CN114057219A - Preparation method of nano metal oxide - Google Patents
Preparation method of nano metal oxide Download PDFInfo
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- CN114057219A CN114057219A CN202010858890.5A CN202010858890A CN114057219A CN 114057219 A CN114057219 A CN 114057219A CN 202010858890 A CN202010858890 A CN 202010858890A CN 114057219 A CN114057219 A CN 114057219A
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- organic solvent
- metal oxide
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- 229910044991 metal oxide Inorganic materials 0.000 title claims abstract description 68
- 150000004706 metal oxides Chemical class 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title abstract description 46
- 239000003960 organic solvent Substances 0.000 claims abstract description 69
- 229910052751 metal Inorganic materials 0.000 claims abstract description 61
- 239000002184 metal Substances 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 47
- 239000000203 mixture Substances 0.000 claims abstract description 14
- 239000000463 material Substances 0.000 claims abstract description 12
- 238000000034 method Methods 0.000 claims description 66
- 239000002086 nanomaterial Substances 0.000 claims description 43
- 238000009210 therapy by ultrasound Methods 0.000 claims description 39
- 239000000126 substance Substances 0.000 claims description 36
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 33
- 229910052733 gallium Inorganic materials 0.000 claims description 21
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 18
- XFNJVJPLKCPIBV-UHFFFAOYSA-N trimethylenediamine Chemical compound NCCCN XFNJVJPLKCPIBV-UHFFFAOYSA-N 0.000 claims description 16
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 14
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 14
- 239000012498 ultrapure water Substances 0.000 claims description 14
- 239000002245 particle Substances 0.000 claims description 13
- 150000003141 primary amines Chemical group 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 10
- KIDHWZJUCRJVML-UHFFFAOYSA-N putrescine Chemical compound NCCCCN KIDHWZJUCRJVML-UHFFFAOYSA-N 0.000 claims description 10
- VHRGRCVQAFMJIZ-UHFFFAOYSA-N cadaverine Chemical compound NCCCCCN VHRGRCVQAFMJIZ-UHFFFAOYSA-N 0.000 claims description 9
- AOHJOMMDDJHIJH-UHFFFAOYSA-N propylenediamine Chemical compound CC(N)CN AOHJOMMDDJHIJH-UHFFFAOYSA-N 0.000 claims description 9
- 150000003335 secondary amines Chemical class 0.000 claims description 7
- KDSNLYIMUZNERS-UHFFFAOYSA-N 2-methylpropanamine Chemical compound CC(C)CN KDSNLYIMUZNERS-UHFFFAOYSA-N 0.000 claims description 6
- QUSNBJAOOMFDIB-UHFFFAOYSA-N Ethylamine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- BAVYZALUXZFZLV-UHFFFAOYSA-N Methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 6
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 6
- WGQKYBSKWIADBV-UHFFFAOYSA-N benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 6
- GVWISOJSERXQBM-UHFFFAOYSA-N n-methylpropan-1-amine Chemical compound CCCNC GVWISOJSERXQBM-UHFFFAOYSA-N 0.000 claims description 6
- DPBLXKKOBLCELK-UHFFFAOYSA-N pentan-1-amine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 6
- WGYKZJWCGVVSQN-UHFFFAOYSA-N propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 claims description 3
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 3
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- HQABUPZFAYXKJW-UHFFFAOYSA-N butan-1-amine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- 239000011651 chromium Substances 0.000 claims description 3
- 229910017052 cobalt Inorganic materials 0.000 claims description 3
- 239000010941 cobalt Substances 0.000 claims description 3
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 3
- 229910052802 copper Inorganic materials 0.000 claims description 3
- 239000010949 copper Substances 0.000 claims description 3
- LIWAQLJGPBVORC-UHFFFAOYSA-N ethylmethylamine Chemical compound CCNC LIWAQLJGPBVORC-UHFFFAOYSA-N 0.000 claims description 3
- 229910052732 germanium Inorganic materials 0.000 claims description 3
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052738 indium Inorganic materials 0.000 claims description 3
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- JJWLVOIRVHMVIS-UHFFFAOYSA-N isopropylamine Chemical compound CC(C)N JJWLVOIRVHMVIS-UHFFFAOYSA-N 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 229910052750 molybdenum Inorganic materials 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- XCVNDBIXFPGMIW-UHFFFAOYSA-N n-ethylpropan-1-amine Chemical compound CCCNCC XCVNDBIXFPGMIW-UHFFFAOYSA-N 0.000 claims description 3
- XHFGWHUWQXTGAT-UHFFFAOYSA-N n-methylpropan-2-amine Chemical compound CNC(C)C XHFGWHUWQXTGAT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052759 nickel Inorganic materials 0.000 claims description 3
- 229910052758 niobium Inorganic materials 0.000 claims description 3
- 239000010955 niobium Substances 0.000 claims description 3
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 claims description 3
- 229940100684 pentylamine Drugs 0.000 claims description 3
- 229910052706 scandium Inorganic materials 0.000 claims description 3
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 claims description 3
- YBRBMKDOPFTVDT-UHFFFAOYSA-N tert-butylamine Chemical compound CC(C)(C)N YBRBMKDOPFTVDT-UHFFFAOYSA-N 0.000 claims description 3
- 229910052716 thallium Inorganic materials 0.000 claims description 3
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 239000011135 tin Substances 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 229910052720 vanadium Inorganic materials 0.000 claims description 3
- 229910052725 zinc Inorganic materials 0.000 claims description 3
- 239000011701 zinc Substances 0.000 claims description 3
- 229910052726 zirconium Inorganic materials 0.000 claims description 3
- LEONUFNNVUYDNQ-UHFFFAOYSA-N vanadium atom Chemical compound [V] LEONUFNNVUYDNQ-UHFFFAOYSA-N 0.000 claims 1
- 238000011031 large-scale manufacturing process Methods 0.000 abstract description 3
- QZQVBEXLDFYHSR-UHFFFAOYSA-N gallium(III) oxide Inorganic materials O=[Ga]O[Ga]=O QZQVBEXLDFYHSR-UHFFFAOYSA-N 0.000 description 29
- 239000000243 solution Substances 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 15
- 238000002441 X-ray diffraction Methods 0.000 description 12
- 239000013078 crystal Substances 0.000 description 12
- 239000000047 product Substances 0.000 description 12
- 239000002904 solvent Substances 0.000 description 11
- 238000006243 chemical reaction Methods 0.000 description 10
- 239000002135 nanosheet Substances 0.000 description 10
- 230000008569 process Effects 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 229910001338 liquidmetal Inorganic materials 0.000 description 8
- 238000005303 weighing Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000011521 glass Substances 0.000 description 7
- 239000012046 mixed solvent Substances 0.000 description 7
