CN114772567B - Hydroxyapatite nanoparticle, preparation method and defluorination application thereof - Google Patents
Hydroxyapatite nanoparticle, preparation method and defluorination application thereof Download PDFInfo
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- 229910052588 hydroxylapatite Inorganic materials 0.000 title claims abstract description 115
- XYJRXVWERLGGKC-UHFFFAOYSA-D pentacalcium;hydroxide;triphosphate Chemical compound [OH-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O XYJRXVWERLGGKC-UHFFFAOYSA-D 0.000 title claims abstract description 111
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 46
- 238000006115 defluorination reaction Methods 0.000 title abstract description 18
- 238000002360 preparation method Methods 0.000 title abstract description 13
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims abstract description 145
- 239000012266 salt solution Substances 0.000 claims abstract description 77
- 159000000007 calcium salts Chemical class 0.000 claims abstract description 47
- 150000003017 phosphorus Chemical class 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 34
- 239000000243 solution Substances 0.000 claims abstract description 17
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 13
- 229910019142 PO4 Inorganic materials 0.000 claims abstract description 11
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000002156 mixing Methods 0.000 claims abstract description 8
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims abstract description 8
- 239000010452 phosphate Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 6
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 4
- 238000000034 method Methods 0.000 claims description 36
- 239000000463 material Substances 0.000 claims description 16
- 238000009388 chemical precipitation Methods 0.000 claims description 14
- 239000011575 calcium Substances 0.000 claims description 12
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 claims description 10
- 238000001308 synthesis method Methods 0.000 claims description 10
- 230000015572 biosynthetic process Effects 0.000 claims description 7
- 238000003786 synthesis reaction Methods 0.000 claims description 7
- BHPQYMZQTOCNFJ-UHFFFAOYSA-N Calcium cation Chemical compound [Ca+2] BHPQYMZQTOCNFJ-UHFFFAOYSA-N 0.000 claims description 6
- OSGAYBCDTDRGGQ-UHFFFAOYSA-L calcium sulfate Chemical compound [Ca+2].[O-]S([O-])(=O)=O OSGAYBCDTDRGGQ-UHFFFAOYSA-L 0.000 claims description 6
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 5
- MNNHAPBLZZVQHP-UHFFFAOYSA-N diammonium hydrogen phosphate Chemical compound [NH4+].[NH4+].OP([O-])([O-])=O MNNHAPBLZZVQHP-UHFFFAOYSA-N 0.000 claims description 5
- 229910000388 diammonium phosphate Inorganic materials 0.000 claims description 5
- 235000019838 diammonium phosphate Nutrition 0.000 claims description 5
- 239000011574 phosphorus Substances 0.000 claims description 5
- 229910052698 phosphorus Inorganic materials 0.000 claims description 5
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 3
- VSGNNIFQASZAOI-UHFFFAOYSA-L calcium acetate Chemical compound [Ca+2].CC([O-])=O.CC([O-])=O VSGNNIFQASZAOI-UHFFFAOYSA-L 0.000 claims description 3
- 239000001639 calcium acetate Substances 0.000 claims description 3
- 235000011092 calcium acetate Nutrition 0.000 claims description 3
- 229960005147 calcium acetate Drugs 0.000 claims description 3
- 239000001110 calcium chloride Substances 0.000 claims description 3
- 229910001628 calcium chloride Inorganic materials 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
- 239000007788 liquid Substances 0.000 claims description 3
- 239000002245 particle Substances 0.000 abstract description 40
- 239000013078 crystal Substances 0.000 abstract description 29
- 238000001179 sorption measurement Methods 0.000 abstract description 13
- 230000002776 aggregation Effects 0.000 abstract description 11
- 238000005054 agglomeration Methods 0.000 abstract description 7
- 230000001105 regulatory effect Effects 0.000 abstract description 6
- 239000000725 suspension Substances 0.000 abstract description 5
- 238000011161 development Methods 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- 230000000052 comparative effect Effects 0.000 description 13
- -1 rare earth ions Chemical class 0.000 description 13
- 230000000694 effects Effects 0.000 description 12
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 11
- 238000001027 hydrothermal synthesis Methods 0.000 description 11
- 230000009471 action Effects 0.000 description 10
- 239000006185 dispersion Substances 0.000 description 7
- 238000002474 experimental method Methods 0.000 description 7
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 6
- 239000012670 alkaline solution Substances 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 6
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 description 6
- 230000007547 defect Effects 0.000 description 5
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 5
- 239000005696 Diammonium phosphate Substances 0.000 description 4
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000011737 fluorine Substances 0.000 description 4
- 229910052731 fluorine Inorganic materials 0.000 description 4
- 230000012010 growth Effects 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 238000001000 micrograph Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 239000007787 solid Substances 0.000 description 4
- QORWJWZARLRLPR-UHFFFAOYSA-H tricalcium bis(phosphate) Chemical compound [Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O QORWJWZARLRLPR-UHFFFAOYSA-H 0.000 description 4
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 3
- 229910052791 calcium Inorganic materials 0.000 description 3
- 229910001424 calcium ion Inorganic materials 0.000 description 3
- WOWHHFRSBJGXCM-UHFFFAOYSA-M cetyltrimethylammonium chloride Chemical compound [Cl-].CCCCCCCCCCCCCCCC[N+](C)(C)C WOWHHFRSBJGXCM-UHFFFAOYSA-M 0.000 description 3
- 230000001276 controlling effect Effects 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 239000002270 dispersing agent Substances 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000000227 grinding Methods 0.000 description 3
- VSIIXMUUUJUKCM-UHFFFAOYSA-D pentacalcium;fluoride;triphosphate Chemical compound [F-].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[Ca+2].[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O.[O-]P([O-])([O-])=O VSIIXMUUUJUKCM-UHFFFAOYSA-D 0.000 description 3
- 230000035484 reaction time Effects 0.000 description 3
- 229920002477 rna polymer Polymers 0.000 description 3
- 239000011775 sodium fluoride Substances 0.000 description 3
- 235000013024 sodium fluoride Nutrition 0.000 description 3
- 238000000733 zeta-potential measurement Methods 0.000 description 3
- RNMDNPCBIKJCQP-UHFFFAOYSA-N 5-nonyl-7-oxabicyclo[4.1.0]hepta-1,3,5-trien-2-ol Chemical compound C(CCCCCCCC)C1=C2C(=C(C=C1)O)O2 RNMDNPCBIKJCQP-UHFFFAOYSA-N 0.000 description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 108020004414 DNA Proteins 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 239000002202 Polyethylene glycol Substances 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 239000012620 biological material Substances 0.000 description 2
