CN114951687A - Room temperature macro preparation method of attapulgite-nano copper powder compound - Google Patents
Room temperature macro preparation method of attapulgite-nano copper powder compound Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 57
- 238000003756 stirring Methods 0.000 claims abstract description 40
- 229960000892 attapulgite Drugs 0.000 claims abstract description 31
- 229910052625 palygorskite Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 26
- 238000005406 washing Methods 0.000 claims abstract description 24
- 239000008367 deionised water Substances 0.000 claims abstract description 23
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 23
- 239000004927 clay Substances 0.000 claims abstract description 12
- 238000001291 vacuum drying Methods 0.000 claims abstract description 12
- 150000001879 copper Chemical class 0.000 claims abstract description 11
- FQENQNTWSFEDLI-UHFFFAOYSA-J sodium diphosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])([O-])=O FQENQNTWSFEDLI-UHFFFAOYSA-J 0.000 claims abstract description 11
- 229940048086 sodium pyrophosphate Drugs 0.000 claims abstract description 11
- 235000019818 tetrasodium diphosphate Nutrition 0.000 claims abstract description 11
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims abstract description 11
- 238000000926 separation method Methods 0.000 claims abstract description 10
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 6
- 238000000227 grinding Methods 0.000 claims abstract description 6
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 6
- 239000002253 acid Substances 0.000 claims abstract description 5
- -1 copper powder compound Chemical class 0.000 claims abstract 2
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 7
- 239000002131 composite material Substances 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 5
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- 239000011668 ascorbic acid Substances 0.000 claims description 4
- 229960005070 ascorbic acid Drugs 0.000 claims description 4
- 235000010323 ascorbic acid Nutrition 0.000 claims description 4
- 229910000365 copper sulfate Inorganic materials 0.000 claims description 4
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical compound O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical group [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- 238000003828 vacuum filtration Methods 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 239000012279 sodium borohydride Substances 0.000 claims description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 3
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 abstract description 31
- 239000010949 copper Substances 0.000 abstract description 27
- 229910052802 copper Inorganic materials 0.000 abstract description 25
- 230000008569 process Effects 0.000 abstract description 7
- 230000008901 benefit Effects 0.000 abstract description 6
- 230000015572 biosynthetic process Effects 0.000 abstract description 3
- 239000002994 raw material Substances 0.000 abstract description 3
- 238000003786 synthesis reaction Methods 0.000 abstract description 3
- 229910000881 Cu alloy Inorganic materials 0.000 abstract description 2
- 238000005516 engineering process Methods 0.000 abstract description 2
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- 238000001914 filtration Methods 0.000 abstract 1
- 239000002105 nanoparticle Substances 0.000 description 18
- 239000002245 particle Substances 0.000 description 16
- 239000000843 powder Substances 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000000694 effects Effects 0.000 description 5
- 230000003647 oxidation Effects 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
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- 238000009826 distribution Methods 0.000 description 4
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- 238000007873 sieving Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- FTXJFNVGIDRLEM-UHFFFAOYSA-N copper;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O FTXJFNVGIDRLEM-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 239000000956 alloy Substances 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
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- 238000006555 catalytic reaction Methods 0.000 description 2
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- 239000007789 gas Substances 0.000 description 2
- 239000011777 magnesium Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 2
- 229940012189 methyl orange Drugs 0.000 description 2
- 239000011858 nanopowder Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical class [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 229910017870 Cu—Ni—Al Inorganic materials 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- MUBKMWFYVHYZAI-UHFFFAOYSA-N [Al].[Cu].[Zn] Chemical compound [Al].[Cu].[Zn] MUBKMWFYVHYZAI-UHFFFAOYSA-N 0.000 description 1
- 230000002378 acidificating effect Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- 229910000323 aluminium silicate Inorganic materials 0.000 description 1
- 238000005576 amination reaction Methods 0.000 description 1
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- 229910010293 ceramic material Inorganic materials 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
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- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 238000009791 electrochemical migration reaction Methods 0.000 description 1
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- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
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- 229910052742 iron Inorganic materials 0.000 description 1
- 239000000314 lubricant Substances 0.000 description 1
- 239000010687 lubricating oil Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000005240 physical vapour deposition Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000004663 powder metallurgy Methods 0.000 description 1
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- 239000010865 sewage Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
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- 239000002904 solvent Substances 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
- B22F1/0545—Dispersions or suspensions of nanosized particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B33/00—Silicon; Compounds thereof
- C01B33/20—Silicates
- C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
- C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
- C01B33/40—Clays
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/04—Particle morphology depicted by an image obtained by TEM, STEM, STM or AFM
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
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Abstract
The invention discloses a room temperature macroscopic quantity preparation method of an attapulgite-nanometer copper powder compound, which comprises the steps of completely dissolving sodium pyrophosphate in deionized water, adding attapulgite clay under stirring, stirring until the attapulgite clay is uniformly dispersed, adding acid, performing ultrasonic treatment, continuing stirring, standing, performing centrifugal separation, washing until the washing water is neutral, performing vacuum drying, and grinding to obtain purified attapulgite clay; slowly adding into copper salt water solution, stirring in water bath, standing, vacuum filtering, washing with water until the water is colorless, and vacuum drying to obtain attapulgite-copper salt complex; the attapulgite-copper salt compound is completely dispersed in deionized water, added with a reducing agent, stirred in a water bath until no bubbles are generated, centrifugally separated, washed and dried in vacuum to prepare the attapulgite-nano copper powder compound. The preparation method has the advantages of simple process, low economic cost, low consumption, environmental protection, rich raw material reserves, realization of mass synthesis and objective economic benefit. Is a key technology which is expected to realize the industrialization of the copper and the copper alloy.
