CN107335403A - Load magnetic core-shell nano composite material, its preparation method and the application of nickel particle - Google Patents
Load magnetic core-shell nano composite material, its preparation method and the application of nickel particle Download PDFInfo
- Publication number
- CN107335403A CN107335403A CN201710514726.0A CN201710514726A CN107335403A CN 107335403 A CN107335403 A CN 107335403A CN 201710514726 A CN201710514726 A CN 201710514726A CN 107335403 A CN107335403 A CN 107335403A
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- China
- Prior art keywords
- magnetic core
- nickel
- shell
- preparation
- particle
- Prior art date
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- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title claims abstract description 209
- 230000005291 magnetic effect Effects 0.000 title claims abstract description 111
- 239000002245 particle Substances 0.000 title claims abstract description 85
- 229910052759 nickel Inorganic materials 0.000 title claims abstract description 77
- 239000011258 core-shell material Substances 0.000 title claims abstract description 73
- 239000000463 material Substances 0.000 title claims abstract description 56
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 26
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 128
- 150000002815 nickel Chemical class 0.000 claims abstract description 41
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 37
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 229920003986 novolac Polymers 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 230000009467 reduction Effects 0.000 claims abstract description 11
- 239000011248 coating agent Substances 0.000 claims abstract description 8
- 238000000576 coating method Methods 0.000 claims abstract description 8
- 239000002131 composite material Substances 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims abstract description 7
- 238000003763 carbonization Methods 0.000 claims abstract description 4
- 238000011068 loading method Methods 0.000 claims abstract description 4
- 229910001453 nickel ion Inorganic materials 0.000 claims abstract description 4
- 150000002828 nitro derivatives Chemical class 0.000 claims abstract description 4
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 119
- GHMLBKRAJCXXBS-UHFFFAOYSA-N resorcinol Chemical compound OC1=CC=CC(O)=C1 GHMLBKRAJCXXBS-UHFFFAOYSA-N 0.000 claims description 38
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 34
- 235000012239 silicon dioxide Nutrition 0.000 claims description 22
- 239000000243 solution Substances 0.000 claims description 22
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 17
- 229910052710 silicon Inorganic materials 0.000 claims description 17
- 239000010703 silicon Substances 0.000 claims description 17
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 16
- 239000003054 catalyst Substances 0.000 claims description 16
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 241001502050 Acis Species 0.000 claims description 8
- 229910021529 ammonia Inorganic materials 0.000 claims description 8
- 150000002148 esters Chemical class 0.000 claims description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 7
- 238000009413 insulation Methods 0.000 claims description 7
- -1 phenolic aldehyde Chemical class 0.000 claims description 7
- 230000015572 biosynthetic process Effects 0.000 claims description 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- UQSXHKLRYXJYBZ-UHFFFAOYSA-N iron oxide Inorganic materials [Fe]=O UQSXHKLRYXJYBZ-UHFFFAOYSA-N 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 238000003786 synthesis reaction Methods 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 239000003463 adsorbent Substances 0.000 claims description 3
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 3
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 3
- 102000004169 proteins and genes Human genes 0.000 claims description 3
- 108090000623 proteins and genes Proteins 0.000 claims description 3
- 238000010792 warming Methods 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- 239000007789 gas Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical group [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 2
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 2
- UQMOLLPKNHFRAC-UHFFFAOYSA-N tetrabutyl silicate Chemical compound CCCCO[Si](OCCCC)(OCCCC)OCCCC UQMOLLPKNHFRAC-UHFFFAOYSA-N 0.000 claims description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 17
- 229920005989 resin Polymers 0.000 abstract description 4
- 239000011347 resin Substances 0.000 abstract description 4
- 239000002086 nanomaterial Substances 0.000 description 65
- 229910052681 coesite Inorganic materials 0.000 description 63
- 229910052906 cristobalite Inorganic materials 0.000 description 63
- 229910052682 stishovite Inorganic materials 0.000 description 63
- 229910052905 tridymite Inorganic materials 0.000 description 63
- 239000011257 shell material Substances 0.000 description 60
- 239000010410 layer Substances 0.000 description 36
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 34
- 238000005245 sintering Methods 0.000 description 25
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 21
- 238000006722 reduction reaction Methods 0.000 description 21
- 230000005540 biological transmission Effects 0.000 description 17
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 13
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- 229920001568 phenolic resin Polymers 0.000 description 13
- 239000005011 phenolic resin Substances 0.000 description 13
