CN114162797A - Cadmium hydroxyphosphate ultra-long nanowire and preparation method and application thereof - Google Patents
Cadmium hydroxyphosphate ultra-long nanowire and preparation method and application thereof Download PDFInfo
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- CN114162797A CN114162797A CN202111535387.7A CN202111535387A CN114162797A CN 114162797 A CN114162797 A CN 114162797A CN 202111535387 A CN202111535387 A CN 202111535387A CN 114162797 A CN114162797 A CN 114162797A
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- 239000002070 nanowire Substances 0.000 title claims abstract description 56
- 229910052793 cadmium Inorganic materials 0.000 title claims abstract description 47
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 18
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- 239000002243 precursor Substances 0.000 claims description 26
- 239000000725 suspension Substances 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 238000006243 chemical reaction Methods 0.000 claims description 21
- 150000001661 cadmium Chemical class 0.000 claims description 19
- 238000010335 hydrothermal treatment Methods 0.000 claims description 16
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 16
- 229940049964 oleate Drugs 0.000 claims description 15
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 13
- 238000003756 stirring Methods 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000007864 aqueous solution Substances 0.000 claims description 10
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 9
- 239000010452 phosphate Substances 0.000 claims description 9
- 235000019832 sodium triphosphate Nutrition 0.000 claims description 9
- 150000004677 hydrates Chemical class 0.000 claims description 8
- BCKXLBQYZLBQEK-KVVVOXFISA-M Sodium oleate Chemical compound [Na+].CCCCCCCC\C=C/CCCCCCCC([O-])=O BCKXLBQYZLBQEK-KVVVOXFISA-M 0.000 claims description 7
- LWIHDJKSTIGBAC-UHFFFAOYSA-K tripotassium phosphate Chemical compound [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 claims description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 6
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 6
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 6
- 229940005740 hexametaphosphate Drugs 0.000 claims description 6
- 239000011591 potassium Substances 0.000 claims description 6
- 229910052700 potassium Inorganic materials 0.000 claims description 6
- 238000007789 sealing Methods 0.000 claims description 6
- UNXRWKVEANCORM-UHFFFAOYSA-I triphosphate(5-) Chemical compound [O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O UNXRWKVEANCORM-UHFFFAOYSA-I 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- 150000001875 compounds Chemical class 0.000 claims description 5
- 150000003013 phosphoric acid derivatives Chemical class 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- 230000001699 photocatalysis Effects 0.000 claims description 4
- 238000007146 photocatalysis Methods 0.000 claims description 4
- 239000011819 refractory material Substances 0.000 claims description 4
- 239000004254 Ammonium phosphate Substances 0.000 claims description 3
- FVFJGQJXAWCHIE-UHFFFAOYSA-N [4-(bromomethyl)phenyl]methanamine Chemical compound NCC1=CC=C(CBr)C=C1 FVFJGQJXAWCHIE-UHFFFAOYSA-N 0.000 claims description 3
- LFVGISIMTYGQHF-UHFFFAOYSA-N ammonium dihydrogen phosphate Chemical compound [NH4+].OP(O)([O-])=O LFVGISIMTYGQHF-UHFFFAOYSA-N 0.000 claims description 3
- 229910000387 ammonium dihydrogen phosphate Inorganic materials 0.000 claims description 3
- 229910000148 ammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019289 ammonium phosphates Nutrition 0.000 claims description 3
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical compound [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 claims description 3
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Inorganic materials [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 claims description 3
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 claims description 3
- 229910000331 cadmium sulfate Inorganic materials 0.000 claims description 3
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 3
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 3
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical compound [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 claims description 3
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 claims description 3
- 235000019837 monoammonium phosphate Nutrition 0.000 claims description 3
- 229910000402 monopotassium phosphate Inorganic materials 0.000 claims description 3
