CN108502924A - 一种金属元素掺杂BiOF材料的制备方法及其应用 - Google Patents
一种金属元素掺杂BiOF材料的制备方法及其应用 Download PDFInfo
- Publication number
- CN108502924A CN108502924A CN201810303986.8A CN201810303986A CN108502924A CN 108502924 A CN108502924 A CN 108502924A CN 201810303986 A CN201810303986 A CN 201810303986A CN 108502924 A CN108502924 A CN 108502924A
- Authority
- CN
- China
- Prior art keywords
- biof
- metallic element
- preparation
- ball
- materials
- 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.)
- Granted
Links
- 239000000463 material Substances 0.000 title claims abstract description 49
- 229910016295 BiOF Inorganic materials 0.000 title claims abstract description 40
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 34
- 238000002360 preparation method Methods 0.000 title claims abstract description 22
- 238000000034 method Methods 0.000 claims abstract description 16
- 239000007788 liquid Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- YCKRFDGAMUMZLT-UHFFFAOYSA-N Fluorine atom Chemical compound [F] YCKRFDGAMUMZLT-UHFFFAOYSA-N 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
- 239000011737 fluorine Substances 0.000 claims abstract description 6
- 229910052731 fluorine Inorganic materials 0.000 claims abstract description 6
- 238000000926 separation method Methods 0.000 claims abstract description 6
- 239000003054 catalyst Substances 0.000 claims abstract description 5
- 239000002270 dispersing agent Substances 0.000 claims abstract description 5
- 239000000049 pigment Substances 0.000 claims abstract description 5
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 4
- 239000003814 drug Substances 0.000 claims abstract description 4
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 claims abstract description 3
- 229910001416 lithium ion Inorganic materials 0.000 claims abstract description 3
- 239000002105 nanoparticle Substances 0.000 claims abstract description 3
- 239000000203 mixture Substances 0.000 claims description 18
- 238000000498 ball milling Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000002253 acid Substances 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 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 7
- 239000000126 substance Substances 0.000 claims description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 6
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-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
- 239000007789 gas Substances 0.000 claims description 6
- -1 manganese, rare earth Chemical class 0.000 claims description 6
- 239000010936 titanium Substances 0.000 claims description 6
- 229910052719 titanium Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- NROKBHXJSPEDAR-UHFFFAOYSA-M potassium fluoride Chemical compound [F-].[K+] NROKBHXJSPEDAR-UHFFFAOYSA-M 0.000 claims description 5