- 150000005207 1,3-dihydroxybenzenes Chemical class 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 229910052799 carbon Inorganic materials 0.000 description 8
- 235000013339 cereals Nutrition 0.000 description 8
- 238000000034 method Methods 0.000 description 7
- 239000000126 substance Substances 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- 239000006185 dispersion Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 230000008859 change Effects 0.000 description 4
- 229910052737 gold Inorganic materials 0.000 description 4
- 239000010931 gold Substances 0.000 description 4
- 239000004005 microsphere Substances 0.000 description 4
- 229910052763 palladium Inorganic materials 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 229910052709 silver Inorganic materials 0.000 description 4
- OEHNVKBOQOXOJN-UHFFFAOYSA-N 2-(4-nitrophenyl)phenol Chemical compound OC1=CC=CC=C1C1=CC=C([N+]([O-])=O)C=C1 OEHNVKBOQOXOJN-UHFFFAOYSA-N 0.000 description 3
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- 238000000862 absorption spectrum Methods 0.000 description 3
- 239000007864 aqueous solution Substances 0.000 description 3
- 229940056319 ferrosoferric oxide Drugs 0.000 description 3
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 3
- 230000005415 magnetization Effects 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000010944 silver (metal) Substances 0.000 description 3
- 239000012279 sodium borohydride Substances 0.000 description 3
- 229910000033 sodium borohydride Inorganic materials 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- IQUPABOKLQSFBK-UHFFFAOYSA-N 2-nitrophenol Chemical compound OC1=CC=CC=C1[N+]([O-])=O IQUPABOKLQSFBK-UHFFFAOYSA-N 0.000 description 2
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 238000005253 cladding Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005307 ferromagnetism Effects 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 238000001027 hydrothermal synthesis Methods 0.000 description 2
- 229910000765 intermetallic Inorganic materials 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910044991 metal oxide Inorganic materials 0.000 description 2
- 150000004706 metal oxides Chemical class 0.000 description 2
- 239000013528 metallic particle Substances 0.000 description 2
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 150000003839 salts Chemical class 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- XKZQKPRCPNGNFR-UHFFFAOYSA-N 2-(3-hydroxyphenyl)phenol Chemical compound OC1=CC=CC(C=2C(=CC=CC=2)O)=C1 XKZQKPRCPNGNFR-UHFFFAOYSA-N 0.000 description 1
- 241000283690 Bos taurus Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 102000001554 Hemoglobins Human genes 0.000 description 1
- 108010054147 Hemoglobins Proteins 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
- 229910052765 Lutetium Inorganic materials 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- VMHLLURERBWHNL-UHFFFAOYSA-M Sodium acetate Chemical class [Na+].CC([O-])=O VMHLLURERBWHNL-UHFFFAOYSA-M 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 229920001807 Urea-formaldehyde Polymers 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical compound [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 239000005539 carbonized material Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002389 environmental scanning electron microscopy Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 229910052735 hafnium Inorganic materials 0.000 description 1
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical compound [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 1
- 239000000017 hydrogel Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 238000003780 insertion Methods 0.000 description 1
- 230000037431 insertion Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- OHSVLFRHMCKCQY-UHFFFAOYSA-N lutetium atom Chemical compound [Lu] OHSVLFRHMCKCQY-UHFFFAOYSA-N 0.000 description 1
- 239000000696 magnetic material Substances 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 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 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
- 239000003094 microcapsule Substances 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical group Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- 229910052758 niobium Inorganic materials 0.000 description 1
- 239000010955 niobium Substances 0.000 description 1
- GUCVJGMIXFAOAE-UHFFFAOYSA-N niobium atom Chemical compound [Nb] GUCVJGMIXFAOAE-UHFFFAOYSA-N 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 229910052762 osmium Inorganic materials 0.000 description 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium atom Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- VDGJOQCBCPGFFD-UHFFFAOYSA-N oxygen(2-) silicon(4+) titanium(4+) Chemical compound [Si+4].[O-2].[O-2].[Ti+4] VDGJOQCBCPGFFD-UHFFFAOYSA-N 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 238000004647 photon scanning tunneling microscopy Methods 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- ODGAOXROABLFNM-UHFFFAOYSA-N polynoxylin Chemical compound O=C.NC(N)=O ODGAOXROABLFNM-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 239000011241 protective layer Substances 0.000 description 1
- 230000005610 quantum mechanics Effects 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 229910052702 rhenium Inorganic materials 0.000 description 1
- WUAPFZMCVAUBPE-UHFFFAOYSA-N rhenium atom Chemical compound [Re] WUAPFZMCVAUBPE-UHFFFAOYSA-N 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 229910052706 scandium Inorganic materials 0.000 description 1