- 235000019796 monopotassium phosphate Nutrition 0.000 claims description 3
- 229910000403 monosodium phosphate Inorganic materials 0.000 claims description 3
- 235000019799 monosodium phosphate Nutrition 0.000 claims description 3
- NMHMNPHRMNGLLB-UHFFFAOYSA-N phloretic acid Chemical compound OC(=O)CCC1=CC=C(O)C=C1 NMHMNPHRMNGLLB-UHFFFAOYSA-N 0.000 claims description 3
- 229940096992 potassium oleate Drugs 0.000 claims description 3
- 229910000160 potassium phosphate Inorganic materials 0.000 claims description 3
- 235000011009 potassium phosphates Nutrition 0.000 claims description 3
- MLICVSDCCDDWMD-KVVVOXFISA-M potassium;(z)-octadec-9-enoate Chemical compound [K+].CCCCCCCC\C=C/CCCCCCCC([O-])=O MLICVSDCCDDWMD-KVVVOXFISA-M 0.000 claims description 3
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 claims description 3
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 3
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 3
- 229910000162 sodium phosphate Inorganic materials 0.000 claims description 3
- 239000001488 sodium phosphate Substances 0.000 claims description 3
- 235000011008 sodium phosphates Nutrition 0.000 claims description 3
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 3
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 claims description 3
- 238000003828 vacuum filtration Methods 0.000 claims description 3
- PJNZPQUBCPKICU-UHFFFAOYSA-N phosphoric acid;potassium Chemical compound [K].OP(O)(O)=O PJNZPQUBCPKICU-UHFFFAOYSA-N 0.000 claims description 2
- -1 hydroxyl cadmium phosphate Chemical compound 0.000 abstract description 19
- 239000000243 solution Substances 0.000 description 16
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- 235000021317 phosphate Nutrition 0.000 description 10
- 239000000463 material Substances 0.000 description 8
- 230000009970 fire resistant effect Effects 0.000 description 7
- OOSZCNKVJAVHJI-UHFFFAOYSA-N 1-[(4-fluorophenyl)methyl]piperazine Chemical compound C1=CC(F)=CC=C1CN1CCNCC1 OOSZCNKVJAVHJI-UHFFFAOYSA-N 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 229940074545 sodium dihydrogen phosphate dihydrate Drugs 0.000 description 4
- 239000002994 raw material Substances 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 239000003995 emulsifying agent Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 238000011031 large-scale manufacturing process Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 235000007686 potassium Nutrition 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 230000006978 adaptation Effects 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 239000003063 flame retardant Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000012450 pharmaceutical intermediate Substances 0.000 description 1
- GNSKLFRGEWLPPA-UHFFFAOYSA-M potassium dihydrogen phosphate Chemical compound [K+].OP(O)([O-])=O GNSKLFRGEWLPPA-UHFFFAOYSA-M 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 238000000967 suction filtration Methods 0.000 description 1
Images
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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
- C01B25/00—Phosphorus; Compounds thereof
- C01B25/16—Oxyacids of phosphorus; Salts thereof
- C01B25/26—Phosphates
- C01B25/37—Phosphates of heavy metals
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H13/00—Pulp or paper, comprising synthetic cellulose or non-cellulose fibres or web-forming material
- D21H13/36—Inorganic fibres or flakes
- D21H13/46—Non-siliceous fibres, e.g. from metal oxides
-
- D—TEXTILES; PAPER
- D21—PAPER-MAKING; PRODUCTION OF CELLULOSE
- D21H—PULP COMPOSITIONS; PREPARATION THEREOF NOT COVERED BY SUBCLASSES D21C OR D21D; IMPREGNATING OR COATING OF PAPER; TREATMENT OF FINISHED PAPER NOT COVERED BY CLASS B31 OR SUBCLASS D21G; PAPER NOT OTHERWISE PROVIDED FOR
- D21H21/00—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties
- D21H21/14—Non-fibrous material added to the pulp, characterised by its function, form or properties; Paper-impregnating or coating material, characterised by its function, form or properties characterised by function or properties in or on the paper
- D21H21/34—Ignifugeants
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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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- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
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Abstract
The invention relates to a hydroxyl cadmium phosphate super-long nanowire and a preparation method and application thereof. The cadmium hydroxyphosphate ultra-long nanowire consists of Cd5(PO4)3OH, diameter of 2-100 nm and length of 10-1000 μm.
