CN109663595A - A kind of copper based composite metal oxidate hollow microsphere, preparation method and the usage - Google Patents
A kind of copper based composite metal oxidate hollow microsphere, preparation method and the usage Download PDFInfo
- Publication number
- CN109663595A CN109663595A CN201910118068.2A CN201910118068A CN109663595A CN 109663595 A CN109663595 A CN 109663595A CN 201910118068 A CN201910118068 A CN 201910118068A CN 109663595 A CN109663595 A CN 109663595A
- Authority
- CN
- China
- Prior art keywords
- hollow microsphere
- copper
- metal
- hollow
- oxide
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000004005 microsphere Substances 0.000 title claims abstract description 118
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 52
- 239000002184 metal Substances 0.000 title claims abstract description 52
- 239000010949 copper Substances 0.000 title claims abstract description 51
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 34
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 74
- 238000000034 method Methods 0.000 claims abstract description 39
- 238000006243 chemical reaction Methods 0.000 claims abstract description 29
- 239000003054 catalyst Substances 0.000 claims abstract description 25
- 239000011324 bead Substances 0.000 claims abstract description 18
- 239000005751 Copper oxide Substances 0.000 claims abstract description 14
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 14
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 8
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 8
- 239000010703 silicon Substances 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 7
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M sodium hydroxide Inorganic materials [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 43
- 239000000243 solution Substances 0.000 claims description 23
- 239000002105 nanoparticle Substances 0.000 claims description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 20
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 16
- 239000000047 product Substances 0.000 claims description 16
- 239000000725 suspension Substances 0.000 claims description 16
- 239000011259 mixed solution Substances 0.000 claims description 14
- XTEGARKTQYYJKE-UHFFFAOYSA-M Chlorate Chemical compound [O-]Cl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-M 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 10
- 239000007788 liquid Substances 0.000 claims description 10
- 239000002135 nanosheet Substances 0.000 claims description 10
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 8
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 8
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 8
- 239000007787 solid Substances 0.000 claims description 8
- 229910052684 Cerium Inorganic materials 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 7
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 7
- 239000012265 solid product Substances 0.000 claims description 7
- 238000005406 washing Methods 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 6
- LIKFHECYJZWXFJ-UHFFFAOYSA-N dimethyldichlorosilane Chemical compound C[Si](C)(Cl)Cl LIKFHECYJZWXFJ-UHFFFAOYSA-N 0.000 claims description 5
- 229910052748 manganese Inorganic materials 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 5
- 238000000926 separation method Methods 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 4
- 150000001879 copper Chemical class 0.000 claims description 4
- 229910001431 copper ion Inorganic materials 0.000 claims description 4
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 claims description 3
- ODWXUNBKCRECNW-UHFFFAOYSA-M bromocopper(1+) Chemical compound Br[Cu+] ODWXUNBKCRECNW-UHFFFAOYSA-M 0.000 claims description 3
- 238000001354 calcination Methods 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- -1 polytetrafluoroethylene Polymers 0.000 claims description 3
- 239000002243 precursor Substances 0.000 claims description 3
- 238000013019 agitation Methods 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- 229910052700 potassium Inorganic materials 0.000 claims 1
- 239000011591 potassium Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000006555 catalytic reaction Methods 0.000 abstract description 7
- 238000004519 manufacturing process Methods 0.000 abstract description 5
- 230000002195 synergetic effect Effects 0.000 abstract description 5
- 239000003960 organic solvent Substances 0.000 abstract description 4
- 239000003814 drug Substances 0.000 abstract description 2
- 230000005622 photoelectricity Effects 0.000 abstract description 2
- 239000004094 surface-active agent Substances 0.000 abstract description 2
- 229910000314 transition metal oxide Inorganic materials 0.000 abstract description 2
- 230000032258 transport Effects 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 25
- 238000012360 testing method Methods 0.000 description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 16
- 239000000463 material Substances 0.000 description 15
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 14
- 238000009616 inductively coupled plasma Methods 0.000 description 14
- 229960004643 cupric oxide Drugs 0.000 description 11
- 239000011863 silicon-based powder Substances 0.000 description 11
- 239000000203 mixture Substances 0.000 description 10
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- NEHMKBQYUWJMIP-UHFFFAOYSA-N chloromethane Chemical compound ClC NEHMKBQYUWJMIP-UHFFFAOYSA-N 0.000 description 9
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 8
- 239000011572 manganese Substances 0.000 description 8
- 229910044991 metal oxide Inorganic materials 0.000 description 8
- 150000004706 metal oxides Chemical class 0.000 description 8
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 7
- 235000013339 cereals Nutrition 0.000 description 7
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Inorganic materials O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 description 7
- 239000001301 oxygen Substances 0.000 description 7
- 229910052760 oxygen Inorganic materials 0.000 description 7
- 239000011701 zinc Substances 0.000 description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 6
- VGBWDOLBWVJTRZ-UHFFFAOYSA-K cerium(3+);triacetate Chemical compound [Ce+3].CC([O-])=O.CC([O-])=O.CC([O-])=O VGBWDOLBWVJTRZ-UHFFFAOYSA-K 0.000 description 6
- 238000009826 distribution Methods 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000002245 particle Substances 0.000 description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 5
- 239000012298 atmosphere Substances 0.000 description 5
- 229960000935 dehydrated alcohol Drugs 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 230000008901 benefit Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 239000007789 gas Substances 0.000 description 4
- 239000000320 mechanical mixture Substances 0.000 description 4
- 238000004611 spectroscopical analysis Methods 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910000420 cerium oxide Inorganic materials 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 235000013399 edible fruits Nutrition 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 3
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 3
- 239000005046 Chlorosilane Substances 0.000 description 2
- 230000000996 additive effect Effects 0.000 description 2
- 150000001335 aliphatic alkanes Chemical class 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 2
- SKEYZPJKRDZMJG-UHFFFAOYSA-N cerium copper Chemical compound [Cu].[Ce] SKEYZPJKRDZMJG-UHFFFAOYSA-N 0.000 description 2
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000011156 evaluation Methods 0.000 description 2
- 239000001257 hydrogen Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000976924 Inca Species 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- POFAUXBEMGMSAV-UHFFFAOYSA-N [Si].[Cl] Chemical compound [Si].[Cl] POFAUXBEMGMSAV-UHFFFAOYSA-N 0.000 description 1
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 229910052789 astatine Inorganic materials 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 239000011805 ball Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 230000031709 bromination Effects 0.000 description 1
- 238000005893 bromination reaction Methods 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 238000004587 chromatography analysis Methods 0.000 description 1
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- MROCJMGDEKINLD-UHFFFAOYSA-N dichlorosilane Chemical compound Cl[SiH2]Cl MROCJMGDEKINLD-UHFFFAOYSA-N 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000004817 gas chromatography Methods 0.000 description 1
- 239000011796 hollow space material Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 239000011806 microball Substances 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229940078494 nickel acetate Drugs 0.000 description 1
- 239000006259 organic additive Substances 0.000 description 1
- 229920006316 polyvinylpyrrolidine Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000010926 purge Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- DWAWYEUJUWLESO-UHFFFAOYSA-N trichloromethylsilane Chemical compound [SiH3]C(Cl)(Cl)Cl DWAWYEUJUWLESO-UHFFFAOYSA-N 0.000 description 1
- 210000002700 urine Anatomy 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/12—Organo silicon halides
- C07F7/16—Preparation thereof from silicon and halogenated hydrocarbons direct synthesis
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/80—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with zinc, cadmium or mercury
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
- B01J35/397—Egg shell like
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Physics & Mathematics (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a kind of copper based composite metal oxidate hollow microsphere, preparation method and the usage, the hollow microsphere is made of the oxide bead of copper oxide shell and the metal M being embedded on shell, and the metal M is transition metal element.Structure is complicated for copper based composite metal oxidate hollow microsphere of the present invention, and pattern is unique, and size uniformity, there is synergistic effect between copper oxide and transition metal oxide；The hollow microsphere does not use any organic solvent and surfactant using hydro-thermal-roasting method synthesis, mild condition, and cost is relatively low, environmentally friendly, reproducible, is suitble to industrialized production；The hollow microsphere is widely used in fields such as catalysis, photoelectricity and medicament transports, and the catalyst as organic silicon monomer synthetic reaction shows excellent catalytic performance.