Description
Technical Field
The invention relates to a room-temperature macro preparation method of an attapulgite-nano copper powder compound.
Background
Generally, powders of aluminum, copper, zinc, iron, copper, silver and alloys thereof are called metal powders, and are classified into micron-sized powders (1 to 100 μm), submicron-sized powders (0.1 to 1 μm) and nano-sized powders (0.001 to 0.1 μm) according to particle size. The nano powder has wide application in the fields of electronic elements, metallurgical industry, chemical industry, bioengineering, advanced ceramic materials, environment, energy and the like due to the nano characteristics of small size effect, surface effect, quantum tunneling effect and the like. Copper powder is one of the most important basic raw materials in the powder metallurgy industry, and has high conductivity, high melting point, low electrochemical migration behavior, strong weldability, and low price. For example: polycrystalline copper powder is used as a catalyst to reduce CO to hydrocarbons and poly-oxygenates using a standard electrochemical cell and three-electrode system. Adopting the amorphous powder of the atomized Zr-Cu-Ni-Al to carry out dealloying treatment to prepare the alloy and Cu 2 Nanoporous copper (Cu) powder with co-existing O. The prepared NPCPs have a core-shell structure, and the specific surface area reaches 7.52 m 2 (ii)/g, exhibits significant hydrogen peroxide (H) in both acidic and neutral environments 2 O 2 ) Degradation capability, and can completely eliminate Methyl Orange (MO). Copper powder can be considered as a self-supported nano-copper catalyst (i.e. nano-copper is supported on copper particles), so that the copper powder has better catalytic performance than the nano-copper catalyst supported by metal oxide as the active catalyst for alcohol amination. In addition, the nano copper powder can also be used for solid lubricants, conductive materials, nano copper material manufacturing, modified phenolic resin, aerospace fields and the like. The copper powder applied to different fields has different requirements on the appearance, surface characteristics and the like of the copper powder due to different use characteristics. Meanwhile, the metal powder has high activity and extremely high requirements on particle size and distribution, so that the preparation of the copper powder faces many challenges.
At present, the production of copper powder comprises chemical precipitation and electrolytic depositionOxidation reduction, water atomization, gas atomization and water-gas combined fog And various methods such as chemical conversion. Also, there are classified into a direct current arc plasma (DC) method, a high frequency plasma (RF) method and a hybrid plasma (hybrid plasma) method. The plasma method can obtain uniform and small-particle nano powder, but the DC method has high temperature The lower electrode is easy to melt or evaporate to pollute the product; the RF method has low energy utilization rate and poor stability. The mechanochemical method being the use of high energy Ball milling and chemical reaction. The method has high yield and simple process, but the prepared crystal grains are not uniform, and the preparation process is simple Impurities are easy to be introduced. Current density, jet flow and scanning speed in process of preparing nanocrystalline copper by scanning jet electrodeposition method Have a great influence on the surface growth morphology of the deposited layer. CuSO in closed cycle hydrogen reduction process 4 ∙5H 2 O and NaOH as original Adding CuSO into the mixture under vigorous stirring at 25 +/-1 DEG C 4 Quickly dripping NaOH aqueous solution into a beaker of the aqueous solution for precipitation Accordingly, a precursor powder was obtained. The precursor powder is reduced by the mixed gas of hydrogen and nitrogen in a closed-cycle hydrogen reducing furnace to obtain the particle size About 40-80 nm, 99.26% nanometer copper powder. The crystal nucleus growth method can prepare uniform nano particles with the particle size of 80-90 nm Copper. In addition, the physical vapor deposition method has the advantages of simple process, no pollution, less material consumption, more complex equipment and larger investment. Gamma ray The linear irradiation method has simple operation, can effectively prevent particle agglomeration, has easily controlled product granularity, higher yield and easy industrialization, but is collected It is difficult. The nano particles prepared by the sol-gel method are uniformly distributed, have high purity and high chemical activity, but have higher cost and pollution. Micro-meter The emulsion method can effectively control the particle size of the product and prevent the particles from agglomerating, but the emulsion method has large using amount of the emulsifier and low yield and is difficult to industrialize.Simple process The solvothermal method which is simple and easy to control also has the problem of low yield and the like。
Disclosure of Invention
The invention provides a room-temperature macroscopic preparation method of an attapulgite-nano copper powder compound, which can prepare a large amount of nano copper powder compounds which are difficult to oxidize.
