CN114524457A - Bismuth oxychloride crystal and preparation method and application thereof - Google Patents
Bismuth oxychloride crystal and preparation method and application thereof Download PDFInfo
- Publication number
- CN114524457A CN114524457A CN202210071933.4A CN202210071933A CN114524457A CN 114524457 A CN114524457 A CN 114524457A CN 202210071933 A CN202210071933 A CN 202210071933A CN 114524457 A CN114524457 A CN 114524457A
- Authority
- CN
- China
- Prior art keywords
- bismuth
- bismuth oxychloride
- crystal
- oxychloride crystal
- water
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 70
- 239000013078 crystal Substances 0.000 title claims abstract description 69
- 229940073609 bismuth oxychloride Drugs 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 19
- 238000010992 reflux Methods 0.000 claims abstract description 19
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000000460 chlorine Substances 0.000 claims abstract description 11
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 11
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 10
- 239000000047 product Substances 0.000 claims abstract description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 4
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 4
- 238000001556 precipitation Methods 0.000 claims abstract description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 24
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 16
- 239000001103 potassium chloride Substances 0.000 claims description 8
- 235000011164 potassium chloride Nutrition 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 235000002639 sodium chloride Nutrition 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 5
- 238000000576 coating method Methods 0.000 claims description 5
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 4
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 4
- 238000009835 boiling Methods 0.000 claims description 4
- WERYXYBDKMZEQL-UHFFFAOYSA-N butane-1,4-diol Chemical compound OCCCCO WERYXYBDKMZEQL-UHFFFAOYSA-N 0.000 claims description 4
- 239000000919 ceramic Substances 0.000 claims description 4
- 239000002537 cosmetic Substances 0.000 claims description 4
- 239000000976 ink Substances 0.000 claims description 4
- 239000010985 leather Substances 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 229920003023 plastic Polymers 0.000 claims description 4
- 239000004033 plastic Substances 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 239000003607 modifier Substances 0.000 claims description 3
- 230000001699 photocatalysis Effects 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 229920000642 polymer Polymers 0.000 claims description 3
- DNIAPMSPPWPWGF-VKHMYHEASA-N (+)-propylene glycol Chemical compound C[C@H](O)CO DNIAPMSPPWPWGF-VKHMYHEASA-N 0.000 claims description 2
- DNIAPMSPPWPWGF-GSVOUGTGSA-N (R)-(-)-Propylene glycol Chemical compound C[C@@H](O)CO DNIAPMSPPWPWGF-GSVOUGTGSA-N 0.000 claims description 2
- YPFDHNVEDLHUCE-UHFFFAOYSA-N 1,3-propanediol Substances OCCCO YPFDHNVEDLHUCE-UHFFFAOYSA-N 0.000 claims description 2
- 229940035437 1,3-propanediol Drugs 0.000 claims description 2
- 229940043375 1,5-pentanediol Drugs 0.000 claims description 2
- KKMOSYLWYLMHAL-UHFFFAOYSA-N 2-bromo-6-nitroaniline Chemical compound NC1=C(Br)C=CC=C1[N+]([O-])=O KKMOSYLWYLMHAL-UHFFFAOYSA-N 0.000 claims description 2
- ALQSHHUCVQOPAS-UHFFFAOYSA-N Pentane-1,5-diol Chemical compound OCCCCCO ALQSHHUCVQOPAS-UHFFFAOYSA-N 0.000 claims description 2
- 235000019270 ammonium chloride Nutrition 0.000 claims description 2
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 2
- 229940093476 ethylene glycol Drugs 0.000 claims description 2
- 229960005150 glycerol Drugs 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 2
- 239000000411 inducer Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- DNIAPMSPPWPWGF-UHFFFAOYSA-N monopropylene glycol Natural products CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 2
- 229920000166 polytrimethylene carbonate Polymers 0.000 claims description 2
- 229960004063 propylene glycol Drugs 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims description 2
- 239000011780 sodium chloride Substances 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims 2
- 230000010355 oscillation Effects 0.000 claims 1
- UWJJYHHHVWZFEP-UHFFFAOYSA-N pentane-1,1-diol Chemical compound CCCCC(O)O UWJJYHHHVWZFEP-UHFFFAOYSA-N 0.000 claims 1