- SIXSYDAISGFNSX-UHFFFAOYSA-N scandium atom Chemical compound [Sc] SIXSYDAISGFNSX-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000010420 shell particle Substances 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 235000011091 sodium acetates Nutrition 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003075 superhydrophobic effect Effects 0.000 description 1
- 229910052715 tantalum Inorganic materials 0.000 description 1
- GUVRBAGPIYLISA-UHFFFAOYSA-N tantalum atom Chemical compound [Ta] GUVRBAGPIYLISA-UHFFFAOYSA-N 0.000 description 1
- 229910052713 technetium Inorganic materials 0.000 description 1
- GKLVYJBZJHMRIY-UHFFFAOYSA-N technetium atom Chemical compound [Tc] GKLVYJBZJHMRIY-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 239000004408 titanium dioxide Substances 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- HRXKRNGNAMMEHJ-UHFFFAOYSA-K trisodium citrate Chemical class [Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O HRXKRNGNAMMEHJ-UHFFFAOYSA-K 0.000 description 1
- 235000019263 trisodium citrate Nutrition 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- GPPXJZIENCGNKB-UHFFFAOYSA-N vanadium Chemical compound [V]#[V] GPPXJZIENCGNKB-UHFFFAOYSA-N 0.000 description 1
- 229910052727 yttrium Inorganic materials 0.000 description 1
- VWQVUPCCIRVNHF-UHFFFAOYSA-N yttrium atom Chemical compound [Y] VWQVUPCCIRVNHF-UHFFFAOYSA-N 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052726 zirconium Inorganic materials 0.000 description 1
Classifications
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
- B01J20/20—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material comprising free carbon; comprising carbon obtained by carbonising processes
-
- 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
- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
- B01J20/02—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising inorganic material
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- B—PERFORMING OPERATIONS; TRANSPORTING
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Abstract
The present invention relates to magnetic core-shell nano composite material, its preparation method and the application of load nickel particle, the composite includes the carbonization shell of magnetic core and the load nickel particle of coated magnetic core, and silica inner casing is also wrapped between magnetic core and carbonization shell.The preparation method of the composite, comprises the following steps：1) magnetic core of coated silica layer is scattered in alkaline alcohol-water system, adds the precursor solution for the novolak resin for being mixed with nickel salt, reaction obtains coating the magnetic core of novolac resin layer, novolac resin layer doping nickel ion.2) magnetic core for coating novolac resin layer is incubated roasting in inert environments, obtains loading the magnetic core-shell nano composite material of nickel particle.The composite has the advantages that magnetic is strong, appearance structure is good and stablized, adsorbs and catalysis is excellent, particularly for the reduction catalystses reaction to fragrant nitro compound.
Description
Technical field
The present invention relates to field of nanometer material technology, magnetic core-shell nano composite material more particularly to load nickel particle, its
Preparation method and application.
Background technology
Nanometer technology is modern technologies (such as computer technology, microelectronics and PSTM technology) and modern science
The product that (molecular biology, quantum mechanics etc.) is combined together.The nano material brought by it have hardness it is big, it is in light weight,
The plurality of advantages such as convenience, long lifespan, maintenance cost be low are designed, compared to the more excellent protrusion of common material performance.Wherein, nucleocapsid knot
The nano composite material of structure typically by center core and be coated on outside shell form, in the nano composite material of core shell structure
Kernel and shell between pass through physics, chemical action be connected with each other.The core shell structure of broad sense not only includes by different material group
Into the nano composite material with core shell structure, in addition to the nano composite material such as hollow microsphere, microcapsules.Core shell structure
The much unique physics of nano composite material and chemical characteristic, super-hydrophobic surface coating, materialogy, chemistry, magnetics, electricity,
The fields such as optics, biomedicine, catalysis all have potential application value.
The template of core-shell structure composite nano material can be carbon ball, SiO2Microballoon or prill and its oxidate microspheres
Deng, wherein, Fe3O4Magnetic ball is widely used due to low toxicity, good water solubility and the advantages that separated and recovered beneficial to material.It is but exposed
Fe3O4The shortcomings of in the presence of easily being corroded by acid etc., and being easier to reunite, it is unfavorable for generating the nano composite material of excellent quality, and finally
Influence the realization of nano composite material function.
SiO2Have the advantages that non-toxic, big rich in oh group, specific surface area, may generally serve as the shell of core-shell material,
Protective effect is carried out to core.Therefore, by SiO2It is coated on Fe3O4Surface obtains magnetic silicon ball Fe3O4@SiO2, to Fe3O4Rise protection and
Anti-agglomeration acts on.Furthermore SiO2Good biocompatibility, it can be modified in the enterprising step of magnetic silicon ball.
