CN114160162A - Au/Co (OH)2Layered metal hydroxide hollow structure photocatalyst and preparation method thereof - Google Patents
Au/Co (OH)2Layered metal hydroxide hollow structure photocatalyst and preparation method thereof Download PDFInfo
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- 229910000000 metal hydroxide Inorganic materials 0.000 title claims abstract description 27
- 150000004692 metal hydroxides Chemical class 0.000 title claims abstract description 27
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000002105 nanoparticle Substances 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 238000003756 stirring Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 7
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 claims abstract description 7
- 239000001509 sodium citrate Substances 0.000 claims abstract description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims abstract description 6
- 239000008367 deionised water Substances 0.000 claims abstract description 6
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 6
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000010931 gold Substances 0.000 claims description 37
- 239000000243 solution Substances 0.000 claims description 26
- 239000003054 catalyst Substances 0.000 claims description 19
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 8
- 239000012498 ultrapure water Substances 0.000 claims description 8
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 239000002253 acid Substances 0.000 claims description 5
- 230000035484 reaction time Effects 0.000 claims description 5
- 238000005119 centrifugation Methods 0.000 claims description 4
- 238000001035 drying Methods 0.000 claims description 4
- 229910004042 HAuCl4 Inorganic materials 0.000 claims description 3
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 238000001291 vacuum drying Methods 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 claims description 2
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 238000004140 cleaning Methods 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- 238000010992 reflux Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims 1
- 239000001257 hydrogen Substances 0.000 abstract description 18
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 18
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 17
- 239000000463 material Substances 0.000 abstract description 15
- 238000004519 manufacturing process Methods 0.000 abstract description 12
- JBANFLSTOJPTFW-UHFFFAOYSA-N azane;boron Chemical compound [B].N JBANFLSTOJPTFW-UHFFFAOYSA-N 0.000 abstract description 9
- 230000007062 hydrolysis Effects 0.000 abstract description 8
- 238000006460 hydrolysis reaction Methods 0.000 abstract description 8
- 239000012621 metal-organic framework Substances 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 3
- 230000015572 biosynthetic process Effects 0.000 abstract description 2
- 239000002086 nanomaterial Substances 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 238000003786 synthesis reaction Methods 0.000 abstract description 2
- 239000000654 additive Substances 0.000 abstract 1
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 abstract 1
- 230000003301 hydrolyzing effect Effects 0.000 abstract 1
- 239000002904 solvent Substances 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 229910000510 noble metal Inorganic materials 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000000047 product Substances 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical group O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 150000002460 imidazoles Chemical class 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000009210 therapy by ultrasound Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
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Classifications
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- B01J35/39—
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/89—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with noble metals
- B01J23/8913—Cobalt and noble metals
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
- C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
- C01B3/06—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents
- C01B3/065—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by reaction of inorganic compounds containing electro-positively bound hydrogen, e.g. water, acids, bases, ammonia, with inorganic reducing agents from a hydride
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention belongs to the field of nano material preparation, and particularly relates to Au/Co (OH)2A preparation method of a layered metal hydroxide hollow structure photocatalyst and application thereof in hydrogen production by ammonia borane hydrolysis. In particular to a method for synthesizing a metal-organic framework ZIF-67 by taking cobalt nitrate hexahydrate and 2-methylimidazole as raw materials and deionized water as a solvent and stirring at normal temperature for reaction. Preparing Au nano-particles by a sodium citrate reduction method, and loading the Au nano-particles on a ZIF-67 nano cube by APTES grafting to obtain Au/Co (OH)2Layered metal hydroxide hollow structures. Au/Co (OH) prepared by the method of the invention2The composite photocatalyst with the layered metal hydroxide hollow structure has a unique structure. In addition, the material of the invention has mild synthesis conditions, low material cost, no need of PVP and other additives, simple and easy operation, low requirement on equipment, high efficiency for design and preparation,The green photocatalyst provides theoretical guidance and technical support. The material can be used for producing hydrogen by hydrolyzing ammonia borane, has higher activity and stability, and has good practicability.
Description
Technical Field
The invention relates to the technical field of MOFs material preparation, in particular to Au/Co (OH)2A layered metal hydroxide hollow structure composite photocatalyst, a preparation method and application thereof.