- 238000001291 vacuum drying Methods 0.000 abstract description 9
- 238000001816 cooling Methods 0.000 abstract description 8
- 239000000725 suspension Substances 0.000 abstract description 8
- 238000005406 washing Methods 0.000 abstract description 8
- 230000000694 effects Effects 0.000 abstract description 5
- 239000000853 adhesive Substances 0.000 abstract description 2
- 230000001070 adhesive effect Effects 0.000 abstract description 2
- 238000000635 electron micrograph Methods 0.000 description 12
- 239000000049 pigment Substances 0.000 description 7
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 6
- 238000006460 hydrolysis reaction Methods 0.000 description 5
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 5
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 5
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 5
- 229960000999 sodium citrate dihydrate Drugs 0.000 description 5
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical compound [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 150000004677 hydrates Chemical class 0.000 description 4
- 230000007062 hydrolysis Effects 0.000 description 4
- 239000002932 luster Substances 0.000 description 4
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 239000010445 mica Substances 0.000 description 3
- 229910052618 mica group Inorganic materials 0.000 description 3
- 238000004729 solvothermal method Methods 0.000 description 3
- 239000012798 spherical particle Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000006228 supernatant Substances 0.000 description 3
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000005411 Van der Waals force Methods 0.000 description 2
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- 238000000985 reflectance spectrum Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- 238000011179 visual inspection Methods 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000004887 air purification Methods 0.000 description 1
- 150000001621 bismuth Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229960004106 citric acid Drugs 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000001939 inductive effect Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- CJJMLLCUQDSZIZ-UHFFFAOYSA-N oxobismuth Chemical compound [Bi]=O CJJMLLCUQDSZIZ-UHFFFAOYSA-N 0.000 description 1
- 239000001508 potassium citrate Substances 0.000 description 1
- 229960002635 potassium citrate Drugs 0.000 description 1
- QEEAPRPFLLJWCF-UHFFFAOYSA-K potassium citrate (anhydrous) Chemical compound [K+].[K+].[K+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O QEEAPRPFLLJWCF-UHFFFAOYSA-K 0.000 description 1
- 235000011082 potassium citrates Nutrition 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000011112 process operation Methods 0.000 description 1
- 238000002310 reflectometry Methods 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 235000011121 sodium hydroxide Nutrition 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 238000003911 water pollution Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/60—Optical properties, e.g. expressed in CIELAB-values
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/10—Energy storage using batteries
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Cosmetics (AREA)
Abstract
The invention discloses a preparation method of a bismuth oxychloride crystal, which comprises the following steps of carrying out reflux reaction on a bismuth source, a chlorine source and water in an organic solvent at normal pressure to prepare a suspension, naturally cooling a product to 35-40 ℃, adding water, oscillating, standing for layering or carrying out centrifugal precipitation, washing precipitates for 2-3 times with water and absolute ethyl alcohol respectively, and carrying out vacuum drying at 40-80 ℃ to obtain the bismuth oxychloride crystal, wherein the synthesis equation in the preparation process is as follows: bi3++H2O+Cl‑＝BiOCl↓+2H+. The preparation method has the advantages of simple process, mild reaction conditions, low cost, stable quality and high yield; the prepared bismuth oxychloride crystal has controllable morphology, obvious pearlescent effect, good adhesive force and good weather resistance.
Description
Technical Field
The invention relates to the technical field of inorganic material chemical industry, in particular to a bismuth oxychloride crystal and a preparation method and application thereof.