Phenolic resin toxicity obtained by phenols and aldehydes condensation is low, cheap and be easy to be coated on lot of materials surface,
It is a kind of common carbon source, there is very big application prospect in terms of ultracapacitor.At present, relevant phenolic resin carbonized function
Property material research concentrate on its it is resistance to burn, high absorption, high score is from, highly conductive, high heat conduction and the performance of high corrosion resistant.It has been reported that
Phenolic resin reduces some metal oxides to form corresponding metal simple-substance particle, such as Ag, Au, Pd, and phenolic resin
The research concentration that the char-forming material of generation is combined with metallic compound is to improve its electric property.Its principle is in phenolic resin
Containing substantial amounts of oh group, there are good reproducibility and coordination ability, phenolic resin reduces metallic compound to be formed relatively
The metal simple-substance particle answered, these metal simple-substance particles correspondingly improve the specific capacitance of phenolic resin carbonized material.
At present, nuclear-shell structured nano-composite material has the nucleocapsids such as metal-metal, metal-oxide, oxide-oxide
Structure, wherein, the metal in composite is mostly using noble metals such as Ag, Au, Pd, Pt, however, Precious Metals Resources are limited, and
It is expensive, the popularization and application of such material are constrained to a certain extent.
Therefore, nuclear-shell structured nano-composite material is prepared instead of noble metal using cheap metal, and expands core shell structure
The popularization and application of nano composite material, it need further to study.
The content of the invention
For technical problem existing for prior art, it is nano combined that the present invention provides a kind of magnetic core-shell for loading nickel particle
Material, its preparation method and application.
To achieve the above object, technical solution of the present invention is：
The magnetic core-shell nano composite material of load nickel particle, including magnetic core, the load nickel particle of coated magnetic core
Carbonization shell and the silicon dioxide layer for being coated on magnetic core between the shell that is carbonized.
Magnetic core is Co Fe2O4Magnetic core, Fe2O3Magnetic core, FeO magnetic cores or Fe3O4The magnetic cores such as magnetic core.
The particle diameter of magnetic core is 110~180nm；The particle diameter of nickel particle is 4~7.5nm；The thickness of silicon dioxide layer be 7~
30nm.Preferably, the particle diameter of magnetic core is 145~155nm；The particle diameter of nickel particle is 4.5~5.5nm；The thickness of silicon dioxide layer
Spend for 20~25nm.More preferably, the particle diameter of magnetic core is 150nm；The particle diameter of nickel particle is 5nm；Silicon dioxide layer
Thickness is 25nm.
The preparation method of the magnetic core-shell nano composite material of nickel particle is loaded, is comprised the following steps：
1) magnetic core of coated silica layer is scattered in alkaline alcohol-water system, adds the synthesis phenol for being mixed with nickel salt
The precursor solution of urea formaldehyde, reaction obtain coating the magnetic core of novolac resin layer, novolac resin layer doping nickel ion.
2) magnetic core for coating novolac resin layer is incubated roasting in inert gas, obtains loading the magnetic core-shell of nickel particle
Nano composite material.
In step 1), coat novolac resin layer used in alkaline alcohol-water system be made up of ethanol, water and ammoniacal liquor, ethanol it is dense
Spend for 0.6~0.75g/mL, the concentration of ammonia is 16~25mg/mL.Preferably, the concentration of ethanol is 0.65~0.70g/mL, ammonia
Concentration be 20.5~21mg/mL.
The Adding Way for being mixed with the precursor solution of the novolak resin of nickel salt is, under stirring, first adds dropwise
Enter the mixed solution of soluble nickel salt and resorcinol, add formaldehyde, the mass ratio of magnetic core and resorcinol is 5~20：
1, the mol ratio of nickel salt and resorcinol is 0.25~4：1, nickel salt includes nickel sulfate, nickel nitrate, nickel acetate or nickel halogenide etc.
Nickel metal salt.Preferably, the mol ratio of nickel salt and resorcinol is 1.5~2：1, nickel salt is nickel chloride or Nickel dichloride hexahydrate.
Step 1), add in the reaction system after precursor solution, the content of Resorcino is 0.20~0.70mg/mL.It is excellent
Selection of land, the content of resorcinol is 0.2~0.35mg/mL, and more excellent is 0.2~0.25mg/mL.
In step 1), the method for preparing the magnetic core of coated silica layer is that magnetic core first is scattered in into alkaline alcohol water
In system, positive esters of silicon acis is added.Positive esters of silicon acis is the matter of tetraethyl orthosilicate or butyl silicate, positive esters of silicon acis and magnetic core
Amount is than being 0.8~5：1, it is preferable that positive esters of silicon acis be tetraethyl orthosilicate, and the mass ratio of positive esters of silicon acis and magnetic core is 2.5~4：
1, more excellent to be, the mass ratio of tetraethyl orthosilicate and magnetic core is 2.5~3：1；Alkaline alcohol water body used in coated silica layer
System is made up of ethanol, water and ammoniacal liquor, and the concentration of ethanol is 0.70~0.75g/mL, and the concentration of ammonia is 20~22mg/mL；It is preferred that
Ground, the alkaline alcohol-water system used in coated silica layer are made up of ethanol, water and ammoniacal liquor, the concentration of ethanol for 0.72~
0.75g/mL, the concentration of ammonia is 21.5~22mg/mL.