Description
Technical Field
The invention relates to a hydroxyl cadmium phosphate super-long nanowire and a preparation method and application thereof, belonging to the field of nano material preparation.
Background
Of the basic phosphates, cadmium hydroxyphosphate (Cd)5(PO4)3(OH)) has attracted the attention of researchers due to the structural characteristics, thermal behavior, spectral characteristics and the like, researchers have synthesized cadmium hydroxyphosphate materials with different morphologies, such as needle-shaped morphology or columnar morphology, by different methods, and have also studied the relationship between the morphology, crystallinity, crystal phase and the like of the cadmium hydroxyphosphate material and preparation conditions. But instead of the other end of the tubeSo far, the report of the hydroxyl cadmium phosphate super-long nanowire is not found in the literature.
Cadmium hydroxyphosphate is useful as a catalyst, fine chemical, pharmaceutical intermediate, and material intermediate; can also be used as phosphorescent material, and has special optical properties. Therefore, the research on the hydroxyl cadmium phosphate material has important academic and application values.
Disclosure of Invention
Therefore, the invention aims to provide the hydroxyl cadmium phosphate super-long nanowire and the preparation method and application thereof.
In one aspect, the invention provides a cadmium hydroxyphosphate ultra-long nanowire, and the cadmium hydroxyphosphate ultra-long nanowire consists of Cd5(PO4)3OH, diameter of 2-100 nm and length of 10-1000 μm.
Preferably, the cadmium hydroxyphosphate ultra-long nanowire has a diameter of 2-100 nm and a length of 200-1000 μm.
On the other hand, the invention provides a preparation method of the hydroxyl cadmium phosphate super-long nanowire, which comprises the following steps:
(1) under stirring, firstly adding oleate into the water-soluble cadmium salt aqueous solution, and then adding the water-soluble phosphorus source aqueous solution to obtain a precursor suspension;
(2) pouring the precursor suspension into a high-temperature high-pressure reaction kettle, sealing, and carrying out hydrothermal treatment at the temperature of 100-250 ℃ for 1-72 hours to obtain a product;
(3) separating the obtained product, and washing with ethanol and water to obtain the cadmium hydroxyphosphate ultra-long nanowire.
In the invention, water-soluble cadmium salt is used as a cadmium source, water-soluble phosphate is used as a phosphorus source, oleate is used as a reactant and an emulsifier, and water is used as a solvent, and a reaction precursor suspension is obtained after mixing and stirring at room temperature; carrying out hydrothermal treatment on the reaction precursor suspension, separating, and washing with ethanol and water to obtain the cadmium hydroxyphosphate ultra-long nanowire
Preferably, the oleate is at least one of sodium oleate, potassium oleate and ammonium oleate; the concentration of the oleate in the precursor suspension is 0.01-5 mol/L, preferably 0.1-2 mol/L.
Preferably, the water-soluble phosphate includes, but is not limited to, at least one of sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium hexametaphosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium tripolyphosphate, potassium hexametaphosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium tripolyphosphate, ammonium hexametaphosphate, and/or hydrates of the above compounds; the molar concentration of the water-soluble phosphate in the precursor suspension is 0.01-10 mol/L, and preferably 0.02-2 mol/L.
Preferably, the water-soluble cadmium salt is at least one of cadmium chloride, cadmium nitrate, cadmium sulfate, cadmium acetate and/or hydrates of the compounds; the concentration of the water-soluble cadmium salt in the precursor suspension is 0.01-10 mol/L, and preferably 0.02-2 mol/L.
Preferably, the molar ratio of the oleate to the water-soluble cadmium salt is 1: 10-20: 1, and preferably 1: 4-6: 1.
Preferably, the molar ratio of the water-soluble cadmium salt to the water-soluble phosphate is 1: 10-10: 1, and preferably 1: 2-2: 1.
The hydrothermal treatment temperature is 100-250 ℃, and the hydrothermal treatment time is 1-72 hours; preferably, the hydrothermal treatment temperature is 180-210 ℃, and the hydrothermal treatment time is 15-36 hours.
