be adopted, and those skilled in the art can select and adjust the stirring conditions according to actual production conditions, raw material conditions and product requirements, and the stirring time in the invention is preferably 0.5-100 h, more preferably 0.5-45 h, more preferably 0.5-10 h, and most preferably 0.5-4 h. The stirring temperature is preferably 0-60 ℃, more preferably 10-50 ℃, and most preferably 20-40 ℃.
The parameters of the prepared Ag nanowire are not particularly limited, and the thickness of the Ag nanowire can be specifically selected and adjusted by a person skilled in the art according to the actual application condition, the raw material condition and the product requirement, and can be 0.2-100 nm, also can be 1.0-80 nm, also can be 2.0-60 nm, also can be 5.0-60 nm, and optimally is 30-40 nm.
In order to improve the mixing uniformity and the reaction uniformity and stability in the preparation process, the Ag nanowires preferably comprise Ag nanowire dispersion liquid, so that the dispersibility of the reaction solution is better improved. The specific conditions of the Ag nanowire dispersion liquid are not particularly limited in the present invention, and the conditions of the Ag nanowire dispersion liquid known to those skilled in the art may be adopted, and those skilled in the art may select and adjust the conditions according to the actual production conditions, raw material conditions and product requirements, and the concentration of the Ag nanowire dispersion liquid in the present invention is preferably 0.1 to 20mg/L, more preferably 0.1 to 15mg/L, more preferably 0.1 to 8.0mg/L, and most preferably 0.1 to 2.0 mg/L.
The soluble metal source is not particularly limited in the present invention, and may be a conventional soluble metal salt well known to those skilled in the art, and may be selected and adjusted by those skilled in the art according to the actual application, raw material conditions and product requirements, and the soluble metal source of the present invention is preferably a soluble metal salt, more preferably includes one or more of a soluble metal halide, a soluble metal nitrate, a soluble metal acetate and a soluble metal sulfate, more preferably a soluble metal halide, a soluble metal nitrate, a soluble metal acetate or a soluble metal sulfate, and most preferably a soluble metal nitrate. The metal elements in the soluble metal source of the present invention are not particularly limited, and may be conventional metal elements well known to those skilled in the art, and those skilled in the art may select and adjust the metal elements according to practical application, raw material conditions and product requirements, and the metal elements in the soluble metal source of the present invention preferably include one or more of Co, Zn, Mn, Fe, Ni and Cu. The amount of the soluble metal source is not particularly limited, and those skilled in the art can select and adjust the amount according to the actual application, raw material conditions and product requirements, and the concentration of the soluble metal source in the reaction solution is preferably 0.001-0.2 mol/L, more preferably 0.005-0.18 mol/L, more preferably 0.008-0.15 mol/L, and most preferably 0.005-0.12 mol/L.
The dosage of the Ag nanowires in the present invention is not particularly limited, and those skilled in the art can select and adjust the dosage according to the actual application, raw material conditions and product requirements, and the molar ratio of the soluble metal source to the Ag nanowires in the present invention is preferably 1: (0.005-2), more preferably 1: (0.02 to 1), most preferably 1: (0.05-0.06). The solvent is preferably one or more of methanol, ethanol, propanol, isopropanol, butanol, pentanol, benzene, phenol, toluene, N-dimethylformamide and water.
The organic coordination is imidazole compound, preferably one or more of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-nitroimidazole, benzimidazole, 3, 4-dichloroimidazole, purine, 5, 6-dimethylbenzimidazole and 5-chlorobenzimidazole.
According to the present invention, it is preferable to mix a soluble metal salt, Ag nanowires, and a first solvent to obtain a first dispersion; mixing the imidazole compound with a second solvent to obtain a second dispersion liquid, and mixing and stirring the first dispersion liquid and the second mixture liquid for reaction to obtain the Ag nanowire/ZIF ultrathin nanosheet composite material.