Background
Bismuth oxychloride (BiOCl) is a ternary structure oxide composed of main group elements V-VI-VII, has a typical crystal structure of tetragonal lead fluorochloride ore, is a layered structure formed by combining Cl-Bi-O-Bi-Cl repeating units through smaller van der Waals force among Cl atomic layers and simultaneously stacking and arranging the Cl-Bi-O-Bi-Cl repeating units alternately along the c axis, and has high anisotropy. The bismuth oxychloride crystal has the same attractive pearl luster as mica titanium pearlescent pigment, has extremely fine and smooth mercerizing effect which the mica titanium pearlescent pigment does not have, has unique surface attachment characteristic and smoothness, is safe, non-toxic and good in compatibility, can be used as the pearlescent pigment to be applied to cosmetics, coatings, printing ink, ceramics, plastics, leather, clothing ornaments, automotive interior materials, electronic products, sports goods and the like, and can be used for manufacturing dry battery cathodes and used as photocatalysts in various occasions such as water pollution treatment, air purification and the like.
At present, the synthesis methods of BiOCl are mainly hydrolysis method and solvothermal method (hydrothermal method). The synthesis of pearlescent pigment mainly uses hydrolysis method, which is simple and low in cost, however, concentrated hydrochloric acid, nitric acid and the like are often needed to adjust the pH value of the solution (see patent documents CN1675317A, CN1678693A, CN103130275A, CN103303975A, CN104310471A, CN104828780A, CN108864758B, CN108910946A, CN109077941B, CN103232731A, CN1653139A, CN101935022A, CN101804965A, CN109678207A, CN104131353A, CN109749483A, US5149369A and EP0315849a1), which is not environment-friendly. The solvothermal method is mainly used for preparing the photocatalyst, is still the hydrolysis of bismuth salt, can not use concentrated hydrochloric acid but needs to adopt a closed pressure-resistant reaction kettle to provide a high-temperature and high-pressure environment to promote the hydrolysis reaction (see patent documents CN108502926A, CN1730568A, CN110560097A, CN110550657A, CN110201685A, CN110193373A, CN109985644A, CN110344239A, CN109590026A, CN110237810A and CN109943336A), has high equipment cost, high reaction temperature, long reaction time, high carbon emission, unsatisfactory finished products and inferior brightness, and is not suitable for industrial production.
Therefore, in order to solve the problems, the preparation method of the bismuth oxychloride crystal, which is simple in process operation, easy for industrial production and stable in product quality, is developed, and the bismuth oxychloride crystal which is controllable in synthetic morphology, has a good bright effect, high brightness and pearlescent luster, meets the social requirements, and has important significance.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a preparation method of bismuth oxychloride crystals.
The second purpose of the invention is to provide the bismuth oxychloride crystal prepared by the preparation method.
The third purpose of the invention is to provide the application of the bismuth oxychloride crystal.
The primary purpose of the invention is realized by the following technical scheme:
a preparation method of a bismuth oxychloride crystal comprises the steps of carrying out reflux reaction on a bismuth source, a chlorine source and water in an organic solvent at normal pressure to prepare a suspension, naturally cooling a product to 35-40 ℃, adding water, oscillating, standing for layering or carrying out centrifugal precipitation, washing precipitates for 2-3 times with water and absolute ethyl alcohol respectively, and carrying out vacuum drying at 40-80 ℃ to obtain the bismuth oxychloride crystal.
The synthesis equation in the preparation process is as follows:
Bi3++H2O+Cl-＝BiOCl↓+2H+
preferably, the bismuth source is a bismuth-containing salt, including but not limited to bismuth nitrate and its hydrates, bismuth chloride and its hydrates, bismuth citrate.
Preferably, the chlorine source is a chlorine-containing salt, including but not limited to potassium chloride, sodium chloride, and ammonium chloride.
Preferably, the organic solvent is a mixture of high boiling point organic solvents.
Preferably, the high boiling point organic solvent includes, but is not limited to, at least one of glycerol, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, pentanol, and β -phenylethyl alcohol.
Preferably, the molar ratio of bismuth atoms of the bismuth source to chlorine atoms of the chlorine source to water is 0.8-1.8: 1: 120 to 150.