- 238000001816 cooling Methods 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 229910001195 gallium oxide Inorganic materials 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- 229910002601 GaN Inorganic materials 0.000 description 5
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 description 5
- AJNVQOSZGJRYEI-UHFFFAOYSA-N digallium;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Ga+3].[Ga+3] AJNVQOSZGJRYEI-UHFFFAOYSA-N 0.000 description 5
- 238000001035 drying Methods 0.000 description 5
- 229910052760 oxygen Inorganic materials 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 239000012535 impurity Substances 0.000 description 4
- 239000001301 oxygen Substances 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000003786 synthesis reaction Methods 0.000 description 4
- 241000222336 Ganoderma Species 0.000 description 3
- -1 batteries Substances 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000002073 nanorod Substances 0.000 description 3
- 230000006911 nucleation Effects 0.000 description 3
- 238000010899 nucleation Methods 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 238000001308 synthesis method Methods 0.000 description 3
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N Iron oxide Chemical compound [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 238000007792 addition Methods 0.000 description 2
- 238000000137 annealing Methods 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 230000001276 controlling effect Effects 0.000 description 2
- 229910021513 gallium hydroxide Inorganic materials 0.000 description 2
- CKHJYUSOUQDYEN-UHFFFAOYSA-N gallium(3+) Chemical compound [Ga+3] CKHJYUSOUQDYEN-UHFFFAOYSA-N 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 description 2
- 239000003456 ion exchange resin Substances 0.000 description 2
- 229920003303 ion-exchange polymer Polymers 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 239000002127 nanobelt Substances 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 230000036632 reaction speed Effects 0.000 description 2
- 238000000527 sonication Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 2
- GOJUJUVQIVIZAV-UHFFFAOYSA-N 2-amino-4,6-dichloropyrimidine-5-carbaldehyde Chemical group NC1=NC(Cl)=C(C=O)C(Cl)=N1 GOJUJUVQIVIZAV-UHFFFAOYSA-N 0.000 description 1
- 241000894006 Bacteria Species 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 description 1
- 239000005751 Copper oxide Substances 0.000 description 1
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 1
- WGLPBDUCMAPZCE-UHFFFAOYSA-N Trioxochromium Chemical compound O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 1
- XHCLAFWTIXFWPH-UHFFFAOYSA-N [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[V+5].[V+5] XHCLAFWTIXFWPH-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 238000000498 ball milling Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- CXKCTMHTOKXKQT-UHFFFAOYSA-N cadmium oxide Inorganic materials [Cd]=O CXKCTMHTOKXKQT-UHFFFAOYSA-N 0.000 description 1
- CFEAAQFZALKQPA-UHFFFAOYSA-N cadmium(2+);oxygen(2-) Chemical compound [O-2].[Cd+2] CFEAAQFZALKQPA-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 229910000423 chromium oxide Inorganic materials 0.000 description 1
- 229910000428 cobalt oxide Inorganic materials 0.000 description 1
- IVMYJDGYRUAWML-UHFFFAOYSA-N cobalt(ii) oxide Chemical compound [Co]=O IVMYJDGYRUAWML-UHFFFAOYSA-N 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229910000431 copper oxide Inorganic materials 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 230000009881 electrostatic interaction Effects 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- YBMRDBCBODYGJE-UHFFFAOYSA-N germanium oxide Inorganic materials O=[Ge]=O YBMRDBCBODYGJE-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910003437 indium oxide Inorganic materials 0.000 description 1
- PJXISJQVUVHSOJ-UHFFFAOYSA-N indium(iii) oxide Chemical compound [O-2].[O-2].[O-2].[In+3].[In+3] PJXISJQVUVHSOJ-UHFFFAOYSA-N 0.000 description 1
- 239000008235 industrial water Substances 0.000 description 1
- 238000005374 membrane filtration Methods 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002120 nanofilm Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910000480 nickel oxide Inorganic materials 0.000 description 1
- 229910000484 niobium oxide Inorganic materials 0.000 description 1
- URLJKFSTXLNXLG-UHFFFAOYSA-N niobium(5+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Nb+5].[Nb+5] URLJKFSTXLNXLG-UHFFFAOYSA-N 0.000 description 1
- QGLKJKCYBOYXKC-UHFFFAOYSA-N nonaoxidotritungsten Chemical compound O=[W]1(=O)O[W](=O)(=O)O[W](=O)(=O)O1 QGLKJKCYBOYXKC-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 1
- PVADDRMAFCOOPC-UHFFFAOYSA-N oxogermanium Chemical compound [Ge]=O PVADDRMAFCOOPC-UHFFFAOYSA-N 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N oxonickel Chemical compound [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 description 1
- WKMKTIVRRLOHAJ-UHFFFAOYSA-N oxygen(2-);thallium(1+) Chemical compound [O-2].[Tl+].[Tl+] WKMKTIVRRLOHAJ-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000004917 polyol method Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000001223 reverse osmosis Methods 0.000 description 1
- HYXGAEYDKFCVMU-UHFFFAOYSA-N scandium oxide Chemical compound O=[Sc]O[Sc]=O HYXGAEYDKFCVMU-UHFFFAOYSA-N 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910003438 thallium oxide Inorganic materials 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 229910001930 tungsten oxide Inorganic materials 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 229910001935 vanadium oxide Inorganic materials 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
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Classifications
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G15/00—Compounds of gallium, indium or thallium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/14—Methods for preparing oxides or hydroxides in general
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G1/00—Methods of preparing compounds of metals not covered by subclasses C01B, C01C, C01D, or C01F, in general
- C01G1/02—Oxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
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Abstract
The invention provides a preparation method of a novel nano metal oxide, which comprises the following steps: a step of treating a mixture including a simple metal, water and an organic solvent using ultrasonic waves. The preparation process and equipment have the advantages of simple requirements, low material cost, few experimental parameters, mild experimental conditions, no need of additional heat source and/or pressure, capability of quickly preparing the nano metal oxide with the nanometer level of more than kilogram under the ambient temperature and the ambient pressure, and suitability for industrial large-scale production.