Mixing soluble metal salt, Ag nanowires and a first organic solvent to obtain a first dispersion liquid; in order to avoid the phenomenon that the reaction solution has dissolved oxygen in the reaction process of part of soluble metal salt, and the preparation and the appearance of subsequent products are influenced, the reaction can be preferably carried out under the anaerobic condition; preferably, the soluble metal salt and the first organic solvent are mixed, and then the Ag nanowire is added; furthermore, in order to improve the mixing uniformity and the reaction uniformity and stability in the preparation process, the Ag nanowires are preferably added in the form of Ag nanowire dispersion liquid, so that the dispersibility of the reaction solution is better improved; the Ag nanowire dispersion is the same as the Ag nanowire dispersion, and is not described again; the first organic solvent is preferably one or more of methanol, ethanol, propanol, isopropanol, butanol, pentanol, benzene, phenol, toluene, N-dimethylformamide and water; the concentration of the soluble metal salt in the first dispersion liquid is preferably 0.001-10 mol/L, more preferably 0.005-5 mol/L, and most preferably 0.01-0.1 mol/L; the molar ratio of the soluble metal source to the Ag nanowires is preferably 1: (0.005-2), more preferably 1: (0.02 to 1), most preferably 1: (0.05-0.06). The mixing time is preferably 10-30 min, and more preferably 20-30 min.
Mixing the imidazole compound with a second organic solvent to obtain a second dispersion liquid; the second solvent is preferably one or more of methanol, ethanol, propanol, isopropanol, butanol, pentanol, benzene, phenol, toluene, N-dimethylformamide and water; the concentration of the imidazole compound in the second dispersion liquid is preferably 0.001-10 mol/L, more preferably 0.005-5 mol/L, still more preferably 0.01-1 mol/L, and most preferably 0.01-0.1 mol/L.
Mixing the first dispersion liquid and the second dispersion liquid for reaction; the mixing reaction time is preferably not less than 30min, more preferably 30min to 48h, still more preferably 30min to 24h, still more preferably 30min to 10h, and most preferably 30min to 4 h.
In addition, in the present invention, in order to improve reaction efficiency, product purity and availability, it is preferable to further include a post-treatment step after the reaction. The present invention is not particularly limited in terms of specific parameters and operations of the post-treatment step, which are well known to those skilled in the art, and can be selected and adjusted by those skilled in the art according to actual production conditions, raw material conditions and product requirements, and the post-treatment of the present invention includes one or more of filtering collection, washing and drying, more preferably includes one or more of filtering collection, washing and drying in sequence, and most preferably includes filtering collection, washing and drying in sequence. The specific conditions of the above specific processes are not particularly limited in the present invention, and may be selected and adjusted by those skilled in the art according to actual experimental conditions, raw material conditions, and product requirements, where the washing is preferably multiple times of washing, more preferably water washing and organic solvent washing, and most preferably water washing and alcohol washing, and specifically may be water washing for 1 to 3 times, and alcohol washing for 1 to 3 times. The drying is preferably room temperature drying, and more preferably room temperature drying for 5-24 h.
According to the invention, a ZIF nanosheet is prepared by taking a one-dimensional Ag nanowire as a template through induction, the Ag nanowire, a soluble metal salt and a solvent are mixed, and then the mixture reacts with an imidazole solution to obtain a ZIF nanosheet, such as a ZIF-8 nanosheet, a ZIF-65 nanosheet, a ZIF-67 nanosheet, a ZIF-68 nanosheet, a ZIF-69 nanosheet, a ZIF-70 nanosheet, a ZIF-11 nanosheet and a ZIF-12 nanosheet; the preparation method has the advantages of simple operation, no need of complex equipment, mild conditions, easily obtained template materials, controllable process, wide raw material sources and contribution to industrial realization.
Furthermore, the ZIF nanosheet is obtained by taking the one-dimensional Ag nanowire as a template material and adopting an epitaxial growth method, has uniform size and grows on the surface of the Ag nanowire. In the preparation process, the research on the one-dimensional nanowire induction effect is helpful for deeply understanding the growth mechanism of the ZIF nanosheet and guiding the preparation of the MOFs derivative material, and the prepared MOFs derivative material has very wide application in the fields of photoelectrocatalysis, energy storage, photoelectric detection and the like.
The invention also provides the Ag nanowire/ZIF ultrathin nanosheet composite material prepared by the method; the size of the ZIF nanosheet in the Ag nanowire/ZIF ultrathin nanosheet composite material is less than or equal to 100 nm, preferably less than or equal to 50nm, more preferably less than or equal to 20nm, and most preferably less than or equal to 10 nm.
The invention also provides application of the Ag nanowire/ZIF ultrathin nanosheet composite material in the aspects of photoelectrocatalysis, electronic devices, energy storage or photoelectric detection.
In order to further illustrate the present invention, the following describes in detail an Ag nanowire/ZIF ultrathin nanosheet composite material, a preparation method thereof, and an application thereof, provided by the present invention, with reference to examples.
