CN108383160A - A kind of preparation method and applications of metallic element doping BiOCl nanometer sheet materials - Google Patents
A kind of preparation method and applications of metallic element doping BiOCl nanometer sheet materials Download PDFInfo
- Publication number
- CN108383160A CN108383160A CN201810323242.2A CN201810323242A CN108383160A CN 108383160 A CN108383160 A CN 108383160A CN 201810323242 A CN201810323242 A CN 201810323242A CN 108383160 A CN108383160 A CN 108383160A
- Authority
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- China
- Prior art keywords
- metallic element
- nanometer sheet
- preparation
- sheet materials
- ball
- Prior art date
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Links
- 239000000463 material Substances 0.000 title claims abstract description 57
- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical compound Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 title claims abstract description 43
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000460 chlorine Substances 0.000 claims abstract description 8
- 229910052801 chlorine Inorganic materials 0.000 claims abstract description 8
- 238000005406 washing Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 239000012752 auxiliary agent Substances 0.000 claims abstract description 6
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 6
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 5
- 239000000049 pigment Substances 0.000 claims abstract description 5
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000003814 drug Substances 0.000 claims abstract description 4
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims description 22
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 11
- 238000000498 ball milling Methods 0.000 claims description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 10
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 10
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 8
- 239000002253 acid Substances 0.000 claims description 8
- -1 manganese, rare earth Chemical class 0.000 claims description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 235000002639 sodium chloride Nutrition 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- 235000019270 ammonium chloride Nutrition 0.000 claims description 5
- 239000010941 cobalt Substances 0.000 claims description 5
- 229910017052 cobalt Inorganic materials 0.000 claims description 5
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 239000011780 sodium chloride Substances 0.000 claims description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 4
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 4
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- 239000002184 metal Substances 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000001103 potassium chloride Substances 0.000 claims description 4
- 235000011164 potassium chloride Nutrition 0.000 claims description 4
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 239000010431 corundum Substances 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 239000007789 gas Substances 0.000 claims description 3
- 235000011167 hydrochloric acid Nutrition 0.000 claims description 3
- 239000011777 magnesium Substances 0.000 claims description 3
- 229910052749 magnesium Inorganic materials 0.000 claims description 3
- 235000012054 meals Nutrition 0.000 claims description 3
- 150000003891 oxalate salts Chemical class 0.000 claims description 3
- 229920002866 paraformaldehyde Polymers 0.000 claims description 3
- 229920001223 polyethylene glycol Polymers 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- 229910052573 porcelain Inorganic materials 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 0.000 claims description 3
- 235000000346 sugar Nutrition 0.000 claims description 3
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-K Citrate Chemical compound [O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O KRKNYBCHXYNGOX-UHFFFAOYSA-K 0.000 claims description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 2
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 2
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003570 air Substances 0.000 claims description 2
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 239000001110 calcium chloride Substances 0.000 claims description 2
- 229910001628 calcium chloride Inorganic materials 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 claims description 2
- 229910052742 iron Inorganic materials 0.000 claims description 2
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 2
- 229910052759 nickel Inorganic materials 0.000 claims description 2
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- PNYYBUOBTVHFDN-UHFFFAOYSA-N sodium bismuthate Chemical compound [Na+].[O-][Bi](=O)=O PNYYBUOBTVHFDN-UHFFFAOYSA-N 0.000 claims description 2
- 239000004094 surface-active agent Substances 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- 239000011592 zinc chloride Substances 0.000 claims description 2
- 235000005074 zinc chloride Nutrition 0.000 claims description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 claims 1
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims 1