Description
Technical Field
The invention belongs to the technical field of nano metal oxide preparation, and relates to a novel preparation method of nano metal oxide.
Background
Due to their unique physical and chemical properties, nano-metal oxides have a wide prospect in practical applications, such as high efficiency catalysts, batteries, semiconductor devices, supercapacitors, energy storage, and magnetic and optical devices. In the scientific research of nano metal oxide materials, the synthesis of nano metal oxides is extremely important, and the difference of synthetic means has great influence on the microstructure and properties of the nano metal oxides.
The traditional synthesis methods of the nano metal oxide include a hydrothermal method, a solvothermal method, a polyol method, a template method, a chemical vapor deposition method, an electrochemical synthesis method and the like. However, these methods usually need to be completed in a high temperature and/or high pressure process and are time-consuming, such as the preparation method of gallium oxide nanorods disclosed in patent application CN 108821331A: heating metal gallium and a substrate to 1100-1200 ℃ in an inert atmosphere, introducing argon and oxygen, preserving the temperature for 1-2h, cooling, washing and drying to obtain a gallium oxide nanorod; the preparation method of the large-size single crystal beta-gallium oxide nanobelt disclosed in patent application CN109881246A comprises the following steps: plating a catalytic thin layer on the gallium nitride film; placing the gallium nitride film into chemical vapor deposition equipment, introducing purge gas, and annealing (500-900 ℃) to form catalytic particles on the surface of the gallium nitride film; forming gallium nitride nanometer seed crystals wrapping the catalytic particles on the gallium nitride film by annealing (1000-1250 ℃) in an oxygen-less environment; growing large-size monocrystal gallium oxide nanobelts in oxygen-less and high-temperature environment (1000-1250 ℃). These preparation methods are all carried out at high temperature, and the prepared products have low yield, are not suitable for large-scale commercial production and have great limitation.
At normal temperature and pressureMild reactions are researched and concerned by many scholars at home and abroad, and the reactions are generally simple in equipment, mild in synthesis process, strong in controllability and good in repeatability. Common normal-temperature normal-pressure mild reaction methods include an electrochemical deposition method, a ball milling method, a sonochemical method and the like. Wherein the chemical reaction energy induced by ultrasonic mainly comes from hot spots (namely the formation, growth and rupture of bubbles in liquid) formed in the acoustic cavitation process, the process greatly concentrates the low energy density of a sound field, the effective temperature reached when the bubbles rupture can reach 5200K, the sound pressure is greater than 20MPa, and meanwhile, the heating and cooling rate in the cavitation bubble rupture process is greater than 1010K/s. The phonochemical reaction can become an effective method for synthesizing nano materials.
Disclosure of Invention
Aiming at the defects of the existing nano metal oxide synthesis method, the invention provides a method for preparing over kilogram nano metal oxide under the conditions of ambient temperature and ambient pressure by ultrasonic treatment without additionally applying heat source and/or pressure.
The above object of the present invention is achieved by the following technical solutions:
a method of preparing a nano-metal oxide, comprising: a step of treating a mixture including a simple metal, water and an organic solvent using ultrasonic waves.
In some embodiments of the preparation method of the present invention, the preparation method of the nano metal oxide is performed at a temperature of 45 ℃ or less and a pressure of 150KPa or less.
In other embodiments of the preparation method of the present invention, the preparation method of the nano metal oxide is performed at a temperature of 37 ℃ or less and a pressure of 120KPa or less.
In other embodiments of the preparation method of the present invention, the preparation method of the nano metal oxide is performed at a temperature of 30 ℃ or less and a pressure of 102KPa or less.
In some embodiments of the preparation method of the present invention, the elemental metal is one or more of gallium, germanium, scandium, titanium, aluminum, vanadium, chromium, zinc, tin, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, tungsten, cadmium, indium, and thallium.
In some embodiments of the preparation method of the present invention, the purity of the metal simple substance is more than or equal to 90%. Further preferably, the purity of the metal simple substance is more than or equal to 95 percent. Further preferably, the purity of the metal simple substance is more than or equal to 99%.
In some embodiments of the preparation method of the present invention, the elemental metal is in a liquid or bulk or powder form. When the metal simple substance is powdery, the average particle size of the metal simple substance is preferably 5-5000 nm; more preferably, the average particle size of the elementary metal is 50 to 500 nm.
In some embodiments of the preparation method of the present invention, the ratio of the mass of the elemental metal to the total volume of water and organic solvent is (0.002-0.3): 1 in g/ml.
In some embodiments of the preparation method of the present invention, the volume ratio of the water to the organic solvent is 1: (0.1-50). Further preferably, the volume ratio of the water to the organic solvent is 1: (0.2-20).
In some embodiments of the preparation method of the present invention, the water is one or more of pure water, deionized water, and ultrapure water.
In some embodiments of the preparation method of the present invention, the organic solvent is a water-soluble organic solvent. More preferably, the organic solvent is a nitrogen-containing organic solvent.
In some embodiments of the preparation method of the present invention, the nitrogen-containing organic solvent is a primary amine-based organic solvent and/or a secondary amine-based organic solvent. More preferably, the nitrogen-containing organic solvent is a primary amine organic solvent.
In some embodiments of the preparation method of the present invention, the primary amine organic solvent is one or more of methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine, pentylamine, benzylamine, ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, and 1, 5-pentylenediamine.
In some embodiments of the preparation method of the present invention, the secondary amine organic solvent is one or more of N-ethylmethylamine, N-methyl-N-propylamine, N-methylisopropylamine, and N-ethyl-N-propylamine.
In some preferred embodiments of the preparation method of the present invention, the nitrogen-containing organic solvent is one or more of ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, and 1, 5-pentylenediamine.