The reagents used in the following examples are all commercially available; in the examples, the drugs and reagents used were purchased from national drug group chemical reagents, ltd, and the Ag nanowires were purchased from the new nano-material, ltd, younitak, su zhou.
Example 1
To 10mL of 20 mmol/L Co (NO)3)2Adding 6 mg of Ag nanowires into the methanol solution, stirring for 10 min, mixing with 10mL of 20 mmol/L2-methylimidazole methanol solution, fully stirring for 4h, washing with ethanol for three times, and vacuum drying for 6h to obtain the Ag nanowire/ZIF-67 ultrathin nanosheet composite material.
The Ag nanowires were analyzed by a scanning electron microscope to obtain a projection electron micrograph thereof, as shown in fig. 1.
The Ag nanowires were analyzed by X-ray diffraction to obtain an X-ray diffraction pattern thereof, as shown in fig. 2.
As shown in FIGS. 1 and 2, the Ag nanowires have a diameter of about 30-40 nm, a length of several micrometers, and a uniform size.
And analyzing the Ag nanowire/ZIF-67 ultrathin nanosheet composite material by using a scanning electron microscope to obtain a scanning electron microscope picture, which is shown in FIG. 3.
And analyzing the Ag nanowire/ZIF-67 ultrathin nanosheet composite material by using a projection electron microscope to obtain a projection electron microscope photo, which is shown in FIG. 4.
As can be seen from fig. 3 and 4, the ZIF-67 nanosheets are uniformly distributed around the Ag nanowires, with a thickness of about 3 nm.
Comparative example 1
10mL of 20 mmol/L Co (NO)3)2And mixing the methanol solution with 10mL of 20 mmol/L2-methylimidazole methanol solution, fully stirring for 4 hours, washing with ethanol for three times, and vacuum-drying for 6 hours to obtain the ZIF-67 material.
The ZIF-67 material was analyzed by scanning electron microscopy to obtain a scanning electron micrograph, as shown in fig. 5.
As can be seen from FIG. 5, the resulting ZIF-67 material was predominantly granular with a particle size of about 1 μm.
Example 2
To 10mL of 20 mmol/L Co (NO)3)2Adding 2 mg of Ag nanowires into the methanol solution, stirring for 10 min, mixing with 10mL of 20 mmol/L2-methylimidazole methanol solution, fully stirring for 4h, washing with ethanol for three times, and vacuum drying for 6h to obtain the Ag nanowire/ZIF-67 ultrathin nanosheet composite material.
And analyzing the Ag nanowire/ZIF-67 ultrathin nanosheet composite material by using a scanning electron microscope to obtain a scanning electron microscope photo, which is shown in FIG. 6.
And analyzing the Ag nanowire/ZIF-67 ultrathin nanosheet composite material by using a projection electron microscope to obtain a projection electron microscope photo, which is shown in FIG. 7.
As can be seen from fig. 6 and 7, in addition to the sheet structure, many particles having a particle size of about several hundred nanometers are present in the product.
Example 3
To 10mL of 20 mmol/L Co (NO)3)2Adding 4 mg of Ag nanowires into the methanol solution, stirring for 10 min, mixing with 10mL of 20 mmol/L2-methylimidazole methanol solution, fully stirring for 4h, washing with ethanol for three times, and vacuum drying for 6h to obtain the Ag nanowire/ZIF-67 ultrathin nanosheet composite material.
And analyzing the Ag nanowire/ZIF-67 ultrathin nanosheet composite material by using a scanning electron microscope to obtain a scanning electron microscope photo, which is shown in FIG. 8. From the figure, it can be seen that the nanosheet induced by the Ag nanowire grows around the nanowire.
Example 4
To 10mL of 20 mmol/L Co (NO)3)2Adding 8 mg of Ag nanowires into the methanol solution, stirring for 10 min, mixing with 10mL of 20 mmol/L2-methylimidazole methanol solution, fully stirring for 4h, washing with ethanol for three times, and vacuum drying for 6h to obtain the Ag nanowire/ZIF-67 ultrathin nanosheet composite material.
And analyzing the Ag nanowire/ZIF-67 ultrathin nanosheet composite material by using a scanning electron microscope to obtain a scanning electron micrograph, which is shown in FIG. 9.