Preferably, the reflux reaction temperature is 100-200 ℃, and the reflux reaction time is 2-12 hours.
Preferably, the reflux reaction temperature is 120-160 ℃, and the reflux reaction time is 2-4 hours.
Preferably, the vacuum drying temperature is 60 ℃.
Preferably, a polymer modifier and an inducer can also be added in the preparation of the bismuth oxychloride crystal.
Preferably, the polymer modifier is polyvinylpyrrolidone.
Preferably, the inducing agent includes, but is not limited to, citric acid, sodium citrate and hydrates thereof, potassium citrate and hydrates thereof, and the like.
The second purpose of the invention is realized by the following technical scheme:
a bismuth oxychloride crystal is prepared by the preparation method.
The third purpose of the invention is realized by the following technical scheme:
the application of the bismuth oxychloride crystal refers to the application in the fields of cosmetics, coatings, printing ink, ceramics, plastics, leather, clothing and ornaments, automotive interior materials, electronic products, sports goods and photocatalysis.
Compared with the prior art, the invention has the following advantages:
(1) the bismuth oxychloride crystal is prepared by reflux reaction of a bismuth source and a chlorine source in a mixed solvent under normal pressure; compared with a hydrolysis method and a solvothermal method, the preparation method has the advantages of simple and convenient process, mild reaction conditions, low cost, stable quality and high yield;
(2) the bismuth oxychloride crystal prepared by the invention has controllable morphology, obvious pearlescent effect, good adhesive force and good weather resistance, and has sufficient function as pearlescent pigment; the bismuth oxychloride crystal prepared by the invention is particularly suitable for cosmetics, coatings, printing ink, ceramics, plastics, leather, clothing ornaments, automotive interior materials, electronic products and sports goods, and can also be used in the fields of photocatalysis and the like.
Drawings
In order to more clearly illustrate the embodiments or technical solutions of the present invention, the drawings that are needed in the description of the embodiments or the prior art will be briefly described below. It should be apparent that the drawings in the following description are merely exemplary, and that other embodiments can be derived from the drawings provided by those of ordinary skill in the art without inventive effort.
FIG. 1 is an X-ray diffraction pattern of a bismuth oxychloride crystal prepared in example 1, wherein the ordinate is relative intensity and the abscissa is diffraction angle;
FIG. 2 is a scanning electron micrograph of a bismuth oxychloride crystal prepared in example 1, wherein a scale is shown in the lower right corner of FIGS. a, b, c and d, and FIG. d is an enlarged view of the encircled portion of FIG. a;
FIG. 3 is a 50000 times electron micrograph of bismuth oxychloride crystals prepared in example 2;
FIG. 4 is a 50000 times electron micrograph of bismuth oxychloride crystals prepared in example 3;
FIG. 5 is a 50000 times electron micrograph of the bismuth oxychloride crystal prepared in example 4, and the inset in the upper right corner is its 20000 times electron micrograph;
FIG. 6 is a 50000 times electron micrograph of bismuth oxychloride crystals prepared in example 5;
FIG. 7 is a 50000 times electron micrograph of bismuth oxychloride crystals prepared in example 6;
fig. 8 is a graph of uv-vis reflectance spectra in air for examples 1 to 6, wherein the ordinate represents percent reflectance and the abscissa represents test wavelength.
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the embodiments of the present invention are not limited thereto.
Example 1:
19.4g of bismuth nitrate pentahydrate, 3g of potassium chloride, 100mL of water and 700mL of glycerol were mixed in a reaction vessel equipped with a stirrer, a heater and a condensing reflux apparatus, stirred at room temperature for 3 hours, and then heated to 120 ℃ and refluxed for 3 hours to obtain a suspension. Naturally cooling to 35 ℃, adding water, oscillating, standing for layering, removing supernatant, washing the precipitate with water and absolute ethyl alcohol for 3 times respectively, and vacuum drying at 60 ℃ to obtain the bismuth oxychloride crystal.