The insulation roasting condition of step 2) is, under nitrogen or inert gas conditions, with 8~12 DEG C/min heating rate liter
After warm to 450~550 DEG C, insulation roasting 4~6 hours.Preferably, under nitrogen or inert gas conditions, with 10 DEG C/min liter
After warm speed is warming up to 500 DEG C, insulation roasting 5 hours.
The magnetic core-shell nano composite material of load nickel particle of the present invention, which has, is catalyzed fragrant nitro compound reduction
Reaction, especially nitrophenol reduction reaction, available for preparing fragrant nitro compound reduction catalyst, especially nitrophenol
Reduction catalyst.
The magnetic core-shell nano composite material of load nickel particle of the present invention can adsorbed proteins, available for preparing
Protein adsorbent, especially bovine hemoglobin adsorbent.
Compared with prior art, the invention has the advantages that：
1st, present invention firstly provides the complex formed using inexpensive transition metal salt nickel salt with phenolic resin, by entering
One step modifiedMethod, magnetic silicon ball surface is successfully coated on, core-shell structure copolymer-shell nano structural material is formed, then in nitrogen
Calcined under gas shielded, form magnetic core-shell structure copolymer-shell composite nano materials.
2nd, magnetic core-shell structure copolymer-shell composite nano materials for preparing of the present invention have that magnetic is strong, appearance structure is good and stablizes, inhales
The advantages that attached and catalysis is excellent, reacted particularly for the reduction catalystses of p-nitrophenol；The magnetic core duplex shell structure nanometer
Material also has preferable use value and application prospect in fields such as environment, the energy.And the magnetic of the core bivalve nano material
Core can provide ferromagnetism, be advantageous to the recycling of material；The size and density for the nickel particle that its surface is loaded are effectively controllable.
3rd, preparation method of the present invention is by adjusting thickness, nickel salt amount and the sintering temperature of silicon dioxide layer, to the magnetic of preparation
Property the nickel metallic particles amount size that is loaded of core duplex shell structure nano material and density carry out Effective Regulation.
4th, preparation method of the present invention, simple and easy to control, due to the ferromagnetism of magnetic core, separating, washing is especially square under external magnetic field
Just, time, human and material resources have greatly been saved, environment-friendly, reagent is easy to get and consumed less, and yield is high, is adapted to scale metaplasia
Production.
5th, preparation method of the present invention can be not added with any reducing agent in calcination process while phenolic resin turns into carbon
In the case of nickel ion is reduced to nickel simple substance particle, the presence of nickel salt promotes the graphite alkylene of carbon in calcination process again, and newborn
Into nickel particle also have magnetic, further enhance magnetism of material.
Brief description of the drawings
Fig. 1 is nano material Fe3O4@SiO2The scanning electricity of@C-Ni and its intermediate product of preparation process under high low power lens
Mirror figure transmission electron microscope picture；In Fig. 1, a, b Fe3O4Magnetic ball；C, d is Fe3O4@SiO2Core-shell nano material；E, f is Fe3O4@SiO2@
RF-Ni2+Core-shell structure copolymer-shell structural nano material；H, i is Fe3O4@SiO2@C-Ni core-shell structure copolymers-shell structural nano material.A, c, e, h are
Scanning electron microscope (SEM) photograph, b, d, f, i are transmission electron microscope picture.
Fig. 2 is to coat the magnetic silicon ball Fe of different-thickness silicon dioxide layer3O4@SiO2The magnetic core prepared for matrix-
Shell-shell structural nano material Fe3O4@SiO2@C-Ni scanning electron microscope (SEM) photograph and transmission electron microscope picture.In Fig. 2, a, b TEOS amounts are
93mg；C, d TEOS amounts are 0.28g；E, f TEOS amounts are 0.46g.A, c, e are scanning electron microscope (SEM) photograph, and b, d, f are transmission electron microscope picture.
Fig. 3 is the Fe of the novolac resin layer of the doping nickel salt of cladding different-thickness3O4@RF-Ni2+Magnetic core-shell structure nano
The scanning electron microscope (SEM) photograph and transmission electron microscope picture of material.In Fig. 3, a, b use 20mg resorcinols amount and 80mg nickel salt amounts；C, d is equal
Using 31mg resorcinols amount and 124mg nickel salt amounts；E, f uses 62mg resorcinols amount and 248mg nickel salt amounts.A, c, e are
Scanning electron microscope (SEM) photograph, b, d, f are transmission electron microscope picture.
