CN114380319B - 一种新型片堆积球形结构稀土硫氧化物及其制备方法和应用 - Google Patents
一种新型片堆积球形结构稀土硫氧化物及其制备方法和应用 Download PDFInfo
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- CN114380319B CN114380319B CN202011127871.1A CN202011127871A CN114380319B CN 114380319 B CN114380319 B CN 114380319B CN 202011127871 A CN202011127871 A CN 202011127871A CN 114380319 B CN114380319 B CN 114380319B
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- nitrate
- oxide
- sulfate
- chloride
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- 229910052761 rare earth metal Inorganic materials 0.000 title claims abstract description 128
- -1 rare earth oxysulfide Chemical class 0.000 title claims abstract description 100
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000006243 chemical reaction Methods 0.000 claims abstract description 21
- 150000002910 rare earth metals Chemical class 0.000 claims abstract description 20
- 239000000463 material Substances 0.000 claims abstract description 12
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 7
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 7
- 239000011593 sulfur Substances 0.000 claims abstract description 7
- 239000002245 particle Substances 0.000 claims abstract description 6
- 230000008569 process Effects 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 48
- JRKICGRDRMAZLK-UHFFFAOYSA-L peroxydisulfate Chemical compound [O-]S(=O)(=O)OOS([O-])(=O)=O JRKICGRDRMAZLK-UHFFFAOYSA-L 0.000 claims description 28
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 27
- 239000002131 composite material Substances 0.000 claims description 25
- 239000002904 solvent Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 20
- 239000012046 mixed solvent Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 238000003837 high-temperature calcination Methods 0.000 claims description 13
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 12
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 12
- 150000005846 sugar alcohols Polymers 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 10
- 239000007795 chemical reaction product Substances 0.000 claims description 9
- 239000000047 product Substances 0.000 claims description 9
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 claims description 8
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 8
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 8
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 8
- 229910052727 yttrium Inorganic materials 0.000 claims description 8
- 229910052692 Dysprosium Inorganic materials 0.000 claims description 7
- 229910052693 Europium Inorganic materials 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 238000000926 separation method Methods 0.000 claims description 7
- DKGAVHZHDRPRBM-UHFFFAOYSA-N Tert-Butanol Chemical compound CC(C)(C)O DKGAVHZHDRPRBM-UHFFFAOYSA-N 0.000 claims description 6
- MRELNEQAGSRDBK-UHFFFAOYSA-N lanthanum(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[La+3].[La+3] MRELNEQAGSRDBK-UHFFFAOYSA-N 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 6
- 229910052684 Cerium Inorganic materials 0.000 claims description 5
- 229910052691 Erbium Inorganic materials 0.000 claims description 5
- 229910052688 Gadolinium Inorganic materials 0.000 claims description 5
- 229910052689 Holmium Inorganic materials 0.000 claims description 5
- 229910052779 Neodymium Inorganic materials 0.000 claims description 5
- 229910052777 Praseodymium Inorganic materials 0.000 claims description 5
- 229910052772 Samarium Inorganic materials 0.000 claims description 5
- 229910052771 Terbium Inorganic materials 0.000 claims description 5
- 229910052775 Thulium Inorganic materials 0.000 claims description 5
- 229910052769 Ytterbium Inorganic materials 0.000 claims description 5
- 238000001354 calcination Methods 0.000 claims description 5
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 claims description 5
- KBQHZAAAGSGFKK-UHFFFAOYSA-N dysprosium atom Chemical compound [Dy] KBQHZAAAGSGFKK-UHFFFAOYSA-N 0.000 claims description 5
- UYAHIZSMUZPPFV-UHFFFAOYSA-N erbium Chemical compound [Er] UYAHIZSMUZPPFV-UHFFFAOYSA-N 0.000 claims description 5
- OGPBJKLSAFTDLK-UHFFFAOYSA-N europium atom Chemical compound [Eu] OGPBJKLSAFTDLK-UHFFFAOYSA-N 0.000 claims description 5
- UIWYJDYFSGRHKR-UHFFFAOYSA-N gadolinium atom Chemical compound [Gd] UIWYJDYFSGRHKR-UHFFFAOYSA-N 0.000 claims description 5