Fig. 1 is an X-ray diffraction pattern of the bismuth oxychloride crystal prepared in this example, wherein the ordinate represents relative intensity and the abscissa represents diffraction angle. According to the standard spectrum of JCPDS NO.06-0249, the main diffraction peaks appear at 2 theta of 11.9 degrees, 25.9 degrees, 32.5 degrees, 33.4 degrees, 40.9 degrees, 46.6 degrees, 49.7 degrees, 54.1 degrees and 58.6 degrees, and respectively correspond to the (001), (101), (110), (102), (112), (200), (113), (211) and (212) crystal faces of BiOCl. This example is consistent with the XRD data in FIG. 1, which shows that the product prepared in this example is tetragonal bismuth oxychloride crystals.
Fig. 2 is a scanning electron micrograph of the bismuth oxychloride crystal prepared in the example, and in fig. 2, the lower right corner of fig. a, b, c and d is a scale, wherein, fig. d is an enlarged view of a circled part in fig. a. It can be seen that both micron-scale flower-ball-like structures and sheet-like structures exist. Theoretically, a structure is constructed by a bismuth-oxygen covalent bond preferentially in the reaction process, and more bismuth oxychloride 110 crystal faces are formed at the moment and are reflected to form 1-2 mu m flower-ball-shaped crystals with gaps; the crystal structure grows towards the c-axis vertical direction, more shows a 001 crystal face, and accords with the phenomenon that a small amount of sheet structures exist. In the process of wafer growth, due to the existence of smaller van der waals force between the chlorine atom layers, screw dislocation occurs in the process of growth, as shown in fig. d, the wafer is bent and stacked into clusters, and at this time, the 102 crystal plane is more exposed, which is consistent with the X-ray diffraction pattern and the bismuth oxychloride crystal structure of fig. 1. The pearl effect of the bismuth oxychloride comes from the interference of reflected light of different crystal planes.
Example 2:
19.41g of bismuth nitrate pentahydrate, 3g of potassium chloride, 6g of sodium citrate dihydrate, 100mL of water and 700mL of glycerol were mixed in a reaction vessel equipped with a stirrer, a heater and a condensing reflux device, stirred at room temperature for 1.5 hours, and then heated to 160 ℃ and refluxed for 9 hours to obtain a suspension. Naturally cooling to 40 ℃, adding water, oscillating, standing for layering, removing supernatant, washing the precipitate with water and absolute ethyl alcohol for 3 times respectively, and vacuum drying at 60 ℃ to obtain the bismuth oxychloride crystal.
FIG. 3 is a 50000 times electron micrograph of bismuth oxychloride crystals prepared in this example; as can be seen from fig. 3, the sample of bismuth oxychloride crystals exhibited spherulites consisting of platelets, similar to those in example 1, with particle sizes of: example 1> example 2.
Example 3:
19.41g of bismuth nitrate pentahydrate, 3g of potassium chloride, 10g of polyvinylpyrrolidone, 3g of sodium citrate dihydrate, 100mL of water and 700mL of glycerol were mixed in a reaction vessel equipped with a stirrer, a heater and a condensing reflux device, stirred at room temperature for 1.5 hours, and then heated to 120 ℃ and refluxed for 12 hours to obtain a suspension. Naturally cooling to 35 ℃, adding water, oscillating, centrifuging, washing the precipitate with water and absolute ethyl alcohol for 3 times respectively, and carrying out vacuum drying at 60 ℃ to obtain the bismuth oxychloride crystal.
Fig. 4 is a 50000 times electron micrograph of the bismuth oxychloride crystal prepared in this example, and it can be seen from fig. 4 that the bismuth oxychloride crystal sample grows into larger lamellae from the lamellae similar to the sample in example 1, and spherical particles are distributed among the lamellae.