Description
Technical field
The invention belongs to micro Nano material synthesis technical fields, and in particular to a kind of copper based composite metal oxidate is hollow micro-
Ball, preparation method and the usage.
Background technique
Since hollow microsphere material has high specific surface area and high atom utilization efficiency, so that it has in many fields
Be widely applied, nowadays such as catalysis, gas sensor, environmental pollution, energy storage, cosmetics and drug delivery have become
For one of the hot spot of material science research field.
Synthesizing has the method for different hollow structure materials varied, and main method includes sol-gal process, template
Method, electrochemical deposition method and reverse micelle method etc..Wherein, template have been found be it is most effective, be currently used method it
One.However, this method and step is extremely complex: firstly the need of synthesis template, target material being then coated on template
On surface, template agent removing is finally removed again.Synthesis cost is undoubtedly increased in this way, and will also tend to during removing removing template
Hollow structure is caused to collapse.
In recent years, more concerns, this method preparation are caused by nano material self assembly hollow microsphere material
Obtained material has both the characteristics of nanometer and micrometer structure.For example, Yao et al. is using ethylene glycol as solvent, with polyvinylpyrrolidine
Ketone (PVP) makees additive, by Co3O4Nanometer sheet is assembled into more shell Co3O4Hollow microsphere (Adv.Funct.Mater.2010,
20,1680-1686)；Lou et al. passes through the Fe being formed in situ using ethylene glycol and ethylenediamine as mixed solvent3O4Nanometer plate carrys out structure
Build Fe3O4Multistage hollow microsphere (Angew.Chem., Int.Ed.2013,52,4165-4168)；Then, Lou et al. again report with
Glycerol, isopropyl alcohol and water are mixed solvent, by assembling Fe3O4Ultrathin nanometer piece is prepared for Fe3O4Hollow microsphere
(Adv.Mater.2015,27,4097-4101).But above-mentioned hollow material is all only made of single metal oxide, and
And in order to control the pattern of product, organic solvent and surfactant are used in synthesis process, not only increases preparation cost, can also
Cause environmental pollution.
Cu oxide has different morphologies and structure as a kind of important metal oxide, in catalysis, bio-sensing
The fields such as device, solar battery have a wide range of applications, however relative to single metal oxide, multi-component metal oxide is past
Toward unique synergistic effect can be shown, advantage has been shown in many fields.Therefore, by multi-component metal oxide and
Hollow structure combines, and using the advantage of the two, improves the Nomenclature Composition and Structure of Complexes of single oxide, it is possible to show unique function
Energy characteristic shows wide application prospect in catalysis and energy conversion field.
Therefore, studying a kind of copper based composite metal oxidate with hollow structure, high catalytic efficiency is current research
One of direction, while keeping preparation method as simple pervasive as possible and can realize prepare with scale.
Summary of the invention
Aiming at the problems existing in the prior art, the purpose of the present invention is to provide in a kind of copper based composite metal oxidate
Empty microballoon, preparation method and the usage, structure is complicated for the hollow microsphere, and pattern is unique, and size is more uniform, by composition metal
Oxide composition；Preparation method is simple, and cost is relatively low, does not use organic solvent, can be used as urging for organic silicon monomer synthetic reaction
Agent shows excellent catalytic performance.
To achieve this purpose, the present invention adopts the following technical scheme:
In a first aspect, the hollow microsphere is by oxygen the present invention provides a kind of copper based composite metal oxidate hollow microsphere
The oxide bead for changing copper shell and the metal M being embedded on shell is constituted, and the metal M is transition metal element.
In the present invention, the hollow microsphere is made of on the Nomenclature Composition and Structure of Complexes two parts, by copper oxide and mistake on composition
Metal oxide composition is crossed, is made of in structure inner hollow shell and the particle being embedded on shell, the special construction
Hollow microsphere in terms of have significant effect, be used as catalysts when, have excellent catalytic properties.
It is used as currently preferred technical solution below, but not as the limitation of technical solution provided by the invention, passes through
Following technical scheme can preferably reach and realize technical purpose and beneficial effect of the invention.
As currently preferred technical solution, the metal M include any one in Ce, Zn, Co, Mn, Fe or Ni or
At least two combination, the combination is typical but non-limiting example has: the combination of the combination of Ce and Zn, Co and Fe, Ce, Zn and
The combination of Mn, the combination of Mn, Fe and Ni, the combination etc. of Ce, Zn, Co and Mn.
Preferably, in the hollow microsphere molar ratio of copper and metal M be (1~100): 1, for example, 1:1,5:1,10:1,
20:1,30:1,40:1,50:1,60:1,70:1,80:1,90:1 or 100:1 etc., it is not limited to cited numerical value, it should
Other unlisted numerical value are equally applicable in numberical range, preferably (10~100): 1.
In the present invention, the molar ratio of copper and metal M are one of an important factor for influencing product structure pattern, if the two is rubbed
You are then unable to get multistage composite structure than excessive；If the two molar ratio is too small, what is obtained is the oxygen of the CuO and M mutually separated
The mixture of compound, rather than composite oxides.
Preferably, the copper oxide shell is from inside to outside successively are as follows: hollow cavity, disorderly arranged nano particle, nanometer
The nanometer rods and porous nano-sheet that grain assembles.
Copper oxide shell in the present invention is assembled by multilayered structure, and inside is hollow structure, outward successively includes receiving
Rice grain layer, nanometer rods and nanometer sheet, copper oxide nanometer particle is disorderly arranged in nano-particle layer, and nanometer rods are by cupric oxide nano
Particle assembles, and is integrally formed the copper oxide shell of unique structure.
Preferably, the oxide bead of the metal M is assembled by the nano particle of metal M oxide.
As currently preferred technical solution, the diameter of the hollow cavity is 1~6 μm, such as 1 μm, 2 μm, 3 μm, 4 μ
M, 5 μm or 6 μm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, the partial size of the disorderly arranged nano particle be 20~100nm, such as 20nm, 30nm, 40nm,
50nm, 60nm, 70nm, 80nm, 90nm or 100nm etc., it is not limited to cited numerical value, in the numberical range, other are not
The numerical value enumerated is equally applicable.