- KJZYNXUDTRRSPN-UHFFFAOYSA-N holmium atom Chemical compound [Ho] KJZYNXUDTRRSPN-UHFFFAOYSA-N 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 239000011159 matrix material Substances 0.000 claims description 5
- QEFYFXOXNSNQGX-UHFFFAOYSA-N neodymium atom Chemical compound [Nd] QEFYFXOXNSNQGX-UHFFFAOYSA-N 0.000 claims description 5
- 229910052757 nitrogen Inorganic materials 0.000 claims description 5
- PUDIUYLPXJFUGB-UHFFFAOYSA-N praseodymium atom Chemical compound [Pr] PUDIUYLPXJFUGB-UHFFFAOYSA-N 0.000 claims description 5
- KZUNJOHGWZRPMI-UHFFFAOYSA-N samarium atom Chemical compound [Sm] KZUNJOHGWZRPMI-UHFFFAOYSA-N 0.000 claims description 5
- GZCRRIHWUXGPOV-UHFFFAOYSA-N terbium atom Chemical compound [Tb] GZCRRIHWUXGPOV-UHFFFAOYSA-N 0.000 claims description 5
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 claims description 5
- 125000004400 (C1-C12) alkyl group Chemical group 0.000 claims description 4
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 4
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- 239000002253 acid Substances 0.000 claims description 4
- 125000003118 aryl group Chemical group 0.000 claims description 4
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 4
- HSJPMRKMPBAUAU-UHFFFAOYSA-N cerium(3+);trinitrate Chemical compound [Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O HSJPMRKMPBAUAU-UHFFFAOYSA-N 0.000 claims description 4
- VQCBHWLJZDBHOS-UHFFFAOYSA-N erbium(iii) oxide Chemical compound O=[Er]O[Er]=O VQCBHWLJZDBHOS-UHFFFAOYSA-N 0.000 claims description 4
- GAGGCOKRLXYWIV-UHFFFAOYSA-N europium(3+);trinitrate Chemical compound [Eu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O GAGGCOKRLXYWIV-UHFFFAOYSA-N 0.000 claims description 4
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 claims description 4
- PLDDOISOJJCEMH-UHFFFAOYSA-N neodymium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Nd+3].[Nd+3] PLDDOISOJJCEMH-UHFFFAOYSA-N 0.000 claims description 4
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 4
- 230000009467 reduction Effects 0.000 claims description 4
- ZIKATJAYWZUJPY-UHFFFAOYSA-N thulium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tm+3].[Tm+3] ZIKATJAYWZUJPY-UHFFFAOYSA-N 0.000 claims description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052765 Lutetium Inorganic materials 0.000 claims description 3
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- 239000012190 activator Substances 0.000 claims description 3
- 230000000694 effects Effects 0.000 claims description 3
- 229910052746 lanthanum Inorganic materials 0.000 claims description 3
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical group [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 claims description 3
- FYDKNKUEBJQCCN-UHFFFAOYSA-N lanthanum(3+);trinitrate Chemical compound [La+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FYDKNKUEBJQCCN-UHFFFAOYSA-N 0.000 claims description 3
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 3
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 claims description 3
- MAYVZUQEFSJDHA-UHFFFAOYSA-N 1,5-bis(methylsulfanyl)naphthalene Chemical compound C1=CC=C2C(SC)=CC=CC2=C1SC MAYVZUQEFSJDHA-UHFFFAOYSA-N 0.000 claims description 2
- LCPVQAHEFVXVKT-UHFFFAOYSA-N 2-(2,4-difluorophenoxy)pyridin-3-amine Chemical compound NC1=CC=CN=C1OC1=CC=C(F)C=C1F LCPVQAHEFVXVKT-UHFFFAOYSA-N 0.000 claims description 2
- OBOSXEWFRARQPU-UHFFFAOYSA-N 2-n,2-n-dimethylpyridine-2,5-diamine Chemical compound CN(C)C1=CC=C(N)C=N1 OBOSXEWFRARQPU-UHFFFAOYSA-N 0.000 claims description 2
- NGDQQLAVJWUYSF-UHFFFAOYSA-N 4-methyl-2-phenyl-1,3-thiazole-5-sulfonyl chloride Chemical compound S1C(S(Cl)(=O)=O)=C(C)N=C1C1=CC=CC=C1 NGDQQLAVJWUYSF-UHFFFAOYSA-N 0.000 claims description 2
- QXPQVUQBEBHHQP-UHFFFAOYSA-N 5,6,7,8-tetrahydro-[1]benzothiolo[2,3-d]pyrimidin-4-amine Chemical compound C1CCCC2=C1SC1=C2C(N)=NC=N1 QXPQVUQBEBHHQP-UHFFFAOYSA-N 0.000 claims description 2
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 claims description 2
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 2
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 claims description 2
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- UPEMFLOMQVFMCZ-UHFFFAOYSA-N [O--].[O--].[O--].[Pm+3].[Pm+3] Chemical compound [O--].[O--].[O--].[Pm+3].[Pm+3] UPEMFLOMQVFMCZ-UHFFFAOYSA-N 0.000 claims description 2