Example 4
19.4g of bismuth nitrate pentahydrate, 3g of potassium chloride, 10g of polyvinylpyrrolidone, 9g of sodium citrate dihydrate, 100mL of water and 700mL of glycerol were mixed in a reaction vessel equipped with a stirrer, a heater and a condensing reflux device, stirred at room temperature for 3 hours, and then heated to 160 ℃ to reflux for 6 hours, thereby obtaining a suspension. Naturally cooling to 40 ℃, adding water, oscillating, standing for layering, removing supernatant, washing the precipitate with water and absolute ethyl alcohol for 3 times respectively, and vacuum drying at 60 ℃ to obtain the bismuth oxychloride crystal.
FIG. 5 is a 50000 times electron micrograph of the bismuth oxychloride crystal prepared in this example, and the inset in the upper right corner is its 20000 times electron micrograph; as can be seen from fig. 5, the sample of bismuth oxychloride crystals exhibited spherulites consisting of platelets, similar to those in example 1, with particle sizes of: example 1> example 2> example 4; and example 2 was significantly more porous than example 4.
Example 5
19.41g of bismuth nitrate pentahydrate, 3g of potassium chloride, 20g of polyvinylpyrrolidone, 6g of sodium citrate dihydrate, 100mL of water and 700mL of glycerol were mixed in a reaction vessel equipped with a stirrer, a heater and a condensing reflux device, stirred at room temperature for 3 hours, and then heated to 120 ℃ and refluxed for 6 hours to obtain a suspension. Naturally cooling to 35 ℃, adding water, oscillating, centrifuging, washing the precipitate with water and absolute ethyl alcohol for 3 times respectively, and carrying out vacuum drying at 60 ℃ to obtain the bismuth oxychloride crystal.
FIG. 6 is a 50000 times electron micrograph of bismuth oxychloride crystals prepared in this example; as can be seen from fig. 6, the sample of bismuth oxychloride crystals had both flat-laid sheets of spherical particles and square-shaped sheets grown like sheets in the sample of example 1.
Example 6
19.4g of bismuth nitrate pentahydrate, 3g of potassium chloride, 30g of polyvinylpyrrolidone, 9g of sodium citrate dihydrate, 90mL of water and 700mL of glycerol were mixed in a reaction vessel equipped with a stirrer, a heater and a condensing reflux device, stirred at room temperature for 3 hours, and then heated to 120 ℃ and refluxed for 9 hours to obtain a suspension. Naturally cooling to 35 ℃, adding water, oscillating, centrifuging, washing the precipitate with water and absolute ethyl alcohol for 3 times respectively, and carrying out vacuum drying at 60 ℃ to obtain the bismuth oxychloride crystal.
FIG. 7 is an electron micrograph of bismuth oxychloride crystals prepared in this example at 50000 times; as can be seen from fig. 7, the sample of bismuth oxychloride crystals had plate-like growth into larger lamellae similar to that of the sample of example 1, with spherical particles distributed between the lamellae.
The actual reflux vapor temperature during the reaction of examples 1 to 6 and the yield of bismuth oxychloride crystals prepared, the pearlescent gloss (visual inspection) are shown in table 1.