Analyzing the Ag nanowire/ZIF-67 ultrathin nanosheet composite material by using a projection electron microscope to obtain a projection electron microscope photograph thereof, as shown in FIG. 10.
From the figure, it can be seen that the nanosheet induced by the Ag nanowire grows around the nanowire.
Example 5
To 10mL of 20 mmol/L Co (NO)3)2Adding 6 mg of Ag nanowires into the methanol solution, stirring for 10 min, mixing with 10mL of 20 mmol/L2-methylimidazole methanol solution, fully stirring for 5 min, washing with ethanol for three times, and vacuum drying for 6h to obtain the Ag nanowire/ZIF-67 ultrathin nanosheet composite material.
And analyzing the Ag nanowire/ZIF-67 ultrathin nanosheet composite material by using a scanning electron microscope to obtain a scanning electron micrograph, which is shown in FIG. 11. As can be seen from the figure, many platelets are grown on the nanowires.
Example 6
To 10mL of 20 mmol/L Co (NO)3)2Adding 6 mg of Ag nanowires into the methanol solution, stirring for 10 min, mixing with 10mL of 20 mmol/L2-methylimidazole methanol solution, fully stirring for 10 min, washing with ethanol for three times, and vacuum drying for 6h to obtain the Ag nanowire/ZIF-67 ultrathin nanosheet composite material.
Analyzing the Ag nanowire/ZIF-67 ultrathin nanosheet composite material by using a scanning electron microscope to obtain a scanning electron micrograph, which is shown in FIG. 12. As can be seen from the figure, the grown nanosheet gradually wraps the Ag nanowire.
Example 7
To 10mL of 20 mmol/L Co (NO)3)2Adding 6 mg of Ag nanowires into the methanol solution, stirring for 10 min, mixing with 10mL of 20 mmol/L2-methylimidazole methanol solution, fully stirring for 30min, washing with ethanol for three times, and vacuum drying for 6h to obtain the Ag nanowire/ZIF-67 ultrathin nanosheet composite material.
And analyzing the Ag nanowire/ZIF-67 ultrathin nanosheet composite material by using a scanning electron microscope to obtain a scanning electron micrograph, which is shown in FIG. 13. As can be seen from the figure, the grown nanosheet gradually wraps the Ag nanowire.
Example 8
To 10mL of 20 mmol/L Co (NO)3)2Adding 6 mg of Ag nanowires into the methanol solution, stirring for 10 min, mixing with 10mL of 20 mmol/L2-methylimidazole methanol solution, fully stirring for 1 h, washing with ethanol for three times, and vacuum drying for 6h to obtain the Ag nanowire/ZIF-67 ultrathin nanosheet composite material.
And analyzing the Ag nanowire/ZIF-67 ultrathin nanosheet composite material by using a scanning electron microscope to obtain a scanning electron micrograph, which is shown in FIG. 14. As can be seen from the figure, the grown nanosheet gradually wraps the Ag nanowire. In addition, the nano-sheets are epitaxially grown into a sheet structure with a larger area.
Example 9
To 10mL of 20 mmol/L Co (NO)3)2Adding 6 mg of Ag nanowires into the methanol solution, stirring for 10 min, mixing with 10mL of 20 mmol/L2-methylimidazole methanol solution, fully stirring for 2 h, washing with ethanol for three times, and vacuum drying for 6h to obtain the Ag nanowire/ZIF-67 ultrathin nanosheet composite material.
And analyzing the Ag nanowire/ZIF-67 ultrathin nanosheet composite material by using a scanning electron microscope to obtain a scanning electron micrograph, which is shown in FIG. 15. These many shaped sheet structures grow around the Ag sheet.
The foregoing detailed description of the method and application of Ag nanowire/ZIF ultrathin nanosheet composite provided by the present invention, and the detailed examples used herein illustrate the principles and embodiments of the present invention and are presented only to aid in understanding the methods and their core concepts, including the best mode, and to enable any person skilled in the art to practice the invention, including making and using any devices or systems and performing any incorporated methods. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention. The scope of the invention is defined by the claims and may include other embodiments that occur to those skilled in the art. Such other embodiments are intended to be within the scope of the claims if they have structural elements that do not differ from the literal language of the claims, or if they include equivalent structural elements with insubstantial differences from the literal languages of the claims.