Fig. 4 is the Fe corresponding to the novolac resin layer of the doping nickel salt of cladding different-thickness3O4- Ni@C magnetic core-shell structures
The scanning electron microscope (SEM) photograph and transmission electron microscope picture of nano material.In Fig. 4, a, b use 20mg resorcinols amount and 80mg nickel salt amounts；c、d
Using 31mg resorcinols amount and 124mg nickel salt amounts；E, f uses 62mg resorcinols amount and 248mg nickel salt amounts.A, c, e are to sweep
Electron microscope is retouched, b, d, f are transmission electron microscope picture.
Fig. 5 is the Fe prepared under the conditions of the different mol ratio of resorcinol and nickel salt3O4@SiO2@C-Ni magnetic core-shell structure copolymer-shell
The scanning electron microscope (SEM) photograph and transmission electron microscope picture of structure nano material.In Fig. 5, Fig. 5 a, b resorcinols and nickel salt mol ratio are 1:
0.25；Fig. 5 c, d resorcinols and nickel salt mol ratio are 1:4.A, c is scanning electron microscope (SEM) photograph, and b, d are transmission electron microscope picture.
Fig. 6 is the Fe prepared under 5 different sintering temperatures of embodiment3O4@SiO2@C-Ni magnetic core-shell structure copolymer-shell structural nano material
The scanning electron microscope (SEM) photograph and transmission electron microscope picture of material.In Fig. 6, a, b sintering temperature are 400 DEG C, and c, d sintering temperature are 500 DEG C；E, f is roasted
It is 600 DEG C to burn temperature, and a, c, e are scanning electron microscope (SEM) photograph, and b, d, f are transmission electron microscope picture.
Fig. 7, Fig. 8, Fig. 9 correspond to 400 DEG C, 500 DEG C, the Fe for preparing under 600 DEG C of sintering temperatures respectively3O4@SiO2@C-Ni magnetic
Property core-shell structure copolymer-shell structural nano material catalysis p-nitrophenol reduction reaction uv-spectrophotometric figure.
Figure 10 is the dynamic uv-spectrophotometric figure during p-nitrophenol reduction reaction.
Figure 11 is Fe3O4@SiO2It is anti-that@C-Ni magnetic core-shell structure copolymer-shell structural nano material circulation is used for p-nitrophenol reduction
The catalytic efficiency figure answered.
Figure 12 is respectively 400 DEG C, 500 DEG C, C/Ni-400, C/Ni-500 and C/Ni- for preparing under 600 DEG C of sintering temperatures
Ln (the C/C of the catalytic reaction of 600 samples0) with time t linear relationship chart.
Figure 13 is the C/C of the catalytic reaction of the C/Ni-500 samples prepared under 500 DEG C of sintering temperatures0With ln (C/C0) and when
Between graph of a relation.
Figure 14 is Fe3O4@SiO2@RF-Ni2+Core-shell structure copolymer-shell structural nano material and Fe3O4@SiO2@C-Ni core-shell structure copolymers-shell knot
The hysteresis curve figure of structure nano material.
Figure 15 is Fe3O4@SiO2@RF-Ni2+Core-shell structure copolymer-shell structural nano material and Fe3O4@SiO2@C-Ni core-shell structure copolymers-shell knot
Corresponding enlarged drawing of the hysteresis curve figure of structure nano material in downfield.A refers to Fe in Figure 153O4@SiO2@C-Ni core-shell structure copolymers-
Shell structural nano material, b refer to Fe3O4@SiO2@RF-Ni2+Core-shell structure copolymer-shell structural nano material.
Embodiment
The present invention is further exemplarily described in detail with reference to specific embodiment.It should be noted that for these
The explanation of embodiment is used to help understand the present invention, but does not form limitation of the invention.
Can act as magnetic core has Co Fe2O4、Fe2O3, FeO or Fe3O4Deng magnetic material, following embodiments are preferred
Technical scheme and effect is expanded on further as magnetic core in ferroso-ferric oxide.
The metal salt adulterated in phenolic resin polymerization process, is reduced to metal simple-substance during phenolic resin carbonized
Grain, and be supported in carburization zone, the metal of the reaction is applicable in addition to the noble metals such as Ag, Au, Pd, Pt disclosed in prior art,
Other transition metal are could be applicable to, for example, the scandium of First Transition system, titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, zinc, the second mistake
Cross the yttrium for being, zirconium, niobium, molybdenum, technetium, ruthenium, rhodium, palladium, silver, cadmium, the lutetium of the 3rd transition system, hafnium, tantalum, tungsten, rhenium, osmium, iridium, platinum, gold,
Mercury, etc..Technical scheme and effect is expanded on further in following preferred nickel metals of embodiment.
Phenolic resin is polymerized by phenol and its homologue with aldehyde material.The preferred resorcinol of following embodiments and first
The resin that aldehyde is polymerized, i.e. RF resins, are expanded on further technical scheme and effect.