Therefore, the invention adopts the following technical scheme: method for preparing attapulgite-nano copper powder compoundAt room temperatureThe macro preparation method comprises the following steps:
1) purification of Attapulgite (ATP):
adding 5-10 mmol of sodium pyrophosphate into 1000-2000 mL of deionized water, stirring at room temperature until the sodium pyrophosphate is completely dissolved, slowly adding 50-100 g of attapulgite under stirring, stirring again for 30 min at room temperature, dispersing uniformly, slowly adding 4-7 mL of acid, performing ultrasonic treatment for 30 min, continuing stirring for 3 h, standing for 12h, performing centrifugal separation, washing precipitates until the water after washing is neutral, performing vacuum drying at 110 ℃ for 12h, grinding, and sieving with a 200-mesh sieve to obtain purified attapulgite;
the acid is hydrochloric acid with a molar concentration of 10 mol/L, sulfuric acid with a molar concentration of 5 mol/L or nitric acid with a molar concentration of 10 mol/L.
) Preparing an attapulgite-copper salt compound:
adding 10-30 mmol of copper salt into 1000-3000 mL of deionized water, stirring until the copper salt is completely dissolved, slowly adding 10-30 g of purified attapulgite, stirring in a water bath at 30 ℃ for 24 hours, standing, carrying out vacuum filtration separation, washing the separated solid with water until the washed water is colorless to remove the copper salt which does not participate in coordination, and carrying out vacuum drying at 60 ℃ for 12 hours to obtain an attapulgite-copper salt compound;
the copper salt is copper sulfate, copper chloride dihydrate, copper acetate monohydrate or copper nitrate hexahydrate.
) Preparing an attapulgite-nano copper powder compound:
adding 5-20 g of the attapulgite-copper salt composite into 1000-4000 mL of deionized water, after complete dispersion, slowly adding 7.5-50 mmol of a reducing agent, stirring in a water bath at 30 ℃ until no bubbles are generated in the reaction, centrifugally separating and collecting the attapulgite-nano copper powder, washing with deionized water, and drying in vacuum at 60 ℃ to obtain the attapulgite-nano copper powder composite.
The reducing agent can be sodium borohydride, ascorbic acid, hydrazine hydrate or oxalic acid.
FIG. 1 is a transmission electron microscope image of the attapulgite-copper powder prepared by the preparation method of the invention, and as can be seen from the image, the nano-copper powder has a limited range in the aperture of the attapulgite, is in the form of dispersed spherical particles and has uniform appearance. FIG. 2 is a graph showing the particle size distribution of the attapulgite-copper powder, and it can be seen that the average particle size of the attapulgite-copper powder was 0.5 nm. FIG. 3 is an XRD pattern of the attapulgite-copper powder prepared by the preparation method of the present invention, and it can be seen from the figure that the prepared sample does not obviously show the characteristic crystal faces of (111), (200) and (220) of copper, which indicates that the attapulgite plays an obvious confinement role, the copper nanoparticles are completely encapsulated in the aperture of the attapulgite, the particle size of the copper nanoparticles is well controlled in the ultra-small size of 0.5nm, and the oxidation of the copper nanoparticles is effectively hindered.
According to the invention, the copper nanoparticles are encapsulated in the attapulgite with a unique chain layered structure, so that the growth of the nanoparticles is effectively inhibited, and the ultra-small copper nanoparticles with the average particle size of 0.5nm are synthesized. Due to the protection of the layered structure of the attapulgite clay chain, the oxidation of copper nano-particles can be effectively prevented, and the method has good practical application prospect in the fields of industrial catalysis and the like.