- BLVQZLMLJMPOIU-UHFFFAOYSA-N [Pm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O Chemical compound [Pm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O BLVQZLMLJMPOIU-UHFFFAOYSA-N 0.000 claims description 2
- YXPNGPLTLPBJPI-UHFFFAOYSA-H [Pm+3].[Pm+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O Chemical compound [Pm+3].[Pm+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O YXPNGPLTLPBJPI-UHFFFAOYSA-H 0.000 claims description 2
- MDARCKRSNKXOPH-UHFFFAOYSA-L [Rb+].[Rb+].[O-]S(=O)(=O)OOS([O-])(=O)=O Chemical compound [Rb+].[Rb+].[O-]S(=O)(=O)OOS([O-])(=O)=O MDARCKRSNKXOPH-UHFFFAOYSA-L 0.000 claims description 2
- 229910021529 ammonia Inorganic materials 0.000 claims description 2
- ZCHPOKZMTJTNHI-UHFFFAOYSA-L barium(2+);sulfonatooxy sulfate Chemical compound [Ba+2].[O-]S(=O)(=O)OOS([O-])(=O)=O ZCHPOKZMTJTNHI-UHFFFAOYSA-L 0.000 claims description 2
- 229910052792 caesium Inorganic materials 0.000 claims description 2
- TVFDJXOCXUVLDH-UHFFFAOYSA-N caesium atom Chemical compound [Cs] TVFDJXOCXUVLDH-UHFFFAOYSA-N 0.000 claims description 2
- 239000011575 calcium Substances 0.000 claims description 2
- 229910052791 calcium Inorganic materials 0.000 claims description 2
- 229910002091 carbon monoxide Inorganic materials 0.000 claims description 2
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 2
- VYLVYHXQOHJDJL-UHFFFAOYSA-K cerium trichloride Chemical compound Cl[Ce](Cl)Cl VYLVYHXQOHJDJL-UHFFFAOYSA-K 0.000 claims description 2
- OZECDDHOAMNMQI-UHFFFAOYSA-H cerium(3+);trisulfate Chemical compound [Ce+3].[Ce+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O OZECDDHOAMNMQI-UHFFFAOYSA-H 0.000 claims description 2
- 229910003440 dysprosium oxide Inorganic materials 0.000 claims description 2
- FLWXWKDFOLALOB-UHFFFAOYSA-H dysprosium(3+);trisulfate Chemical compound [Dy+3].[Dy+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O FLWXWKDFOLALOB-UHFFFAOYSA-H 0.000 claims description 2
- NLQFUUYNQFMIJW-UHFFFAOYSA-N dysprosium(iii) oxide Chemical compound O=[Dy]O[Dy]=O NLQFUUYNQFMIJW-UHFFFAOYSA-N 0.000 claims description 2
- YBYGDBANBWOYIF-UHFFFAOYSA-N erbium(3+);trinitrate Chemical compound [Er+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YBYGDBANBWOYIF-UHFFFAOYSA-N 0.000 claims description 2
- SYDXSHCNMKOQFW-UHFFFAOYSA-H erbium(3+);trisulfate Chemical compound [Er+3].[Er+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O SYDXSHCNMKOQFW-UHFFFAOYSA-H 0.000 claims description 2
- HDGGAKOVUDZYES-UHFFFAOYSA-K erbium(iii) chloride Chemical compound Cl[Er](Cl)Cl HDGGAKOVUDZYES-UHFFFAOYSA-K 0.000 claims description 2
- 229910001940 europium oxide Inorganic materials 0.000 claims description 2
- 229940075616 europium oxide Drugs 0.000 claims description 2
- AEBZCFFCDTZXHP-UHFFFAOYSA-N europium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Eu+3].[Eu+3] AEBZCFFCDTZXHP-UHFFFAOYSA-N 0.000 claims description 2
- NNMXSTWQJRPBJZ-UHFFFAOYSA-K europium(iii) chloride Chemical compound Cl[Eu](Cl)Cl NNMXSTWQJRPBJZ-UHFFFAOYSA-K 0.000 claims description 2
- WLYAEQLCCOGBPV-UHFFFAOYSA-N europium;sulfuric acid Chemical compound [Eu].OS(O)(=O)=O WLYAEQLCCOGBPV-UHFFFAOYSA-N 0.000 claims description 2
- 229910001938 gadolinium oxide Inorganic materials 0.000 claims description 2
- 229940075613 gadolinium oxide Drugs 0.000 claims description 2
- MEANOSLIBWSCIT-UHFFFAOYSA-K gadolinium trichloride Chemical compound Cl[Gd](Cl)Cl MEANOSLIBWSCIT-UHFFFAOYSA-K 0.000 claims description 2
- QLAFITOLRQQGTE-UHFFFAOYSA-H gadolinium(3+);trisulfate Chemical compound [Gd+3].[Gd+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O QLAFITOLRQQGTE-UHFFFAOYSA-H 0.000 claims description 2
- MWFSXYMZCVAQCC-UHFFFAOYSA-N gadolinium(iii) nitrate Chemical compound [Gd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O MWFSXYMZCVAQCC-UHFFFAOYSA-N 0.000 claims description 2
- CMIHHWBVHJVIGI-UHFFFAOYSA-N gadolinium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Gd+3].[Gd+3] CMIHHWBVHJVIGI-UHFFFAOYSA-N 0.000 claims description 2
- JYTUFVYWTIKZGR-UHFFFAOYSA-N holmium oxide Inorganic materials [O][Ho]O[Ho][O] JYTUFVYWTIKZGR-UHFFFAOYSA-N 0.000 claims description 2
- OWCYYNSBGXMRQN-UHFFFAOYSA-N holmium(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ho+3].[Ho+3] OWCYYNSBGXMRQN-UHFFFAOYSA-N 0.000 claims description 2
- WDVGLADRSBQDDY-UHFFFAOYSA-N holmium(3+);trinitrate Chemical compound [Ho+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O WDVGLADRSBQDDY-UHFFFAOYSA-N 0.000 claims description 2