TABLE 1
| Examples of the invention | Reflux steam temperature/. degree.C | Yield/%) | Pearlescent luster (visual inspection) |
| Example 1 | 109 | 99.79 | Good taste |
| Example 2 | 137 | 95.86 | Good taste |
| Example 3 | 108 | 77.24 | Is preferably used |
| Example 4 | 138 | 22.11 | Good taste |
| Example 5 | 112 | 20.05 (near half loss at centrifugation) | With metallic luster |
| Example 6 | 114 | 46.41 | Good taste |
Fig. 8 is a graph of uv-vis reflectance spectra in air for examples 1 to 6, wherein the ordinate represents percent reflectance and the abscissa represents test wavelength. According to optical theory, the larger the difference between the refractive indices of a substance and the surrounding medium, the higher the reflectivity of the substance. From FIG. 8, it can be seen that the reflectance in the visible light region, i.e., between wavelengths of 400-800 nm, of examples 1-6 all exceed 40%, indicating that the value of the refractive index is higher, and compared with the reflectance of the foreign mica-titanium dioxide pearlescent pigment (Zhang Shi, Wangberkang, Unihenzhen, Wangshi. measurement of gloss and reflectance of mica pearlescent pigment [ J ]. coating industry, 1995(01):34-35+46), the higher the reflectance under white light, the better the pearlescent gloss, which is consistent with the results in Table 1.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (10)
1. A preparation method of a bismuth oxychloride crystal is characterized in that a bismuth source, a chlorine source and water are subjected to reflux reaction in an organic solvent at normal pressure to prepare turbid liquid, the product is naturally cooled to 35-40 ℃, water is added for oscillation, then the turbid liquid is subjected to standing layering or centrifugal precipitation, precipitates are respectively washed for 2-3 times by water and absolute ethyl alcohol, and the precipitates are dried in vacuum at 40-80 ℃ to obtain the bismuth oxychloride crystal, wherein the synthesis equation in the preparation process is as follows: bi3++H2O+Cl-＝BiOCl↓+2H+。
2. The method for preparing a bismuth oxychloride crystal of claim 1, wherein the bismuth source is a bismuth-containing salt including but not limited to bismuth nitrate and its hydrate, bismuth chloride and its hydrate, and bismuth citrate.
3. The method for preparing bismuth oxychloride crystals of claim 1, wherein the chlorine source is a chlorine-containing salt, including but not limited to potassium chloride, sodium chloride and ammonium chloride.
4. The method for producing a bismuth oxychloride crystal according to claim 1, wherein the organic solvent is a mixture of high-boiling point organic solvents.
5. The method for preparing bismuth oxychloride crystals according to claim 5, wherein the high-boiling organic solvent includes, but is not limited to, at least one of glycerol, ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol, pentanediol, and β -phenylethyl alcohol.
6. The method for producing a bismuth oxychloride crystal according to claim 1, wherein the molar ratio of bismuth atoms of the bismuth source to chlorine atoms of the chlorine source to water is 0.8 to 1.8: 1: 120-150.
7. The method for preparing a bismuth oxychloride crystal according to claim 1, wherein the reflux reaction temperature is 100 to 200 ℃ and the reflux reaction time is 2 to 12 hours.
8. The method for preparing bismuth oxychloride crystals according to claim 1, wherein a polymer modifier and an inducer can be further added to the preparation of the bismuth oxychloride crystals.
9. A bismuth oxychloride crystal characterized by being produced by the production method according to any one of claims 1 to 8.
10. The application of the bismuth oxychloride crystal is characterized in that the application of the bismuth oxychloride crystal is in the fields of cosmetics, coatings, printing ink, ceramics, plastics, leather, clothing and ornaments, automotive interior materials, electronic products, sports goods and photocatalysis.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210071933.4A CN114524457A (en) | 2022-01-21 | 2022-01-21 | Bismuth oxychloride crystal and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210071933.4A CN114524457A (en) | 2022-01-21 | 2022-01-21 | Bismuth oxychloride crystal and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114524457A true CN114524457A (en) | 2022-05-24 |
Family
ID=81620405