As an aqueous magnesium-rich aluminosilicate clay mineral, attapulgite clay is often used as a mechanical carrier for dispersing and stabilizing nanoparticles due to its large specific surface area and porous structure. The invention utilizes H through the acidification treatment of the attapulgite + The part K between the stone layers + 、Na + 、Ca 2+ 、Mg 2+ And (3) displacing the plasma to increase the specific surface area of the attapulgite, and reducing the attapulgite-copper salt compound formed by coordination of silicon hydroxyl of the attapulgite and copper ions into an attapulgite-copper nanoparticle compound by using reducing agents such as sodium borohydride, ascorbic acid, hydrazine hydrate or oxalic acid, so that the copper nanoparticles are packaged in the holes of the attapulgite, and the oxidation of the copper nanoparticles is relieved on the basis of dispersing the copper nanoparticles.
The attapulgite-nano copper powder compound prepared by the preparation method can be applied to the fields of catalysis, lubricating oil additives, conductive coatings, energy sources and the like.
The preparation method disclosed by the invention is used for preparing the attapulgite-copper powder at room temperature, and has the advantages of simple process, low economic cost, low consumption, environmental friendliness, abundant raw material reserves, capability of realizing mass synthesis and objective economic benefit. Is a key technology which is expected to realize the industrialization of the copper and the copper alloy, and has important theoretical and practical significance. The prepared attapulgite-copper powder has the advantages of uniform appearance, difficult oxidation, narrow particle size distribution range, super-small size (average particle size of 0.5 nm) and the like, and the domain-limiting effect of the attapulgite also effectively hinders the oxidation of copper nanoparticles, so that the attapulgite-copper powder is expected to show good catalytic activity. And the synthesis of the attapulgite-copper powder only needs deionized water as a solvent, and the whole preparation process has no pollutant and sewage, thereby meeting the requirement of green production.
Drawings
FIG. 1 is a transmission image (TEM) showing the attapulgite-copper nanoparticle composite prepared by the preparation method of the present invention.
FIG. 2 is a particle size distribution diagram of the attapulgite-copper nanoparticle composite prepared by the preparation method of the invention.
FIG. 3 is an X-ray diffraction (XRD) pattern of the attapulgite-copper nanopowder composite obtained by the process of the present invention.
Detailed Description
Example 1
Adding 5mmol of sodium pyrophosphate into 1000 mL of deionized water, stirring at room temperature until the sodium pyrophosphate is completely dissolved, slowly adding 50g of attapulgite clay under stirring, stirring at room temperature for 30 min, uniformly dispersing, slowly adding 6 mL of hydrochloric acid with the molar concentration of 10 mol/L, performing ultrasonic treatment for 30 min, continuously stirring for 3 h, standing for 12h, performing centrifugal separation, washing the precipitate with water until the water is neutral after washing, performing vacuum drying at 110 ℃ for 12h, grinding, and sieving with a 200-mesh sieve to obtain the purified attapulgite clay. Adding 20 mmol of copper sulfate into 2000mL of deionized water, stirring until the copper sulfate is completely dissolved, slowly adding 20 g of purified attapulgite, stirring for 24 h in a water bath at 30 ℃, standing, performing vacuum filtration separation, washing the separated solid with water until the washed water is colorless to remove copper salt which does not participate in coordination, and performing vacuum drying for 12h at 60 ℃ to obtain the attapulgite-copper salt compound. Adding 10 g of attapulgite-copper salt compound into 2000mL of deionized water, after complete dispersion, slowly adding 30 mmol of ascorbic acid, stirring in a water bath at 30 ℃ until no bubbles are generated in the reaction, centrifugally separating, washing with deionized water, and drying under vacuum at 60 ℃ to obtain the attapulgite-nano copper powder compound.