Background
Zeolitic imidazoles framework materials (ZIFs) are a very important branch of the family of metal organic framework Materials (MOFs). ZIF series materials are MOF materials with zeolite structures, which are formed by coordination of imidazole and derivatives thereof and divalent metal Zn or Co. The MOFs material has ultrahigh specific surface area and porosity as a catalyst, has the characteristic of stable chemical property, and is widely applied to the field of catalysis. In addition to these features, ZIFs exhibit superior performance in some respects. The zeolite imidazole framework material (ZIF) has the advantages of various structures, ultrahigh porosity, high surface area, adjustable pore diameter, open metal sites, good thermal stability and the like. Is widely applied to the fields of selective gas adsorption, catalysis, hydrogen storage and the like, and has the value of wide scientific research and practical application.
In recent years, due to the energy crisis and the increasing environmental pollution, people are beginning to search for new alternative energy. Hydrogen energy is a generally accepted clean energy source, has the advantages of environmental friendliness, high calorific value and the like, and plays a very important role in solving the problems of energy crisis, environmental pollution and the like. In addition to the traditional hydrogen production mode by using fossil raw materials, the currently widely used hydrogen production methods mainly include hydrogen production by water electrolysis, hydrogen production by borohydride hydrolysis, hydrogen production by direct photolysis of water by solar energy, and the like. The ammonia borane hydrolysis hydrogen production has the advantages of good safety, simple operation, mild reaction conditions, controllable hydrogen production quantity and hydrogen production rate, no toxicity, relatively low cost and the like, so the method is closely concerned.
The noble metal catalyst has high catalytic activity and low activation energy for catalyzing ammonia borane hydrolysis to prepare hydrogen, so that the noble metal catalyst is widely concerned by people. Although the noble metal has excellent catalytic performance for hydrogen production by ammonia borane hydrolysis, the noble metal is loaded by a proper carrier so as to exert the optimal catalytic activity of the catalyst. At present, a great deal of research reports exist, and ZIFs materials are used as carriers, and noble metals are loaded on the ZIFs materials to be used as integral catalysts for ammonia borane hydrolysis hydrogen production reactions. Wherein Co in the ZIF framework also has a certain catalytic effect on the hydrolysis of ammonia borane to prepare hydrogen.
This patent is to mix precious goldThe method belongs to the combination of Au nano particles and a metal organic framework material ZIF-67, takes a ZIF-67 metal-organic framework nanocube as a carrier to prepare Au/Co (OH)2The invention has the advantages of simple operation, mild reaction condition, environmental protection, low cost and the like. Au/Co (OH) to be prepared2The layered metal hydroxide hollow structure catalyst is subjected to ammonia borane hydrolysis hydrogen production test, the result shows that the catalyst has good catalytic activity, and the catalyst still keeps good stability after five times of circulation.
Disclosure of Invention
The invention aims to provide a nano material Au/Co (OH)2A layered metal hydroxide hollow structure composite photocatalyst, a preparation method and application thereof. The invention designs and synthesizes a nanometer material catalyst Au/Co (OH)2The layered metal hydroxide hollow structure has high stability and high porosity and can be catalyzed efficiently. In addition, the surface-supported Au nanoparticles directly affect the catalytic reaction. Experimental evidence Au/Co (OH)2The layered metal hydroxide hollow structure photocatalyst can efficiently catalyze ammonia borane to hydrolyze to produce hydrogen under mild conditions, and can be recycled for multiple times under the condition of keeping high activity.
The nanometer material of the invention Au/Co (OH)2The preparation method of the composite photocatalyst with the layered metal hydroxide hollow structure comprises the following steps:
step 1: ZIF-67 is synthesized by conventional method, adding a certain amount of Co (NO) into Cetyl Trimethyl Ammonium Bromide (CTAB) water solution with a certain concentration3)2·6H2And O, stirring to dissolve, adding the solution into deionized water solution containing 2-methylimidazole, and stirring to react for 5-90min at room temperature. The product was collected by centrifugation to give a purple precipitate, washed several times and dried to give a ZIF-67 nanocube.