- 229910052761 rare earth metal Inorganic materials 0.000 claims description 5
- 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
- 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
- 229910052786 argon Inorganic materials 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
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 3
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 239000001569 carbon dioxide Substances 0.000 claims description 3
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000010431 corundum Substances 0.000 claims description 3
- 229910052593 corundum Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 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
- 229910052757 nitrogen Inorganic materials 0.000 claims description 3
- 150000003891 oxalate salts Chemical class 0.000 claims description 3
- 229920002866 paraformaldehyde 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
- 235000003270 potassium fluoride Nutrition 0.000 claims description 3
- 230000001681 protective effect Effects 0.000 claims description 3
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims description 3
- 239000010935 stainless steel Substances 0.000 claims description 3
- 229910001220 stainless steel Inorganic materials 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
- 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
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims description 2
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 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
- 229920002472 Starch Polymers 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 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
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 239000010949 copper Substances 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000000428 dust Substances 0.000 claims description 2
- 235000019441 ethanol Nutrition 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
- 229910000040 hydrogen fluoride Inorganic materials 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
- 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
- 239000011698 potassium fluoride Substances 0.000 claims description 2
- 150000003839 salts Chemical class 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
- 235000013024 sodium fluoride Nutrition 0.000 claims description 2
- 235000019698 starch Nutrition 0.000 claims description 2
- 239000008107 starch Substances 0.000 claims description 2
- 239000004094 surface-active agent Substances 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
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims 1
- KVBCYCWRDBDGBG-UHFFFAOYSA-N azane;dihydrofluoride Chemical compound [NH4+].F.[F-] KVBCYCWRDBDGBG-UHFFFAOYSA-N 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