In some embodiments of the preparation method of the present invention, a mixture comprising the elemental metal, water, and the organic solvent is subjected to ultrasonic treatment in an ultrasonic apparatus.
In some embodiments of the methods of the present invention, the ultrasonic device is one or more of an ultrasonic cell disruptor, an ultrasonic washer, and an ultrasonic material stripper.
In some embodiments of the preparation method of the present invention, the ultrasonic treatment frequency is 20-100KHz, and the power is greater than or equal to 100W.
In some embodiments of the preparation method of the present invention, the ultrasonic treatment frequency is 20-50KHz, and the power is 400W or more.
In some embodiments of the methods of the present invention, the method produces nanometal oxide in mg or greater.
In some embodiments of the methods of the present invention, the method produces kilogram or greater quantities of the nano-sized metal oxide.
In some embodiments of the preparation methods of the present invention, the prepared nano metal oxide is a zero-dimensional, one-dimensional or two-dimensional nanomaterial.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention uses ultrasonic treatment to prepare the nanometer metal oxide by the mixture of simple metal, water and organic solvent, does not need to additionally apply heat source and/or pressure, and can quickly prepare the nanometer metal oxide at ambient temperature and ambient pressure;
(2) the nano metal oxide prepared by the method has high purity and yield, and the yield can reach 90%;
(3) the preparation process and equipment of the nano metal oxide have simple requirements, low material cost, few experimental parameters, mild experimental conditions and high product purity and yield, can realize the rapid preparation of the nano metal oxide with the kilogram level and is suitable for industrial large-scale production;
(4) the organic solvent adopted by the invention is preferably one or more of ethylenediamine, 1, 2-propanediamine, 1, 3-propanediamine, 1, 4-butanediamine and 1, 5-pentanediamine, 2 amino groups of organic solvent molecules and a metal simple substance have better coordination effect, and the purity and the yield of the nano metal oxide can be improved;
(5) the invention can realize the shape regulation of the nano metal oxide by changing the process conditions;
(6) the preparation method is a universal method for synthesizing the nano metal oxide and controlling the appearance.
Drawings
FIG. 1 shows γ -Ga in an example of the present invention2O3Preparing a schematic diagram of the nano material;
FIG. 2(a) shows γ -Ga in the course of ultrasonic preparation2O3Flow chart of the evolution of the nanomaterial with time, FIGS. 2(b) - (d) are gamma-Ga obtained by ultrasonic treatment for 4h, 5h and 6h in examples 1-3 of the present invention, respectively2O3Scanning Electron Microscope (SEM) images of nanomaterials;
FIG. 3 shows γ -Ga obtained in example 3 of the present invention2O3An X-ray diffraction pattern (XRD) of the nanomaterial;
FIG. 4 shows γ -Ga obtained in example 3 of the present invention2O3Scanning Electron Microscope (SEM) images of nanomaterials;
FIG. 5 shows γ -Ga obtained in example 3 of the present invention2O3High Resolution Transmission Electron Microscopy (HRTEM) images of nanomaterials;
FIG. 6 shows γ -Ga obtained in example 3 of the present invention2O3XPS full spectrum energy scan of 0 to 1200eV of the nanomaterial;
FIG. 7 is an X-ray diffraction pattern of the products prepared in examples 4 to 6 of the present invention and comparative examples 1 to 2;
FIG. 8 is a scanning electron micrograph of products prepared in examples 4 to 6 of the present invention and comparative examples 1 to 2.
Detailed Description
The method for preparing the nano metal oxide of the present invention will be described in detail below, and technical terms or scientific terms used at this time have meanings that are generally understood by those skilled in the art of the present invention, if not otherwise defined.
A method of preparing a nano-metal oxide, comprising: a step of treating a mixture including a simple metal, water and an organic solvent using ultrasonic waves.
The nano metal oxide prepared by the invention refers to a metal oxide with at least one dimension in a three-dimensional space in a nano size (the nano size refers to the length size less than or equal to 100 nm), and can be a zero-dimensional, one-dimensional or two-dimensional nano material. Zero-dimensional nanomaterials refer to nanomaterials with three dimensions in the nanometer size range, such as nanoparticles; the one-dimensional nano material refers to two dimensions in a nano size range, such as a nanowire, a nanorod, a nanotube and the like; two-dimensional nanomaterials refer to materials with one dimension in the nanometer size range, such as nanosheets, nanofilms, and the like. The nanometer metal oxides with different structural appearances can be obtained by adopting different metal simple substances and/or regulating and controlling process conditions.
Ultrasonic treatment, namely placing a mixture comprising a metal simple substance, water and an organic solvent in an ultrasonic instrument for ultrasonic treatment; preferably, the mixture of the metal simple substance, water and the organic solvent is placed in a reaction bottle, and then the reaction bottle is placed in an ultrasonic instrument for ultrasonic treatment, wherein the reaction bottle can be a glass container.
Any ultrasonic instrument that can release ultrasonic waves and can contain a mixture of the simple metal, water and the organic solvent can be applied to the invention, and one or more of an ultrasonic cell disruptor, an ultrasonic cleaning machine and an ultrasonic material stripper are preferred.
Applying ultrasonic waves to a mixture comprising a metal simple substance, water and an organic solvent, wherein the frequency of the applied ultrasonic waves is preferably 20-100KHz, and the power of the ultrasonic waves is preferably more than or equal to 100W; when the nano metal oxide is prepared in a large scale, the ultrasonic treatment frequency is preferably 20-50KHz, and the ultrasonic power is preferably more than or equal to 400W. The ultrasonic treatment time is different according to the ultrasonic power and the metal simple substance: when the same ultrasonic instrument is used, the higher the applied ultrasonic power is, the faster the preparation speed of the nano metal oxide is, and the shorter the ultrasonic treatment time is; the ultrasonic treatment time is different for different metal simple substances. The ultrasonic treatment time is preferably 1 to 20 hours, more preferably 2 to 10 hours, and still more preferably 2 to 7 hours by adjusting the ultrasonic power for different metal simple substances.