- 210000000988 bone and bone Anatomy 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 239000001506 calcium phosphate Substances 0.000 description 2
- 229910000389 calcium phosphate Inorganic materials 0.000 description 2
- 235000011010 calcium phosphates Nutrition 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 2
- 235000020971 citrus fruits Nutrition 0.000 description 2
- 235000019797 dipotassium phosphate Nutrition 0.000 description 2
- 229910000396 dipotassium phosphate Inorganic materials 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 235000019800 disodium phosphate Nutrition 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 229910052587 fluorapatite Inorganic materials 0.000 description 2
- 229940077441 fluorapatite Drugs 0.000 description 2
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical class [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 2
- 229910052739 hydrogen Chemical group 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001506 inorganic fluoride Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000010979 pH adjustment Methods 0.000 description 2
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 2
- 229920001223 polyethylene glycol Polymers 0.000 description 2
- LWIHDJKSTIGBAC-UHFFFAOYSA-K potassium phosphate Substances [K+].[K+].[K+].[O-]P([O-])([O-])=O LWIHDJKSTIGBAC-UHFFFAOYSA-K 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 238000004062 sedimentation Methods 0.000 description 2
- 239000001488 sodium phosphate Substances 0.000 description 2
- 239000013598 vector Substances 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- 229910014497 Ca10(PO4)6(OH)2 Inorganic materials 0.000 description 1
- 229910052684 Cerium Inorganic materials 0.000 description 1
- 102000053602 DNA Human genes 0.000 description 1
- 244000208060 Lawsonia inermis Species 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- IGFHQQFPSIBGKE-UHFFFAOYSA-N Nonylphenol Natural products CCCCCCCCCC1=CC=C(O)C=C1 IGFHQQFPSIBGKE-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 229910052586 apatite Inorganic materials 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 239000003462 bioceramic Substances 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 238000002296 dynamic light scattering Methods 0.000 description 1
- 239000005447 environmental material Substances 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 238000001415 gene therapy Methods 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 235000010755 mineral Nutrition 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- SNQQPOLDUKLAAF-UHFFFAOYSA-N nonylphenol Chemical compound CCCCCCCCCC1=CC=CC=C1O SNQQPOLDUKLAAF-UHFFFAOYSA-N 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229940051841 polyoxyethylene ether Drugs 0.000 description 1
- 229920000056 polyoxyethylene ether Polymers 0.000 description 1
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 210000002966 serum Anatomy 0.000 description 1
- DAJSVUQLFFJUSX-UHFFFAOYSA-M sodium;dodecane-1-sulfonate Chemical compound [Na+].CCCCCCCCCCCCS([O-])(=O)=O DAJSVUQLFFJUSX-UHFFFAOYSA-M 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 230000017423 tissue regeneration Effects 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
Classifications
-
- 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
- C01B25/32—Phosphates of magnesium, calcium, strontium, or barium
- C01B25/325—Preparation by double decomposition
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/04—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium
- B01J20/048—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising compounds of alkali metals, alkaline earth metals or magnesium containing phosphorus, e.g. phosphates, apatites, hydroxyapatites
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/30—Processes for preparing, regenerating, or reactivating
-
- 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
-
- 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
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
-
- C—CHEMISTRY; METALLURGY
- 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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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Analytical Chemistry (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Manufacturing & Machinery (AREA)
- Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Solid-Sorbent Or Filter-Aiding Compositions (AREA)
Abstract
The invention discloses a hydroxyapatite nanoparticle, a preparation method thereof and a defluorination application, wherein the preparation method of the hydroxyapatite nanoparticle comprises the following steps: (1) Dissolving soluble phosphate with water to prepare a phosphorus salt solution: (2) Dissolving soluble calcium salt with water to obtain calcium salt solution; (3) Adding citric acid into the calcium salt solution, mixing and stirring, then dropwise adding the phosphorus salt solution, and adjusting the pH value of the mixed solution to be alkaline after the dropwise adding is completed to obtain an alkaline mixed solution; (4) And synthesizing a product by taking the alkaline mixed solution as a precursor solution, centrifuging, and drying to obtain the hydroxyapatite nano particles. According to the invention, the crystal development and agglomeration degree of the hydroxyapatite are regulated and controlled through different adsorption forces of different crystal faces of the citric acid and the hydroxyapatite, and the synthesized hydroxyapatite nanoparticles have small particle size, can be rapidly dispersed in water, and have better suspension stability.
Description
Technical Field
The invention belongs to the technical field of materials, and particularly relates to a spherical hydroxyapatite nanoparticle, a preparation method thereof and application thereof in the field of inorganic fluoride ion removal.
Background
Hydroxyapatite (Ca 10(PO4)6(OH)2, abbreviated as HAP) is a bioceramic material with extremely wide application, and is commonly used as a bone tissue repair material and a carrier of targeted drugs because of its consistency with human teeth and bone components. In the fields of medicine and biological materials, nano hydroxyapatite can be used as a gene vector for gene therapy, and in order to solve the problem that nano hydroxyapatite crystals are easy to agglomerate, li Wo and the like modify HAP (HAP) synthesized by utilizing CTAB (cetyl trimethyl ammonium chloride), PEG (polyethylene glycol) 2000 and human serum, and the result shows that the CTAB surface modified hydroxyapatite nano particles have better dispersibility and suspension stability and stronger DNA/RNA (deoxyribonucleic acid)/RNA (ribonucleic acid) binding capacity compared with other two surfactant complexes. The nano hydroxyapatite nano particles have wide application prospect in the aspect of gene vectors.