Embodiment 1
Fe3O4@SiO2The preparation of@C-Ni nano materials
a)Fe3O4The preparation of microballoon：Using solvent hydro-thermal method, 3g Nickel dichloride hexahydrates, 0.83g trisodium citrates are disperseed
In 70mL ethylene glycol, 4.8g sodium acetates are added, is stirred in beaker and forms homogeneous solution, then turn above-mentioned homogeneous solution
In the reactor for entering 50mL, the hydro-thermal reaction 10h at 200 DEG C, reaction is cooled to room temperature after terminating, and takes out reactor, will react
Reaction solution in kettle pours into beaker, is separated in the presence of magnet and is washed for several times with water and ethanol, dry Fe3O4Receive
Meter Wei Qiu, Fe3O4Microspherulite diameter scope 110~180nm, Fe3O4Microsphere average grain diameter is in 150nm or so.
B) core-shell structured nanomaterials Fe3O4@SiO2Preparation：By 100mg Fe3O4Microballoon be scattered in 82mL by ethanol, go
The alkaline alcohol-water system of ionized water and ammoniacal liquor composition, in the alkaline alcohol-water system, the concentration of ethanol is 0.722g/mL, ammonia it is dense
Spend for 21.53mg/mL, after ultrasonic disperse is good stirring be allowed to well mixed, 0.28gTEOS is then added dropwise with vigorous stirring
(tetraethyl orthosilicate), it is stirred at room temperature 15 hours, then separating, washing is carried out in the presence of magnet, dry Fe3O4@SiO2
Core-shell particles, wherein silicon dioxide layer thickness about 25nm or so, Fe3O4@SiO2Average grain diameter is about 175nm or so.
C) core-shell structure copolymer-shell structural nano material Fe3O4@SiO2@RF-Ni2+Preparation：By 310mg Fe3O4@SiO2It is scattered in
The alkaline alcohol-water system that 86mL is made up of ethanol, deionized water and ammoniacal liquor, in the alkaline alcohol-water system, the concentration of ethanol is
0.688g/mL, the concentration of ammonia is 20.53mg/mL, is stirred after ultrasonic disperse is good and is allowed to well mixed, then with vigorous stirring
Be added dropwise mixed aqueous solution that 4mL is made up of 20mg resorcinols and 80mg Nickel dichloride hexahydrates (nickel salt and resorcinol
About 1.85) mol ratio, adds 0.23g formaldehyde, be stirred at room temperature 14 hours, then carries out separation in the presence of magnet and wash
Wash, dry Fe3O4@SiO2@RF-Ni2+Core-shell structure copolymer-shell structural nano material, RF-Ni2+Thickness degree is about 10nm or so, Fe3O4@
SiO2@RF-Ni2+Average grain diameter is about 187nm or so.
D) core-shell structure copolymer-shell structural nano material Fe3O4@SiO2@C-Ni preparation：Finally by obtained Fe3O4@SiO2@RF-
Ni2+Nano material is warming up to 500 DEG C and at this temperature insulation roasting 5 under nitrogen protection, with 10 DEG C/min heating rate
Hour, that is, obtain the magnetic core duplex shell structure nano material Fe of nickel-loaded particle3O4@SiO2@C-Ni, Fe3O4@SiO2@C-Ni are put down
Equal particle diameter is about 182nm or so.
Nano material Fe3O4@SiO2The scanning electron microscope (SEM) photograph of@C-Ni and its intermediate product of preparation process under high low power lens
It is as shown in Figure 1 with transmission electron microscope picture.From Fig. 1 a, b, intermediate product Fe3O4Magnetic ball, size is more uniform, rough surface, pattern
Structure is good, good dispersion；From Fig. 1 c, d, intermediate product magnetic silicon ball Fe3O4@SiO2Surface is smooth, good dispersion, possesses
Fine core shell structure, wherein, silicon dioxide layer thickness about 25nm；From Fig. 1 e, f, intermediate product core duplex shell structure material
Fe3O4@SiO2@RF-Ni2+, surface is still smooth, dispersed still good；From Fig. 1 h, i, final product core bivalve material
Fe3O4@SiO2@C-Ni, are the magnetic silicon ball of area load uniform particle diameter and the larger metal nickel particle of density, and nickel particle point
It is good to dissipate property, Fe3O4@SiO2Due to there is newly-generated magnetic nickel particle, magnetism of material is strengthened@C-Ni, contributes to materials application
In recycling.Wherein, nickel particle average grain diameter is about 5nm.