The metal simple substance is a metal simple substance corresponding to the nano metal oxide to be prepared, the purity of the metal simple substance is preferably equal to or more than 99.5%, and more preferably equal to or more than 99.8%, and the higher the purity of the metal simple substance is, the higher the nano metal oxide with high purity can be obtained. The metal simple substance is preferably one or more of gallium, germanium, scandium, titanium, aluminum, vanadium, chromium, zinc, tin, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, tungsten, cadmium, indium and thallium, and the nano metal oxide obtained by the metal simple substance is gallium oxide, germanium oxide, scandium oxide, titanium oxide, aluminum oxide, vanadium oxide, chromium oxide, zinc oxide, tin oxide, manganese oxide, iron oxide, cobalt oxide, nickel oxide, copper oxide, zirconium oxide, niobium oxide, molybdenum oxide, tungsten oxide, cadmium oxide, indium oxide and thallium oxide.
The metal simple substance is liquid, blocky or powdery, and when the metal simple substance is powdery, the average particle size of the metal simple substance is preferably 5-5000 nm; more preferably, the average particle diameter is 50 to 500 nm. The average particle diameter is defined as an average value of particle diameters of 100 particles arbitrarily selected among the observed particles by an observation method using an electron microscope such as a transmission electron microscope or a scanning electron microscope. The smaller the average particle size of the metal elementary powder is, the faster the reaction speed is, and the shorter the time for preparing the nano metal oxide is.
The addition amount of the simple metal is not particularly limited, and it is preferable that the ratio of the mass of the simple metal to the total volume of water and the organic solvent is (0.002-0.3): 1 in g/ml. The smaller the amount of the simple metal added relative to the total volume of water and the organic solvent, the faster the reaction speed.
Water is used as reaction medium and as oxygen source for preparing nano metal oxide. The water used in the present invention is not particularly limited, and industrial water and domestic water containing a small amount of ionic impurities may be preferably one or more of pure water, deionized water, and ultrapure water. Pure water refers to water free of impurities or bacteria; deionized water refers to pure water obtained by removing ionic impurities in water through ion exchange resin; ultrapure water is defined as water having a resistivity of 18M Ω cm or more at 25 ℃ and produced by distillation, ion exchange resin deionization, reverse osmosis, nano-membrane filtration or other suitable supercritical fine techniques.
Under high energy generated by ultrasonic cavitation, water serving as a high-polarity solvent can generate strong electrostatic interaction with a metastable solute, and the metastable solute can be well dissolved, so that metastable solute crystals cannot be nucleated and separated out. In the invention, the organic solvent is added while adding water, the organic solvent is preferably a water-soluble organic solvent which is a poor solvent of the metastable state solute, the poor solvent can rapidly reduce the solubility of the metastable state solute and increase the supersaturation of the metastable state solute, and the surface energy of the solution can be increased at the moment; when the solution is in a high supersaturation state in the nucleation stage, the number of crystals will increase, the diameter will decrease, and both the increase of the number of crystals and the decrease of the size of the crystals can increase the total surface energy of the system, thereby consuming the excess energy in the solution phase, so that the chemical potentials of the solid phase and the solution phase tend to be balanced, and the nano-crystals are obtained. The volume ratio of water to organic solvent in the present invention is preferably 1: (0.1-50); further preferably, the volume ratio of the water to the organic solvent is 1: (0.5-10). Aiming at different metal simple substances, the volume ratio of water to an organic solvent used for preparing corresponding nano metal oxide is different, and if the metal simple substance is gallium, the volume ratio of the water to the organic solvent is 1: (0.5-10), gamma-Ga can be successfully obtained2O3And (3) nano materials.
The organic solvent is preferably a nitrogen-containing organic solvent, the nitrogen-containing organic solvent refers to an organic solvent with N element in the molecule, the nitrogen-containing organic solvent can be used as a poor solvent of a metastable solute, the N element has strong coordination effect, a metal simple substance (abbreviated as M) can be protected to form an M-N bond, an MOOH compound is prevented from being generated, and the purity and the yield of the nano metal oxide are improved.
The nitrogen-containing organic solvent is more preferably a primary amine-based organic solvent and/or a secondary amine-based organic solvent. The primary amine or secondary amine organic solvent has N-H bonds in molecules and strong coordination capacity.
The nitrogen-containing organic solvent is preferably a primary amine organic solvent, and the primary amine organic solvent has an H-N-H bond and has better coordination performance.
The primary amine organic solvent is preferably one or more of methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine, pentylamine, benzylamine, ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, and 1, 5-pentylenediamine.
The secondary amine organic solvent is preferably one or more of N-ethylmethylamine, N-methyl-N-propylamine, N-methylisopropylamine and N-ethyl-N-propylamine.
The nitrogen-containing organic solvent of the present invention is more preferably one or more of ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, and 1, 5-pentylenediamine. The two molecular ends of the ethylenediamine, the 1, 2-propane diamine, the 1, 3-propane diamine, the 1, 4-butane diamine and the 1,5 pentane diamine are provided with amino groups, so that the coordination effect with the metal simple substance is better.
The principle of the present invention for preparing nano metal oxide will be explained below, taking Ga as the metal simple substance and Ethylenediamine (EDA) as the organic solvent as an example. As shown in fig. 1, before the ultrasonic treatment, the liquid metal gallium sample is in the form of droplets, and after the ultrasonic treatment is started, the droplets are rapidly cracked into small nano-sized droplets; gallium and H when water alone is used as the solvent2H decomposed by O molecules+Act to form gallium ions, which are then reacted with OH-Reaction to form Ga (OH)3，Ga(OH)3Unstable, decomposing into GaOOH, so that only GaOOH microrod formation is observed when only water is used as a solvent; when only Ethylenediamine (EDA) is used as a solvent, Ga (EDA) compound is formed by metal gallium Ga and EDA, and the Ga (EDA) compound cannot further generate Ga due to the lack of water molecules in the solution as an oxygen source2O3A crystal; when EDA and water are used as mixed solvent, EDA is opposite to OH-For metal gallium ion Ga3+And Ga have better affinity, thus forming Ga (EDA)3+And Ga (EDA) complex in water molecule and OH-By the action of Ga (EDA)3+And decomposition of the Ga (EDA) complex into Ga2O3And (3) nano materials. The preparation principle of other nano metal oxides is the same as that of Ga2O3According to the preparation principle of the nano material, Ga is replaced by a corresponding metal simple substance.