Except for the application in the aspect of biological materials, as the microscopic dimensions of the OH - and the F - ions are very close, the hydroxyl groups in the hydroxyapatite are easy to exchange with F-to generate fluorapatite with low solubility (the solubility product constant (K sp（25℃）=6.3×10-59) of the hydroxyapatite and the fluorapatite (K sp（25℃）=1×10-120)) so as to achieve the purpose of fixing inorganic F-.
Hydroxyapatite has a certain reserve in the nature and is an important type in an apatite mineral family, but natural hydroxyapatite has the defects of serious crystal agglomeration phenomenon, less exposure of active sites and more impurities, and is difficult to be used for high-efficiency defluorination. Current research on hydroxyapatite defluorinating materials is mainly focused on two aspects:
Firstly, by compounding the material with high specific surface area with the hydroxyapatite material, the dispersity of the hydroxyapatite material is improved, and meanwhile, the defect of too small specific surface area is overcome. The disadvantage of this method is that materials with high specific surface area, such as graphene, carbon nanotubes, etc., are expensive and cannot be used on a large scale.
Secondly, metal ions are used for doping, crystal defects are formed, one or more of calcium, magnesium, aluminum, cerium, lanthanum, iron and other ions are used for replacing part of calcium ions, and a coordination effect is formed with F - to improve the defluorination effect; the disadvantage of this direction is that a lot of impurity ions are introduced into the effluent, secondary pollution is caused, and the cost of water treatment is affected by the price of part of rare earth ions.
Therefore, there is a need to provide a means for adjusting and controlling hydroxyapatite nanoparticles, which is capable of simultaneously achieving cost and environmental friendliness, effectively solving the serious condition of crystal agglomeration, improving the dispersity, and remarkably improving the defluorination efficiency compared with the traditional hydroxyapatite.
Disclosure of Invention
The present invention aims to solve at least one of the technical problems in the prior art described above. It is therefore an object of embodiments of the present invention to provide a method for effectively reducing the degree of crystal agglomeration of hydroxyapatite nanoparticles.
Another object of the embodiment of the invention is to provide a hydroxyapatite nanoparticle with small particle size and high dispersity.
It is still another object of the embodiment of the present invention to provide the use of the above hydroxyapatite nanoparticles as a defluorination material, since the product of the hydroxyapatite nanoparticles has high purity and does not contain harmful components, does not cause secondary pollution to raw water, and has a good application prospect in terms of inorganic fluoride ion removal.
The preparation method of the hydroxyapatite nano particle provided by the embodiment of the invention comprises the following steps:
(1) Dissolving soluble phosphate with water to prepare a phosphorus salt solution:
(2) Dissolving soluble calcium salt with water to obtain calcium salt solution;
(3) Adding citric acid into the calcium salt solution, mixing and stirring, then dropwise adding a phosphorus salt solution, and adjusting the pH value of the mixed solution to be alkaline after the dropwise adding is completed to obtain an alkaline mixed solution;
(4) And synthesizing a product by taking the alkaline mixed solution as a precursor solution, centrifuging, and drying to obtain the hydroxyapatite nano particles.
In the embodiment of the invention, in order to solve the problem that crystals of hydroxyapatite nano particles are easy to agglomerate in the related technology, the growth of the hydroxyapatite particles is regulated and controlled by utilizing three carboxyl groups and one hydroxyl group contained in a special structure-molecular structure of citric acid. Citric acid is a natural organic carboxylic acid with smaller molecular weight, is widely used in citrus fruits, can generate adsorption action with a plurality of crystal faces such as (001), (100) and (110) of hydroxyapatite crystals, and particularly comprises coordination action of citrate ions and calcium ions, electrostatic action, hydrogen bonding action with hydroxyl groups on the surface of the hydroxyapatite and other actions. When the hydroxyapatite modified by citric acid is dissolved in water, repulsive force (mainly electrostatic repulsive force and steric hindrance) is generated among crystal particles, so that the purpose of reducing the degree of crystal aggregation is achieved, the hydroxyapatite is rapidly dispersed in the water, and the hydroxyapatite has better suspension stability.
In some embodiments, the soluble phosphate salt is one or more of diammonium phosphate, disodium phosphate, or dipotassium phosphate. Preferably, the soluble phosphate is diammonium phosphate, which is favorable for releasing ammonium ions in the form of ammonia gas and improving the purity of the hydroxyapatite.
In some embodiments, the concentration of PO4 3+ in the phosphorus salt solution is 0.06-0.25 mol/L.
In some embodiments, the soluble calcium salt is one or more of calcium nitrate, calcium chloride, calcium sulfate, or calcium acetate. Preferably, the soluble calcium salt is calcium nitrate.
In some embodiments, the concentration of Ca 2+ in the calcium salt solution is 0.1-0.5 mol/L.
In some embodiments, the ratio of the calcium salt solution to the phosphorus salt solution in step (3) satisfies: the molar ratio of the calcium element to the phosphorus element is (1.55-1.85): 1. preferably, the molar ratio is 1.67:1, a step of; the molar ratio of the calcium and the phosphorus elements is controlled to be corresponding to the structure of the product, so that the synthesized product can be accurately controlled to be the high-purity hydroxyapatite.
In some embodiments, the citric acid is added in an amount of 0.01% -0.1% of the sum of the mass of the calcium salt solution and the mass of the phosphorus salt solution.
In the embodiment of the invention, the citric acid is uniformly adsorbed on the surface of the hydroxyapatite crystal nucleus by strictly controlling the adding amount, so that the crystal growth is inhibited, if the citric acid is excessively added, the cost is increased, the consumption of alkali liquor is increased during pH adjustment, and the negative charge on the surface of the hydroxyapatite crystal particle is excessively increased, so that fluoride ions are repelled to combine with the surface of the hydroxyapatite, and the defluorination effect is reduced.
In some embodiments, the pH in step (3) is 9-11.