- MKPJADFELTTXAV-UHFFFAOYSA-H holmium(3+);trisulfate Chemical compound [Ho+3].[Ho+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O MKPJADFELTTXAV-UHFFFAOYSA-H 0.000 claims description 2
- 150000002431 hydrogen Chemical class 0.000 claims description 2
- 239000011261 inert gas Substances 0.000 claims description 2
- VQEHIYWBGOJJDM-UHFFFAOYSA-H lanthanum(3+);trisulfate Chemical compound [La+3].[La+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O VQEHIYWBGOJJDM-UHFFFAOYSA-H 0.000 claims description 2
- ICAKDTKJOYSXGC-UHFFFAOYSA-K lanthanum(iii) chloride Chemical compound Cl[La](Cl)Cl ICAKDTKJOYSXGC-UHFFFAOYSA-K 0.000 claims description 2
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229950010610 lutetium chloride Drugs 0.000 claims description 2
- 229910003443 lutetium oxide Inorganic materials 0.000 claims description 2
- APRNQTOXCXOSHO-UHFFFAOYSA-N lutetium(3+);trinitrate Chemical compound [Lu+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O APRNQTOXCXOSHO-UHFFFAOYSA-N 0.000 claims description 2
- GJENVQFRSQOLAE-UHFFFAOYSA-H lutetium(3+);trisulfate Chemical compound [Lu+3].[Lu+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GJENVQFRSQOLAE-UHFFFAOYSA-H 0.000 claims description 2
- AEDROEGYZIARPU-UHFFFAOYSA-K lutetium(iii) chloride Chemical compound Cl[Lu](Cl)Cl AEDROEGYZIARPU-UHFFFAOYSA-K 0.000 claims description 2
- 229910052748 manganese Inorganic materials 0.000 claims description 2
- 239000011572 manganese Substances 0.000 claims description 2
- CFYGEIAZMVFFDE-UHFFFAOYSA-N neodymium(3+);trinitrate Chemical compound [Nd+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O CFYGEIAZMVFFDE-UHFFFAOYSA-N 0.000 claims description 2
- RHVPCSSKNPYQDU-UHFFFAOYSA-H neodymium(3+);trisulfate;hydrate Chemical compound O.[Nd+3].[Nd+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RHVPCSSKNPYQDU-UHFFFAOYSA-H 0.000 claims description 2
- ATINCSYRHURBSP-UHFFFAOYSA-K neodymium(iii) chloride Chemical compound Cl[Nd](Cl)Cl ATINCSYRHURBSP-UHFFFAOYSA-K 0.000 claims description 2
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 2
- MPARYNQUYZOBJM-UHFFFAOYSA-N oxo(oxolutetiooxy)lutetium Chemical compound O=[Lu]O[Lu]=O MPARYNQUYZOBJM-UHFFFAOYSA-N 0.000 claims description 2
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 claims description 2
- MMKQUGHLEMYQSG-UHFFFAOYSA-N oxygen(2-);praseodymium(3+) Chemical compound [O-2].[O-2].[O-2].[Pr+3].[Pr+3] MMKQUGHLEMYQSG-UHFFFAOYSA-N 0.000 claims description 2
- UZLYXNNZYFBAQO-UHFFFAOYSA-N oxygen(2-);ytterbium(3+) Chemical compound [O-2].[O-2].[O-2].[Yb+3].[Yb+3] UZLYXNNZYFBAQO-UHFFFAOYSA-N 0.000 claims description 2
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 2
- 229910003447 praseodymium oxide Inorganic materials 0.000 claims description 2
- YWECOPREQNXXBZ-UHFFFAOYSA-N praseodymium(3+);trinitrate Chemical compound [Pr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YWECOPREQNXXBZ-UHFFFAOYSA-N 0.000 claims description 2
- LHBNLZDGIPPZLL-UHFFFAOYSA-K praseodymium(iii) chloride Chemical compound Cl[Pr](Cl)Cl LHBNLZDGIPPZLL-UHFFFAOYSA-K 0.000 claims description 2
- HWZAHTVZMSRSJE-UHFFFAOYSA-H praseodymium(iii) sulfate Chemical compound [Pr+3].[Pr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O HWZAHTVZMSRSJE-UHFFFAOYSA-H 0.000 claims description 2
- 229910001954 samarium oxide Inorganic materials 0.000 claims description 2
- 229940075630 samarium oxide Drugs 0.000 claims description 2
- YZDZYSPAJSPJQJ-UHFFFAOYSA-N samarium(3+);trinitrate Chemical compound [Sm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YZDZYSPAJSPJQJ-UHFFFAOYSA-N 0.000 claims description 2
- LVSITDBROURTQX-UHFFFAOYSA-H samarium(3+);trisulfate Chemical compound [Sm+3].[Sm+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O LVSITDBROURTQX-UHFFFAOYSA-H 0.000 claims description 2
- BHXBZLPMVFUQBQ-UHFFFAOYSA-K samarium(iii) chloride Chemical compound Cl[Sm](Cl)Cl BHXBZLPMVFUQBQ-UHFFFAOYSA-K 0.000 claims description 2
- FKTOIHSPIPYAPE-UHFFFAOYSA-N samarium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Sm+3].[Sm+3] FKTOIHSPIPYAPE-UHFFFAOYSA-N 0.000 claims description 2
- 229910052706 scandium Inorganic materials 0.000 claims description 2
- DVMZCYSFPFUKKE-UHFFFAOYSA-K scandium chloride Chemical compound Cl[Sc](Cl)Cl DVMZCYSFPFUKKE-UHFFFAOYSA-K 0.000 claims description 2
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 claims description 2
- 229910000346 scandium sulfate Inorganic materials 0.000 claims description 2