The preparation method of the nano metal oxide can be carried out at the temperature of less than or equal to 45 ℃ and the pressure of less than or equal to 150KPa, can be carried out at the temperature of less than or equal to 37 ℃ and the pressure of less than or equal to 150KPa, can be carried out at the temperature of less than or equal to 30 ℃ and the pressure of less than or equal to 150KPa, can be carried out at the temperature of less than or equal to 37 ℃ and the pressure of less than or equal to 120KPa, can be carried out at the temperature of less than or equal to 30 ℃ and the pressure of less than or equal to 120KPa, can be carried out at the temperature of less than or equal to 37 ℃ and the pressure of less than or equal to 102KPa, and can be carried out at the temperature of less than or equal to 30 ℃ and the pressure of less than or equal to 102 KPa.
The preparation method of the nano metal oxide does not need to additionally apply a heat source and/or pressure, namely an ultrasonic instrument does not need to heat and/or pressurize, and the mixture comprising the metal simple substance, the water and the organic solvent is subjected to ultrasonic treatment at ambient temperature and ambient pressure.
The preparation method of the nano metal oxide can realize the preparation of the nano metal oxide under normal temperature and normal pressure (the normal temperature is defined as 25 ℃, and the normal pressure is defined as one standard atmospheric pressure, namely 101 kPa).
The preparation method of the nano metal oxide can prepare the nano metal oxide with the milligram level or more. The weight of the prepared nano metal oxide depends on the processing volume of an ultrasonic instrument, the processing volume of the ultrasonic instrument is large, and the more mixture comprising the metal simple substance, water and the organic solvent is processed, the more the nano metal oxide is prepared.
The invention can adopt a large-capacity ultrasonic instrument to prepare the nanometer metal oxide with the kilogram level or more, thereby realizing the industrial scale production.
The yield of the nano metal oxide prepared by the preparation method of the nano metal oxide is more than or equal to 85 percent, and the yield is more than or equal to 90 percent preferably. The yield was calculated as: yield% — actual nano metal oxide yield/theoretical nano metal oxide yield × 100%.
Hereinafter, the technical solution of the present invention will be further described and illustrated by specific examples. However, these embodiments are exemplary, and the present disclosure is not limited thereto. Unless otherwise specified, the raw materials used in the following specific examples of the present invention are those commonly used in the art, and the methods used in the examples are those conventional in the art.
In the following examples and comparative examples, the purity of metallic gallium was 99.9%, the ambient temperature was 32 ℃ and the ambient pressure was 101.33 KPa.
Example 1
Measuring 6mL of ultrapure water and 9mL of ethylenediamine in a glass vial to form a mixed solvent, adding 1mmol (69.72mg) of liquid metal gallium into the mixed solvent, placing the glass vial in an ultrasonic two-dimensional material stripper (Scientz-CHF-5A, Xinzhi, China) for ultrasonic treatment, wherein the ultrasonic treatment frequency is 40KHz, and the power is adjusted to 252W; ultrasonic treatment is carried out for 4 hours under the stirring condition; naturally cooling to room temperature after ultrasonic treatment, suction filtering, storing the obtained solution for recycling, reducing reagent consumption, washing the obtained white powder for 3 times by using 75 v/v% ethanol solution, and finally drying at 80 ℃ for 12h to obtain gamma-Ga2O3And (3) nano materials. Weighing to obtain gamma-Ga2O3The mass of the nano material is 86.02mg, and the calculated yield is 91.8%.
Example 2
Example 2 sonication was carried out for 5h, and the other experimental procedures were the same as in example 1. Weighing to obtain gamma-Ga2O3The mass of the nano material is 85.53mg, and the calculated yield is 91.3%.
Example 3
Example 3 sonication for 6h, the other experimental procedures were the same as in example 1. Weighing to obtain gamma-Ga2O3The mass of the nano material is 85.81mg, and the calculated yield is 91.6%.
FIG. 2(a) shows γ -Ga2O3The nanometer material is prepared at any timeFlow chart of the inter-evolution, as can be seen from the figure, gamma-Ga2O3The synthesis process of the nano material is mainly divided into 3 stages, and the nucleation, growth and assembly processes are as follows: the early stage of ultrasonic treatment is mainly a crystal nucleation process, and small crystal nuclei are precipitated from solute; with the increase of the ultrasonic treatment time, crystal nuclei grow to gradually form large gamma-Ga blocks2O3Nanosheets; grown gamma-Ga2O3The nano-sheet is formed into a whole body, tends to be more stable, and is self-assembled to form a hollow spherical structure. FIGS. 2(b) - (d) are gamma-Ga obtained by ultrasonic treatment of 4h, 5h and 6h in examples 1-3 of the present invention, respectively2O3The scanning electron microscope image of the nano material can clearly see the gamma-Ga of the large-sheet nano sheet shape2O3Nanomaterial, gamma-Ga2O3The nanosheets are self-assembled into spheres, and the sample formed by ultrasonic treatment for 4-6h is stable in structure and appearance and does not change greatly with time.
FIG. 3 shows γ -Ga obtained in example 3 of the present invention2O3X-ray diffraction patterns (XRD) of the nanomaterials. An XRD (X-ray diffraction) spectrum shows that the gallium oxide obtained by the method is a gamma phase; the gamma phase has a face-centered cubic (fcc) structure, the space group is Fd3m (JCPDS 20-0426) and no impurity peak is detected, which indicates that the invention obtains high-purity gamma-Ga2O3And (3) nano materials. Ga2O3There are five different phases, alpha, beta, gamma, delta and epsilon, respectively, in which gamma-Ga is metastable2O3The synthesis conditions are very harsh, such as high temperature, high pressure, long reaction time, poor separation effect of reaction products and the like. The invention can rapidly prepare high-purity gamma-phase Ga at ambient temperature and ambient pressure by ultrasonic treatment without additional heat source and/or pressure2O3。
FIG. 4 shows γ -Ga obtained in example 3 of the present invention2O3Scanning Electron Microscope (SEM) images of nanomaterials; as can be seen from the figure, the preparation method of the invention obtains the gamma-Ga with large-sheet nanosheet shape2O3，γ-Ga2O3The nano-sheet is formed into a whole body, tends to be more stable, and is self-assembled to form a hollow spherical structure.