- 239000001301 oxygen Substances 0.000 claims 1
- 229910052760 oxygen Inorganic materials 0.000 claims 1
- 239000011775 sodium fluoride Substances 0.000 claims 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-L sulfite Chemical compound [O-]S([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-L 0.000 claims 1
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000000694 effects Effects 0.000 abstract 1
- 238000003682 fluorination reaction Methods 0.000 abstract 1
- 238000000713 high-energy ball milling Methods 0.000 abstract 1
- 239000007787 solid Substances 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
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 6
- 229910052782 aluminium Inorganic materials 0.000 description 4
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 4
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 4
- 238000005253 cladding Methods 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- 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 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 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 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 229910052708 sodium Inorganic materials 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 239000002202 Polyethylene glycol Substances 0.000 description 1
- XSTXAVWGXDQKEL-UHFFFAOYSA-N Trichloroethylene Chemical compound ClC=C(Cl)Cl XSTXAVWGXDQKEL-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- SWLVFNYSXGMGBS-UHFFFAOYSA-N ammonium bromide Chemical compound [NH4+].[Br-] SWLVFNYSXGMGBS-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 239000002131 composite material Substances 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
- SNRUBQQJIBEYMU-UHFFFAOYSA-N dodecane Chemical class CCCCCCCCCCCC SNRUBQQJIBEYMU-UHFFFAOYSA-N 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000012776 electronic material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 150000002085 enols Chemical class 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- RSEIMSPAXMNYFJ-UHFFFAOYSA-N europium(III) oxide Inorganic materials O=[Eu]O[Eu]=O RSEIMSPAXMNYFJ-UHFFFAOYSA-N 0.000 description 1
- 230000003760 hair shine Effects 0.000 description 1
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 235000014413 iron hydroxide Nutrition 0.000 description 1
- NCNCGGDMXMBVIA-UHFFFAOYSA-L iron(ii) hydroxide Chemical class [OH-].[OH-].[Fe+2] NCNCGGDMXMBVIA-UHFFFAOYSA-L 0.000 description 1
- 238000004020 luminiscence type Methods 0.000 description 1
- 238000003701 mechanical milling Methods 0.000 description 1
- 238000010303 mechanochemical reaction Methods 0.000 description 1
- 239000012567 medical material Substances 0.000 description 1
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 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