- DFCYEXJMCFQPPA-UHFFFAOYSA-N scandium(3+);trinitrate Chemical compound [Sc+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O DFCYEXJMCFQPPA-UHFFFAOYSA-N 0.000 claims description 2
- QHYMYKHVGWATOS-UHFFFAOYSA-H scandium(3+);trisulfate Chemical compound [Sc+3].[Sc+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O QHYMYKHVGWATOS-UHFFFAOYSA-H 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- CHQMHPLRPQMAMX-UHFFFAOYSA-L sodium persulfate Substances [Na+].[Na+].[O-]S(=O)(=O)OOS([O-])(=O)=O CHQMHPLRPQMAMX-UHFFFAOYSA-L 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 229910003451 terbium oxide Inorganic materials 0.000 claims description 2
- YJVUGDIORBKPLC-UHFFFAOYSA-N terbium(3+);trinitrate Chemical compound [Tb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O YJVUGDIORBKPLC-UHFFFAOYSA-N 0.000 claims description 2
- UFPWIQQSPQSOKM-UHFFFAOYSA-H terbium(3+);trisulfate Chemical compound [Tb+3].[Tb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O UFPWIQQSPQSOKM-UHFFFAOYSA-H 0.000 claims description 2
- GFISHBQNVWAVFU-UHFFFAOYSA-K terbium(iii) chloride Chemical compound Cl[Tb](Cl)Cl GFISHBQNVWAVFU-UHFFFAOYSA-K 0.000 claims description 2
- SCRZPWWVSXWCMC-UHFFFAOYSA-N terbium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[Tb+3].[Tb+3] SCRZPWWVSXWCMC-UHFFFAOYSA-N 0.000 claims description 2
- LLZBVBSJCNUKLL-UHFFFAOYSA-N thulium(3+);trinitrate Chemical compound [Tm+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O LLZBVBSJCNUKLL-UHFFFAOYSA-N 0.000 claims description 2
- NEEAOWXTIOQDFM-UHFFFAOYSA-H thulium(3+);trisulfate Chemical compound [Tm+3].[Tm+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O NEEAOWXTIOQDFM-UHFFFAOYSA-H 0.000 claims description 2
- ILOTUXNTERMOJL-UHFFFAOYSA-K thulium(iii) chloride Chemical compound Cl[Tm](Cl)Cl ILOTUXNTERMOJL-UHFFFAOYSA-K 0.000 claims description 2
- PYOOBRULIYNHJR-UHFFFAOYSA-K trichloroholmium Chemical compound Cl[Ho](Cl)Cl PYOOBRULIYNHJR-UHFFFAOYSA-K 0.000 claims description 2
- KAKNBYVEBALXNX-UHFFFAOYSA-K trichloropromethium Chemical compound [Cl-].[Cl-].[Cl-].[Pm+3] KAKNBYVEBALXNX-UHFFFAOYSA-K 0.000 claims description 2
- 229910003454 ytterbium oxide Inorganic materials 0.000 claims description 2
- 229940075624 ytterbium oxide Drugs 0.000 claims description 2
- KUBYTSCYMRPPAG-UHFFFAOYSA-N ytterbium(3+);trinitrate Chemical compound [Yb+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O KUBYTSCYMRPPAG-UHFFFAOYSA-N 0.000 claims description 2
- KVCOOBXEBNBTGL-UHFFFAOYSA-H ytterbium(3+);trisulfate Chemical compound [Yb+3].[Yb+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O KVCOOBXEBNBTGL-UHFFFAOYSA-H 0.000 claims description 2
- CKLHRQNQYIJFFX-UHFFFAOYSA-K ytterbium(III) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Yb+3] CKLHRQNQYIJFFX-UHFFFAOYSA-K 0.000 claims description 2
- 229910000347 yttrium sulfate Inorganic materials 0.000 claims description 2
- RTAYJOCWVUTQHB-UHFFFAOYSA-H yttrium(3+);trisulfate Chemical compound [Y+3].[Y+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RTAYJOCWVUTQHB-UHFFFAOYSA-H 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 239000003795 chemical substances by application Substances 0.000 claims 1
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- 150000002500 ions Chemical class 0.000 description 36
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- 230000007704 transition Effects 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 8
- 238000000295 emission spectrum Methods 0.000 description 8
- 238000012512 characterization method Methods 0.000 description 7
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- 238000001914 filtration Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 3
- 238000002284 excitation--emission spectrum Methods 0.000 description 3
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- 238000001878 scanning electron micrograph Methods 0.000 description 3
- MCVAAHQLXUXWLC-UHFFFAOYSA-N [O-2].[O-2].[S-2].[Gd+3].[Gd+3] Chemical compound [O-2].[O-2].[S-2].[Gd+3].[Gd+3] MCVAAHQLXUXWLC-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
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- GFKJCVBFQRKZCJ-UHFFFAOYSA-N oxygen(2-);yttrium(3+);trisulfide Chemical compound [O-2].[O-2].[O-2].[S-2].[S-2].[S-2].[Y+3].[Y+3].[Y+3].[Y+3] GFKJCVBFQRKZCJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000007605 air drying Methods 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- BIGPRXCJEDHCLP-UHFFFAOYSA-N ammonium bisulfate Chemical compound [NH4+].OS([O-])(=O)=O BIGPRXCJEDHCLP-UHFFFAOYSA-N 0.000 description 1