The preparation method of the gold nanoparticles in the step 2 comprises the following steps: adding sodium citrate solution with certain concentration into chloroauric acid solution, HAuCl4The volume ratio of the solution to the ultrapure water is1: 20-1: 30. Reacting for a certain time to obtain nano particles, wherein the molar ratio of the sodium citrate to the chloroauric acid is 10: 1-0.5: 1, the reaction temperature is 90-130 ℃, the reaction time is 5-45 minutes, and then naturally cooling to room temperature to obtain a colloidal solution of the gold nano particles;
said step 3 Au/Co (OH)2Preparing a layered metal hydroxide hollow structure catalyst: uniformly dispersing the ZIF-67 nanocubes obtained in the step (1) into an ethanol solution, and then adding a certain amount of APTES, wherein the volume ratio of absolute ethanol to APTES is 43: 1-83: 1. After the reaction is carried out for 2 to 10 hours by condensing, refluxing and stirring, the reaction is stopped. Naturally cooling to room temperature, centrifugally separating, and rinsing for three times. Adding the 15nm Au nanoparticles prepared in the step (2) into an aqueous solution of a centrifuged product under the condition of stirring, wherein the reaction temperature is 20-85 ℃ and the reaction time is 1-8 hours, then centrifuging and collecting, and respectively cleaning a sample by using ultrapure water and absolute ethyl alcohol for 3 times, wherein the vacuum drying temperature is 60 ℃ and the drying time is 3-6 hours. To obtain Au/Co (OH)2Layered metal hydroxide hollow structure catalyst.
Drawings
FIG. 1 is an SEM photograph of ZIF-67 nanocubes prepared in example 1.
FIG. 2 is a photograph showing the preparation of Au/Co (OH) according to example 32SEM photograph of the layered metal hydroxide hollow structure photocatalyst.
FIG. 3 is a TEM photograph of ZIF-67 nanocubes prepared in example 1.
FIG. 4 shows Au/Co (OH) prepared in example 32TEM photograph of the layered metal hydroxide hollow structure photocatalyst.
FIG. 5 shows Au/Co (OH)2XRD patterns before and after the circulation experiment of the layered metal hydroxide hollow structure catalyst.
Detailed Description
The technical solution of the present invention is described below by way of specific examples, but the technical solution of the present invention is not limited to the examples.
Example 1: and preparing ZIF-67 nanocubes. 0.01mmol of cetyltrimethylammonium bromide (CTAB) was weighed out and dissolved in 10m1 of deionized water,adding 1mmol Co (NO) after the solution is completely dissolved3)2·6H2O, stirring for about 5min, adding the solution into 70mL of deionized water containing 55mmol of 2-methylimidazole, and stirring at room temperature for reaction for about 10 min. After the reaction was completed, the product was centrifuged at 8000rad for 5min, and the supernatant was discarded and then washed four times with absolute ethanol. And (4) after centrifugation, drying in a vacuum drying oven at 60 ℃ to obtain the ZIF-67 nanocubes.
Example 2: synthesis of colloidal solution of 15nm Au nanoparticles: a100 mL three-neck flask is taken and added with about 2mL of HAuCl4(concentration: 25mM) solution, 50mL of ultrapure water was added thereto, the mixture was stirred, heated to about 100 ℃ and then refluxed by opening condensation, and then 5mL of a sodium citrate solution (concentration: 38.8mM) was added thereto and reacted for about 10 min. The heating was stopped. And cooling to room temperature to obtain a colloidal solution of 15nm Au nanoparticles.
Example 3: Au/Co (OH)2Preparing a layered metal hydroxide hollow structure photocatalyst: 0.1g of ZIF-67 nanocubes was weighed into a 100ml three-necked flask, 50ml of absolute ethanol was added thereto, and ultrasonic dispersion was carried out for 30 minutes. And after the ultrasonic treatment is finished, 2ml of APTES is added, a heating device is turned on, the mixture is heated to 55 ℃, stirred, and condensed and refluxed for about 2 hours, and then the reaction is stopped. After natural cooling to room temperature, 6000rad is centrifuged for 5min, the supernatant is discarded, and then the mixture is rinsed with absolute ethyl alcohol for three times.
The product was washed with ultrapure water into a beaker and stirred to disperse the solid powder in ultrapure water. And then adding the prepared 15nm Au nanoparticle solution into a beaker, stirring and reacting for 1h to load Au nanoparticles, collecting the generated precipitate by centrifugation at the rotating speed of 6000rad for 5min, discarding the supernatant, washing the precipitate with ultrapure water three times respectively, and then washing the precipitate with absolute ethyl alcohol three times. Then the precipitate was dried in a vacuum oven at 60 ℃ for 4 hours to obtain Au/Co (OH)2Layered metal hydroxide hollow structure catalyst.