- 239000003990 capacitor Substances 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 229910052737 gold Inorganic materials 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 17
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 5
- 230000000694 effects Effects 0.000 abstract description 2
- 238000005660 chlorination reaction Methods 0.000 abstract 1
- 238000000713 high-energy ball milling Methods 0.000 abstract 1
- 230000001360 synchronised effect Effects 0.000 abstract 1
- 238000001914 filtration Methods 0.000 description 7
- 239000000047 product Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 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 description 6
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 5
- 239000011572 manganese Substances 0.000 description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 4
- 239000000654 additive Substances 0.000 description 4
- 230000000996 additive effect Effects 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 230000001699 photocatalysis Effects 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 3
- 238000005253 cladding Methods 0.000 description 3
- 238000001027 hydrothermal synthesis Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 241001481828 Glyptocephalus cynoglossus Species 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 229920002472 Starch Polymers 0.000 description 1
- 239000013504 Triton X-100 Substances 0.000 description 1
- 229920004890 Triton X-100 Polymers 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 125000005211 alkyl trimethyl ammonium group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 150000008107 benzenesulfonic acids Chemical class 0.000 description 1
- 229940073609 bismuth oxychloride Drugs 0.000 description 1
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 235000015165 citric acid Nutrition 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical class [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical class [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 238000010303 mechanochemical reaction Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 239000002736 nonionic surfactant Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 125000000913 palmityl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000004323 potassium nitrate Substances 0.000 description 1
- 235000010333 potassium nitrate Nutrition 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- GEHJYWRUCIMESM-UHFFFAOYSA-L sodium sulfite Chemical class [Na+].[Na+].[O-]S([O-])=O GEHJYWRUCIMESM-UHFFFAOYSA-L 0.000 description 1
- 235000010265 sodium sulphite Nutrition 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000019698 starch Nutrition 0.000 description 1
- 239000008107 starch Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 150000008163 sugars Chemical class 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 description 1
- HPGGPRDJHPYFRM-UHFFFAOYSA-J tin(iv) chloride Chemical compound Cl[Sn](Cl)(Cl)Cl HPGGPRDJHPYFRM-UHFFFAOYSA-J 0.000 description 1
- ZSDSQXJSNMTJDA-UHFFFAOYSA-N trifluralin Chemical compound CCCN(CCC)C1=C([N+]([O-])=O)C=C(C(F)(F)F)C=C1[N+]([O-])=O ZSDSQXJSNMTJDA-UHFFFAOYSA-N 0.000 description 1
- 239000011882 ultra-fine particle Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G29/00—Compounds of bismuth
-
- 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
- C01P2004/20—Particle morphology extending in two dimensions, e.g. plate-like
-
- 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
- C01P2006/12—Surface area
Abstract
The present invention relates to the preparation method and applications that a kind of metallic element adulterates BiOCl nanometer sheet materials.The present invention uses bismuthates, doped source, reducing agent, chlorine source, auxiliary agent for raw material, by the mechanical force synchronous effect of high-energy ball milling in redox, doping and chlorination reaction, using heat treatment, washing impurity-removing, it is separated by solid-liquid separation, is dried to obtain metallic element and adulterates BiOCl nanometer sheet materials.The molar ratio of doped metallic elements and bismuth element is (0.01~0.3) in resulting materials:1, material by planar dimension is 20~500nm, the nanometer sheet that thickness is 1~20nm is constituted, and specific surface area is 3~300m2/g.Present invention process is simple, easily realizes that industrialized production, manufacturing process are at low cost, environmentally friendly；Prepared metallic element doping BiOCl nanometer sheets material has extensive use in ultracapacitor, alkaline secondary cell, lithium ion battery, photochemical catalyst, pearlescent pigment, medicine and other fields.
Description
Technical field
The present invention relates to the preparation method and applications that a kind of metallic element adulterates BiOCl nanometer sheet materials, belong to novel
Field of functional materials.
Background technology
Bismuth oxychloride is a kind of important functional material, due to its unique microstructure and physicochemical properties, and
It is nontoxic, at low cost, in electrode active material, catalyst, pigment, cosmetics, gas sensor, electronic material, medical material etc.
Field has a wide range of applications.In order to further increase the performance of BiOCl materials, metallic element doping is a kind of important hand
Section.