In the invention, the precursor suspension is subjected to hydro-thermal treatment to obtain the hydroxyl cadmium phosphate ultra-long nanowire, the washing times with ethanol and water are determined according to requirements, and the washing times with ethanol and water are 2-3 times respectively.
In another aspect, the invention provides an application of the hydroxyl cadmium phosphate super-long nanowire in the fields of refractory materials, electronic devices, photocatalysis and energy. The cadmium hydroxyphosphate ultra-long nanowire refractory paper can be obtained by vacuum filtration of the cadmium hydroxyphosphate ultra-long nanowire. The thickness range of the cadmium hydroxyphosphate ultra-long nanowire refractory paper can be 20-2000 mu m, and preferably 100-500 mu m.
Has the advantages that:
according to the invention, the hydroxyl cadmium phosphate super-long nanowire is prepared by adopting oleate, so that the preparation method has the advantages of simple process, low cost and the like, and is a preparation method suitable for large-scale production. The cadmium hydroxyphosphate ultra-long nanowire prepared by the method has an ultra-high length-diameter ratio and good flexibility, can be used for preparing high-strength and high-flexibility inorganic refractory paper and three-dimensional cadmium hydroxyphosphate nanostructured materials, and has good application prospects in the fields of refractory materials, electronic devices, photocatalysis, energy sources and the like. The ultra-long nanowire can be used as an ideal two-dimensional film material and a building unit of a three-dimensional material in a plurality of shapes due to the ultra-high length-diameter ratio.
Drawings
FIG. 1 is a Scanning Electron Microscope (SEM) image of cadmium hydroxyphosphate ultra-long nanowires prepared in example 1;
FIG. 2 is an X-ray diffraction (XRD) pattern of the cadmium hydroxyphosphate ultra-long nanowires prepared in example 1;
FIG. 3 is a Scanning Electron Microscope (SEM) image of the cadmium hydroxyphosphate ultra-long nanowires prepared in example 2;
FIG. 4 is a Scanning Electron Microscope (SEM) image of cadmium hydroxyphosphate ultra-long nanowires prepared in example 3;
FIG. 5 is a Scanning Electron Microscope (SEM) image of cadmium hydroxyphosphate ultra-long nanowires prepared in example 4;
FIG. 6 is a Scanning Electron Microscope (SEM) image of the novel fire-resistant paper prepared by a suction filtration method by using the cadmium hydroxyphosphate ultra-long nanowire prepared in example 4 as a raw material;
FIG. 7 is a digital picture of the cadmium hydroxyphosphate ultra-long nanowire-based refractory paper synthesized in example 4;
fig. 8 is a fire-resistant experiment digital picture of the cadmium hydroxyphosphate ultra-long nanowire-based refractory paper.
Detailed Description
The present invention is further illustrated by the following examples, which are to be understood as merely illustrative of, and not restrictive on, the present invention.
The invention provides a preparation method of a cadmium hydroxyphosphate ultra-long nanowire, which takes oleate as a reactant and an emulsifier, water-soluble cadmium salt as a cadmium source, water-soluble phosphate as a phosphorus source and water as a solvent, and after mixing and stirring aqueous solutions at room temperature, a reaction precursor suspension is obtained; and carrying out hydrothermal treatment on the obtained reaction precursor suspension, separating, and washing with ethanol and water to obtain the cadmium hydroxyphosphate ultra-long nanowire.
The composition of the hydroxyl cadmium phosphate super-long nanowire prepared by the method is Cd5(PO4)3OH, the diameter of the nanowire can be 2-100 nanometers, and the length can be 10-1000 micrometers.
In the invention, the oleate is at least one of sodium oleate, potassium oleate and ammonium oleate, and the concentration of the oleate in the reaction precursor suspension is 0.01-5 mol/L, preferably 0.1-2 mol/L. The cadmium hydroxyphosphate ultra-long nanowire can be prepared by adopting one oleate or a mixture of two or more oleates.