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- FRNOGLGSGLTDKL-UHFFFAOYSA-N thulium atom Chemical compound [Tm] FRNOGLGSGLTDKL-UHFFFAOYSA-N 0.000 description 1
Classifications
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- C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
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- C01F17/10—Preparation or treatment, e.g. separation or purification
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- C01F17/00—Compounds of rare earth metals
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- C01F17/288—Sulfides
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Abstract
本发明公开了一种新型片堆积球形结构稀土硫氧化物及其制备方法和应用,利用过硫酸盐作为硫源及形貌调控剂,与稀土盐前驱体溶液混合均匀后通过水热法制得单分散、尺寸均一、片堆积球形结构的复合型稀土硫氧化物,再通过高温煅烧还原后,制得了性能优异的单一相型稀土硫氧化物。本发明方法避免了固热反应硫挥发所产生的蒸汽污染环境,具有绿色环保、低能耗、经济效益高、工艺流程简单,且产物分散性好,粒径分布均匀,为片堆积而成的球状结构,同时产物化学稳定性好等优点;并实现了两种不同相型结构的稀土硫氧化物的可控调节,由此制备的稀土掺杂硫氧化物发光材料均具备较好的发光性能。
Description
技术领域
本发明涉及稀土发光材料领域,尤其涉及一种新型单分散、片堆积球形结构稀土硫氧化物及其制备方法和在发光材料方面的应用。
背景技术
稀土硫氧化物是一种优秀的发光基质,其具备谱带窄、色纯度高,光吸收和转换效率高,物理和化学稳定性好等特点,在信息、照明、显像等领域都有重要的应用。理想的发光材料必须具有窄的粒径分布,无团聚且尽可能为球形结构,这有利于获得高质量的器件涂层,从而提高发光效率和使用寿命。目前制备稀土硫氧化物发光材料的主要方法是高温固相法(1000℃~1500℃),该方法具有制备过程简易、颗粒填充性好、易于产业化等优点。但该方法存在反应所需温度高、能耗大,产物尺寸不均、形貌不规则,且使用的固体硫单质在高温下产生的蒸汽会污染环境等缺点。因此,如何在保证材料优良性能的前提下,通过制备工艺的改进,降低反应温度及环境污染、缩短合成时间、实现产物的形貌结构可控制备将是今后稀土硫氧化物制备方法的发展方向。
发明内容
为了克服上述技术问题,本发明提供一种新型片堆积球形结构稀土硫氧化物及其制备方法和应用,以过硫酸盐作为硫源及形貌调控剂,与稀土盐前驱体溶液混合均匀后通过水热法制得单分散、尺寸均一、片堆积球形结构的复合相型稀土硫氧化物;然后通过高温煅烧还原后可制得单一相型稀土硫氧化物。本发明具有制备方法简易、产率高、能耗低,产物分散均匀,且可有效控制产物形貌、尺寸及结构等优点;且基于球形结构较高的堆积密度和低散色光,因而是理想的发光材料结构。
本发明是通过如下技术方案实现所述技术效果的:
一种新型片堆积结构稀土硫氧化物的制备方法,包括如下步骤:以过硫酸盐作为硫源及形貌调控剂,与稀土盐前驱体溶液通过水热法制得复合相型稀土硫氧化物。
根据本发明的实施方案,所述过硫酸盐选自过硫酸锂、过硫酸钠、过硫酸钾、过硫酸铷、过硫酸铯、过硫酸铵、过硫酸氢铵、过硫酸锰、过硫酸钙、过硫酸银、过硫酸钡等中的至少一种;优选为过硫酸铵。在此步反应过程中选择过硫酸盐作为硫源及形貌调控剂,用以控制垂直片堆积球状结构形貌的生成。
根据本发明的实施方案,所述稀土盐前驱体选自稀土的硝酸盐、氯化盐、硫酸盐中的至少一种;稀土盐中的稀土为镧(La)、铈(Ce)、镨(Pr)、钕(Nd)、钐(Sm)、铕(Eu)、钆(Gd)、铽(Tb)、镝(Dy)、钬(Ho)、铒(Er)、铥(Tm)、镱(Yb)、镥(Lu)、钇(Y)中一种或两种;优选包括两种稀土元素,一种选自镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、钇作为基体稀土,另一种选自铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱作为激活剂稀土,用以增强制备的稀土硫氧化物的发光效果。
根据本发明的实施方案,所述基体稀土与激活剂稀土的摩尔比为1:0.01~0.25;示例性为1:0.01,9:1,1:0.25。
根据本发明的实施方案,所述稀土盐可以通过稀土的氧化物与酸反应制得;优选地,所述稀土的氧化物选自氧化钪、氧化钇、氧化镧、氧化铈、氧化镨、氧化钕、氧化钷、氧化钐、氧化铕、氧化钆、氧化铽、氧化镝、氧化钬、氧化铒、氧化铥、氧化镱、氧化镥等中的一种;所述酸包括硝酸、盐酸、硫酸等。
以硝酸镧为例,可以通过在反应体系中加入氧化镧以及硝酸的方法制备。
根据本发明的实施方案,所述稀土的硝酸盐选自硝酸钪,硝酸钇,硝酸镧,硝酸铈,硝酸镨,硝酸钕,硝酸钷,硝酸钐,硝酸铕,硝酸钆,硝酸铽,硝酸镝,硝酸钬,硝酸铒,硝酸铥,硝酸镱,硝酸镥中的至少一种。
根据本发明的实施方案,所述稀土的氯化盐选自氯化钪,氯化钇,氯化镧,氯化铈,氯化镨,氯化钕,氯化钷,氯化钐,氯化铕,氯化钆,氯化铽,氯化镝,氯化钬,氯化铒,氯化铥,氯化镱,氯化镥中的至少一种。
根据本发明的实施方案,所述稀土的硫酸盐选自硫酸钪,硫酸钇,硫酸镧,硫酸铈,硫酸镨,硫酸钕,硫酸钷,硫酸钐,硫酸铕,硫酸钆,硫酸铽,硫酸镝,硫酸钬,硫酸铒,硫酸铥,硫酸镱,硫酸镥等中的至少一种。
根据本发明的实施方案,所述稀土盐和过硫酸盐的摩尔比为1:0.05~20;例如为1:0.1~10;优选为1:0.5~5;示例性为1:0.05,1:0.1,1:0.5,1:1,1:1.2,1:1.5,1:3,1:5,1:8,1:10,1:15,1:20。
根据本发明的实施方案,所述水热反应采用醇类溶剂或水中的至少一种。
根据本发明的实施方案,所述醇类溶剂包括C1-C12烷基的一元醇以及多元醇;优选地,所述一元醇可以为甲醇、乙醇、丙醇、异丙醇、正丁醇、异丁醇、叔丁醇、正戊醇,含芳香基的苯甲醇,苯乙醇等中的至少一种:所述多元醇为乙二醇、甘油等中的至少一种。
优选地,所述水热反应采用醇类溶剂与水的混合溶剂;例如醇类溶剂与水的体积比值为0.1~10的混合溶剂;示例性为0.1,1,5,10;优选醇类溶剂与水的体积比值为1。
优选地,所述水热反应可以采用一元醇与多元醇的混合溶剂。例如一元醇与多元醇的体积比值为0.1~10的混合溶剂;示例性为0.1,1,5,10;优选一元醇与多元醇的体积比值为1;
根据本发明的实施方案,所述水热反应温度不高于220℃;例如为80~200℃;优选为110~180℃;示例性为80℃、110℃、120℃、150℃、180℃、200℃、220℃。
根据本发明的实施方案,所述水热反应时间为1-48h;优选为1~24h;示例性为1h、3h、6h、9h、12h、18h、24h、36h、48h。
根据本发明的实施方案,所述水热反应体系包括任何化工用的搅拌反应釜、溶剂热反应釜、水热反应釜、超临界反应釜、微波反应釜等。优选为水热反应釜。
根据本发明的实施方案,所述制备方法还包括待反应结束后,对反应体系进行固液分离得到反应产物的过程。例如,所述固液分离可以采用本领域已知手段,比如过滤、离心。
根据本发明的实施方案,所述制备方法还包括对固液分离得到的反应产物进行洗涤。例如,采用能够溶解所述复合相型稀土硫氧化物的溶剂对反应产物进行洗涤。优选地,所述溶剂可以为醇类溶剂与水的混合溶剂;例如,醇类溶剂与水的体积比值为0.1~10的混合溶剂;示例性为0.1,1,5,10;优选醇类溶剂与水的体积比值为1。
根据本发明的实施方案,所述洗涤采用的醇类溶剂包括C1-C12烷基的一元醇以及多元醇;优选地,所述一元醇可以为甲醇、乙醇、丙醇、异丙醇、正丁醇、异丁醇、叔丁醇、正戊醇,含芳香基的苯甲醇,苯乙醇等中的至少一种;所述多元醇以为乙二醇、甘油等中的至少一种。
根据本发明的实施方案,所述制备方法还包括对洗涤后的反应产物进行干燥;例如,采用喷雾干燥、冷冻干燥、风干、烘干等进行干燥。
根据本发明的实施方案,所述制备方法包括如下步骤:
按照摩尔比为1:0.05~20分别称取将稀土盐和过硫酸盐置于水热反应釜中,加入醇类溶剂与水的混合溶剂,搅拌超声溶解至无明显颗粒存在,经水热反应;待反应完成后,固液分离,对得到的反应产物进行洗涤、干燥,得到复合相型稀土硫氧化物。
根据本发明的实施方案,所述制备方法还包括对制得的复合相型稀土硫氧化物进行高温煅烧还原后制得单一相型稀土硫氧化物。
根据本发明的实施方案,所述高温煅烧在管式炉或者马弗炉中进行。
根据本发明的实施方案,所述高温煅烧在还原性气体气氛下进行;优选地,所述还原性气体包括氢气、一氧化碳、氨气中的至少一种;例如,可以为还原性气体与惰性气体的混合气体;优选为氢气与氮气按照体积比为2:98~20:80的混合气体;优选为5:95~10:90的混合气体;示例性为2:98,5:95,10:90,20:80。
根据本发明的实施方案,所述高温煅烧温度为200-1000℃;优选为400~900℃;示例性为200℃、400℃、600℃、850℃、900℃、1000℃。
根据本发明的实施方案,所述高温煅烧时间为0.1-48h;例如为2~36h;优选为4~24h;示例性为1h,2h,4h,8h,12h,18h,24h,36h,48h。