In the step (3), the pH value is adjusted by an alkaline solution, wherein the alkaline solution is a NaOH solution or a KOH solution. Optionally, the concentration of the alkaline solution is: 1.0 mol/L. The embodiment of the invention can ensure that one of the important components of the hydroxyapatite is sufficiently supplied by regulating the pH, so that the yield of the product is ensured.
In some embodiments, the stirring rate in step (3) is 700-1000 r/min.
In some embodiments, the phosphorous salt solution is added at a rate of 1.0 to 1.5 mL/min.
In some embodiments, step (4) synthesis employs one or more combinations of hydrothermal synthesis, chemical precipitation, or ultrasonic synthesis.
In some embodiments, when the hydrothermal synthesis method is adopted in the step (4), the adding amount of the citric acid in the step (3) is 0.01% -0.05% of the sum of the mass of the calcium salt solution and the mass of the phosphorus salt solution.
In some embodiments, when the chemical precipitation method is adopted in the step (4), the adding amount of the citric acid in the step (3) is 0.01% -0.05% of the sum of the mass of the calcium salt solution and the mass of the phosphorus salt solution.
In some embodiments, when the ultrasonic synthesis method is adopted in the step (4), the adding amount of the citric acid in the step (3) is 0.03% -0.1% of the sum of the mass of the calcium salt solution and the mass of the phosphorus salt solution.
In some embodiments, the reaction temperature of the hydrothermal synthesis method is 120-160 ℃, and the reaction time is 4-10 h. The product synthesized by the hydrothermal synthesis method has smaller regular shape and size, and the size of the nano hydroxyapatite is concentrated to 10-100 nm.
In some embodiments, the chemical precipitation method is to seal, stand and age the alkaline mixed solution for 16-24 hours. The chemical precipitation method has low preparation cost, wide product particle size distribution and more crystal defects, and is more suitable for removing fluorine.
In some embodiments, the ultrasonic frequency of the ultrasonic synthesis method is 20-50 KHz, and the mixing time is 10-30 min.
According to the method provided by the embodiment of the invention, the product does not need to be calcined, so that the phenomenon that the calcium phosphate is generated by the hydroxyapatite in the calcining process in the related art is avoided, and the defluorination effect is further influenced.
The method of the embodiment of the invention does not need to carry out conventional washing steps on the product, and mainly aims to keep citric acid components as much as possible, adsorb more on the surface of the hydroxyapatite, improve the steric hindrance among particles, reduce the aggregation degree of the particles and further improve the dispersion stability of the hydroxyapatite particles in water.
The embodiment of the invention also provides the hydroxyapatite nano-particles prepared by the preparation method.
In some embodiments, the hydroxyapatite nanoparticles are spheroid in morphology, 10-100 nm in diameter, preferably 30-60 nm in diameter.
The embodiment of the invention also provides the application of the hydroxyapatite nano particle as a defluorination material.
The invention has the following beneficial effects:
(1) According to the embodiment of the invention, the crystal development and agglomeration degree of the citric acid and the hydroxyapatite are regulated and controlled by different adsorption forces of different crystal faces, and the synthesized hydroxyapatite nanoparticles have small particle size, can be rapidly dispersed in water, and have better suspension stability.
(2) The hydroxyapatite nanoparticle provided by the embodiment of the invention is green and environment-friendly, has no negative effect on the environment and organisms, does not cause secondary pollution to raw water, and has good application prospects in the aspect of environmental materials.
(3) In the preparation method of the hydroxyapatite nano particles, the prepared precursor liquid can adopt a plurality of synthesis methods, and different methods have positive effects, and the synthesis methods can be flexibly selected according to the product requirements and the use scenes or are combined by a plurality of synthesis methods.
Drawings
The foregoing and/or additional aspects and advantages of the present invention will become apparent and may be better understood from the following description of embodiments, taken in conjunction with the accompanying drawings.
FIG. 1 is a scanning electron microscope image of nano-hydroxyapatite particles prepared in example 1.
FIG. 2 shows the measurement result of the fluoride ion adsorbing capacity of nano-hydroxyapatite prepared in example 2.
FIG. 3 is a scanning electron microscope image of nano-hydroxyapatite particles prepared in example 2.
FIG. 4 shows the measurement result of the fluoride ion adsorbing capacity of nano-hydroxyapatite prepared in example 3.
FIG. 5 is a scanning electron microscope image of nano-hydroxyapatite particles prepared in example 3.
Fig. 6 shows Zeta potential values at neutral pH for five different hydroxyapatite particles.
Fig. 7 shows the defluorination effect of five different hydroxyapatite particles.
Detailed Description
The following detailed description of embodiments of the invention is exemplary and intended to be illustrative of the invention and not to be construed as limiting the invention.
The experimental methods used in the examples below are conventional methods unless otherwise specified.
Materials, reagents, devices and the like used in the following examples are commercially available unless otherwise specified.
The preparation method of the hydroxyapatite nano particle provided by the embodiment of the invention comprises the following steps:
(1) Dissolving soluble phosphate with water to prepare a phosphorus salt solution:
(2) Dissolving soluble calcium salt with water to obtain calcium salt solution;
(3) Adding citric acid into the calcium salt solution, mixing and stirring, then dropwise adding a phosphorus salt solution, and adjusting the pH value of the mixed solution to be alkaline after the dropwise adding is completed to obtain an alkaline mixed solution;
(4) And synthesizing a product by taking the alkaline mixed solution as a precursor solution, centrifuging, and drying to obtain the hydroxyapatite nano particles.
In the embodiment of the invention, in order to solve the problem that crystals of hydroxyapatite nano particles are easy to agglomerate in the related technology, the growth of the hydroxyapatite particles is regulated and controlled by utilizing three carboxyl groups and one hydroxyl group contained in a special structure-molecular structure of citric acid. Citric acid is a natural organic carboxylic acid with smaller molecular weight, is widely used in citrus fruits, can generate adsorption action with a plurality of crystal faces such as (001), (100) and (110) of hydroxyapatite crystals, and particularly comprises coordination action of citrate ions and calcium ions, electrostatic action, hydrogen bonding action with hydroxyl groups on the surface of the hydroxyapatite and other actions. When the hydroxyapatite modified by citric acid is dissolved in water, repulsive force (mainly electrostatic repulsive force and steric hindrance) is generated among crystal particles, so that the purpose of reducing the degree of crystal aggregation is achieved, the hydroxyapatite is rapidly dispersed in the water, and the hydroxyapatite has better suspension stability.