The water-soluble cadmium salt includes, but is not limited to cadmium chloride, cadmium nitrate, cadmium acetate, cadmium sulfate and/or hydrates thereof, it being understood that one water-soluble cadmium salt may be used, or a mixture of two or more water-soluble cadmium salts may be used; in addition, hydrates of water-soluble cadmium salts, such as CdCl, can also be used2·2.5H2And O. The molar concentration of the water-soluble cadmium salt in the reaction precursor suspension is 0.01-10 mol/L, and preferably 0.02-2 mol/L.
The water-soluble phosphorus source comprises, but is not limited to, sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium hexametaphosphate, potassium phosphate, dipotassium hydrogen phosphate, monopotassium phosphate, potassium tripolyphosphate, potassium hexametaphosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium tripolyphosphate, ammonium hexametaphosphate and/or hydrates of the above compounds, one water-soluble phosphate can be used, and a mixture of two or more water-soluble phosphates can also be used; in addition, hydrates of water-soluble phosphates, such as NaH, may be employed2PO4·2H2And O. The molar concentration of the water-soluble phosphate in the reaction precursor suspension is 0.01-10 mol/L, and preferably 0.02-2 mol/L.
In alternative embodiments, the molar ratio of oleate to water-soluble cadmium salt may be 1:10 to 20:1, preferably 1:4 to 6: 1.
In alternative embodiments, the molar ratio of the water-soluble cadmium salt to the water-soluble phosphate salt may be 1:10 to 10:1, preferably 1:2 to 2: 1.
In an alternative embodiment, the temperature of the hydrothermal treatment may be 100 to 250 ℃, preferably 180 to 210 ℃.
In an alternative embodiment, the time of the hydrothermal treatment may be 1 to 72 hours, preferably 15 to 36 hours.
In the invention, the product obtained after hydrothermal treatment is separated and washed by ethanol and water to obtain the hydroxyl cadmium phosphate super-long nanowire; the separation method comprises centrifugal separation, filtration separation, standing precipitation separation and the like; the times of washing with ethanol and water are determined according to needs, and the washing with ethanol and water is generally carried out for 2-3 times respectively.
The present invention will be described in detail by way of examples. It is also to be understood that the following examples are illustrative of the present invention and are not to be construed as limiting the scope of the invention, and that certain insubstantial modifications and adaptations of the invention by those skilled in the art may be made in light of the above teachings. The specific process parameters and the like in the following examples are also only one example of suitable ranges, and the skilled person can make a selection within the suitable ranges through the description herein, and are not limited to the specific values exemplified below.
Example 1
At room temperature, 0.475 g of CdCl2·2.5H2Dissolving O in 25 ml of deionized water to form a solution A;
2.436 g of sodium oleate was dissolved in 25 ml of deionized water to form solution B;
dropwise adding the solution A into the solution B while stirring, and after stirring for 20 minutes at room temperature, adding 25 ml of an aqueous solution containing 0.281g of sodium dihydrogen phosphate dihydrate to obtain a reaction precursor suspension;
then transferring the reaction precursor suspension into a 100 ml reaction kettle, sealing, carrying out hydrothermal treatment at 180 ℃ for 24 hours, and then naturally cooling to room temperature;
and (3) centrifugally separating the product, and washing the product for 2 times by using ethanol and deionized water respectively to obtain the hydroxyl cadmium phosphate ultra-long nanowire. As can be seen from the attached figure 1, in most cases, a plurality of cadmium hydroxyphosphate ultra-long nanowires are self-assembled along the length direction to form cadmium hydroxyphosphate ultra-long nanowire bundles. The X-ray diffraction (XRD) result shows that the product contains cadmium hydroxyphosphate, and as shown in figure 2, the prepared cadmium hydroxyphosphate is highly coincident with the spectrogram of standard card PDF #14-0302 and belongs to the hexagonal system.
Example 2
At room temperature, 0.475 g of CdCl2·2.5H2Dissolving O in 25 ml of deionized water to form a solution A;
2.741 g of sodium oleate was dissolved in 25 ml of deionized water to form solution B;
dropwise adding the solution A into the solution B while stirring, and after stirring for 20 minutes at room temperature, adding 25 ml of an aqueous solution containing 0.281g of sodium dihydrogen phosphate dihydrate to obtain a reaction precursor suspension;
then transferring the reaction precursor suspension into a 100 ml reaction kettle, sealing, carrying out hydrothermal treatment at 180 ℃ for 24 hours, and then naturally cooling to room temperature;
and (3) centrifugally separating the product, and washing the product for 2 times by using ethanol and deionized water respectively to obtain the hydroxyl cadmium phosphate ultra-long nanowire as shown in the attached figure 3.