The structure of material is closely related with process of preparing with performance.At present synthesis superfine function powder method according to
Composition principle can be divided into Physical and chemical method.These methods are widely applied in terms of the synthesis of powder, but there is also
Respective deficiency.The easily-controllable ultrafine particle of grain size can be made in Physical, but required equipment is expensive；Chemical method is at low cost, is easy to logical
Process control adjustment particle size is crossed, but technological process is complicated and is possible to bring environmental pollution.Mechanochemical reaction is by physics
Method is combined with chemical method, and basic principle is the energy that reactive material is provided by process of lapping, improves the chemistry of reactant
Activity so that it is generally necessary to which the reaction carried out at high temperature can be carried out quickly at a lower temperature.Mechanochemical synthesis is
A kind of cheap, environmental-friendly, high efficiency and the high synthetic method of controllability, this preparation method make the structure of material with
Performance has more designabilities and is easy to industrialized production.
B.Sarwan etc. [258 (2011) 247-253 of Applied Surface Science] is with bismuth oxide, hydrochloric acid, chlorine
Change manganese is raw material, is prepared for additive Mn BiOCl materials by Hydrolyze method and has studied its photocatalysis performance.Yang etc.
[Phys.Chem.Chem.Phys.16 (2014) 21349-21355] using bismuth nitrate, tungsten chloride, potassium chloride, urea as raw material, second
Glycol is solvent, is prepared for witch culture bismuthyl chloride material by solvent-thermal method and has studied its photocatalysis performance.Zhang etc.
[Applied Catalysis B:Environmental 221 (2018) 320-328] with bismuth nitrate, sodium chloride, cobalt chloride is
Raw material is prepared for cobalt doped BiOCl materials using ethylene glycol, Triton X-100 as auxiliary agent by hydro-thermal method, and has studied can
The photocatalysis performance of light-exposed lower degradation bisphenol-A.[the Separation and Purification Technology 162 such as Dou
(2016) 114-119] using bismuth nitrate, ferric nitrate, ammonium chloride, urea as raw material, Fe2O3 doping BiOCl materials are prepared for by combustion method
Material, and have studied the photocatalytic activity of degradation rhodamine.
Patent of invention [application publication number CN103421511A] discloses that " a kind of rare earth ion doped BiOX shines
Bismuth nitrate, rare earth nitrades, potassium halide are dissolved in solvent by material and preparation method thereof ", the invention by certain molar ratio mixing
In, be added surfactant stir evenly, then adjust pH value of solution be transferred in reaction kettle carry out hydro-thermal reaction prepare rare earth ion
The BiOX luminescent material of doping.Patent of invention [application publication number CN105478149A] discloses a kind of " chlorine of tin dope
Certain density bismuth nitrate solution is added drop-wise to centainly by the preparation of bismuth oxide visible light catalyst ", the invention under agitation
It in the tin chloride solution of concentration, then adjusts pH to its mixed solution and dripping sodium hydroxide solution and reacts 2h, by washing, doing
The dry BiOCl materials for preparing tin dope.Patent of invention [application publication number CN105032452A] discloses a kind of " high visible
The preparation method of active K doping BiOCl photochemical catalysts ", which a certain amount of potassium nitrate, ammonium chloride and citric acid are added
Into bismuth nitrate solution, heating evaporation solvent prepares K doping BiOCl materials at 250~400 DEG C.
Have the research for much adulterating BiOCl material preparations about metallic element at present, mainly there is hydro-thermal method, solvent heat
Method, sol-gel processing etc..However these method generally existings building-up processes are complicated, it is of high cost the problems such as.
Invention content
The preparation method of BiOCl nanometer sheet materials is adulterated the purpose of the present invention is to provide a kind of metallic element and its is answered
With.The molar ratio of doped metallic elements and bismuth element is (0.01~0.3) in material prepared:1, material is 20 by planar dimension
~500nm, the nanometer sheet that thickness is 1~20nm are constituted, and specific surface area is 3~300m2/g。
The invention is realized by the following technical scheme：
A kind of preparation method of metallic element doping BiOCl nanometer sheet materials, includes the following steps：
(1) bismuthates, doped source, reducing agent, chlorine source and auxiliary agent are pressed 1:(0.01~0.3):(0.25~2):(0.25~
2):The molar ratio (the ratio between amount of substance) of (0.001~0.3) is uniformly mixed, and obtains raw mixture；
(2) raw mixture obtained by step (1) and abrading-ball are pressed 1:The mass ratio of (0.5~100) is put into ball mill,
Ball milling 0.2h~20h under protective atmosphere；
(3) ball-milled mixtures that step (2) obtains are placed in high temperature furnace 0.5~10h of heat treatment at 100~600 DEG C,
Product after heat treatment is subjected to washing impurity-removing with distilled water and absolute ethyl alcohol respectively, be then separated by solid-liquid separation, dry to get
Metallic element adulterates BiOCl nanometer sheet materials.