In some embodiments, the soluble phosphate salt is one or more of diammonium phosphate, disodium phosphate, or dipotassium phosphate. Preferably, the soluble phosphate is diammonium phosphate, which is favorable for releasing ammonium ions in the form of ammonia gas and improving the purity of the hydroxyapatite.
In some embodiments, the concentration of PO4 3+ in the phosphorus salt solution is 0.06-0.25 mol/L. Non-limiting examples are: 0.06mol/L, 0.09mol/L, 0.1mol/L, 0.12mol/L, 0.15mol/L, 0.18mol/L, 0.2mol/L, 0.25mol/L.
In some embodiments, the soluble calcium salt is one or more of calcium nitrate, calcium chloride, calcium sulfate, or calcium acetate. Preferably, the soluble calcium salt is calcium nitrate.
In some embodiments, the concentration of Ca 2+ in the calcium salt solution is 0.1-0.5 mol/L. Non-limiting examples are: 0.1mol/L, 0.15mol/L, 0.2mol/L, 0.25mol/L, 0.3mol/L, 0.4mol/L, 0.5mol/L.
In some embodiments, the ratio of the calcium salt solution to the phosphorus salt solution in step (3) satisfies: the molar ratio of the calcium element to the phosphorus element is (1.55-1.85): 1. preferably, the molar ratio is 1.67:1, a step of; the molar ratio of the calcium and the phosphorus elements is controlled to be corresponding to the structure of the product, so that the synthesized product can be accurately controlled to be the high-purity hydroxyapatite.
In some embodiments, the citric acid is added in an amount of 0.01% -0.1% of the sum of the mass of the calcium salt solution and the mass of the phosphorus salt solution. Non-limiting examples are: 0.01%, 0.02%, 0.025%, 0.03%, 0.045%, 0.05%, 0.06%, 0.07%, 0.075%, 0.08%, 0.09%, 0.1%, etc.
In the embodiment of the invention, the citric acid is uniformly adsorbed on the surface of the hydroxyapatite crystal nucleus by strictly controlling the adding amount, so that the crystal growth is inhibited, if the citric acid is excessively added, the cost is increased, the consumption of alkali liquor is increased during pH adjustment, and the negative charge on the surface of the hydroxyapatite crystal particle is excessively increased, so that fluoride ions are repelled to combine with the surface of the hydroxyapatite, and the defluorination effect is reduced.
In some embodiments, the pH in step (3) is 9-11. Non-limiting examples are: the pH value is 9, 9.5, 10, 10.5, 11, etc.
In the step (3), the pH value is adjusted by an alkaline solution, wherein the alkaline solution is a NaOH solution or a KOH solution. Optionally, the concentration of the alkaline solution is: 1.0 mol/L. The embodiment of the invention can ensure that one of the important components of the hydroxyapatite is sufficiently supplied by regulating the pH, so that the yield of the product is ensured.
In some embodiments, the agitation rate of step (3) is 700-1000 r/min. Non-limiting examples are: 700 r/min, 800 r/min, 850 r/min, 900 r/min, 1000 r/min, and so forth.
In some embodiments, the phosphorous salt solution is added at a rate of 1.0 to 1.5 mL/min. Non-limiting examples are: 1.0 mL/min, 1.1 mL/min, 1.2 mL/min, 1.3mL/min, 1.4 mL/min, 1.5 mL/min, etc.
In some embodiments, step (4) synthesis employs one or more combinations of hydrothermal synthesis, chemical precipitation, or ultrasonic synthesis.
In some embodiments, when the hydrothermal synthesis method is adopted in the step (4), the adding amount of the citric acid in the step (3) is 0.01% -0.05% of the sum of the mass of the calcium salt solution and the mass of the phosphorus salt solution. Non-limiting examples are: 0.01%, 0.02%, 0.025%, 0.03%, 0.045%, 0.05%, etc.
In some embodiments, when the chemical precipitation method is adopted in the step (4), the adding amount of the citric acid in the step (3) is 0.01% -0.05% of the sum of the mass of the calcium salt solution and the mass of the phosphorus salt solution. Non-limiting examples are: 0.01%, 0.02%, 0.025%, 0.03%, 0.045%, 0.05%, etc.
In some embodiments, when the ultrasonic synthesis method is adopted in the step (4), the adding amount of the citric acid in the step (3) is 0.03% -0.1% of the sum of the mass of the calcium salt solution and the mass of the phosphorus salt solution. Non-limiting examples are: 0.03%, 0.045%, 0.05%, 0.06%, 0.07%, 0.075%, 0.08%, 0.09%, 0.1%, etc.
In some embodiments, the reaction temperature of the hydrothermal synthesis method is 120-160 ℃, and the reaction time is 4-10 h. Non-limiting examples are: the reaction temperature may be 120 ℃, 130 ℃, 135 ℃, 142 ℃, 150 ℃, 160 ℃, etc., and the reaction time may be 4 h, 5h, 6.5 h, 7 h, 8.5 h, 9 h, 10 hours, etc.
The product synthesized by the hydrothermal synthesis method has smaller regular shape and size, and the size of the nano hydroxyapatite is concentrated to 10-100 nm.
In some embodiments, the chemical precipitation method is to seal, stand and age the alkaline mixed solution for 16-24 hours. Non-limiting examples are: the aging time may be 16 h, 18 h, 19.5 h, 20 h, 21 h, 22.5 h, 24 h, etc. The chemical precipitation method has low preparation cost, wide product particle size distribution and more crystal defects, and is more suitable for removing fluorine.