Example 3
At room temperature, 0.475 g of CdCl2·2.5H2Dissolving O in 25 ml of deionized water to form a solution A;
3.046 g of sodium oleate was dissolved in 25 ml of deionized water to form solution B;
dropwise adding the solution A into the solution B while stirring, and after stirring for 20 minutes at room temperature, adding 25 ml of an aqueous solution containing 0.281g of sodium dihydrogen phosphate dihydrate to obtain a reaction precursor suspension;
then transferring the reaction precursor suspension into a 100 ml reaction kettle, sealing, carrying out hydrothermal treatment at 180 ℃ for 24 hours, and then naturally cooling to room temperature;
and (3) centrifugally separating the product, and washing the product for 2 times by using ethanol and deionized water respectively to obtain the hydroxyl cadmium phosphate ultra-long nanowire as shown in the attached figure 4.
Example 4
At room temperature, 0.475 g of CdCl2·2.5H2Dissolving O in 25 ml of deionized water to form a solution A;
2.436 g of sodium oleate was dissolved in 25 ml of deionized water to form solution B;
dropwise adding the solution A into the solution B while stirring, and after stirring for 20 minutes at room temperature, adding 25 ml of an aqueous solution containing 0.281g of sodium dihydrogen phosphate dihydrate to obtain a reaction precursor suspension;
then transferring the reaction precursor suspension into a 100 ml reaction kettle, sealing, carrying out hydrothermal treatment at 200 ℃ for 36 hours, and then naturally cooling to room temperature;
and centrifugally separating the product, and washing the product for 2 times by using ethanol and deionized water respectively to obtain the hydroxyl cadmium phosphate ultra-long nanowire as shown in the attached figure 5.
The cadmium hydroxyphosphate overlength nanowire is used as a raw material, the cadmium hydroxyphosphate overlength nanowire refractory paper is prepared by a vacuum filtration method, and a scanning electron micrograph of the refractory paper is shown as an attached figure 6. As can be seen from FIG. 6, the cadmium hydroxyphosphate ultra-long nanowires are mutually assembled and stacked to form the refractory paper with a compact structure. The size of the cadmium hydroxyphosphate ultra-long nanowire fire-resistant paper is shown in figure 7, the paper is circular with the diameter approximately equal to 9.4cm, the paper is cut into strips with the size of 7.3cm multiplied by 2.1cm multiplied by 0.059mm by a paper cutter to carry out fire-resistant experiments, and as a result, the cadmium hydroxyphosphate ultra-long nanowire fire-resistant paper is burnt on the flame of an alcohol lamp, the fire-resistant paper only has a small carbonization phenomenon (because the surface of the cadmium hydroxyphosphate ultra-long nanowire has a small amount of oleic acid groups for adsorption), does not burn, and has good fire-resistant and flame-retardant properties as shown in figure 8.
Industrial applicability: the preparation method has the advantages of simple process, low cost and the like, and is expected to realize large-scale production. The hydroxyl cadmium phosphate super-long nanowire prepared by the invention is an excellent raw material for constructing a macroscopically assembled two-dimensional film or three-dimensional block functional material. The hydroxyl cadmium phosphate super-long nanowire prepared by the method can be used for preparing high-flexibility inorganic refractory paper and high-performance three-dimensional functional materials, and has good application prospects in the fields of refractory materials, electronic devices, photocatalysis, energy sources and the like.
Claims (9)
1. The cadmium hydroxyphosphate ultra-long nanowire is characterized in that the cadmium hydroxyphosphate ultra-long nanowire consists of Cd5(PO4)3OH, diameter of 2-100 nm and length of 10-1000 μm.