Claims (10)
1. A preparation method of an Ag nanowire/ZIF ultrathin nanosheet composite material is characterized by comprising the following steps:
mixing a soluble metal source, an organic ligand, an Ag nanowire and a solvent to form a reaction solution, and stirring for a period of time to obtain the Ag nanowire/ZIF ultrathin nanosheet composite material.
2. A preparation method of an Ag nanowire/ZIF ultrathin nanosheet composite material is characterized by comprising the following specific steps: and mixing the soluble metal source, the dispersion liquid of the Ag nanowire and the dispersion liquid of the organic ligand to form a reaction solution, and stirring for a period of time to obtain the Ag nanowire/ZIF ultrathin nanosheet composite material.
3. A preparation method of an Ag nanowire/ZIF ultrathin nanosheet composite material is characterized by comprising the following specific steps:
s1) mixing a soluble metal source, Ag nanowires and a first solvent to obtain a first dispersion liquid; the concentration of the soluble metal source in the first dispersion liquid is 0.001-10 mol/L;
mixing an organic ligand with a second solvent to obtain a second dispersion liquid, wherein the concentration of the organic ligand in the second dispersion liquid is 0.001-10 mol/L;
s2) mixing the first dispersion liquid and the second dispersion liquid to form a reaction solution, and stirring for a period of time to obtain the Ag nanowire/ZIF ultrathin nanosheet composite material.
4. The method of claim 1, wherein the solvent is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, pentanol, benzene, phenol, toluene, N-dimethylformamide, and water.
5. The method of claim 2, wherein the solvent of the dispersion is selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, pentanol, benzene, phenol, toluene, N-dimethylformamide, and water.
6. The method of claim 3, wherein the first solvent and the second solvent are selected from one or more of methanol, ethanol, propanol, isopropanol, butanol, pentanol, benzene, phenol, toluene, N-dimethylformamide, and water.
7. The method of any of claims 1 to 3, wherein the soluble metal source is a soluble metal salt comprising one or more of a soluble metal halide, a soluble metal nitrate, a soluble metal acetate and a soluble metal sulfate, and the metal element comprises one or more of Co, Zn, Mn, Fe, Ni, Cu.
8. A method according to any one of claims 1 to 3 wherein the organic ligand is an imidazole based compound including one or more of imidazole, 2-methylimidazole, 2-ethylimidazole, 2-nitroimidazole, benzimidazole, 3, 4-dichloroimidazole, purine, 5, 6-dimethylbenzimidazole and 5-chlorobenzimidazole.
9. The method according to any one of claims 1 to 3, wherein the Ag nanowires have a diameter of 0.2 to 100 nm.
10. The method of claim 3, wherein the concentration of Ag nanowires in the first dispersion is 0.1 to 100 mg/mL.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010042693.6A CN111234245A (en) | 2020-01-15 | 2020-01-15 | Ag nanowire/ZIF ultrathin nanosheet composite material, preparation method and application |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010042693.6A CN111234245A (en) | 2020-01-15 | 2020-01-15 | Ag nanowire/ZIF ultrathin nanosheet composite material, preparation method and application |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111234245A true CN111234245A (en) | 2020-06-05 |
Family
ID=70868479
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010042693.6A Pending CN111234245A (en) | 2020-01-15 | 2020-01-15 | Ag nanowire/ZIF ultrathin nanosheet composite material, preparation method and application |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111234245A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113181881A (en) * | 2021-04-29 | 2021-07-30 | 郑州大学 | Novel ZIF-8@ Ag complex core-shell structure hybrid material and preparation method and application thereof |
| CN113845777A (en) * | 2021-10-14 | 2021-12-28 | 南开大学 | Preparation method of copper nanowire-metal organic framework core-shell composite material |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0090432B1 (en) * | 1982-03-31 | 1987-10-07 | Nec Corporation | Electro-magnetic wave absorbing material |
| CN104174388A (en) * | 2014-08-08 | 2014-12-03 | 复旦大学 | Metal organic frame composite material and preparation method thereof |
| CN106710884A (en) * | 2016-11-14 | 2017-05-24 | 江苏华富储能新技术股份有限公司 | Metal-organic complex and silver nano-wire compound as well as preparation method and application thereof |
| CN109758474A (en) * | 2019-03-06 | 2019-05-17 | 大连民族大学 | A kind of Ag/ZIF-8 antibacterial agent and preparation method thereof |