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 229920001223 polyethylene glycol Polymers 0.000 description 1
- 238000004886 process control Methods 0.000 description 1
- 150000002910 rare earth metals Chemical class 0.000 description 1
- 239000000376 reactant Substances 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
- 229940043267 rhodamine b Drugs 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 150000003385 sodium Chemical class 0.000 description 1
- 229910052938 sodium sulfate Inorganic materials 0.000 description 1
- 235000011152 sodium sulphate Nutrition 0.000 description 1
- MZSDGDXXBZSFTG-UHFFFAOYSA-M sodium;benzenesulfonate Chemical compound [Na+].[O-]S(=O)(=O)C1=CC=CC=C1 MZSDGDXXBZSFTG-UHFFFAOYSA-M 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000003746 solid phase reaction Methods 0.000 description 1
- 239000006104 solid solution Substances 0.000 description 1
- 238000010671 solid-state reaction Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- HDUMBHAAKGUHAR-UHFFFAOYSA-J titanium(4+);disulfate Chemical class [Ti+4].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HDUMBHAAKGUHAR-UHFFFAOYSA-J 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
-
- 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
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/50—Agglomerated particles
-
- 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
-
- 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
- C01P2006/40—Electric properties
-
- 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
- C01P2006/80—Compositional purity
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Battery Electrode And Active Subsutance (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
Abstract
本发明涉及一种金属元素掺杂BiOF材料的制备方法及其应用。本发明以铋酸盐、掺杂源、还原剂、氟源、分散剂为原料,将高能球磨的机械力同步作用于氧化还原、掺杂及其氟化反应,再经过热处理、洗涤除杂、固液分离、干燥制备出金属元素掺杂BiOF材料。所制备的材料是由厚度为2~100nm纳米片或纳米颗粒构成,比表面积为3~300m2/g,所制备材料中掺杂金属元素与铋元素的摩尔比为(0.01~0.3):1。本发明具有工艺简单、易实现工业化生产、制造工艺成本低、环境友好等优势;所制备的金属元素掺杂BiOF材料在超级电容器、碱性二次电池、锂离子电池、光催化剂、珠光颜料、医药等领域具有广泛应用。
Description
技术领域
本发明涉及一种金属元素掺杂BiOF材料的制备方法及其应用,属于新型功能材料领域。
背景技术
卤氧化铋由于其独特的微观结构及物理化学性质,并且无毒、低成本,使其具有潜在的广泛应用,已广泛应用在电极活性材料、催化剂、颜料、化妆品、气体传感器、电子材料、医药材料等领域。
材料的结构与性能与制备工艺方法密切相关。目前合成超细功能粉体的方法根据合成原理可分为物理法和化学法。物理法可制得粒径易控的超细粒子,但所需设备昂贵;化学法成本低,易于通过过程控制调整粒子大小,但工艺流程复杂、并有可能带来环境污染。机械化学法是将物理法与化学法相结合,其基本原理是反应物质通过研磨过程提供的能量,提高反应物的化学活性,使得通常需要在高温下进行的反应能在较低温度下快速进行。机械化学合成方法是一种价格低廉、环境友好、高效率和可控性高的合成方法,这一制备方法使得材料的结构与性能具有更多的设计可能性、且易于工业化生产。
N.Balasubramanian等[Materials Science in Semiconductor Processing 41(2016)59–66]以氟化铵、硝酸铋、硝酸银、六亚甲基四铵为原料,乙二醇为溶剂通过溶剂热法合成了Ag-BiOF/g-C3N4复合材料并研究了其光催化降解罗丹明B的性能。C.Shivakumara等[RSC Adv 5(2015)9241-9254]以Bi2O3、NH4F、Eu2O3为原料,通过高温固相反应制备了Eu3+活化的Bi0F荧光粉材料,并研究了它的光致发光、光催化等性能。