Preferably, the length of the nanometer rods be 100~300nm, such as 100nm, 120nm, 150nm, 180nm,
200nm, 220nm, 240nm, 260nm, 280nm or 300nm etc., it is not limited to cited numerical value, in the numberical range
Other unlisted numerical value are equally applicable；Width be 50~150nm, such as 50nm, 60nm, 70nm, 80nm, 100nm, 120nm,
130nm, 140nm or 150nm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
Sample is applicable in.
Preferably, the porous nano-sheet with a thickness of 10~100nm, such as 10nm, 20nm, 30nm, 40nm, 50nm,
60nm, 70nm, 80nm, 90nm or 100nm etc., it is not limited to cited numerical value, other are unlisted in the numberical range
Numerical value it is equally applicable.
Preferably, the partial size of the oxide bead of the metal M be 100~600nm, such as 100nm, 150nm, 200nm,
250nm, 300nm, 350nm, 400nm, 450nm, 500nm, 550nm or 600nm etc., it is not limited to cited numerical value,
Other unlisted numerical value are equally applicable in the numberical range.
Preferably, the partial size of the nano particle of the metal M oxide be 5~20nm, such as 5nm, 8nm, 10nm,
12nm, 15nm, 18nm or 20nm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range
It is equally applicable.
Preferably, the hollow microsphere is porous structure, and the partial size of the hollow microsphere is 2~8 μm, for example, 2 μm, 3 μm,
4 μm, 5 μm, 6 μm, 7 μm or 8 μm etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range
It is equally applicable.
In the present invention, the porous structure of hollow microsphere makes the specific surface area of hollow microsphere larger, facilitates the suction of substance
It is attached, shorten the path of electron transmission, improves mass transfer efficiency.
Second aspect, the present invention provides a kind of preparation method of above-mentioned copper based composite metal oxidate hollow microsphere, institutes
The method of stating includes the following steps:
(1) lye is added into copper presoma and metal M precursor mixed solution, obtains suspension；
(2) suspension for obtaining step (1) carries out hydro-thermal reaction, and products therefrom is separated by solid-liquid separation, and obtains solid product；
(3) the solid product calcination process for obtaining step (2), obtains copper based composite metal oxidate hollow microsphere.
In the present invention, the preparation process of the hollow microsphere is relatively simple, and presoma mixed liquor successively carries out hydro-thermal, roasting
Processing, by the control to reactant, reaction condition, is prepared the hollow microsphere of unique structure.
As currently preferred technical solution, in step (1) described mixed solution, copper ion and metal M ion rub
You than be (1~100): 1, for example, 1:1,5:1,10:1,20:1,30:1,40:1,50:1,60:1,70:1,80:1,90:1 or
100:1 etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable, and preferably (10
~100): 1.
In the present invention, the molar ratio of copper and metal M are one of an important factor for influencing product structure pattern, if the two is rubbed
You are then unable to get multistage composite structure, if the two molar ratio is too small, what is obtained is the oxygen of the CuO and M mutually separated than excessive
The mixture of compound, rather than composite oxides.
Preferably, in step (1) described mixed solution, the concentration of copper ion is 0.05~0.4mol/L, such as
0.05mol/L、0.08mol/L、0.1mol/L、0.15mol/L、0.2mol/L、0.25mol/L、0.3mol/L、0.35mol/L
Or 0.4mol/L etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, step (1) the copper presoma is soluble copper salt, and metal M presoma is soluble metal M salt.
Preferably, the soluble copper salt is any in copper nitrate, copper acetate, copper chloride, copper sulphate or copper bromide
It is a kind of or at least two combination, the combination is typical but non-limiting example has: the combination of copper nitrate and copper chloride, copper nitrate
With the combination of copper acetate, the combination of copper chloride and copper sulphate, the combination of copper nitrate, copper chloride and copper sulphate, copper acetate, copper chloride
With the combination of copper bromide etc., preferably copper nitrate.
Preferably, the soluble metal M salt is selected from nitrate, acetate, chlorate, sulfate or the bromination of metal M
In salt any one or at least two combination, the combination is typical but non-limiting example has: the nitrate and chlorate of M
Combination, the combination of the nitrate and acetate of M, the combination of the chlorate and sulfate of M, nitrate, chlorate and the acetic acid of M
The combination etc. of salt, the preferably nitrate of M.
As currently preferred technical solution, step (1) described lye includes sodium carbonate liquor, solution of potassium carbonate, urine
In plain solution or sodium hydroxide solution any one or at least two combination, the combination is typical but non-limiting example
Have: the combination of the combination of sodium carbonate liquor and solution of potassium carbonate, sodium carbonate liquor and urea liquid, sodium carbonate liquor and hydroxide
The combination of sodium solution, the combination of sodium carbonate liquor, solution of potassium carbonate and sodium hydroxide solution, solution of potassium carbonate, urea liquid with
The combination etc. of sodium hydroxide solution.
Preferably, the concentration of step (1) described lye is 0.1~4mol/L, such as 0.1mol/L, 0.5mol/L, 1mol/
L, 1.5mol/L, 2mol/L, 2.5mol/L, 3mol/L, 3.5mol/L or 4mol/L etc., it is not limited to cited number
Value, other interior unlisted numerical value of the numberical range are equally applicable.
Preferably, the volume ratio of step (1) lye and mixed solution is 1:3~3:1, such as 1:3,1:2,2:3,1:
1,3:2,2:1 or 3:1 etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are equally suitable
With.
Preferably, the adding manner of step (1) described lye is to be added dropwise.
Preferably, step (1) described lye is added under agitation.
Preferably, the rate of the stirring be 400~1200r/min, such as 400r/min, 500r/min, 600r/min,
700r/min, 800r/min, 900r/min, 1000r/min or 1200r/min etc., it is not limited to cited numerical value, it should
Other unlisted numerical value are equally applicable in numberical range.
As currently preferred technical solution, the temperature of step (2) described hydro-thermal reaction is 60~180 DEG C, such as 60
DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160 DEG C or 180 DEG C etc., it is not limited to cited numerical value, the numberical range
Other interior unlisted numerical value are equally applicable, and preferably 120 DEG C.
Preferably, the time of step (2) described hydro-thermal reaction be 0.5~for 24 hours, such as 0.5h, 2h, 4h, 6h, 8h, 10h,
12h, 16h, 20h or for 24 hours etc., it is not limited to cited numerical value, other unlisted numerical value are same in the numberical range
It is applicable in, preferably 12h.
Preferably, step (2) described hydro-thermal reaction carries out in hydrothermal reaction kettle.
Preferably, the volume of the hydrothermal reaction kettle be 100~1000mL, such as 100mL, 200mL, 300mL, 500mL,
600mL, 800mL or 1000mL etc., it is not limited to cited numerical value, other interior unlisted numerical value of the numberical range are same
Sample is applicable in.
Preferably, the liner of the hydrothermal reaction kettle is polytetrafluoroethylene (PTFE).
As currently preferred technical solution, after step (2) described separation of solid and liquid, washing, drying obtain solid production
Object.
Preferably, the temperature of the drying is 60~200 DEG C, such as 60 DEG C, 80 DEG C, 100 DEG C, 120 DEG C, 140 DEG C, 160
DEG C, 180 DEG C or 200 DEG C etc., it is not limited to cited numerical value, other unlisted numerical value are equally suitable in the numberical range
With.