Example 2
Adding 10mmol of sodium pyrophosphate into 2000mL of deionized water, stirring at room temperature until the sodium pyrophosphate is completely dissolved, slowly adding 100g of raw soil under the stirring state, stirring at room temperature for 30 min, slowly adding 4 mL of sulfuric acid with the molar concentration of 5 mol/L, performing ultrasonic treatment for 30 min, continuously stirring for 3 h, standing for 12h, performing centrifugal separation, washing precipitates with water until the water is neutral after washing, performing vacuum drying at 110 ℃ for 12h, grinding, and sieving with a 200-mesh sieve to obtain the purified attapulgite. Adding 10mmol of copper chloride dihydrate into 1000 mL of deionized water, stirring until the copper chloride dihydrate is completely dissolved, slowly adding 10 g of purified attapulgite, stirring in a water bath at 30 ℃ for 24 h, standing, carrying out vacuum filtration separation, washing the separated solid with water until the washed water is colorless to remove the copper salt which does not participate in coordination, and carrying out vacuum drying at 60 ℃ for 12h to obtain the attapulgite-copper salt composite. Adding 5 g of attapulgite-copper salt compound into 1000 mL of deionized water, completely dispersing, slowly adding 7.5mmol of oxalic acid, stirring in a water bath at 30 ℃ until no bubbles are generated in the reaction, centrifugally separating and collecting, washing with deionized water, and drying under vacuum at 60 ℃ to obtain the attapulgite-nano copper powder compound.
Example 3
Adding 8mmol of sodium pyrophosphate into 1500 mL of deionized water, stirring at room temperature until the sodium pyrophosphate is completely dissolved, slowly adding 75 g of attapulgite clay under stirring, stirring at room temperature for 30 min, slowly adding 7mL of nitric acid with the molar concentration of 10 mol/L, performing ultrasonic treatment for 30 min, continuously stirring for 3 h, standing for 12h, performing centrifugal separation, washing the precipitate with water until the water is neutral after washing, performing vacuum drying at 110 ℃ for 12h, grinding, and sieving with a 200-mesh sieve to obtain the purified attapulgite clay. Adding 30 mmol of copper nitrate hexahydrate into 3000 mL of deionized water, stirring until the copper nitrate hexahydrate is completely dissolved, slowly adding 30 g of purified attapulgite, stirring in a water bath at 30 ℃ for 24 hours, standing, performing suction filtration separation, washing the separated solid with water until the washed water is colorless to remove copper salt which does not participate in coordination, and performing vacuum drying at 60 ℃ for 12 hours to obtain the attapulgite-copper salt compound. Adding 20 g of attapulgite-copper salt compound into 4000 mL of deionized water, after complete dispersion, slowly adding 50 mmol of hydrazine hydrate, stirring in a water bath at 30 ℃ until no bubbles are generated in the reaction, centrifugally separating and collecting, washing with deionized water, and drying under vacuum at 60 ℃ to obtain the attapulgite-nano copper powder compound.
Claims (5)
1. A room temperature macro preparation method of an attapulgite-nanometer copper powder compound is characterized by comprising the following steps:
1) adding 5-10 mmol of sodium pyrophosphate into 1000-2000 mL of deionized water, stirring at room temperature until the sodium pyrophosphate is completely dissolved, slowly adding 50-100 g of attapulgite clay under stirring, stirring at room temperature until the attapulgite clay is uniformly dispersed, slowly adding 4-7 mL of acid, performing ultrasonic treatment, continuously stirring, standing, performing centrifugal separation, washing, performing vacuum drying, and grinding to obtain purified attapulgite clay;
2) adding 10-30 mmol of copper salt into 1000-3000 mL of deionized water, stirring until the copper salt is completely dissolved, slowly adding 10-30 g of purified attapulgite, stirring in a water bath at 30 ℃ for 24 hours, standing, performing vacuum filtration, washing with water until the washed water is colorless, and performing vacuum drying to obtain an attapulgite-copper salt compound;
3) adding 5-20 g of attapulgite-copper salt compound into 1000-4000 mL of deionized water, after complete dispersion, slowly adding 7.5-50 mmol of reducing agent, stirring in a water bath at 30 ℃ until no bubbles are generated in the reaction, centrifugally separating, washing with deionized water, and drying in vacuum to obtain the attapulgite-nano copper powder compound.
2. The method for preparing attapulgite-nano copper powder compound on a large scale at room temperature according to claim 1, wherein in the step 1), hydrochloric acid with the molar concentration of 10 mol/L, sulfuric acid with the molar concentration of 5 mol/L or nitric acid with the molar concentration of 10 mol/L is used as acid.
3. The method for the room-temperature macro-preparation of the attapulgite-nano copper powder compound according to claim 1, wherein in the step 1), the washing is carried out until the water is neutral after the washing.
4. The method for the room-temperature macro-preparation of the attapulgite-copper nanopowder composite according to claim 1 wherein in step 2) the copper salt is copper sulfate, copper chloride dihydrate, copper acetate monohydrate or copper nitrate.
5. The method for preparing attapulgite-nano copper powder compound at room temperature on a large scale according to claim 1, wherein in the step 3), sodium borohydride, ascorbic acid, hydrazine hydrate or oxalic acid is used as a reducing agent.
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