发明专利[申请公布号CN103421511A]公开了“一种稀土离子掺杂的卤氧化铋发光材料及其制备方法”,该发明将硝酸铋,稀土硝酸盐,卤化钾按一定的摩尔比混合溶于溶剂中、加入表面活性剂搅拌均匀,进行水热反应制备出稀土离子掺杂的卤氧化铋发光材料。
目前仅有少量关于金属元素掺杂BiOF材料制备的研究,主要有水热法,溶剂热法,溶胶—凝胶法等。然而这些方法普遍存在合成过程复杂,成本高等问题。
发明内容
本发明的目的在于提出一种金属元素掺杂BiOF材料的制备方法及其应用。所制备的材料是由厚度为2~100nm纳米片或纳米颗粒构成,比表面积为3~300m2/g,所制备材料中掺杂金属元素与铋元素的摩尔比为(0.01~0.3):1。
本发明通过以下技术方案实现:
一种金属元素掺杂BiOF材料的制备方法,包括如下步骤:
(1)将铋酸盐、掺杂源、还原剂、氟源、分散剂按1:(0.01~0.3):(0.25~2):(0.25~2):(0.001~0.3)的摩尔比(物质的量之比)混合均匀,得到原料混合物;
(2)将步骤(1)得到的原料混合物和磨球按1:(0.5~100)的质量比放入球磨罐中,在保护气氛下球磨0.2h~20h;
(3)将步骤(2)得到的球磨混合物置于高温炉中在100~600℃下热处理0.5~10h,将热处理后的产物分别用蒸馏水和无水乙醇进行洗涤除杂,然后进行固液分离和干燥,即得金属元素掺杂BiOF材料。
进一步地,所述的铋酸盐为铋酸钠、铋酸锂、铋酸钾、铋酸镁中的一种或两种以上。
进一步地,掺杂源金属元素为铁、铜、镍、钴、钛、锰、稀土中的一种或两种以上,掺杂源为这些金属元素的单质、氧化物、氢氧化物、草酸盐、醋酸盐、柠檬酸盐、硝酸盐、碳酸盐、硫酸盐、卤化物中的一种或两种以上。
进一步地,所述的还原剂为掺杂源金属元素的还原态物质、金属铋粉、碳粉、亚硫酸盐、甲醛(或多聚甲醛)、甲酸、还原糖、苯酚中的一种或两种以上。
进一步地,所述的氟源为含氟离子的化合物,优选氟化钠、氟化钾、氟化铵、氟化氢铵、氟化氢一种或两种以上。
进一步地,所述的分散剂包括十二烷基磺酸钠、十二烷基苯磺酸钠、十六烷基三甲基溴化铵、聚乙烯吡咯烷酮、聚乙二醇、聚乙烯醇、三乙醇胺、乙二醇、丙三醇、非离子型表面活性剂、糖类物质、可溶性淀粉中的一种或两种以上。
进一步地,所述的球磨过程中的保护气氛为氮气、氩气、二氧化碳、空气中的一种或两种以上。
进一步地,球磨机的转速为30~3000rpm。
进一步地,所述的球磨机选自市场上的各种机型;所述的磨球为玛瑙球、刚玉球、氧化锆球、瓷球、不锈钢球中的一种或两种以上。
上述制备方法所得到的金属元素掺杂BiOF材料在超级电容器、碱性二次电池、锂离子电池、光催化剂、珠光颜料或医药领域中的应用。
本发明的有益效果在于:
(1)本发明方法制备工艺简单、工艺条件温和、易于工业化生产、生产过程环境友好,产品纯度高、产品微观形貌及大小易于控制。
(2)本发明所制备的金属元素掺杂BiOF材料应用广泛,能够应用的领域包括但不限于在超级电容器、碱性二次电池、锂离子电池、光催化剂、珠光颜料、医药等。
附图说明
图1为实施例1所制备的铁掺杂BiOF材料的扫描电子显微镜图。
图2为实施例2所制备的铜掺杂BiOF材料的扫描电子显微镜图。
图3为实施例3所制备的钛掺杂BiOF材料的X射线衍射图。
图4为实施例4中二次碱性电池循环寿命图。
具体实施方式
下面以具体实施例进一步说明本发明的技术方案,但本发明并不局限于实施例。
实施例1
(1)将2mmol铋酸钠,1mmol金属铋粉,0.01mmol草酸高铁铵、2mmol氟化钾,0.02mmol聚乙烯吡咯烷酮混合均匀得到原料混合物;将原料混合物和刚玉磨球按1:60的质量比加到球磨罐中,通入氮气,在转速为800rpm条件下进行球磨8h,将球磨后的混合物在200℃下恒温热处理5h,再将热处理产物用去离子水和无水乙醇洗涤除杂、采用过滤进行固液分离,最后将过滤所得的固体产物在100℃下真空干燥12h,即得5%铁掺杂BiOF材料。
(2)采用JEOLJEM-3010型扫描电子显微镜对实施例1所得铁掺杂BiOF材料进行表征,如图1所示,铁掺杂BiOF材料由厚度为10~20nm的纳米片及附着在纳米片上30~50nm的颗粒组成。
实施例2
(1)将2mmol铋酸镁,1mmol碳粉,0.016mmol乙酸铜、2mmol氟化铵,0.05mmol十二烷基苯磺酸钠混合均匀得到原料混合物;将原料混合物和瓷球磨球按1:50的质量比加到球磨罐中,通入氩气,在转速为1200rpm条件下进行球磨10h,将球磨后的混合物在400℃下恒温热处理5h,再将热处理产物用去离子水和无水乙醇洗涤除杂、采用过滤进行固液分离,最后将过滤所得的固体产物在110℃下干燥8h,即得8%铜掺杂BiOF材料。
(2)采用JEOLJEM-3010型扫描电子显微镜对实施例2所得铜掺杂BiOF材料进行表征,如图2所示,铜掺杂BiOF材料由厚度15~30nm的纳米片以及粒径为50~100nm的纳米颗粒混合组成。
实施例3
(1)将2mmol铋酸钠,1mmol多聚甲醛,0.1mmol硫酸钛,2mmol氟化钠,0.1mmol聚乙烯醇混合均匀得到原料混合物;将原料混合物和氧化锆球磨球按1:60的质量比加到球磨罐中,通入二氧化碳气体,在转速为1500rpm条件下进行球磨6h,再将热处理产物用去离子水和无水乙醇洗涤除杂、采用过滤进行固液分离,最后将过滤所得的固体产物在100℃下真空干燥6h,即得到5%钛掺杂BiOF材料。
(2)采用XRD-6000型X-射线衍射仪对实施例3所制备的钛掺杂BiOF材料进行测试,如图3所示,图谱没有明显的钛掺杂元素衍射峰,与BiOF的标准谱图基本一致,说明掺杂元素进入到BiOF的晶格中形成了固溶体。
实施例4
(1)将2mmol铋酸钾,2mmol硫酸钠,0.016mmol氢氧化铁,3mmol氟化铵,0.1mmol丙三醇混合均匀得到原料混合物;将原料混合物和不锈钢球磨球按1:50的质量比加到球磨罐中,通入氩气,在转速为500rpm条件下进行球磨12h,再将热处理产物用去离子水和无水乙醇洗涤除杂、采用过滤进行固液分离,最后将过滤所得的固体产物在90℃下真空干燥12h,即得到8%铁掺杂BiOF材料。
(2)将所制备的8%铁掺杂BiOF样品制成电极片,与氢氧化镍正极片、6mol/L KOH溶液组装成碱性二次电池,采用BTS-3000电池测试仪,在室温下进行对该电池进行循环寿命测试,由图4可知,所制备的电池在1A/g的电流密度下,经过200次充放电循环后保持213mAh/g比容量、为首次比容量的89%,说明其具有良好的循环稳定性能。
Claims (10)
1.一种金属元素掺杂BiOF材料的制备方法,其特征在于,所述的掺杂BiOF材料由厚度为2~100nm纳米片或纳米颗粒构成,比表面积为3~300m2/g,所制备材料中掺杂金属元素与铋元素的摩尔比为(0.01~0.3):1;其制备方法包括如下步骤:
(1)将铋酸盐、掺杂源、还原剂、氟源、分散剂按1:(0.01~0.3):(0.25~2):(0.25~2):(0.001~0.3)的摩尔比为混合均匀,得到原料混合物;
(2)将步骤(1)得到的原料混合物和磨球按1:(0.5~100)的质量比放入球磨罐中,在保护气氛下球磨0.2h~20h;
(3)将步骤(2)得到的球磨混合物置于高温炉中在100~600℃下热处理0.5~10h,将热处理后的产物分别用蒸馏水和无水乙醇进行洗涤除杂,然后进行固液分离和干燥,即得金属元素掺杂BiOF材料。
2.根据权利要求1所述的金属元素掺杂BiOF材料的制备方法,其特征在于,所述的铋酸盐为铋酸钠、铋酸锂、铋酸钾、铋酸镁中的一种或两种以上。
3.根据权利要求1所述的金属元素掺杂BiOF材料的制备方法,其特征在于,掺杂源金属元素为铁、铜、镍、钴、钛、锰、稀土中的一种或两种以上,掺杂源为这些金属元素的单质、氧化物、氢氧化物、草酸盐、醋酸盐、柠檬酸盐、硝酸盐、碳酸盐、硫酸盐、卤化物中的一种或两种以上。
4.根据权利要求1所述的金属元素掺杂BiOF材料的制备方法,其特征在于,所述的还原剂为掺杂源金属元素的还原态物质、金属铋粉、碳粉、亚硫酸盐、甲醛、多聚甲醛、甲酸、还原糖、苯酚中的一种或两种以上。
5.根据权利要求1所述的金属元素掺杂BiOF材料的制备方法,其特征在于,所述的氟源为含氟离子的化合物。
6.根据权利要求1所述的金属元素掺杂BiOF材料的制备方法,其特征在于,所述的氟源为氟化钠、氟化钾、氟化铵、氟化氢铵、氟化氢一种或两种以上。
7.根据权利要求1所述的金属元素掺杂BiOF材料的制备方法,其特征在于,所述分散剂为十二烷基磺酸钠、十二烷基苯磺酸钠、十六烷基三甲基溴化铵、聚乙烯吡咯烷酮、聚乙二醇、聚乙烯醇、三乙醇胺、乙二醇、丙三醇、非离子型表面活性剂、糖类物质、可溶性淀粉中的一种或两种以上。
8.根据权利要求2所述的金属元素掺杂BiOF材料的制备方法,其特征在于,所述的球磨过程中的保护气氛为氮气、氩气、二氧化碳、空气中的一种或两种以上;球磨机的转速为30~3000rpm。
9.根据权利要求2所述的金属元素掺杂BiOF材料的制备方法,其特征在于,所述的球磨机选自市场上的各种机型;所述的磨球为玛瑙球、刚玉球、氧化锆球、瓷球、不锈钢球中的一种或两种以上。
10.权利要求1至9任一项所述的制备方法得到的金属元素掺杂BiOF材料在超级电容器、碱性二次电池、锂离子电池、光催化剂、珠光颜料或医药领域中的应用。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810303986.8A CN108502924B (zh) | 2018-04-04 | 2018-04-04 | 一种金属元素掺杂BiOF材料的制备方法及其应用 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201810303986.8A CN108502924B (zh) | 2018-04-04 | 2018-04-04 | 一种金属元素掺杂BiOF材料的制备方法及其应用 |
Publications (2)
Publication Number | Publication Date |
---|---|
CN108502924A true CN108502924A (zh) | 2018-09-07 |
CN108502924B CN108502924B (zh) | 2020-04-07 |
Family
ID=63380486
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN201810303986.8A Expired - Fee Related CN108502924B (zh) | 2018-04-04 | 2018-04-04 | 一种金属元素掺杂BiOF材料的制备方法及其应用 |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN108502924B (zh) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109201114A (zh) * | 2018-10-19 | 2019-01-15 | 清华大学深圳研究生院 | 一种水性光催化材料溶胶及其制备方法和用途 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103252244A (zh) * | 2013-04-17 | 2013-08-21 | 太原理工大学 | 一种可见光响应型氯氧铋光催化剂的制备及其应用方法 |
CN103611554A (zh) * | 2013-12-02 | 2014-03-05 | 镇江市高等专科学校 | 光催化材料钛掺杂氯氧化铋微球的制备方法 |
CN103920510A (zh) * | 2014-05-06 | 2014-07-16 | 阜阳师范学院 | Mn-BiOCl光催化剂的制备方法和应用 |
CN104891444A (zh) * | 2015-05-07 | 2015-09-09 | 南京信息工程大学 | 一种制备BiOF光催化剂的方法及催化剂用途 |
CN105032452A (zh) * | 2015-07-14 | 2015-11-11 | 聊城大学 | 一种高可见光活性的K掺杂BiOCl光催化剂的制备方法 |
CN105452169A (zh) * | 2013-08-05 | 2016-03-30 | 耶路撒冷希伯来大学伊萨姆研究开发有限公司 | 基于卤氧化铋的光催化剂、其制备方法及其用途 |
CN106938340A (zh) * | 2016-08-30 | 2017-07-11 | 江苏大学 | 一种铋金属自掺杂的卤化氧铋的制备方法及其用途 |
CN107840365A (zh) * | 2016-09-20 | 2018-03-27 | 天津工业大学 | 一种氯氧化铋纳米花球的制备方法 |
-
2018
- 2018-04-04 CN CN201810303986.8A patent/CN108502924B/zh not_active Expired - Fee Related