Preferably, the time of the drying be 6~20h, such as 6h, 8h, 10h, 12h, 15h, 16h, 18h or 20h etc., but
It is not limited in cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
As currently preferred technical solution, the temperature of step (3) described roasting is 200~800 DEG C, such as 200 DEG C,
250 DEG C, 300 DEG C, 350 DEG C, 400 DEG C, 450 DEG C, 500 DEG C, 550 DEG C, 600 DEG C, 650 DEG C, 700 DEG C, 750 DEG C or 800 DEG C etc., but
It is not limited in cited numerical value, other unlisted numerical value are equally applicable in the numberical range.
Preferably, the time of step (3) described roasting be 2~for 24 hours, such as 2h, 4h, 6h, 8h, 10h, 12h, 14h, 16h,
18h, 20h, 22h or for 24 hours etc., it is not limited to cited numerical value, other unlisted numerical value are same in the numberical range
It is applicable in.
The third aspect, the present invention provides a kind of purposes of above-mentioned copper based composite metal oxidate hollow microsphere, it is described in
Empty microballoon is used as the catalyst of organic silicon monomer synthetic reaction.
Preferably, the hollow microsphere is used as the catalyst of dimethyldichlorosilane selectivity synthesis.
Dimethyldichlorosilane be prepare organosilicon material it is most important be also the maximum monomer of dosage, it is to pass through Rochow
Directly reaction obtains under the action of copper-based catalysts for reaction, i.e. monochloro methane (MeCl) and silicon powder (Si), reaction equation are as follows:
In above-mentioned reaction equation, M1 is Trichloromethyl silane, and M2 is dimethyldichlorosilane, and M3 is one chlorine silicon of trimethyl
Alkane, M1H are methyl hydrogen dichlorosilane, and M2H is one chlorosilane of dimethyl hydrogen, and LBR is low-boiling-point substance, and HBR is high-boiling components.And it is of the invention
The hollow microsphere is the selectivity of M2 product and the conversion ratio of silicon powder in improving the reaction as the purpose of catalyst.
Compared with prior art, the invention has the following advantages:
(1) structure is complicated for copper based composite metal oxidate hollow microsphere of the present invention, and pattern is unique, and size uniformity,
There is synergistic effect between copper oxide and transition metal oxide, is expected to obtain extensively in fields such as catalysis, photoelectricity and medicament transports
General application；
(2) hollow microsphere of the present invention is using hydro-thermal-roasting method synthesis, and preparation method is easy, and universality is strong, reproducibility
It is good, the hollow microsphere of various ingredients can be prepared, cost is relatively low, and does not use any organic solvent and additive, is suitble to industry rule
Modelling production；
(3) hollow microsphere of the present invention can be used as the catalyst of organic silicon monomer synthetic reaction, show excellent urge
Change performance, the selectivity of target product dimethyldichlorosilane reaches 86.0% or more, and silicon power raw material conversion ratio reaches 40.0%
More than.
Detailed description of the invention
Fig. 1 is CuO-CeO made from the embodiment of the present invention 12The XRD diagram of composite oxides hollow microsphere；
Fig. 2 a, Fig. 2 b and Fig. 2 c are CuO-CeO made from embodiment 12The SEM of composite oxides hollow microsphere schemes；
Fig. 3 a is CuO-CeO made from embodiment 12SEM figure inside composite oxides hollow microsphere；
Fig. 3 b is CuO-CeO made from embodiment 12The SEM of composite oxides hollow microsphere shell layer surface schemes；
Fig. 4 is CuO-CeO made from embodiment 12The TEM of composite oxides hollow microsphere schemes；
Fig. 5 is CuO-CeO made from embodiment 12The Element area profile of composite oxides hollow microsphere；
Fig. 6 is the XRD diagram of CuO-ZnO composite oxides hollow microsphere made from embodiment 2；
Fig. 7 a is the SEM figure of CuO-ZnO composite oxides hollow microsphere made from embodiment 2；
Fig. 7 b is the Element area profile of CuO-ZnO composite oxides hollow microsphere made from embodiment 2；
Fig. 8 is CuO-Co made from embodiment 33O4The XRD diagram of composite oxides hollow microsphere；
Fig. 9 a is CuO-Co made from embodiment 33O4The SEM of composite oxides hollow microsphere schemes；
Fig. 9 b is CuO-Co made from embodiment 33O4The Element area profile of composite oxides hollow microsphere；
Figure 10 is CuO-MnO made from embodiment 42The XRD diagram of composite oxides hollow microsphere；
Figure 11 a is CuO-MnO made from embodiment 42The SEM of composite oxides hollow microsphere schemes；
Figure 11 b is CuO-MnO made from embodiment 42The Element area profile of composite oxides hollow microsphere.
Specific embodiment
In order to better illustrate the present invention, it is easy to understand technical solution of the present invention, below further specifically to the present invention
It is bright.But following embodiments is only simple example of the invention, does not represent or limit the scope of the present invention, this hair
Bright protection scope is subject to claims.
Specific embodiment of the invention part provides a kind of copper based composite metal oxidate hollow microsphere and its preparation side
Method, the hollow microsphere are made of the oxide bead of copper oxide shell and the metal M being embedded on shell, and the metal M is
Transition metal element.
Preparation method includes the following steps:
(1) lye is added into copper presoma and metal M precursor mixed solution, obtains suspension；
(2) suspension for obtaining step (1) carries out hydro-thermal reaction, and products therefrom is separated by solid-liquid separation, and obtains solid product；
(3) the solid product calcination process for obtaining step (2), obtains copper based composite metal oxidate hollow microsphere.
The following are typical but non-limiting embodiments of the invention:
Embodiment 1:
Present embodiments provide a kind of CuO-CeO2Composite oxides hollow microsphere, the hollow microsphere by CuO shell and
The CeO being embedded on shell2Bead is constituted, and the CuO shell is from inside to outside successively are as follows: hollow cavity, disorderly arranged nanometer
The nanometer rods and porous nano-sheet that grain, nano particle assemble.
The preparation method of the hollow microsphere includes the following steps:
(1) 1.1g copper acetate and 0.095g cerous acetate are dissolved in (Cu in 60mL water2+Concentration be 0.1mol/L, nCu:nCe
=20:1), the sodium carbonate liquor 20mL for being 0.3mol/L to obtained mixed solution and dripping concentration, in 1000r/min revolving speed
Lower stirring 0.5h, obtains suspension；
(2) suspension is transferred in the water heating kettle of polytetrafluoroethyllining lining of 100mL, the hydro-thermal reaction at 140 DEG C
11h, cooled and filtered, obtained solid deionized water and dehydrated alcohol dry 12h after washing for several times under the conditions of 60 DEG C；
(3) product after drying is roasted into 12h under the conditions of 400 DEG C under oxygen atmosphere, obtains CuO-CeO2Combined oxidation
Object hollow microsphere.
By CuO-CeO obtained2Composite oxides hollow microsphere is produced using Panalytical company, Holland (Panaco)
X ' Pert PRO MPD type Multi-functional X ray diffractometer carry out XRD test, as a result as shown in Figure 1；By hollow microsphere obtained
Its microscopic appearance is observed using the JSM-7001F type scanning electron microscope that Japanese JEOL company produces, SEM figure in surface is as schemed
Shown in 2a-2c, as shown in Figure 3a, the SEM figure of hollow microsphere shell layer surface is as shown in Figure 3b for the SEM figure inside hollow microsphere；It will
Hollow microsphere obtained observes its internal junction on the JEM-2010F type transmission electron microscope using the production of JEOL company, Japan
Structure, TEM figure are as shown in Figure 4；Hollow microsphere obtained is used to the INCA X-MAX type energy disperse spectroscopy of England Oxford company production
Test elements distribution situation, Element area profile are as shown in Figure 5；Hollow microsphere obtained is used into U.S. Pekin-Elmer
Inductively coupled plasma atomic emission spectrometer carries out ICP test.