For the obtained Au/Co (OH)2The morphology of the layered metal hydroxide hollow structure photocatalyst is analyzed, and an SEM photo is shown in figure 2, and a TEM photo is shown in figure 4. As can be seen from figures 2 and 4,Au/Co(OH)2the composite photocatalyst with the layered metal hydroxide hollow structure is successfully prepared.
The prepared catalyst was subjected to stability test. As can be seen from XRD patterns before and after the catalyst cycle experiment in FIG. 5, the patterns before and after the cycle are basically consistent, which shows that Au nanoparticles are very stable in the reaction process and can be firmly attached to Co (OH)2The stable SPR effect is kept on the surface of the layered metal hydroxide hollow structure cube, and the stability of the catalyst is better and the catalyst can be recycled for multiple times.
Claims (6)
1. Au/Co (OH)2The composite photocatalyst with the layered metal hydroxide hollow structure and the preparation method thereof are characterized by comprising the following steps:
(1): preparing a ZIF-67 nanocube;
(2): preparing 15nm Au nanoparticles;
(3)：Au/Co(OH)2preparing the layered metal hydroxide hollow structure photocatalyst.
2. An Au/Co (OH) according to claim 12The composite photocatalyst with the layered metal hydroxide hollow structure and the preparation method thereof are characterized by comprising the following steps of (1) preparing the ZIF-67 nanocube: taking a clean beaker, adding a certain amount of Cetyl Trimethyl Ammonium Bromide (CTAB), adding deionized water, and weighing a certain amount of Co (NO)3)2·6H2And O, adding the solution, stirring until the solution is dissolved, then adding the solution into a deionized water solution containing 2-methylimidazole, and stirring and reacting for 5-90min at room temperature. The product was collected by centrifugation, washed several times and dried to give ZIF-67 nanocubes. (2) The preparation of the 15nm Au nano-particles comprises the following steps: adding sodium citrate water solution with certain concentration into chloroauric acid water solution under the condition of stirring, reacting for certain time to obtain nano particles, wherein the molar ratio of the sodium citrate to the chloroauric acid is 10: 1-0.5: 1, the reaction temperature is 90-130 ℃, the reaction time is 5-45 minutes, and then the sodium citrate is added into the chloroauric acid water solutionThen cooling to room temperature to obtain a colloidal solution of gold nanoparticles;
(3) the Au/Co (OH)2Preparing a layered metal hydroxide hollow structure catalyst: and (2) uniformly dispersing the ZIF-67 nanocubes obtained in the step (1) into a certain amount of ethanol solution, then adding a certain amount of APTES, condensing, refluxing, stirring and reacting for 2-10h, and stopping the reaction. Naturally cooling to room temperature, centrifugally separating, and rinsing for three times. Adding the 15nm Au nanoparticles prepared in the step (2) into an aqueous solution of a centrifuged product under stirring, wherein the reaction temperature is 20-85 ℃ and the reaction time is 1-8 hours, centrifuging, collecting, washing for several times and drying. To obtain Au/Co (OH)2Layered metal hydroxide hollow structure catalyst.
3. An Au/Co (OH) according to claim 22The layered metal hydroxide hollow structure photocatalyst and the preparation method thereof are characterized in that: in the step (1), Co (NO)3)2·6H2The molar ratio of O and 2-methylimidazole is 1: 40-1: 70, the reaction time is 5min-90min, and the reaction temperature is normal temperature.
4. The method of claim 2, wherein: in the step (2), HAuCl4The volume ratio of the solution to the ultrapure water is 1: 20-1: 30.
5. The method of claim 2, wherein: in the step (3), the volume ratio of the absolute ethyl alcohol to the APTES is 43: 1-83: 1, and the rotating speed is 600 rad.
6. The method of claim 2, wherein: and (4) respectively cleaning the sample in the step (3) for 3 times by using ultrapure water and absolute ethyl alcohol, wherein the vacuum drying temperature is 60 ℃, and the drying time is 3-6 hours.
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