根据本发明的实施方案,所述单一相型稀土硫氧化物的制备方法,包括如下步骤:
将上述制得的复合相型稀土硫氧化物产物置于管式炉或者马弗炉中,在还原性气体气氛下,于200-1000℃下高温煅烧0.1-48h,制得单一相型稀土硫氧化物。
本发明还提供由上述制备方法制得的稀土硫氧化物,所述稀土硫氧化物以化学式Ln2O2S表示;其中RE代表稀土元素,选自Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Tb和Dy中的至少一种;优选选自上述稀土元素中的两种;示例性为Y、Eu、Gd中的两种。
本发明还提供由上述制备方法制得的复合相型稀土硫氧化物和/或单一相型稀土硫氧化物在发光材料方面的应用。
本发明还提供一种发光材料,其含有上述复合相型稀土硫氧化物和/或单一相型稀土硫氧化物。
有益效果:
本发明利用过硫酸盐作为硫源及形貌调控剂,与稀土盐前驱体溶液混合均匀后通过水热法制得单分散、尺寸均一、片堆积球形结构的复合型稀土硫氧化物,再通过高温煅烧还原后,制得了性能优异的单一相型稀土硫氧化物。且本发明稀土硫氧化物的制备方法简易、产率高、可控性强、能耗低、绿色、经济效益好,且可有效控制稀土硫氧化物的形貌、尺寸及结构,同时产物化学稳定性好,可广泛应用于发光材料领域。
附图说明
图1中(a)为实施例1制得的复合相型和单一相型稀土硫氧化钆的xrd表征图;图1中(b)为实施例2制得的Eu3+离子掺杂的复合相型和单一相型稀土硫氧化钆的xrd表征图。
图2中左图(a)~(d)、右图(e)~(h)分别是实施例1制得的复合相型和单一相型稀土硫氧化钆的扫描电子显微镜表征图。
图3中左图(a)~(c)、右图(d)~(f)分别是实施例2制得的复合相型和单一相型Eu3+离子掺杂稀土硫氧化钆(Gd2O2S:Eu3+)的扫描电子显微镜表征图。
图4中左图(a)为实施例3制得的Eu3+离子掺杂的复合相型和单一相型稀土硫氧化钇的xrd表征图;右图(b)~(c)、(d)~(e)分别为实施例3制得的复合相型和单一相型Eu3+离子掺杂稀土硫氧化钇(Y2O2S:Eu3+)的扫描电子显微镜表征图。
图5中(a)、(b)分别为复合相型Eu3+离子掺杂的稀土硫氧化钆的激发光谱、发射光谱;图5中(c)、(d)分别为复合相型Eu3+离子掺杂的硫氧化钇的激发光谱、发射光谱。
图6中(a)、(b)分别为单一相型Eu3+离子掺杂的稀土硫氧化钆的激发光谱、发射光谱;图6中(c)、(d)分别为Eu3+离子掺杂的稀土硫氧化钇的激发光谱、发射光谱。
具体实施方式
下文将结合具体实施例对本发明的技术方案做更进一步的详细说明。应当理解,下列实施例仅为示例性地说明和解释本发明,而不应被解释为对本发明保护范围的限制。凡基于本发明上述内容所实现的技术均涵盖在本发明旨在保护的范围内。
除非另有说明,以下实施例中使用的原料和试剂均为市售商品,或者可以通过已知方法制备。
实施例1
称取1mmol稀土硝酸钆(0.451g),1.2mmol过硫酸铵(0.274g)于25mL玻璃瓶,加入8mL乙醇和8mL水,在水热反应釜中,搅拌均匀,然后将反应釜升温至110℃,保持3h。取出反应釜冷却至室温,并用体积比为1:1的乙醇/水混合溶剂洗涤抽滤干燥得到复合相型稀土硫氧化钆。再在5%H2/95%N2的混合气氛下,于850℃下煅烧2h,得到单一相型稀土硫氧化钆(Gd2O2S)。
图1中(a)为本实施例制得的复合相型和单一相型稀土硫氧化钆的xrd表征图,从图中结果可以看出,在还原气氛下可实现稀土硫氧化物由复合相型向单一相型产物晶相的转变。
图2中(a)~(d)、(e)~(h)分别为本实施例制得的复合相型、单一相型稀土硫氧化钆的SEM图。从图中可以看出,本实施例所制备的两种相型的稀土硫氧化物产物粒径、形貌均匀,为尺寸均一的垂直纳米片堆积形成的球状结构。
实施例2
称取1mmol稀土硝酸钆(0.406g)和硝酸铕(0.045g)的混合物(控制Eu3+离子的摩尔量占稀土离子总摩尔量的10%),1.5mmol(0.342g)过硫酸铵于25mL玻璃瓶中,加入8mL乙醇和8mL水,在水热反应釜中,搅拌均匀,然后将反应釜升温至110℃,保持3h。取出反应釜冷却至室温,并用体积比为1:1的乙醇/水混合溶剂洗涤抽滤干燥得到Eu3+离子掺杂的复合相型稀土硫氧化钆。再在5%H2/95%N2的混合气氛下,于850℃下煅烧2h,得到单一相型Eu3+离子掺杂稀土硫氧化钆(Gd2O2S:Eu3+)。
图1中(b)为Eu3+离子掺杂的复合相型和单一相型稀土硫氧化钆的xrd表征图,从图中结果可以看出,Eu3+离子掺杂不会改变稀土硫氧化物的原有晶相结构。
图3中(a)~(c)、(d)~(f)分别为本实施例制得的Eu3+离子掺杂的复合相型和单一相型稀土硫氧化钆的SEM图。从图中结果可以看出,Eu3+离子掺杂后片堆积球状结构形貌保持不变。
图5中(a)、(b)分别为本实施例制得的Eu3+离子掺杂的复合型稀土硫氧化钆的激发和发射光谱。从图5中(a)可以看出,激发光谱中200nm到390nm之间激发光谱峰归属于Eu3+-O2-及Eu3+-S2-之间电荷转移态跃迁,激发光谱主激发峰在394nm,对应为Eu3+-Gd3+之间电荷转移态跃迁。从图5中(b)可以看出,Eu3+离子掺杂的复合型稀土硫氧化钆的发射光谱主峰为617nm,其归属于Eu3+离子5D0-7F2跃迁。由此表明本实施例制得的复合相型Eu3+离子掺杂的稀土硫氧化钆呈现较好的红光发射。
图6中(a)、(b)分别为本实施例制得的Eu3+离子掺杂的单一相型硫氧化钆的激发和发射光谱,从图6中(a)可以看出,200nm到390nm之间激发光谱峰明显宽化,这有利于吸收较大波长范围内的激发光以提高发光强度;而Eu3+离子掺杂的单一相型硫氧化钆的发射光谱主峰为626nm,其归属于Eu3+离子的5D0-7F2跃迁,由此表明本实施例制得的单一相型Eu3+离子掺杂的稀土硫氧化钆同样呈现出较好的红光发射。
实施例3
称取1mmol稀土硝酸钇(0.364g)和硝酸铕(0.023g)的混合物(控制Eu3+离子的摩尔量占稀土离子总摩尔量的5%),1.5mmol(0.342g)过硫酸铵于25mL玻璃瓶中,加入8mL乙醇和8mL水,在水热反应釜中,搅拌均匀,然后将反应釜升温至110℃,保持3h。取出反应釜冷却至室温,并用体积比为1:1的乙醇/水混合溶剂洗涤抽滤干燥得到Eu3+离子掺杂的复合相型稀土硫氧化钇。再在5%H2/95%N2的混合气氛下,于850℃下煅烧2h,得到单一相型Eu3+离子掺杂稀土硫氧化钇(Y2O2S:Eu3+)。
图4中(a)为Eu3+离子掺杂的复合相型和单一相型稀土硫氧化钇的xrd表征图,从图中结果可以看出,Eu3+离子掺杂不会改变稀土硫氧化物的原有晶相结构。图4中(b)~(c)、(d)~(e)分别为本实施例制得的Eu3+离子掺杂的复合相型和单一相型稀土硫氧化钇的SEM图。从图中结果可以看出,Eu3+离子掺杂后片堆积球状结构形貌保持不变。
图5中(c)、(d)分别为本实施例制得的Eu3+离子掺杂的复合型稀土硫氧化钇的激发和发射光谱。从图5中(c)可以看出,激发光谱中200nm到390nm之间激发光谱峰归属于Y3+-O2-及Y3+-S2-之间电荷转移态跃迁,激发光谱主激发峰在394nm,对应为Eu3+-Y3+之间电荷转移态跃迁。从图5中(d)可以看出,Eu3+离子掺杂的复合型稀土硫氧化钆的发射光谱主峰为617nm,其归属于Eu3+离子5D0-7F2跃迁。由此表明本实施例制得的复合相型Eu3+离子掺杂的稀土硫氧化钆呈现较好的红光发射。
图6中(c)、(d)分别为本实施例制得的Eu3+离子掺杂的单一相型硫氧化钇的激发和发射光谱,从图6中(c)可以看出,200nm到390nm之间激发光谱峰明显宽化,这有利于吸收较大波长范围内的激发光以提高发光强度;而Eu3+离子掺杂的单一相型硫氧化钆的发射光谱主峰为627nm,其归属于Eu3+离子的5D0-7F2跃迁,由此表明本实施例制得的单一相型Eu3+离子掺杂的稀土硫氧化钆同样呈现出较好的红光发射。
以上,对本发明的实施方式进行了说明。但是,本发明不限定于上述实施方式。凡在本发明的精神和原则之内,所做的任何修改、等同替换、改进等,均应包含在本发明的保护范围之内。
Claims (24)
1.一种新型片堆积结构稀土硫氧化物的制备方法,其特征在于,包括如下步骤:以过硫酸盐作为硫源及形貌调控剂,与稀土盐前驱体溶液通过水热法制得复合相型稀土硫氧化物;
所述过硫酸盐选自过硫酸锂、过硫酸钠、过硫酸钾、过硫酸铷、过硫酸铯、过硫酸铵、过硫酸氢铵、过硫酸锰、过硫酸钙、过硫酸银、过硫酸钡中的至少一种;
所述稀土盐前驱体包括两种稀土元素,一种选自镧、铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱、镥、钇作为基体稀土,另一种选自铈、镨、钕、钐、铕、钆、铽、镝、钬、铒、铥、镱作为激活剂稀土,用以增强制备的稀土硫氧化物的发光效果;
所述基体稀土与激活剂稀土的摩尔比为1:0.01~0.25。
2.如权利要求1所述的制备方法,其特征在于,所述稀土盐通过稀土的氧化物与酸反应制得;
所述稀土的氧化物选自氧化钪、氧化钇、氧化镧、氧化铈、氧化镨、氧化钕、氧化钷、氧化钐、氧化铕、氧化钆、氧化铽、氧化镝、氧化钬、氧化铒、氧化铥、氧化镱、氧化镥中的一种;所述酸包括硝酸、盐酸、硫酸;
所述稀土的硝酸盐选自硝酸钪,硝酸钇,硝酸镧,硝酸铈,硝酸镨,硝酸钕,硝酸钷,硝酸钐,硝酸铕,硝酸钆,硝酸铽,硝酸镝,硝酸钬,硝酸铒,硝酸铥,硝酸镱,硝酸镥中的至少一种;
所述稀土的氯化盐选自氯化钪,氯化钇,氯化镧,氯化铈,氯化镨,氯化钕,氯化钷,氯化钐,氯化铕,氯化钆,氯化铽,氯化镝,氯化钬,氯化铒,氯化铥,氯化镱,氯化镥中的至少一种;
所述稀土的硫酸盐选自硫酸钪,硫酸钇,硫酸镧,硫酸铈,硫酸镨,硫酸钕,硫酸钷,硫酸钐,硫酸铕,硫酸钆,硫酸铽,硫酸镝,硫酸钬,硫酸铒,硫酸铥,硫酸镱,硫酸镥中的至少一种。
3.如权利要求1所述的制备方法,其特征在于,所述稀土盐和过硫酸盐的摩尔比为1:0.05~20。
4.如权利要求3所述的制备方法,其特征在于,所述稀土盐和过硫酸盐的摩尔比为1:0.1~10。
5.如权利要求4所述的制备方法,其特征在于,所述稀土盐和过硫酸盐的摩尔比为1:0.5~5。
6.如权利要求1所述的制备方法,其特征在于,水热反应采用醇类溶剂或水中的至少一种;