In the present embodiment, as shown in Figure 1, the diffraction maximum of the hollow microsphere includes CuO and CeO2Characteristic diffraction peak,
In, " ▼ " represents the characteristic diffraction peak of CuO,Represent CeO2Characteristic diffraction peak, show the material be CuO and CeO2Answer
Close oxide；
By Fig. 2 a it is found that the material morphology and size uniformity, spherical in shape, particle size is about 5 μm, rough surface；By
Fig. 2 b and Fig. 2 c are it is found that the microballoon is hollow structure, and a large amount of porous nano-sheet vertical-growths are in microsphere surface, nanometer sheet thickness
About 20nm；By Fig. 3 a it is found that being disorderly arranged nano particle, average grain diameter 30nm, by Fig. 3 b inside the microballoon
It is found that being nanometer rods above nano-particle layer, length is about 200nm, and width is about 80nm；Bead is embedded in shell layer surface, greatly
Small about 600nm, is formed by nano-particles self assemble；Equally, as shown in Figure 4, the microballoon be hollow structure, hollow cavity it is straight
Diameter is about 4 μm；
By the Element area profile of Fig. 5 hollow microsphere it is found that Cu element is uniformly distributed in microballoon shell, Ce element uniformly divides
The bead being distributed in shell layer surface, and O element is uniformly distributed in entire microballoon；
By ICP test result it is found that CuO-CeO2The molar ratio of Cu and Ce is about 20:1 in composite oxides hollow microsphere.
Embodiment 2:
A kind of CuO-ZnO composite oxides hollow microsphere is present embodiments provided, the hollow microsphere is by CuO shell and edge
ZnO bead on shell is constituted, and the CuO shell is from inside to outside successively are as follows: hollow cavity, disorderly arranged nano particle,
The nanometer rods and porous nano-sheet that nano particle assembles.
The preparation method of the hollow microsphere includes the following steps:
(1) 0.55g copper acetate and 0.057g zinc nitrate are dissolved in (Cu in 60mL water2+Concentration be 0.05mol/L, nCu:
nZn=10:1), the solution of potassium carbonate 100mL for being 0.1mol/L to obtained mixed solution and dripping concentration turns in 800r/min
Speed is lower to stir 0.8h, obtains suspension；
(2) suspension is transferred in the water heating kettle of polytetrafluoroethyllining lining of 200mL, the hydro-thermal reaction 4h at 180 DEG C,
Cooled and filtered, obtained solid deionized water and dehydrated alcohol dry 10h after washing for several times under the conditions of 80 DEG C；
(3) 2h will be roasted under the conditions of the product after drying in air atmosphere 800 DEG C, obtains CuO-ZnO composite oxides
Hollow microsphere.
By CuO-CeO obtained2Composite oxides hollow microsphere carries out XRD test, knot using Multi-functional X ray diffractometer
Fruit is as shown in Figure 6；Hollow microsphere obtained is observed into its microscopic appearance using scanning electron microscope, SEM schemes such as Fig. 7 a institute
Show；Hollow microsphere obtained is used into energy disperse spectroscopy test elements distribution situation, Element area profile is as shown in Figure 7b；It will be made
Hollow microsphere ICP test, above-mentioned test instrument and reality are carried out using inductively coupled plasma atomic emission spectrometer
It is identical to apply example 1.
In the present embodiment, it will be appreciated from fig. 6 that the diffraction maximum of the hollow microsphere includes the characteristic diffraction peak of CuO and ZnO,
In, " ▼ " represents the characteristic diffraction peak of CuO,The characteristic diffraction peak for representing ZnO shows that the material is answering for CuO and ZnO
Close oxide；
By Fig. 7 a it is found that material graininess spherical in shape, particle size are about 5 μm, rough surface, surface vertical-growth
There are nanometer rods or nanometer sheet；By Fig. 7 b it is found that Cu element is uniformly distributed in microballoon shell, Zn element is uniformly distributed in embedded in shell
Bead on surface, and O element is uniformly distributed in entire microballoon；
By ICP test result it is found that the molar ratio of Cu and Zn is about 10:1 in CuO-ZnO composite oxides hollow microsphere.
Embodiment 3:
Present embodiments provide a kind of CuO-Co3O4Composite oxides hollow microsphere, the hollow microsphere by CuO shell and
The Co being embedded on shell3O4Bead is constituted, and the CuO shell is from inside to outside successively are as follows: hollow cavity, disorderly arranged nanometer
The nanometer rods and porous nano-sheet that grain, nano particle assemble.
The preparation method of the hollow microsphere includes the following steps:
(1) 3.24g copper chloride and 0.039g cobalt chloride are dissolved in (Cu in 60mL water2+Concentration be 0.4mol/L, nCu:nCo
=80:1), the urea liquid 20mL for being 1mol/L to obtained mixed solution and dripping concentration is stirred under 400r/min revolving speed
1.5h obtains suspension；
(2) suspension is transferred in the water heating kettle of polytetrafluoroethyllining lining of 100mL, at 60 DEG C hydro-thermal reaction for 24 hours,
Cooled and filtered, obtained solid deionized water and dehydrated alcohol dry 8h after washing for several times under the conditions of 100 DEG C；
(3) product after drying is roasted into 20h under the conditions of 250 DEG C under oxygen atmosphere, obtains CuO-Co3O4Combined oxidation
Object hollow microsphere.
By CuO-Co obtained3O4Composite oxides hollow microsphere carries out XRD test, knot using Multi-functional X ray diffractometer
Fruit is as shown in Figure 8；Hollow microsphere obtained is observed into its microscopic appearance using scanning electron microscope, SEM schemes such as Fig. 9 a institute
Show；Hollow microsphere obtained is used into energy disperse spectroscopy test elements distribution situation, Element area profile is as shown in figure 9b；It will be made
Hollow microsphere ICP test, above-mentioned test instrument and reality are carried out using inductively coupled plasma atomic emission spectrometer
It is identical to apply example 1.
In the present embodiment, as shown in Figure 8, the diffraction maximum of the hollow microsphere includes CuO and Co3O4Characteristic diffraction peak,
In, " ▼ " represents the characteristic diffraction peak of CuO,Represent Co3O4Characteristic diffraction peak, show the material be CuO and Co3O4's
Composite oxides；
By Fig. 9 a it is found that material graininess spherical in shape, particle size are about 5 μm, rough surface, surface vertical-growth
There are nanometer rods or nanometer sheet；By Fig. 9 b it is found that Cu element is uniformly distributed in microballoon shell, Co element is uniformly distributed in embedded in shell
Bead on surface, and O element is uniformly distributed in entire microballoon；
By ICP test result it is found that CuO-Co3O4The molar ratio of Cu and Co is about 80:1 in composite oxides hollow microsphere.