Further, the bismuthates is one or more of sodium bismuthate, bismuthic acid lithium, bismuthic acid potassium, bismuthic acid magnesium.
Further, doped source metallic element is one or more of iron, copper, nickel, cobalt, titanium, manganese, rare earth, is mixed
Miscellaneous source is simple substance, oxide, hydroxide, oxalates, acetate, citrate, nitrate, the carbonic acid of these metallic elements
One or more of salt, sulfate, halide.
Further, the reducing agent is reduction-state substance, metal bismuth meal, carbon dust, the sulfurous of doped source metallic element
One or more of hydrochlorate, formaldehyde (or paraformaldehyde), formic acid, reduced sugar, phenol.
Further, the chlorine source be chloride ion-containing compound, preferably hydrochloric acid, sodium chloride, potassium chloride, ammonium chloride,
One or more of zinc chloride, iron chloride, copper chloride, aluminium chloride, calcium chloride, magnesium chloride.
Further, the auxiliary agent is dodecyl sodium sulfate, neopelex, cetyl trimethyl bromination
Ammonium, polyvinylpyrrolidone, polyethylene glycol, polyvinyl alcohol, triethanolamine, ethylene glycol, glycerine, non-ionic surfactant
One or more of agent, glucide, soluble starch.
Further, the protective atmosphere is one or more of nitrogen, argon gas, carbon dioxide, air.
Further, the rotating speed of ball mill is 30~3000rpm.
Further, the ball mill is selected from various types in the market；The abrading-ball be agate ball, corundum ball,
One or more of zirconia ball, porcelain ball, stainless steel ball.
The above-mentioned obtained metallic element of preparation method adulterates BiOCl nanometer sheets material in ultracapacitor, alkali secondary
Application in battery, lithium ion battery, photochemical catalyst, pearlescent pigment or medicine and other fields.
The beneficial effects of the present invention are：
(1) the method for the present invention preparation process is simple, process conditions are relatively mild, is easy to industrialized production, production process environment
Close friend, product purity height, product microscopic appearance and size are easily controllable.
(2) the metallic element doping BiOCl nanometer sheet materials prepared by the present invention are widely used, the field packet that can be applied
It includes but is not limited in ultracapacitor, alkaline secondary cell, lithium ion battery, photochemical catalyst, pearlescent pigment, medicine intermediate etc.
Field.
Description of the drawings
Fig. 1 is the scanning electron microscope diagram of the Fe2O3 doping BiOCl nanometer sheet materials prepared by embodiment 1.
Fig. 2 is the scanning electron microscope diagram of the Copper-cladding Aluminum Bar BiOCl nanometer sheet materials prepared by embodiment 2.
Fig. 3 is the secondary alkaline electro of the cobalt doped BiOCl nanometer sheets and nickel hydroxide composition prepared by embodiment 3 in difference
Cyclic voltammetric electrical measurement under sweep speed attempts.
Fig. 4 is the nitrogen Adsorption and desorption isotherms figure of the additive Mn BiOCl nanometer sheet materials prepared by embodiment 4.
Specific implementation mode
The technical solution further illustrated the present invention below with specific embodiment, but the invention is not limited in embodiments.
Embodiment 1
(1) by 2mmol sodium bismuthates, 0.6mmol metal bismuth meals, 0.01mmol ammonium ferric oxalates, 2mmol potassium chloride,
0.02mmol polyvinylpyrrolidones are uniformly mixed, and obtain raw mixture；Raw mixture and corundum abrading-ball are pressed 1:60
Mass ratio is added in ball mill, is passed through air, and ball milling 8h is carried out under the conditions of rotating speed is 800rpm, the mixture after ball milling is existed
Constant temperature is heat-treated 5h at 300 DEG C, then is consolidated by heat-treated products deionized water and absolute ethyl alcohol washing impurity-removing, using filtering
Liquid detaches, and finally the solid product of filtering gained is used at 90 DEG C and is dried in vacuo 12h to get 5% Fe2O3 doping BiOCl nanometer sheets
Material.