In some embodiments, the ultrasonic frequency of the ultrasonic synthesis method is 20-50 KHz, and the mixing time is 10-30 min.
Non-limiting examples are: the ultrasonic frequencies may be 20 KHz, 25 KHz, 30 KHz, 40 KHz, 50 KHz, etc., and the mixing times may be 10min, 15 min, 20 min, 24 min, 28 min, 30 min, etc.
According to the method provided by the embodiment of the invention, the product does not need to be calcined, so that the phenomenon that the calcium phosphate is generated by the hydroxyapatite in the calcining process in the related art is avoided, and the defluorination effect is further influenced.
The method of the embodiment of the invention does not need to carry out conventional washing steps on the product, and mainly aims to keep citric acid components as much as possible, adsorb more on the surface of the hydroxyapatite, improve the steric hindrance among particles, reduce the aggregation degree of the particles and further improve the dispersion stability of the hydroxyapatite particles in water.
The embodiment of the invention also provides the hydroxyapatite nano-particles prepared by the preparation method.
In some embodiments, the hydroxyapatite nanoparticles are spheroid in morphology, 10-100 nm in diameter, preferably 30-60 nm in diameter.
The embodiment of the invention also provides the application of the hydroxyapatite nano particle as a defluorination material.
In some embodiments of the present invention, the fluoride ion adsorption capacity of the hydroxyapatite material may be as high as 4.5-5.5 mg/g with a raw water fluoride ion concentration of 6.0 mg/L, and in some embodiments, the adsorption material of 1.0 g may treat the 6.0 mg/L fluoride-containing wastewater of 1.0L to below 1.0 mg/L. The treatment effect is better in the surface of the low-concentration fluoride ion capturing scene.
The following are non-limiting examples:
Example 1
In the embodiment, ca (NO 3)2·4H2 O and (NH 4)2HPO4) prepared precursor solution are subjected to hydrothermal reaction to prepare hydroxyapatite nano particles, which comprises the following steps:
A method for preparing hydroxyapatite nanoparticles, comprising the following steps:
(1) Dissolving (NH 4)2HPO4 with water to obtain a phosphorus salt solution with PO 4 3+ concentration of 0.15 mol/L;
(2) Dissolving Ca (NO 3)2·4H2 O with water to obtain calcium salt solution, wherein the concentration of Ca 2+ is 0.25 mol/L;
(3) Taking 100 mL calcium salt solution, adding 0.02g of citric acid solid under 800 rpm stirring, stirring for 10 minutes, then dropwise adding 100 mL phosphorus salt solution with the dropwise adding rate of 1.0 mL/min, and adjusting the pH to 10.0 by using 1.0 mol/L sodium hydroxide solution after the dropwise adding is finished. After the pH of the system is stable, stirring is continued for 1h under a sealed condition, and finally, the precursor liquid is subpackaged into a polytetrafluoroethylene lining of 50mL for hydrothermal reaction. The product obtained by the reaction is subjected to centrifugal sedimentation, the product is placed in an oven, dried overnight at 80 ℃, and the product is ground into powder for standby. FIG. 1 is a scanning electron microscope image of a synthesized hydroxyapatite solid powder, and it is known from FIG. 1 that the diameter of nano hydroxyapatite is 30-60 nm.
Example 2
In the embodiment, ca (NO 3)2·4H2 O and (NH 4)2HPO4) prepared precursor solution are used for chemical precipitation synthesis to prepare hydroxyapatite nano particles, which comprises the following steps:
A method for preparing hydroxyapatite nanoparticles, comprising the following steps:
(1) Dissolving (NH 4)2HPO4 with water to obtain a phosphorus salt solution with PO 4 3+ concentration of 0.15 mol/L;
(2) Dissolving Ca (NO 3)2·4H2 O with water to obtain calcium salt solution, wherein the concentration of Ca 2+ is 0.25 mol/L;
(3) Taking 100 mL calcium salt solution, adding citric acid solid under 700 rpm stirring condition, stirring for 10 minutes, dropwise adding 100 mL phosphorus salt solution with the dropwise adding rate of 1.2 mL/min, and adjusting the pH to 10.0 by using 1.0 mol/L sodium hydroxide solution after the dropwise adding is finished. After the system pH was stabilized, stirring was continued under sealed conditions for 1h, and the solution was sealed and allowed to stand for 24: 24 h. And (3) centrifugally settling a product obtained by the reaction, placing the product in an oven, drying the product at 80 ℃ overnight, and grinding the product into powder for later use.
The scanning electron micrograph of the synthesized hydroxyapatite (the addition amount of citric acid is 0.01% of the sum of the mass of the calcium salt solution and the mass of the phosphorus salt solution) is shown in fig. 3, which shows that more large particle agglomerates appear in the chemical precipitation method compared with the hydrothermal method.
In this example, adsorption experiments were performed on products obtained by adding citric acid in an amount of 0.001%, 0.003%, 0.005%, 0.007%, 0.009%, 0.01%, 0.03%, 0.05%, 0.07%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, and 0.6% of the sum of the mass of the calcium salt solution and the phosphorus salt solution, respectively.
The grinding product 0.1 g is placed in a water sample (prepared by deionized water and sodium fluoride) with the fluoride ion concentration of 6.0 mg/L of 100mL for adsorption experiments, the experimental result is shown in figure 2, and as can be seen from figure 2, the adsorption capacity is maximum when the adding amount is 0.01%, and the defluorination capacity is obviously reduced when the adding amount is too high or too low, because a large amount of anions and fluoride ions are introduced to generate electrostatic repulsion under the condition of high citric acid adding amount; and the low citric acid addition amount can lead to lower dispersity of crystals, and the agglomeration phenomenon is not completely solved.
Example 3
In the embodiment, ca (NO 3)2·4H2 O and (NH 4)2HPO4) prepared precursor solution are subjected to ultrasonic synthesis to prepare the hydroxyapatite nano particles.