Embodiment 4:
Present embodiments provide a kind of CuO-MnO2Composite oxides hollow microsphere, the hollow microsphere by CuO shell and
The MnO being embedded on shell2Bead is constituted, and the CuO shell is from inside to outside successively are as follows: hollow cavity, disorderly arranged nanometer
The nanometer rods and porous nano-sheet that grain, nano particle assemble.
The preparation method of the hollow microsphere includes the following steps:
(1) 1.692g copper nitrate and 0.0136g manganese sulfate are dissolved in (Cu in 30mL water2+Concentration be 0.3mol/L, nCu:
nMn=100:1), the sodium hydroxide solution 10mL for being 3mol/L to obtained mixed solution and dripping concentration turns in 600r/min
Speed is lower to stir 1h, obtains suspension；
(2) suspension is transferred in the water heating kettle of polytetrafluoroethyllining lining of 100mL, the hydro-thermal reaction at 100 DEG C
12h, cooled and filtered, obtained solid deionized water and dehydrated alcohol dry 6h after washing for several times under the conditions of 150 DEG C；
(3) product after drying is roasted into 8h under the conditions of 600 DEG C under oxygen atmosphere, obtains CuO-MnO2Composite oxides
Hollow microsphere.
By CuO-MnO obtained2Composite oxides hollow microsphere carries out XRD test, knot using Multi-functional X ray diffractometer
Fruit is as shown in Figure 10；Hollow microsphere obtained is observed into its microscopic appearance, SEM figure such as Figure 11 a using scanning electron microscope
It is shown；Hollow microsphere obtained is used into energy disperse spectroscopy test elements distribution situation, Element area profile is as shown in figure 11b；It will
Hollow microsphere obtained carries out ICP test, above-mentioned test instrument using inductively coupled plasma atomic emission spectrometer
It is same as Example 1.
In the present embodiment, as shown in Figure 10, the diffraction maximum of the hollow microsphere includes CuO and MnO2Characteristic diffraction peak,
Wherein, " ▼ " represents the characteristic diffraction peak of CuO,Represent MnO2Characteristic diffraction peak, show the material be CuO and MnO2's
Composite oxides；
By Figure 11 a it is found that material graininess spherical in shape, particle size are about 5 μm, rough surface；It can by Figure 11 b
Know, Cu element is uniformly distributed in microballoon shell, and Mn element is uniformly distributed in the bead in shell layer surface, and O element is uniform
It is distributed in entire microballoon；
By ICP test result it is found that CuO-MnO2The molar ratio of Cu and Mn is about 100 in composite oxides hollow microsphere:
1。
Embodiment 5:
A kind of CuO-NiO composite oxides hollow microsphere is present embodiments provided, the hollow microsphere is by CuO shell and edge
NiO bead on shell is constituted, and the CuO shell is from inside to outside successively are as follows: hollow cavity, disorderly arranged nano particle,
The nanometer rods and porous nano-sheet that nano particle assembles.
The preparation method of the hollow microsphere includes the following steps:
(1) 2.184g copper acetate and 2.124g nickel acetate are dissolved in (Cu in 60mL water2+Concentration be 0.2mol/L, nCu:
nMn=1:1), the sodium carbonate liquor 20mL for being 4mol/L to obtained mixed solution and dripping concentration, under 1000r/min revolving speed
0.5h is stirred, suspension is obtained；
(2) suspension is transferred in the water heating kettle of polytetrafluoroethyllining lining of 100mL, the hydro-thermal reaction 6h at 150 DEG C,
Cooled and filtered, obtained solid deionized water and dehydrated alcohol dry 6h after washing for several times under the conditions of 120 DEG C；
(3) product after drying is roasted into 16h under the conditions of 300 DEG C under oxygen atmosphere, obtains CuO-NiO composite oxides
Hollow microsphere.
By CuO-NiO composite oxides hollow microsphere obtained using inductively coupled plasma atomic emission spectrometer into
Row ICP test, test instrument are same as Example 1.
By ICP test result it is found that the molar ratio of Cu and Ni is about 1:1 in CuO-NiO composite oxides hollow microsphere.
Comparative example 1:
This comparative example provides a kind of preparation method of CuO hollow microsphere, the method referring to the method in embodiment 1,
Difference is only that: step is added without cerous acetate in (1).
Comparative example 2:
This comparative example provides a kind of CeO2The preparation method of nanosphere, the method referring to the method in embodiment 1,
Difference is only that: step is added without copper acetate in (1).
Comparative example 3:
This comparative example provides a kind of CuO-CeO2The preparation method of composite oxides, the method is referring in embodiment 1
Method, difference is only that: the additional amount of cerous acetate is 0.0159g, i.e. n in step (1)Cu:nCe=120:1, cerous acetate add
It is relatively low to enter amount.
Comparative example 4:
This comparative example provides a kind of CuO-CeO2The preparation method of composite oxides, the method is referring in embodiment 1
Method, difference is only that: the additional amount of cerous acetate is 2.108g, i.e. n in step (1)Cu:nCe=1:1.1, cerous acetate add
It is higher to enter amount.
Comparative example 5:
This comparative example provides a kind of CuO and CeO2Mixture, the CuO is using the method preparation in comparative example 1, institute
State CeO2Using the method preparation in comparative example 2, it is 20:1 mechanical mixture that the two, which is pressed copper cerium molar ratio,.
Comparative example 6:
This comparative example provides the mixture of a kind of commercial oxidation copper and commercial oxidation cerium, and the two is by copper cerium molar ratio
20:1 mechanical mixture.
Material described in embodiment 1-5 and comparative example 1-6 is used as catalysis monochloro methane and silicon powder reaction generates dimethyl two
The catalyst of chlorosilane, and evaluate the catalytic performance of above-mentioned catalyst.Catalyst performance evaluation experiment is filled using miniature fixed bed
Set progress, reactor inside diameter 20cm, length 50cm, evaluation procedure is as follows: by catalyst made from 10g Si powder and 0.5g
Ground and mixed forms contact；When reaction, N is used first2Then purging reaction system is switched to MeCl gas, after preheating
It reacts with contact, reaction condition are as follows: preheating temperature is 350 DEG C, and reaction temperature is 325 DEG C, and reaction pressure is normal pressure, MeCl
Flow velocity be 25mL/min, the reaction time be for 24 hours.
Product after reaction is collected after condensing tube condensation using toluene, and extra tail gas is absorbed with lye；The mixing of collection
Quantitative analysis is carried out using gas-chromatography (Agilent 7890B, KB-210 chromatographic column, TCD detector) after liquid constant volume.
The results are shown in Table 1 for the active testing of catalyst in above-described embodiment and comparative example, wherein product distribution passes through
The percentage of reaction product corresponding area calculates in gas chromatographic analysis result, the calculation formula of silicon conversion are as follows:
Wherein, W is the weight of contact.