FIG. 5 shows an embodiment of the present inventionExample 3 Gamma-Ga2O3High Resolution Transmission Electron Microscopy (HRTEM) images of nanomaterials. Wherein (a) shows γ -Ga2O3The nano-sheets self-assemble to form a hollow spherical structure, corresponding to the SEM image of FIG. 4; (b) shows that the distance between adjacent crystal planes is measured to be 0.29nm, and the gamma-Ga is measured to be face-centered cubic2O3The d-spacing values of the medium (220) plane have a good match.
To determine gamma-Ga2O3The chemical composition of elements in the nanomaterial was subjected to X-ray photoelectron spectroscopy (XPS) test, and FIG. 6 shows γ -Ga obtained in example 3 of the present invention2O3XPS full spectrum energy scanning graph of 0-1200 eV of nano material, only Ga and O elements and trace carbon exist in the graph, and the fact that high-purity gamma-Ga is prepared is shown2O3And (3) nano materials.
Example 4
Measuring 7.5mL of ultrapure water and 7.5mL of ethylenediamine in a glass vial to form a mixed solvent, wherein the volume ratio of the ultrapure water to the ethylenediamine is 1:1, adding 1mmol (69.72mg) of liquid metal gallium into the mixed solvent, placing the glass vial in an ultrasonic two-dimensional material stripper (Scientz-CHF-5A, New Chinese Ganoderma) for ultrasonic treatment, wherein the ultrasonic treatment frequency is 40KHz, the power is adjusted to 252W, and carrying out ultrasonic treatment for 6h under the stirring condition; naturally cooling to room temperature after ultrasonic treatment, performing suction filtration, storing the obtained solution for recycling, reducing reagent consumption, washing the obtained white powder for 3 times by using 75 v/v% ethanol solution, and finally drying at 80 ℃ for 12h to obtain gamma-Ga2O3And (3) nano materials. Weighing to obtain gamma-Ga2O3The mass of the nano material is 85.02mg, and the calculated yield is 90.7%.
Example 5
Adding 1mmol (69.72mg) of liquid metal gallium into a mixed solvent of 3ml of ultrapure water and 12ml of ethylenediamine, wherein the volume ratio of the ultrapure water to the ethylenediamine is 1: 4; the other experimental procedures were the same as in example 4. Obtaining gamma-Ga2O3And (3) nano materials. Weighing to obtain gamma-Ga2O3The mass of the nano material is 86.33mg, and the calculated yield is 92.1%.
Example 6
To be 1mmol (69.72mg) of liquid metal gallium is added into a mixed solvent of 5ml of ultrapure water and 10ml of ethylenediamine, and the volume ratio of the ultrapure water to the ethylenediamine is 1: 2; the other experimental procedures were the same as in example 4. Obtaining gamma-Ga2O3And (3) nano materials. Weighing to obtain gamma-Ga2O3The mass of the nano material is 86.15mg, and the calculated yield is 91.9%.
Comparative example 1
1mmol (69.72mg) of liquid metal gallium was added to 15ml of ultrapure water, and the other experimental procedures were the same as in example 4 to obtain a powder material.
Comparative example 2
1mmol (69.72mg) of liquid gallium metal was added to 15ml of ethylenediamine, and the other experimental procedures were the same as in example 4 to obtain a powdery material.
FIG. 7 is an X-ray diffraction pattern (XRD) of the products of examples 4-6 of the present invention and comparative examples 1-2, wherein (a) is the XRD of the product of comparative example 1 of the present invention, from which it can be seen that the product of comparative example 1 is GaOOH; comparative example 1 gallium and H metals with water alone as solvent2H decomposed by O molecules+Act to form gallium ions, which are then reacted with OH-Reaction to form Ga (OH)3，Ga(OH)3Unstable and decomposed to GaOOH, so comparative example 1, which used only water as a solvent, only GaOOH formation was observed. FIG. 7(b) is an XRD of the products prepared in examples 4 to 6 of the present invention and comparative example 2, and it can be seen from the XRD patterns that the products prepared in examples 4 to 6 are γ -Ga2O3While comparative example 2 did not prepare gamma-Ga2O3(ii) a Comparative example 2 only EDA was present, and the complex formed by Ga and EDA could not further form gamma-Ga due to lack of oxygen source in the solution2O3Crystal, therefore comparative example 2 only gave Ga (EDA) composite, and γ -Ga could not be prepared2O3。
FIG. 8 is a Scanning Electron Microscope (SEM) image of products prepared in examples 4-6 of the present invention and comparative examples 1-2, wherein (b) - (d) are SEM images of products prepared in examples 4-6 of the present invention, respectively, and it can be seen from the SEM images that examples 4-6 obtain gamma-Ga in nanosheet form2O3，γ-Ga2O3The nanoplatelets can tend to be more stable for reduced overall formationAssembled to form a hollow spherical structure. No γ -Ga observed in FIGS. (a) and (e)2O3Nanosheet morphology.
Example 7
This example synthesizes gamma-Ga in large quantities2O3The method comprises the following steps of (1) taking a mixed solution of 6L of ultrapure water and 9L of ethylenediamine measured by a 20L large-and-small-mouth glass bottle as a solvent, adding 20mol (1394g) of liquid metal gallium, uniformly mixing, and carrying out ultrasonic treatment by using an ultrasonic cleaner (SB-1500DT, New Chinese Ganoderma) at the ultrasonic treatment frequency of 28KHz and the power of 1050W for 5 h; naturally cooling to room temperature after ultrasonic treatment, performing suction filtration, storing the obtained solution for recycling, reducing reagent consumption, washing the obtained white powder for 3 times by using 75 v/v% ethanol solution, and finally drying at 80 ℃ for 12h to obtain gamma-Ga2O3And (3) nano materials. Weighing to obtain gamma-Ga2O3The mass of the nano material is 1738g, and the calculated yield is 92.7%.