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210071933.4A Pending CN114524457A (en) | 2022-01-21 | 2022-01-21 | Bismuth oxychloride crystal and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114524457A (en) |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1252797A (en) * | 1968-06-12 | 1971-11-10 | ||
| CN108525702A (en) * | 2018-04-16 | 2018-09-14 | 成都新柯力化工科技有限公司 | A kind of support type bismuth oxychloride photocatalyst and preparation method for sewage disposal |
| CN110013864A (en) * | 2019-04-30 | 2019-07-16 | 西北师范大学 | The preparation of cobalt acid nickel/bismuthyl chloride nano composite material and its application in catalysis reduction organic matter |
| CN110639610A (en) * | 2019-09-18 | 2020-01-03 | 江苏大学 | Preparation method and application of defect-rich BiOCl/TPP composite photocatalyst |
| CN112264053A (en) * | 2020-11-04 | 2021-01-26 | 南京工业大学 | Synthesis method of CdSe-BiOCl heterojunction |
| CN113174146A (en) * | 2021-04-30 | 2021-07-27 | 吉林工程技术师范学院 | Preparation method of bismuth oxychloride pearlescent pigment |
-
2022
- 2022-01-21 CN CN202210071933.4A patent/CN114524457A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB1252797A (en) * | 1968-06-12 | 1971-11-10 | ||
| CN108525702A (en) * | 2018-04-16 | 2018-09-14 | 成都新柯力化工科技有限公司 | A kind of support type bismuth oxychloride photocatalyst and preparation method for sewage disposal |
| CN110013864A (en) * | 2019-04-30 | 2019-07-16 | 西北师范大学 | The preparation of cobalt acid nickel/bismuthyl chloride nano composite material and its application in catalysis reduction organic matter |
| CN110639610A (en) * | 2019-09-18 | 2020-01-03 | 江苏大学 | Preparation method and application of defect-rich BiOCl/TPP composite photocatalyst |
| CN112264053A (en) * | 2020-11-04 | 2021-01-26 | 南京工业大学 | Synthesis method of CdSe-BiOCl heterojunction |
| CN113174146A (en) * | 2021-04-30 | 2021-07-27 | 吉林工程技术师范学院 | Preparation method of bismuth oxychloride pearlescent pigment |
Non-Patent Citations (1)
| Title |
|---|
| GANG CHENG ET AL.: "Facile template-free and fast refluxing synthesis of 3D desertrose-like BiOCl nanoarchitectures with superior photocatalytic activity", 《RSC PUBLISHING》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US5244649A (en) | Production of hematite pigments in the form of platelets | |
| Kim et al. | Homogeneous precipitation of TiO2 ultrafine powders from aqueous TiOCl2 solution | |
| EP0565342B1 (en) | Titanium dioxide pigment and method of preparation | |
| JP5199894B2 (en) | Titanium dioxide pigment coated with hollow body and method for producing the same | |
| US7611688B2 (en) | Rutile titania nano sols and process for manufacturing the same | |
| JP5208342B2 (en) | Continuous process for producing titanium dioxide pigments | |
| JPS63112663A (en) | Thin plate-shaped pigment based on iron oxide and its production | |
| GB2070636A (en) | Iron blue nacreous pigments | |
| AU2012275783B2 (en) | Treated inorganic particle | |
| EP0654509B1 (en) | Durable pigmentary titanium dioxide and methods of producing the same | |
| AU2001255328A1 (en) | Methods for producing titanium dioxide having improved gloss at low temperatures | |
| CN112745105B (en) | High-sintering-activity alumina ceramic powder and preparation method thereof | |
| FI125473B (en) | Titanium dioxide pigment | |
| CN1891632A (en) | Method for preparing nano zinc oxide powder | |
| US6395081B1 (en) | Methods for producing titanium dioxide pigments having improved gloss at low temperatures | |
| CN114524457A (en) | Bismuth oxychloride crystal and preparation method and application thereof | |
| CN113896231A (en) | Preparation method of titanium dioxide material | |
| JPS5879818A (en) | Colloidal sol, fine powder of crystalline zirconia and preparation thereof | |
| JP2011042535A (en) | Multi-needle type titanium dioxide particle, multi-needle type titanium dioxide particle coating, titanium dioxide-based device, and methods for manufacturing them | |
| JPH04500501A (en) | Opaque kaolin pigment and method for producing the same | |
| US4075032A (en) | Antimony oxide pigment and process of manufacture | |
| JPH06116508A (en) | Production of flaky material coated with titania or zirconia | |
| JP6546593B2 (en) | Method for producing single crystal TiO2 flakes | |
| KR102257545B1 (en) | Alumina single crystal particles having hexagonal plate type structure and manufacturing method of the same | |
| CN108217704B (en) | Hydrothermal preparation method of gamma alumina nano powder |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20220524 |