所述醇类溶剂包括C1-C12烷基的一元醇以及多元醇;所述一元醇为甲醇、乙醇、丙醇、异丙醇、正丁醇、异丁醇、叔丁醇、正戊醇,含芳香基的苯甲醇,苯乙醇中的至少一种;所述多元醇为乙二醇、甘油中的至少一种。
7.如权利要求6所述的制备方法,其特征在于,所述水热反应采用醇类溶剂与水的混合溶剂;醇类溶剂与水的体积比值为0.1~10的混合溶剂。
8.如权利要求6所述的制备方法,其特征在于,所述水热反应采用一元与多元醇的混合溶剂;一元醇与多元醇的体积比值为0.1~10的混合溶剂。
9.如权利要求1所述的制备方法,其特征在于,水热反应温度不高于220℃。
10.如权利要求9所述的制备方法,其特征在于,所述水热反应温度为80~200℃。
11.如权利要求10所述的制备方法,其特征在于,所述水热反应温度为110~180℃。
12. 如权利要求1所述的制备方法,其特征在于,水热反应时间为1 -48h。
13.如权利要求12所述的制备方法,其特征在于,所述水热反应时间为1~24h。
14.如权利要求1-13任一项所述的制备方法,其特征在于,所述制备方法还包括待反应结束后,对反应体系进行固液分离得到反应产物的过程。
15.如权利要求14所述的制备方法,其特征在于,所述制备方法还包括对固液分离得到的反应产物进行洗涤;采用能够溶解所述复合相型稀土硫氧化物的溶剂对反应产物进行洗涤;
所述溶剂为醇类溶剂与水的混合溶剂;醇类溶剂与水的体积比值为0.1~10的混合溶剂;
所述洗涤采用的醇类溶剂包括C1-C12烷基的一元醇以及多元醇;
所述一元醇为甲醇、乙醇、丙醇、异丙醇、正丁醇、异丁醇、叔丁醇、正戊醇,含芳香基的苯甲醇,苯乙醇中的至少一种;所述多元醇为乙二醇、甘油中的至少一种。
16.如权利要求1-13任一项所述的制备方法,其特征在于,所述制备方法包括如下步骤:
按照摩尔比为1:0.05~20分别称取将稀土盐和过硫酸盐置于水热反应釜中,加入醇类溶剂与水的混合溶剂,搅拌超声溶解至无明显颗粒存在,经水热反应;待反应完成后,固液分离,对得到的反应产物进行洗涤、干燥,得到复合相型稀土硫氧化物。
17.如权利要求1-13任一项所述的制备方法,其特征在于,所述制备方法还包括对制得的复合相型稀土硫氧化物进行高温煅烧还原后制得单一相型稀土硫氧化物;
所述高温煅烧在管式炉或者马弗炉中进行;
所述高温煅烧在还原性气体气氛下进行;所述还原性气体包括氢气、一氧化碳、氨气中的至少一种。
18.如权利要求17所述的制备方法,其特征在于,所述还原性气体为还原性气体与惰性气体的混合气体;
氢气与氮气按照体积比为2:98~20:80的混合气体;
所述高温煅烧温度为200-1000℃;
所述高温煅烧时间为0.1-48h。
19.如权利要求18所述的制备方法,其特征在于,所述高温煅烧温度为400~900℃;时间为2~36h。
20.如权利要求17所述的制备方法,其特征在于,所述单一相型稀土硫氧化物的制备方法,包括如下步骤:
将上述制得的复合相型稀土硫氧化物产物置于管式炉或者马弗炉中,在还原性气体气氛下,于200-1000℃下高温煅烧0.1-48h,制得单一相型稀土硫氧化物。
21.如权利要求1-13、18任一项所述的制备方法,其特征在于,所述稀土硫氧化物以化学式Ln2O2S表示;其中Ln代表稀土元素,选自Sc、Y、La、Ce、Pr、Nd、Pm、Sm、Eu、Gd、Tb、Dy、Ho、Er、Tm、Yb、Lu、Tb和Dy中的两种。
22.如权利要求21所述的制备方法,其特征在于,所述稀土元素为Y、Eu、Gd中的两种。
23.如权利要求21所述的制备方法,其特征在于,所述稀土硫氧化物在发光材料方面的应用。
24.一种发光材料,其含有权利要求1-23任一项所述制备方法制得的稀土硫氧化物。
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Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63101479A (ja) * | 1986-10-20 | 1988-05-06 | Kasei Optonix Co Ltd | 希土類酸硫化物蛍光体 |
WO1996001297A1 (en) * | 1994-07-01 | 1996-01-18 | David Sarnoff Research Center, Inc. | Method of preparing small particle size phosphors |
JPH10237443A (ja) * | 1997-02-21 | 1998-09-08 | Nichia Chem Ind Ltd | X線増感紙用希土類酸硫化物系蛍光体の製造方法 |
US5958295A (en) * | 1997-09-24 | 1999-09-28 | Osram Sylvania Inc. | Terbium-activated rare earth oxysulfide phosphor with enhanced blue emission |
JPH11344599A (ja) * | 1997-11-11 | 1999-12-14 | Fuji Photo Film Co Ltd | 放射線増感スクリーン |
JP2006078901A (ja) * | 2004-09-10 | 2006-03-23 | Fuji Photo Film Co Ltd | 熱現像感光材料および画像形成方法 |
JP2006206892A (ja) * | 2004-12-28 | 2006-08-10 | Showa Denko Kk | 蛍光体及びその製造方法並びにランプ |
CN101811722A (zh) * | 2010-04-19 | 2010-08-25 | 中国科学院长春应用化学研究所 | 一种稀土硫氧化物的制备方法 |
DE102011090093A1 (de) * | 2011-12-29 | 2013-07-04 | Siemens Aktiengesellschaft | Seltenerdoxysulfid mit plättchenförmiger Struktur |
CN106520121A (zh) * | 2016-10-27 | 2017-03-22 | 东北大学 | 稀土掺杂硫氧化钆和含氧硫酸钆上转换荧光粉的制备方法 |
CN110876386A (zh) * | 2019-11-20 | 2020-03-13 | 厦门稀土材料研究所 | 一种稀土氧化物协同纳米银抗菌剂及其制备方法 |
-
2020
- 2020-10-19 CN CN202011127871.1A patent/CN114380319B/zh active Active
Patent Citations (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS63101479A (ja) * | 1986-10-20 | 1988-05-06 | Kasei Optonix Co Ltd | 希土類酸硫化物蛍光体 |
WO1996001297A1 (en) * | 1994-07-01 | 1996-01-18 | David Sarnoff Research Center, Inc. | Method of preparing small particle size phosphors |
JPH10237443A (ja) * | 1997-02-21 | 1998-09-08 | Nichia Chem Ind Ltd | X線増感紙用希土類酸硫化物系蛍光体の製造方法 |
US5958295A (en) * | 1997-09-24 | 1999-09-28 | Osram Sylvania Inc. | Terbium-activated rare earth oxysulfide phosphor with enhanced blue emission |
JPH11344599A (ja) * | 1997-11-11 | 1999-12-14 | Fuji Photo Film Co Ltd | 放射線増感スクリーン |
JP2006078901A (ja) * | 2004-09-10 | 2006-03-23 | Fuji Photo Film Co Ltd | 熱現像感光材料および画像形成方法 |
JP2006206892A (ja) * | 2004-12-28 | 2006-08-10 | Showa Denko Kk | 蛍光体及びその製造方法並びにランプ |
CN101811722A (zh) * | 2010-04-19 | 2010-08-25 | 中国科学院长春应用化学研究所 | 一种稀土硫氧化物的制备方法 |
DE102011090093A1 (de) * | 2011-12-29 | 2013-07-04 | Siemens Aktiengesellschaft | Seltenerdoxysulfid mit plättchenförmiger Struktur |
CN106520121A (zh) * | 2016-10-27 | 2017-03-22 | 东北大学 | 稀土掺杂硫氧化钆和含氧硫酸钆上转换荧光粉的制备方法 |
CN110876386A (zh) * | 2019-11-20 | 2020-03-13 | 厦门稀土材料研究所 | 一种稀土氧化物协同纳米银抗菌剂及其制备方法 |
Non-Patent Citations (2)
Title |
---|
an orderly arrangement of layered carbon nanosheet TiO2 nanosheet stack with superior artificially interfacial lithium pseudocapacity;wenwu fu et al;《journal of powder sources》;20200601;全文 * |
微纳米稀土硫氧化物的合成方法研究进展;杨利颖;王进贤;董相廷;刘桂霞;于文生;徐佳;;中国稀土学报;20111215(06);全文 * |
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