Example 8
This example synthesizes gamma-Ga in large quantities2O3The nano material is prepared by taking a mixed solution of 5L of ultrapure water and 10L of 1, 2-propane diamine measured by a 20L large-and-small-mouth glass bottle as a solvent, adding 20mol (1394g) of liquid metal gallium, uniformly mixing, and carrying out ultrasonic treatment by using an ultrasonic cleaner (SB-1500DT, New Chinese Ganoderma) with the ultrasonic treatment frequency of 28KHz and the power of 1050W for 5.5 h; naturally cooling to room temperature after ultrasonic treatment, performing suction filtration, storing the obtained solution for recycling, reducing reagent consumption, washing the obtained white powder for 4 times by using 70 v/v% ethanol solution, and finally drying at 80 ℃ for 15h to obtain gamma-Ga2O3And (3) nano materials. Weighing to obtain gamma-Ga2O3The mass of the nano material is 1711g, and the calculated yield is 91.3%.
The preparation method of the nano metal oxide can prepare and obtain products of more than kilogram level at ambient temperature and ambient pressure, realizes simple, quick and large-scale preparation of the nano metal oxide, and is easy to realize industrial large-scale production.
The specific embodiments described herein are merely illustrative of the spirit of the invention. Various modifications or additions may be made to the described embodiments or alternatives may be employed by those skilled in the art without departing from the spirit or ambit of the invention as defined in the appended claims.
Claims (28)
1. A method for preparing nano metal oxide is characterized by comprising the following steps: a step of treating a mixture including a simple metal, water and an organic solvent using ultrasonic waves.
2. The method as claimed in claim 1, wherein the method is carried out at a temperature of 45 ℃ or less and a pressure of 150KPa or less.
3. The method as claimed in claim 1, wherein the method is carried out at a temperature of 37 ℃ or less and a pressure of 120KPa or less.
4. The method as claimed in claim 1, wherein the method is carried out at a temperature of 30 ℃ or less and a pressure of 102KPa or less.
5. The method as claimed in claim 1, wherein the metal element is one or more of gallium, germanium, scandium, titanium, aluminum, vanadium, chromium, zinc, tin, manganese, iron, cobalt, nickel, copper, zirconium, niobium, molybdenum, tungsten, cadmium, indium and thallium.
6. The method for preparing nano metal oxide according to claim 1 or 5, wherein the purity of the metal simple substance is more than or equal to 90%.
7. The method for preparing nano metal oxide according to claim 6, wherein the purity of the metal simple substance is not less than 95%.
8. The method for preparing nano metal oxide according to claim 7, wherein the purity of the metal simple substance is not less than 99%.
9. The method as claimed in claim 1 or 5, wherein the metal is in the form of liquid, bulk or powder.
10. The method as claimed in claim 9, wherein when the elemental metal is in a powder form, the average particle diameter of the elemental metal is 5 to 5000 nm.
11. The method as claimed in claim 10, wherein when the elemental metal is in a powder form, the average particle diameter of the elemental metal is 50-500 nm.
12. The method of claim 1, wherein the ratio of the mass of the elemental metal to the total volume of water and the organic solvent is (0.002-0.3): 1.
13. the method for preparing nano metal oxide according to claim 1, wherein the volume ratio of the water to the organic solvent is 1: (0.1-50).
14. The method of claim 1, wherein the water is one or more of pure water, deionized water, and ultrapure water.
15. The method according to claim 1, wherein the organic solvent is a water-soluble organic solvent.
16. The method as claimed in claim 15, wherein the organic solvent is a nitrogen-containing organic solvent.
17. The method of claim 16, wherein the nitrogen-containing organic solvent is a primary amine organic solvent and/or a secondary amine organic solvent.
18. The method as claimed in claim 17, wherein the nitrogen-containing organic solvent is a primary amine organic solvent.
19. The method as claimed in claim 18, wherein the primary amine organic solvent is one or more of methylamine, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, tert-butylamine, pentylamine, benzylamine, ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, and 1, 5-pentyldiamine.
20. The method as claimed in claim 17, wherein the secondary amine organic solvent is one or more of N-ethylmethylamine, N-methyl-N-propylamine, N-methylisopropylamine, and N-ethyl-N-propylamine.
21. The method of any one of claims 16-19, wherein the nitrogen-containing organic solvent is one or more of ethylenediamine, 1, 2-propylenediamine, 1, 3-propylenediamine, 1, 4-butylenediamine, and 1, 5-pentylenediamine.
22. The method of claim 1, wherein the mixture of the elemental metal, water and the organic solvent is subjected to ultrasonic treatment in an ultrasonic apparatus.
23. The method as claimed in claim 22, wherein the ultrasonic device is one or more of an ultrasonic cell disruptor, an ultrasonic cleaner, and an ultrasonic material stripper.
24. The method for preparing nano metal oxide according to claim 1, wherein the ultrasonic treatment frequency is 20-100KHz, and the power is not less than 100W.
25. The method for preparing nano metal oxide according to claim 1, wherein the ultrasonic treatment frequency is 20-50KHz, and the power is not less than 400W.
26. The method of claim 1, wherein the nano metal oxide is prepared in milligram or more.
27. The method of claim 1, wherein the method is used to prepare nano metal oxide with a kilogram level or more.
28. The method of claim 1, wherein the nano metal oxide is a zero-dimensional, one-dimensional or two-dimensional nano material.
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| CN112010342A (en) * | 2020-07-29 | 2020-12-01 | 宁波工程学院 | Gamma-Ga2O3Preparation method of nanosheet |
| CN114408970B (en) * | 2022-01-25 | 2023-07-18 | 重庆邮电大学 | Preparation method of hollow mesoporous carbon-doped gallium trioxide nanospheres and product thereof |
| CN114573027B (en) * | 2022-03-09 | 2023-08-18 | 北方民族大学 | Vanadium pentoxide nanobelt and preparation method thereof |
| CN116072844A (en) * | 2023-01-16 | 2023-05-05 | 宁波工程学院 | Ga (gallium) 2 O 3 Nano material of@rGO core-shell, preparation method and application thereof |
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