2. The method for preparing the cadmium hydroxyphosphate ultra-long nanowire according to claim 1, which comprises the following steps:
(1) adding a water-soluble cadmium salt aqueous solution into an oleate aqueous solution under stirring, and then adding a water-soluble phosphorus source aqueous solution to obtain a precursor suspension;
(2) pouring the precursor suspension into a high-temperature high-pressure reaction kettle, sealing, and carrying out hydrothermal treatment at the temperature of 100-250 ℃ for 1-72 hours to obtain a product;
(3) separating the obtained product, and washing with ethanol and water to obtain the cadmium hydroxyphosphate ultra-long nanowire.
3. The method according to claim 2, wherein the oleate is at least one of sodium oleate, potassium oleate and ammonium oleate, and the concentration of oleate in the precursor suspension is 0.01 to 5 mol/l, preferably 0.1 to 2 mol/l.
4. The method of claim 2, wherein the water-soluble phosphate comprises, but is not limited to, at least one of sodium phosphate, sodium dihydrogen phosphate, disodium hydrogen phosphate, sodium tripolyphosphate, sodium hexametaphosphate, potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, potassium tripolyphosphate, potassium hexametaphosphate, ammonium phosphate, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, ammonium tripolyphosphate, ammonium hexametaphosphate, and/or hydrates of the above compounds; the molar concentration of the water-soluble phosphate in the precursor suspension is 0.01-10 mol/L, and preferably 0.02-2 mol/L.
5. The preparation method according to claim 2, wherein the water-soluble cadmium salt is at least one of cadmium chloride, cadmium nitrate, cadmium sulfate, cadmium acetate and/or hydrates of the above compounds; the concentration of the water-soluble cadmium salt in the precursor suspension is 0.01-10 mol/L, and preferably 0.02-2 mol/L.
6. The preparation method of claim 2, wherein the molar ratio of the oleate to the water-soluble cadmium salt is 1:10 to 20:1, preferably 1:4 to 6: 1.
7. The method according to any one of claims 2 to 6, wherein the molar ratio of the water-soluble cadmium salt to the water-soluble phosphate salt is 1:10 to 10:1, preferably 1:2 to 2: 1.
8. The cadmium hydroxyphosphate ultra-long nanowire refractory paper is characterized by being obtained by vacuum filtration of the cadmium hydroxyphosphate ultra-long nanowire disclosed by claim 1.
9. The use of the ultralong cadmium hydroxyphosphate nanowires of claim 1 in the fields of refractory materials, electronic devices, photocatalysis and energy.
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| CN106522015A (en) * | 2016-10-20 | 2017-03-22 | 中国科学院上海硅酸盐研究所 | Hydroxyapatite overlength nanowire flameproof paper with waterproof function |
| CN106853961A (en) * | 2016-12-02 | 2017-06-16 | 中国科学院上海硅酸盐研究所 | Hydroxyapatite nano line, nano wire assembling network structure and preparation method thereof |
| CN107487765A (en) * | 2017-07-06 | 2017-12-19 | 中国科学院上海硅酸盐研究所 | A kind of hydroxyapatite overlong nanowire base fluorescence incombustible paper and its application |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106522015A (en) * | 2016-10-20 | 2017-03-22 | 中国科学院上海硅酸盐研究所 | Hydroxyapatite overlength nanowire flameproof paper with waterproof function |
| CN106853961A (en) * | 2016-12-02 | 2017-06-16 | 中国科学院上海硅酸盐研究所 | Hydroxyapatite nano line, nano wire assembling network structure and preparation method thereof |
| CN107487765A (en) * | 2017-07-06 | 2017-12-19 | 中国科学院上海硅酸盐研究所 | A kind of hydroxyapatite overlong nanowire base fluorescence incombustible paper and its application |
Non-Patent Citations (4)
| Title |
|---|
| 张元广等: ""在油酸表面活性剂中制备高晶度纳米CaCO3微晶"" * |
| 张元广等: "《在油酸表面活性剂中制备高晶度纳米CaCO3微晶》" * |
| 管文菲: ""磷酸盐材料的结构调控及光催化性能研究"" * |
| 管文菲: "磷酸盐材料的结构调控及光催化性能研究" * |
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