A method for preparing hydroxyapatite nanoparticles, comprising the following steps:
(1) Dissolving (NH 4)2HPO4 with water to obtain a phosphorus salt solution with PO 4 3+ concentration of 0.15 mol/L;
(2) Dissolving Ca (NO 3)2·4H2 O with water to obtain calcium salt solution, wherein the concentration of Ca 2+ is 0.25 mol/L;
(3) Taking 100 mL calcium salt solution, adding citric acid solid under 700 rpm stirring condition, stirring for 10 minutes, then dropwise adding 100 mL phosphorus salt solution with the dropwise adding rate of 1.5 mL/min, and adjusting the pH to 10.0 by using 1.0 mol/L sodium hydroxide solution. After the pH of the system is stable, carrying out centrifugal sedimentation on the product obtained by the reaction under the sealed condition by ultrasonic 30min, placing the product into an oven, drying overnight at 80 ℃, and grinding the product into powder for later use.
The scanning electron microscope photograph of the synthesized hydroxyapatite product (the addition amount of citric acid is 0.1% of the sum of the mass of the calcium salt solution and the mass of the phosphate solution) is shown in fig. 5, and can be seen from fig. 5: because of the effect of ultrasonic wave, crystals in the visual field have fewer large aggregates, the whole appearance is in a short rod shape and a sphere shape, the length-diameter ratio is different, and the phenomenon is caused by the fact that the adding amount of citric acid is possibly insufficient, so that the proportion of the citric acid can be properly increased, and the loss in the ultrasonic process is complemented.
In this example, adsorption experiments were performed on the products obtained by adding citric acid in an amount of 0.01%, 0.03%, 0.05%, 0.07%, 0.09%, 0.1%, 0.2%, 0.3%, 0.4%, 0.5%, 0.6%, and 0.7% of the sum of the mass of the calcium salt solution and the phosphorus salt solution, respectively.
The ground product 0.1g was placed in a 100 mL water sample (prepared from deionized water and sodium fluoride) with a fluoride ion concentration of 6.0. 6.0 mg/L for adsorption experiments. The experimental results are shown in fig. 4, and it can be seen from fig. 4 that the ultrasonic preparation sample reaches the highest adsorption capacity when the addition amount of citric acid is 0.03%, and the addition ratio is higher than that of the chemical precipitation group, which may be caused by that part of citric acid is lost due to cavitation phenomenon in the ultrasonic process. At values below or above this, a significant drop occurs and a high addition ratio is detrimental to fluorine removal.
Comparative example 1
The comparative example uses sodium dodecyl sulfate to replace the citric acid in example 1, and the addition amount is 0.01% of the sum of the mass of the calcium salt solution and the phosphorus salt solution.
Comparative example 2
The comparative example uses sodium dodecyl sulfonate to replace the citric acid in example 1, and the addition amount is 0.01% of the sum of the mass of the calcium salt solution and the phosphorus salt solution.
Comparative example 3
The citric acid in the example 1 is replaced by the polyoxyethylene nonylphenol ether in the comparative example, and the addition amount is 0.01 percent of the sum of the mass of the calcium salt solution and the mass of the phosphorus salt solution.
The information disclosing this comparative example is intended only to increase understanding of the innovation of the present invention and should not be taken as an admission or any form of suggestion that this information constitutes prior art that is well known to a person of ordinary skill in the art.
Evaluation of stability of Dispersion (measurement of Zeta potential)
And measuring the particle size of the sample and the Zeta potential of the sample modified by the organic dispersing agent by using a Zetasizer series laser particle sizer. For dispersion systems with stable electrostatic force, the higher the Zeta potential is, the larger the repulsive force among particles is, and the more stable the system is, and the absolute value of the Zeta potential is more than 30 mV and is generally used as a system stability standard. The dispersion effect and stability of the organic dispersant-modified sample in an aqueous solution were evaluated by means of Zeta potential measurement values.
The model is as follows: zetasizer Lab nanoparticle size and ZETA potential analyzer manufactured by Markov (MALVERN PANALYTICAL) under the GmbH Spectis group, the measurement technique is classical dynamic light scattering (90 °), the particle size range: 0.5 nm to 15 μm. The Zeta potential measurement technology comprises mixed mode measurement, phase analysis light scattering (M3-PALS) and constant current mode, wherein the dispersing agent is water, and the granularity range is 3.8 nm-100 mu M.
The Zeta potential measurement can be used to evaluate the stability of the dispersion, and for dispersions in which electrostatic forces are stable, generally the higher the Zeta potential the more stable the overall system. Because a larger repulsive force exists between particles in a high-potential state, the sample is stable; if the potential is low, even reaches zero potential, the particles in the solution can generate agglomeration and flocculation phenomena, and finally, precipitation is generated. The absolute value of Zeta potential is generally greater than 30 mV as the standard for system stability.
FIG. 6 shows Zeta test results of various samples, wherein a is comparative example 1 (hydroxyapatite particles prepared by adding sodium dodecyl sulfate), b is comparative example 2 (hydroxyapatite particles prepared by adding sodium dodecyl sulfate), c is comparative example 3 (hydroxyapatite particles prepared by adding polyoxyethylene nonylphenol ether (NP-40)), d is example 1 (hydroxyapatite particles prepared by adding citric acid), and e is control group (hydroxyapatite powder of Henan Yankeen environmental protection Co., ltd.).
At ph=7.0, the Zeta potential values of a, b, c, d, e groups of samples were-19.2 mV, -26.2 mV, -16.74 mV, -25.54 mV, -13.5 mV, respectively. Wherein the absolute value of the group b and the group d, namely the two groups of hydroxyapatite modified by sodium dodecyl sulfate and citric acid, is maximum and is close to 30 mV, and compared with the other three groups of hydroxyapatite samples, the group b and the group d can exist in an aqueous phase more stably. And in the e group without adding any organic dispersing agent, the surface of the sample does not contain a large amount of same charges, so that the repulsive force among particles is small, and the sample can be quickly settled when being applied to a fluorine-containing water sample, and is not beneficial to the exposure of active sites.