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN103252244A (zh) * | 2013-04-17 | 2013-08-21 | 太原理工大学 | 一种可见光响应型氯氧铋光催化剂的制备及其应用方法 |
CN105452169A (zh) * | 2013-08-05 | 2016-03-30 | 耶路撒冷希伯来大学伊萨姆研究开发有限公司 | 基于卤氧化铋的光催化剂、其制备方法及其用途 |
CN103611554A (zh) * | 2013-12-02 | 2014-03-05 | 镇江市高等专科学校 | 光催化材料钛掺杂氯氧化铋微球的制备方法 |
CN103920510A (zh) * | 2014-05-06 | 2014-07-16 | 阜阳师范学院 | Mn-BiOCl光催化剂的制备方法和应用 |
CN104891444A (zh) * | 2015-05-07 | 2015-09-09 | 南京信息工程大学 | 一种制备BiOF光催化剂的方法及催化剂用途 |
CN105032452A (zh) * | 2015-07-14 | 2015-11-11 | 聊城大学 | 一种高可见光活性的K掺杂BiOCl光催化剂的制备方法 |
CN106938340A (zh) * | 2016-08-30 | 2017-07-11 | 江苏大学 | 一种铋金属自掺杂的卤化氧铋的制备方法及其用途 |
CN107840365A (zh) * | 2016-09-20 | 2018-03-27 | 天津工业大学 | 一种氯氧化铋纳米花球的制备方法 |
Non-Patent Citations (1)
Title |
---|
AZADEH TADJARODI ET.AL: "Mechanochemically prepared BiOCl nanoplates for removalof rhodamine B and pentachlorophenol", 《MONATSH CHEM 》 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN109201114A (zh) * | 2018-10-19 | 2019-01-15 | 清华大学深圳研究生院 | 一种水性光催化材料溶胶及其制备方法和用途 |
Also Published As
Publication number | Publication date |
---|---|
CN108502924B (zh) | 2020-04-07 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN108383160A (zh) | 一种金属元素掺杂BiOCl纳米片材料的制备方法及其应用 | |
US5169811A (en) | Beneficiated lanthanum chromite for low temperature firing | |
CN108408773B (zh) | 一种BiOCl材料的制备方法及其应用 | |
US9412486B2 (en) | Composite oxide powder for solid oxide fuel cell and its production method | |
CN108383159B (zh) | 一种Bi2O3纳米片材料的制备方法及其应用 | |
CN105336980A (zh) | 一种通过中间相合成的钽掺杂立方石榴石结构Li7La3Zr2-xTaxO12材料及合成方法 | |
CN112342605A (zh) | 一种低成本低钴单晶三元正极材料及其制备方法 | |
CN108275721A (zh) | 一种{010}高能晶面暴露BiOCl纳米片材料的制备方法及其应用 | |
CN108448113A (zh) | 一种掺杂改性的磷酸铁锂正级材料的制备方法 | |
CN108383158A (zh) | 一种金属元素掺杂Bi2O3材料的制备方法及其应用 | |
CN108502924A (zh) | 一种金属元素掺杂BiOF材料的制备方法及其应用 | |
CN103936082A (zh) | 一种钴酸钐纳米粉体的合成方法 | |
CN107473737B (zh) | 用于固体氧化物燃料电池的复合氧化锆粉及其制备方法 | |
CN115321509B (zh) | 一种固态电解质磷酸钛铝锂及其制备方法 | |
JP4955142B2 (ja) | 希土類・アルミニウム・ガーネット微粉末および該粉末を用いた焼結体 | |
EP4005999A1 (en) | Ceramic powder material, method for producing ceramic powder material, molded body, sintered body, and battery | |
JP6161613B2 (ja) | 固体酸化物型燃料電池用燃料極材料の製造方法 | |
RU2681860C1 (ru) | Способ получения высокотемпературного термоэлектрического материала на основе кобальтита кальция | |
Inagaki et al. | Synthesis and sintering of Li2SnO3 | |
CN104961162A (zh) | 一种基于离子补偿制备单一纯相铁酸铋材料的方法 | |
CN108483495B (zh) | 一种BiOF材料的制备方法及其应用 | |
JP2012025593A (ja) | セリア系複合酸化物の製造方法 | |
CN110483038A (zh) | 一种反铁电无铅陶瓷及其制备方法和应用 | |
CN110444805A (zh) | 一种铒掺杂的立方相石榴石型固态电解质材料及其合成方法 | |
CN115650726B (zh) | 一种钆基石榴石闪烁陶瓷及其制备方法 |
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 | ||
GR01 | Patent grant | ||
GR01 | Patent grant | ||
CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20200407 |
|
CF01 | Termination of patent right due to non-payment of annual fee |