-
2020
- 2020-01-15 CN CN202010042693.6A patent/CN111234245A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0090432B1 (en) * | 1982-03-31 | 1987-10-07 | Nec Corporation | Electro-magnetic wave absorbing material |
| CN104174388A (en) * | 2014-08-08 | 2014-12-03 | 复旦大学 | Metal organic frame composite material and preparation method thereof |
| CN106710884A (en) * | 2016-11-14 | 2017-05-24 | 江苏华富储能新技术股份有限公司 | Metal-organic complex and silver nano-wire compound as well as preparation method and application thereof |
| CN109758474A (en) * | 2019-03-06 | 2019-05-17 | 大连民族大学 | A kind of Ag/ZIF-8 antibacterial agent and preparation method thereof |
Non-Patent Citations (1)
| Title |
|---|
| YUYIN WANG ETAL: ""Facile synthesis of silver nanowire-zeolitic imidazolate framework 67 composites as high highperformance"", 《NANOSCALE》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113181881A (en) * | 2021-04-29 | 2021-07-30 | 郑州大学 | Novel ZIF-8@ Ag complex core-shell structure hybrid material and preparation method and application thereof |
| CN113181881B (en) * | 2021-04-29 | 2023-04-14 | 郑州大学 | ZIF-8@ Ag complex core-shell structure hybrid material and preparation method and application thereof |
| CN113845777A (en) * | 2021-10-14 | 2021-12-28 | 南开大学 | Preparation method of copper nanowire-metal organic framework core-shell composite material |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | A review of recent work on using metal–organic frameworks to grow carbon nanotubes | |
| CN109956463B (en) | Carbon nano tube and preparation method thereof | |
| Cao et al. | Rational design of hollow oxygen deficiency-enriched NiFe2O4@ N/rGO as bifunctional electrocatalysts for overall water splitting | |
| CN110105583B (en) | Metal oxide/ZIF composite material, and preparation method and application thereof | |
| US20210316286A1 (en) | Core-shell structured nise2@nc electrocatalytic material and preparation method and use thereof | |
| CN112108164B (en) | Carbon-coated two-dimensional transition metal phosphide as well as preparation method and application thereof | |
| CN111659401A (en) | Three-dimensional porous carbon nanotube graphene composite membrane and preparation method thereof | |
| CN113908874A (en) | Nitrogen-rich porous composite carbon material, and preparation method and application thereof | |
| CN113477270B (en) | Preparation method of copper-iron bimetal confined nitrogen-doped carbon nano tube composite material | |
| US11732370B2 (en) | Core-shell FE2P@c-FE3C electrocatalyst and preparation method and application thereof | |
| Zheng et al. | Formation of Co3O4 hollow polyhedrons from metal-organic frameworks and their catalytic activity for CO oxidation | |
| CN111036247B (en) | Cobalt-iron oxide-cobalt phosphate electrocatalytic oxygen evolution composite material and preparation method and application thereof | |
| CN111234245A (en) | Ag nanowire/ZIF ultrathin nanosheet composite material, preparation method and application | |
| CN113005568B (en) | Method for preparing porous Co/C nano fiber by PVP (polyvinyl pyrrolidone) assisted ZIF (zinc-doped carbon) growth | |
| CN113540476B (en) | Preparation method and application of non-noble metal cathode catalyst of fuel cell | |
| CN113398944B (en) | Composite material of bismuth vanadate surface modified nickel cobaltate spinel and preparation and application thereof | |
| Li et al. | MOF derived porous Co@ C hexagonal-shaped prisms with high catalytic performance | |
| CN111498830B (en) | Undoped one-dimensional porous carbon material and preparation method thereof | |
| CN111924820A (en) | Preparation method of hollow-structure metal single-atom-site carbon composite material | |
| CN113698617A (en) | Synthesis method of ultrathin two-dimensional hierarchical porous ZIF-67 | |
| CN102776565B (en) | Method for preparing nano-structure single crystal silver | |
| CN114566662B (en) | High-entropy intermetallic compound with ordered structure, preparation method thereof and application of high-entropy intermetallic compound as cathode catalyst of fuel cell | |
| CN114540840B (en) | FeCo/N-C nano composite material and preparation method and application thereof | |
| CN114950482A (en) | Metal modified Zn 2 In 2 S 5 Polarized photocatalytic material and preparation method and application thereof | |
| CN114381758A (en) | Nickel-doped boehmite and reduced graphene oxide composite electrocatalyst and preparation and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20200605 |
|
| RJ01 | Rejection of invention patent application after publication |