1 catalyst activity test result table of table
As can be seen from Table 1, when using copper-base composite oxidate hollow microsphere made from embodiment 1-5 as catalyst
When, catalytic activity is higher, and the selectivity of M2 reaches 86.0% or more, Si powder conversion ratio and reaches 40.0% or more, wherein M2
Selectivity up to 89.9%, silicon powder conversion ratio is up to 45.2%；And single copper oxide prepared by comparative example 1 is hollow micro-
Sphere catalyst, M2 are selectively only that 70.2%, Si powder conversion ratio is 15.2%；Single cerium oxide catalyst prepared by comparative example 2
Organic silicon monomer reaction is not suitable for, without obvious catalytic activity；In comparative example 3, work as CeO2Content it is relatively low when, obtained catalysis
Agent does not have multistage composite structure, in comparative example 4, works as CeO2Content it is higher when, CuO and CeO in gained catalyst2It can not shape
At composite oxides, interaction between the two weakens, and therefore, the catalytic activity in above-mentioned two comparative example is lower than in embodiment
The activity of catalyst；Copper oxide and cerium oxide mechanical mixture type catalyst prepared by comparative example 5, catalytic activity compare comparative example 1
Promoted, M2 be selectively 77.2%, Si powder conversion ratio be 26.8%, similarly, comparative example 6 prepare commercial oxidation copper and
Commercial oxidation cerium mechanical mixture type catalyst, catalytic activity M2 are selectively also only 73.5%, Si powder conversion ratio and are only
23.2%, although showing CeO2To the promotion of CuO catalytic performance, there are facilitations, but both there is no compound in embodiment
Synergistic effect between metal oxide, catalytic performance are still below the data of the embodiment of the present invention.
Above-described embodiment and comparative example the result shows that, the catalyst that method provided by the invention is prepared is in catalytic performance
Aspect has significant advantage, mainly has the reason of following tripartite face: first is that hollow microsphere catalyst morphology provided by the invention, grain
Diameter distribution is uniform；Second is that hollow ball catalyst structure provided by the invention is unique, hollow porous structure is conducive to reactant chloromethane
The diffusion of alkane and the desorption of gaseous product；Third is that copper oxide and cerium oxide are assembled by nano unit, contact is close, phase
Interreaction force is strong, and there are apparent synergistic effect, this structure greatly increases its effective contact probability between silicon powder also,
To promote the raising of M2 selectivity and silicon powder conversion ratio.
The Applicant declares that the present invention is explained by the above embodiments method detailed and application of the invention, but the present invention
It is not limited to above-mentioned method detailed and application, that is, does not mean that the present invention must rely on above-mentioned method detailed and application could be real
It applies.It should be clear to those skilled in the art, any improvement in the present invention, to the raw materials used in the present invention, operation
Addition, selection of concrete mode of equivalence replacement and auxiliary element etc., all fall within protection scope of the present invention and the open scope it
It is interior.
Claims (10)
1. a kind of copper based composite metal oxidate hollow microsphere, which is characterized in that the hollow microsphere is by copper oxide shell and edge
The oxide bead of metal M on shell is constituted, and the metal M is transition metal element.
2. hollow microsphere according to claim 1, which is characterized in that the metal M includes Ce, Zn, Co, Mn, Fe or Ni
In any one or at least two combination；
Preferably, the molar ratio of copper and metal M are (1~100): 1, preferably (10~100): 1 in the hollow microsphere；
Preferably, the copper oxide shell is from inside to outside successively are as follows: hollow cavity, disorderly arranged nano particle, nano particle group
Nanometer rods and porous nano-sheet made of dress；
Preferably, the oxide bead of the metal M is assembled by the nano particle of metal M oxide.
3. hollow microsphere according to claim 2, which is characterized in that the diameter of the hollow cavity is 1~6 μm；
Preferably, the partial size of the disorderly arranged nano particle is 20~100nm；
Preferably, the length of the nanometer rods is 100~300nm, and width is 50~150nm；
Preferably, the porous nano-sheet with a thickness of 10~100nm；
Preferably, the partial size of the oxide bead of the metal M is 100~600nm；
Preferably, the partial size of the nano particle of the metal M oxide is 5~20nm；
Preferably, the hollow microsphere is porous structure, and the partial size of the hollow microsphere is 2~8 μm.
4. the preparation method of any one of -3 hollow microspheres according to claim 1, which is characterized in that the method includes following
Step:
(1) lye is added into copper presoma and metal M precursor mixed solution, obtains suspension；
(2) suspension for obtaining step (1) carries out hydro-thermal reaction, and products therefrom is separated by solid-liquid separation, and obtains solid product；
(3) the solid product calcination process for obtaining step (2), obtains copper based composite metal oxidate hollow microsphere.
5. according to the method described in claim 4, it is characterized in that, in step (1) described mixed solution, copper ion and metal M
The molar ratio of ion is (1~100): 1, preferably (10~100): 1；
Preferably, in step (1) described mixed solution, the concentration of copper ion is 0.05~0.4mol/L；
Preferably, step (1) the copper presoma is soluble copper salt, and metal M presoma is soluble metal M salt；
Preferably, any one of the soluble copper salt in copper nitrate, copper acetate, copper chloride, copper sulphate or copper bromide
Or at least two combination, preferably copper nitrate；
Preferably, in nitrate, acetate, chlorate, sulfate or Bromide of the soluble metal M salt selected from metal M
Any one or at least two combination, the preferably nitrate of metal M.
6. method according to claim 4 or 5, which is characterized in that step (1) described lye includes sodium carbonate liquor, carbon
In sour potassium solution, urea liquid or sodium hydroxide solution any one or at least two combination；
Preferably, the concentration of step (1) described lye is 0.1~4mol/L；
Preferably, the volume ratio of step (1) lye and mixed solution is 1:3~3:1；
Preferably, the adding manner of step (1) described lye is to be added dropwise；
Preferably, step (1) described lye is added under agitation；
Preferably, the rate of the stirring is 400~1200r/min.
7. according to the described in any item methods of claim 4-6, which is characterized in that the temperature of step (2) described hydro-thermal reaction is
60~180 DEG C, preferably 120 DEG C；
Preferably, the time of step (2) described hydro-thermal reaction be 0.5~for 24 hours, preferably 12h；
Preferably, step (2) described hydro-thermal reaction carries out in hydrothermal reaction kettle；
Preferably, the volume of the hydrothermal reaction kettle is 100~1000mL；
Preferably, the liner of the hydrothermal reaction kettle is polytetrafluoroethylene (PTFE).
8. according to the described in any item methods of claim 4-7, which is characterized in that after step (2) described separation of solid and liquid, washing,
It is dry, obtain solid product；
Preferably, the temperature of the drying is 60~200 DEG C；
Preferably, the time of the drying is 6~20h.
9. according to the described in any item methods of claim 4-8, which is characterized in that the temperature of step (3) described roasting be 200~
800℃；
Preferably, the time of step (3) described roasting be 2~for 24 hours.