(2) use JEOLJEM-3010 types scanning electron microscope to 1 gained Fe2O3 doping BiOCl nanometer sheet materials of embodiment
It is characterized, as shown in Figure 1, Fe2O3 doping BiOCl nanometer sheets material by thickness is 5~10nm, planar dimension is 200~400nm
Rectangular nanometer sheet composition.
Embodiment 2
(1) by 2mmol bismuthic acid potassium, 2mmol sodium sulfites, 0.016mmol copper acetates, 2mmol ammonium chlorides, 0.01mmol is poly-
Ethylene glycol is uniformly mixed, and obtains raw mixture；Raw mixture and porcelain ball milling ball are pressed 1:100 mass ratio is added to ball grinder
In, it is passed through nitrogen, ball milling 6h is carried out under the conditions of rotating speed is 1500rpm, by the mixture after ball milling at 400 DEG C at constant temperature heating
Manage 3h, then be separated by solid-liquid separation by heat-treated products deionized water and absolute ethyl alcohol washing impurity-removing, using filtering, finally incited somebody to action
The solid product of filter gained, which is used at 110 DEG C, dries 10h to get 8% Copper-cladding Aluminum Bar BiOCl nanometer sheet materials.
(2) use JEOLJEM-3010 types scanning electron microscope to 2 gained Copper-cladding Aluminum Bar BiOCl nanometer sheet materials of embodiment
It is characterized, as shown in Fig. 2, material by thickness is 5~10nm, the rectangular nanometer sheet that planar dimension is 300nm or so forms.
Embodiment 3
(1) by 2mmol bismuthic acid magnesium, 0.5mmol paraformaldehydes, 0.2mmol cobaltous sulfates, 2mmol sodium chloride, 0.03mmol ten
Dialkyl benzene sulfonic acids sodium is uniformly mixed, and obtains raw mixture；Raw mixture and zirconia ball abrading-ball are pressed 1:70 quality
Than being added in ball grinder, it is passed through carbon dioxide, ball milling 6h is carried out under the conditions of rotating speed is 1000rpm, by the mixture after ball milling
Constant temperature is heat-treated 4h at 300 DEG C, then is carried out by heat-treated products deionized water and absolute ethyl alcohol washing impurity-removing, using filtering
It is separated by solid-liquid separation, the solid product of filtering gained is finally used at 120 DEG C dry 10h to get to BiOCl nanometers of 10% cobalt doped
Sheet material.
(2) electrode slice is made in prepared sample, alkalinity is assembled into nickel hydroxide positive plate piece, 6mol/L KOH solutions
Secondary cell, the CHI660A electrochemical workstations produced using Shanghai Chen Hua company, to the secondary alkaline batteries that are constructed in room
Temperature is lower to carry out cyclic voltammetry.As shown in figure 3, cyclic voltammetry curve of the battery under different scanning rates, sweeps higher
Under speed, the invertibity of redox peaks is good, shows preferable chemical property.
Embodiment 4
(1) by 2mmol sodium bismuthates, 1mmol reduced sugars, 0.016mmol manganese sulfates, 2mmol sodium chloride, 0.06mmol 16
Alkyl trimethyl ammonium bromide is uniformly mixed, and obtains raw mixture；Raw mixture and stainless steel ball abrading-ball are pressed 1:50 matter
Amount ratio is added in ball grinder, is passed through nitrogen, and ball milling 15h is carried out under the conditions of rotating speed is 900rpm, the mixture after ball milling is existed
Constant temperature is heat-treated 3h at 400 DEG C, then is consolidated by heat-treated products deionized water and absolute ethyl alcohol washing impurity-removing, using filtering
Liquid detaches, and the solid product of filtering gained is finally used at 80 DEG C dry 12h to get to 8% additive Mn BiOCl Nano sheet materials
Material.