Defluorination experiment
Five different hydroxyapatite particles, 0.1 g, were placed in a water sample (configured from deionized water and sodium fluoride) having a fluoride ion concentration of 6.0. 6.0 mg/L, respectively, and subjected to adsorption experiments, and fig. 7 shows the defluorination effect of the five different hydroxyapatite particles. a is comparative example 1 (hydroxyapatite particles prepared by adding sodium dodecyl sulfate), b is comparative example 2 (hydroxyapatite particles prepared by adding sodium dodecyl sulfate), c is comparative example 3 (hydroxyapatite particles prepared by adding nonylphenol polyoxyethylene ether (NP-40)), d is example 1 (hydroxyapatite particles prepared by adding citric acid), and e is a control group (hydroxyapatite powder of henna environmental protection technologies, inc.).
As can be seen from fig. 7, the citric acid group hydroxyapatite sample of the embodiment of the present invention has the highest defluorination efficiency, which is higher than the other four groups.
In the present invention, the meaning of "plurality" means at least two, unless specifically defined otherwise.
For purposes of this disclosure, the terms "one embodiment," "some embodiments," "example," "a particular example," or "some examples," etc., mean that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the invention. In this specification, schematic representations of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, the different embodiments or examples described in this specification and the features of the different embodiments or examples may be combined and combined by those skilled in the art without contradiction.
While embodiments of the present invention have been shown and described above, it will be understood that the above embodiments are illustrative and not to be construed as limiting the invention, and that variations, modifications, alternatives and variations may be made to the above embodiments by one of ordinary skill in the art within the scope of the invention.
Claims (9)
1. A method for preparing hydroxyapatite nanoparticles, comprising the following steps:
(1) Dissolving soluble phosphate with water to prepare a phosphorus salt solution:
(2) Dissolving soluble calcium salt with water to obtain calcium salt solution;
(3) Adding citric acid into the calcium salt solution, mixing and stirring, then dropwise adding a phosphorus salt solution, and adjusting the pH value of the mixed solution to be alkaline after the dropwise adding is completed to obtain an alkaline mixed solution;
(4) Synthesizing a product by taking the alkaline mixed solution as a precursor solution, centrifuging, and drying to obtain hydroxyapatite nanoparticles;
The soluble phosphate is one or more of diammonium hydrogen phosphate, disodium hydrogen phosphate or dipotassium hydrogen phosphate;
the addition amount of the citric acid is 0.01% -0.1% of the sum of the mass of the calcium salt solution and the mass of the phosphorus salt solution;
the synthesis of the step (4) adopts one or a combination of a plurality of chemical precipitation methods or ultrasonic synthesis methods;
the product is not washed or calcined;
The concentration of PO4 3+ in the phosphorus salt solution is 0.06-0.25 mol/L; the concentration of Ca 2+ in the calcium salt solution is 0.1-0.5 mol/L;
The ratio relationship between the calcium salt solution and the phosphorus salt solution in the step (3) is as follows: the molar ratio of the calcium element to the phosphorus element is (1.55-1.85): 1.
2. The method of claim 1, wherein the soluble calcium salt is one or more of calcium nitrate, calcium chloride, calcium sulfate, or calcium acetate.
3. The method for preparing hydroxyapatite nanoparticles according to claim 1, wherein the pH value in step (3) is 9 to 11.
4. The method for preparing hydroxyapatite nanoparticles according to any one of claims 1 to 3, wherein the chemical precipitation method is to seal, stand and age alkaline mixed liquid for 16 to 24 hours;
the ultrasonic frequency of the ultrasonic synthesis method is 20-50 KHz, and the mixing time is 10-30 min.
5. The method for preparing hydroxyapatite nanoparticles according to claim 4, wherein,
When a chemical precipitation method is adopted in the step (4), the addition amount of the citric acid in the step (3) is 0.01% -0.05% of the sum of the mass of the calcium salt solution and the mass of the phosphorus salt solution;
When the ultrasonic synthesis method is adopted in the step (4), the addition amount of the citric acid in the step (3) is 0.03% -0.1% of the sum of the mass of the calcium salt solution and the mass of the phosphorus salt solution.
6. A hydroxyapatite nanoparticle prepared by the method of any one of claims 1 to 5.
7. The hydroxyapatite nanoparticle according to claim 6, wherein the hydroxyapatite nanoparticle is spherical in shape and has a diameter of 10-100 nm.
8. The hydroxyapatite nanoparticle according to claim 7, wherein said diameter is 30 to 60 nm.
9. Use of hydroxyapatite nanoparticles according to any of claims 6 to 8 as a defluorinating material.
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| KR100977195B1 (en) * | 2008-07-25 | 2010-08-20 | 국민대학교산학협력단 | Method for manufacturing hydroxy apatite |
| JP2014084232A (en) * | 2012-10-19 | 2014-05-12 | Meiji Univ | Spherical hydroxyapatite and method for producing the same |
| US20170056304A1 (en) * | 2015-08-26 | 2017-03-02 | Honeywell International Inc. | Particulate hydroxyapatite compositions and methods for preparing the same |
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2022
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Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105905877A (en) * | 2016-04-18 | 2016-08-31 | 南京信息工程大学 | A method of preparing nanorod crystal hydroxylapatite hydrosol |
Non-Patent Citations (5)
| Title |
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| Synthesis of hydroxyapatite nanorods for application in water defluoridation and optimization of process variables: Advantage of ultrasonication with precipitation method over conventional method;Dhiraj Mehta;Ultrasonics Sonochemistry;第37卷;56-70 * |
| 柠檬酸优化水热合成羟基磷灰石及矿井水除氟性能;赵佳昕;洁净煤技术;第28卷(第2期);175-185 * |
| 柠檬酸改性纳米羟基磷灰石的水热合成及除氟机理研究;赵佳昕;中国优秀硕士学位论文 * |
| 表面活性剂对水热合成纳米羟基磷灰石粉体影响;赵佳昕;中国陶瓷;第58卷(第6期);37-42, 58 * |
| 赵佳昕.柠檬酸优化水热合成羟基磷灰石及矿井水除氟性能.洁净煤技术.2022,第28卷(第2期),175-185. * |
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