10. the purposes of hollow microsphere according to claim 1-3, which is characterized in that the hollow microsphere is used as
The catalyst of organic silicon monomer synthetic reaction；
Preferably, the hollow microsphere is used as the catalyst of dimethyldichlorosilane selectivity synthesis.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201811512700 | 2018-12-11 | ||
| CN2018115127003 | 2018-12-11 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN109663595A true CN109663595A (en) | 2019-04-23 |
Family
ID=66152057
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910118068.2A Pending CN109663595A (en) | 2018-12-11 | 2019-02-15 | A kind of copper based composite metal oxidate hollow microsphere, preparation method and the usage |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109663595A (en) |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109755032A (en) * | 2019-02-21 | 2019-05-14 | 东南大学 | A kind of more shell CuCo2O4The preparation and its application of hollow nano-sphere |
| CN110152670A (en) * | 2019-05-29 | 2019-08-23 | 华南理工大学 | A kind of Co3O4/ CuO efficiency light thermocatalyst and the preparation method and application thereof |
| CN110514700A (en) * | 2019-09-27 | 2019-11-29 | 西安电子科技大学 | A kind of copper oxide and cobaltosic oxide heterogeneous structural nano line composite sensitive material, ethylene glycol sensor and preparation method |
| CN112295515A (en) * | 2020-11-30 | 2021-02-02 | 江南大学 | Preparation method of zinc oxide/cerium oxide hollow microspheres with inverted blueberry-shaped structures |
| CN113600213A (en) * | 2021-06-21 | 2021-11-05 | 北京工商大学 | Copper-based oxide/phosphide composite mesomorphic material and preparation method and application thereof |
| CN114073951A (en) * | 2020-08-17 | 2022-02-22 | 中国科学院理化技术研究所 | Low-density floating type composite microsphere catalyst with thin-wall spherical shell structure and preparation method and application thereof |
| CN115634693A (en) * | 2022-09-30 | 2023-01-24 | 惠州学院 | Preparation method of nano composite material with hollow tube structure and application of nano composite material in catalysis of ammonia borane alcoholysis for hydrogen production |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491404A (en) * | 2011-12-19 | 2012-06-13 | 天津理工大学 | Copper oxide micro-nano composite structural material and preparation method thereof |
| CN105582935A (en) * | 2016-03-07 | 2016-05-18 | 中国科学院过程工程研究所 | Copper-zinc composite oxide and preparation method and application thereof |
| CN107039649A (en) * | 2017-06-06 | 2017-08-11 | 中国科学院过程工程研究所 | A kind of multistage hollow microsphere of copper based composite metal oxidate, preparation method and the usage |
-
2019
- 2019-02-15 CN CN201910118068.2A patent/CN109663595A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102491404A (en) * | 2011-12-19 | 2012-06-13 | 天津理工大学 | Copper oxide micro-nano composite structural material and preparation method thereof |
| CN105582935A (en) * | 2016-03-07 | 2016-05-18 | 中国科学院过程工程研究所 | Copper-zinc composite oxide and preparation method and application thereof |
| CN107039649A (en) * | 2017-06-06 | 2017-08-11 | 中国科学院过程工程研究所 | A kind of multistage hollow microsphere of copper based composite metal oxidate, preparation method and the usage |
Non-Patent Citations (1)
| Title |
|---|
| YONGJUN JI等: "Rambutan-like hierarchically heterostructured CeO2-CuO hollow microspheres: Facile hydrothermal synthesis and applications", 《NANO RESEARCH》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109755032A (en) * | 2019-02-21 | 2019-05-14 | 东南大学 | A kind of more shell CuCo2O4The preparation and its application of hollow nano-sphere |
| CN110152670A (en) * | 2019-05-29 | 2019-08-23 | 华南理工大学 | A kind of Co3O4/ CuO efficiency light thermocatalyst and the preparation method and application thereof |
| CN110514700A (en) * | 2019-09-27 | 2019-11-29 | 西安电子科技大学 | A kind of copper oxide and cobaltosic oxide heterogeneous structural nano line composite sensitive material, ethylene glycol sensor and preparation method |
| CN114073951A (en) * | 2020-08-17 | 2022-02-22 | 中国科学院理化技术研究所 | Low-density floating type composite microsphere catalyst with thin-wall spherical shell structure and preparation method and application thereof |
| CN114073951B (en) * | 2020-08-17 | 2023-08-01 | 中国科学院理化技术研究所 | Low-density floating composite microsphere catalyst with thin-wall spherical shell structure and preparation method and application thereof |
| CN112295515A (en) * | 2020-11-30 | 2021-02-02 | 江南大学 | Preparation method of zinc oxide/cerium oxide hollow microspheres with inverted blueberry-shaped structures |
| CN113600213A (en) * | 2021-06-21 | 2021-11-05 | 北京工商大学 | Copper-based oxide/phosphide composite mesomorphic material and preparation method and application thereof |
| CN113600213B (en) * | 2021-06-21 | 2022-04-22 | 北京工商大学 | Copper-based oxide/phosphide composite mesomorphic material and preparation method and application thereof |
| CN115634693A (en) * | 2022-09-30 | 2023-01-24 | 惠州学院 | Preparation method of nano composite material with hollow tube structure and application of nano composite material in catalysis of ammonia borane alcoholysis for hydrogen production |
| CN115634693B (en) * | 2022-09-30 | 2024-01-26 | 惠州学院 | Preparation method of nanocomposite with hollow tube structure and application of nanocomposite in catalyzing aminoborane alcoholysis to produce hydrogen |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109663595A (en) | A kind of copper based composite metal oxidate hollow microsphere, preparation method and the usage | |
| CN108097316B (en) | Preparation method of MOFs nano material loaded with nano metal particles | |
| Chen et al. | Multicomponent metal oxides derived from Mn-BTC anchoring with metal acetylacetonate complexes as excellent catalysts for VOCs and CO oxidation | |
| Kumari et al. | Bimetallic metal organic frameworks heterogeneous catalysts: Design, construction, and applications | |
| CN101565194B (en) | Method for preparing superfine mesoporous magnesium aluminate spinel | |
| CN105772027B (en) | A kind of support type cobaltosic oxide catalyst and its preparation method and application | |
| CN105582935B (en) | A kind of copper zinc composite oxide, preparation method and the usage | |
| CN109208030A (en) | A kind of Metal Hydroxide-Metal organic frame composite material and preparation method | |
| CN111068783B (en) | Preparation method and application of metal MOF (Metal organic framework) based composite material | |
| CN104028269A (en) | Graphene loaded metal nano composite material, and preparation method and application thereof | |
| CN107597109A (en) | Load type gold catalyst of nano-metal-oxide doping and preparation method and application | |
| CN110711581B (en) | Copper-based composite metal oxide mesomorphic microsphere and preparation method and application thereof | |
| Yousaf et al. | Synergistic effect of interfacial phenomenon on enhancing catalytic performance of Pd loaded MnO x–CeO 2–C hetero-nanostructure for hydrogenation and electrochemical reactions | |
| CN110854392A (en) | Metal organic framework-based cereal-grain-shaped carbon material and preparation and application thereof | |
| CN106861693B (en) | A kind of copper based composite metal oxidate mesomorphic material and its preparation method and application | |
| CN109926060A (en) | A kind of nuclear shell structured nano cu-ce composite oxidation catalyst, preparation method and application | |
| CN105110384B (en) | Porous cobaltosic oxide and preparation method thereof | |
| CN107335446A (en) | A kind of cobalt-base catalyst and its preparation and application that mixed alcohol is produced for one-step method from syngas | |
| Sun et al. | Recent progress of Ga-based liquid metals in catalysis | |
| CN109718787A (en) | Cerium/yttrium stable Zirconia carrier and catalyst | |
| CN109926048A (en) | A kind of one pack system double activated position Cu2O-CuO nanometers of mixed phase structure copper oxide catalysts, preparation method and application | |
| CN108948366A (en) | A kind of preparation and its desulfurization application of the Fe-MOF catalyst with abundant Lewis acidic site | |
| CN110339844A (en) | Fe nanometer rods and Pt@Fe Nanorods Catalyst and synthesis and application | |
| CN112536070A (en) | Preparation method of visible light response type MIL-100(Fe) photocatalytic composite material | |
| CN105198006B (en) | The application of porous cobaltosic oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20190423 |