(2) 3020 type specific surface areas of TriStar II and pore-size distribution instrument is used to test specimen material, such as Fig. 4
Shown, the specific surface area of additive Mn BiOCl nanometer sheet materials is 12.8m2/g。
Claims (10)
1. a kind of preparation method of metallic element doping BiOCl nanometer sheet materials, which is characterized in that adulterate gold in the material
The molar ratio for belonging to element and bismuth element is (0.01~0.3):1, material by planar dimension is 20~500nm, thickness is 1~20nm
Nanometer sheet constitute, specific surface area be 3~300m2/g；Preparation method includes the following steps：
(1) bismuthates, doped source, reducing agent, chlorine source and auxiliary agent are pressed 1:(0.01~0.3):(0.25~2):(0.25~2):
The molar ratio of (0.001~0.3) is uniformly mixed, and obtains raw mixture；
(2) raw mixture obtained by step (1) and abrading-ball are pressed 1:The mass ratio of (0.5~100) is put into ball mill, is being protected
Ball milling 0.2h~20h under atmosphere；
(3) ball-milled mixtures that step (2) obtains are placed in high temperature furnace 0.5~10h of heat treatment at 100~600 DEG C, it will be hot
Treated, and product carries out washing impurity-removing with distilled water and absolute ethyl alcohol respectively, is then separated by solid-liquid separation, is dried to get metal
Element doping BiOCl nanometer sheet materials.
2. the preparation method of metallic element doping BiOCl nanometer sheet materials according to claim 1, which is characterized in that institute
The bismuthates stated is one or more of sodium bismuthate, bismuthic acid lithium, bismuthic acid potassium, bismuthic acid magnesium.
3. the preparation method of metallic element doping BiOCl nanometer sheet materials according to claim 1, which is characterized in that mix
Miscellaneous source metallic element is one or more of iron, copper, nickel, cobalt, titanium, manganese, rare earth；Doped source is these metallic elements
One in simple substance, oxide, hydroxide, oxalates, acetate, citrate, nitrate, carbonate, sulfate, halide
Kind is two or more.
4. the preparation method of metallic element doping BiOCl nanometer sheet materials according to claim 1, which is characterized in that institute
The reducing agent stated be the reduction-state substance of doped source metallic element, metal bismuth meal, carbon dust, sulphite, formaldehyde, paraformaldehyde,
One or more of formic acid, reduced sugar, phenol.
5. the preparation method of metallic element doping BiOCl nanometer sheet materials according to claim 1, which is characterized in that institute
The chlorine source stated is the compound of chloride ion-containing.
6. the preparation method of metallic element doping BiOCl nanometer sheet materials according to claim 1, which is characterized in that institute
The chlorine source stated is hydrochloric acid, sodium chloride, potassium chloride, ammonium chloride, zinc chloride, iron chloride, copper chloride, aluminium chloride, calcium chloride, magnesium chloride
One or more of.
7. the preparation method of metallic element doping BiOCl nanometer sheet materials according to claim 1, which is characterized in that institute
State auxiliary agent be dodecyl sodium sulfate, neopelex, cetyl trimethylammonium bromide, polyvinylpyrrolidone,
Polyethylene glycol, polyvinyl alcohol, triethanolamine, ethylene glycol, glycerine, nonionic surface active agent, glucide, soluble shallow lake
One or more of powder.
8. the preparation method of metallic element doping BiOCl nanometer sheet materials according to claim 1, which is characterized in that institute
The protective atmosphere stated is one or more of nitrogen, argon gas, carbon dioxide, air.
9. the preparation method of metallic element doping BiOCl nanometer sheet materials according to claim 1, which is characterized in that institute
The ball mill stated is selected from various types in the market；The abrading-ball is agate ball, corundum ball, zirconia ball, porcelain ball, stainless steel
One or more of ball；The rotating speed of ball mill is 30~3000rpm.
10. the metallic element doping BiOCl nanometer sheets material that claim 1 to 9 any one of them preparation method obtains is super
Application in grade capacitor, alkaline secondary cell, lithium ion battery, photochemical catalyst, pearlescent pigment or field of medicaments.
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