Fe3O4@SiO2@RF-Ni2+Core-shell structure copolymer-shell structural nano material and Fe3O4@SiO2@C-Ni core-shell structure copolymers-shell structural nano
The hysteresis curve figure of material is as shown in figure 14.From Figure 14 hysteresis curve, Fe3O4@SiO2@C-Ni core-shell structure copolymers-shell structure is received
The saturated magnetization amount of rice material is relative to Fe3O4@SiO2@RF-Ni2+Core-shell structure copolymer-shell structural nano material increase 23.6emu/g.It is former
Because being, in heat treatment process, Fe3O4The aggregation of nano particle, and the generation of magnetic nickel nano particle.
From the insertion figure in Figure 14 upper left corners, when cancelling external magnetic field, weak vibrations are mixed with Fe3O4@SiO2@C-Ni
Solution bottle, solution bottle is that the turbid solution positioned at left side is converted into by the settled solution positioned at right side；When setting up external magnetic field,
Fe3O4@SiO2@C-Ni assemble under external magnetic field, and solution bottle is converted into the clear of right side in 2min by the turbid solution in left side
Clear solution.
Fe3O4@SiO2@RF-Ni2+Core-shell structure copolymer-shell structural nano material and Fe3O4@SiO2@C-Ni core-shell structure copolymers-shell structural nano
Corresponding enlarged drawing of the hysteresis curve figure of material in downfield is as shown in figure 15.Fe3O4@SiO2@C-Ni remanent magnetization
For 3.58emu/g, Fe3O4@SiO2@RF-Ni2+Remanent magnetization be 0.87emu/g；Fe3O4@SiO2@C-Ni coercivity
Compare Fe3O4@SiO2@RF-Ni2+Greatly.
Embodiment 2
Influence of the different silicon dioxide layer thickness to nickel particle particle diameter and density
The present embodiment experiment condition and the difference of embodiment 1 are, change TEOS (tetraethyl orthosilicate) amount, respectively will
TEOS amounts are adjusted to 93mg and 0.46g, obtain coating the magnetic silicon ball Fe of different-thickness silicon dioxide layer3O4@SiO2, then prepare
Load different-grain diameter and the core bivalve material Fe of density nickel particle3O4@SiO2@C-Ni.Wherein, when TEOS amounts are 93mg, 0.28g
And during 0.46g, corresponding silicon dioxide layer thickness is respectively 7nm, 25nm and 30nm.
To coat the magnetic silicon ball Fe of different-thickness silicon dioxide layer3O4@SiO2Magnetic core-shell structure copolymer-shell the knot prepared for matrix
Structure nano material Fe3O4@SiO2@C-Ni scanning electron microscope (SEM) photograph and transmission electron microscope picture are as shown in Figure 2.
From Fig. 2 a, b：When TEOS amounts are 93mg, the silicon dioxide layer coated only has 7nm or so, so that obtaining
Fe3O4@SiO2The nickel particle of@C-Ni magnetic core-shell structure copolymer-shell structural nano material surface load is reunited and density is little, Fe3O4@
SiO2@C-Ni pattern is not mellow and full, also maintains the more coarse surface of ferroso-ferric oxide.
From Fig. 2 c, d：When TEOS amounts are 0.28g, the silicon dioxide layer coated is 25nm or so, due to titanium dioxide
The thickness of silicon layer is enough, therefore, obtains the good Fe of overall appearance structure3O4@SiO2@C-Ni magnetic core-shell structure copolymer-shell structural nano material
Material, the Fe3O4@SiO2The nickel particle good dispersion of@C-Ni area loads and it is homogeneous, area load particle diameter is more homogeneous.Understand,
As long as silicon dioxide layer is sufficiently thick, you can the effectively nickel particle particle diameter and size of control material surface load.
From Fig. 2 e, f：When TEOS amounts are 0.46g, the silicon dioxide layer coated is 30nm or so, due to titanium dioxide
Silicon layer thickness has reached, and therefore, obtains the good Fe of overall appearance structure3O4@SiO2@C-Ni magnetic core-shell structure copolymer-shell structural nano material
Material, the nickel particle particle diameter of its area load is still more homogeneous, good dispersion and homogeneous.But silicon dioxide layer is thicker, it is to four
The magnetic of Fe 3 O magnetic core weakens more.
Embodiment 3
Fe3O4The preparation of@C-Ni nano materials
The present embodiment and the difference of embodiment 1 are, directly with Fe3O4Microballoon is that matrix prepares core-shell nano material
Fe3O4@RF-Ni2+, wherein, the amount of resorcinol and Nickelous nitrate hexahydrate sets three investigation groups, is respectively, 20mg isophthalic
Diphenol amount and 80mg nickel salt amounts；31mg resorcinols amount and 124mg nickel salt amounts；62mg resorcinols amount and 248mg nickel salt amounts；Three
Fe used in individual investigation group3O4The amount of microballoon is 310mg.
Coat the Fe of the phenolic resin of the doping nickel salt of different-thickness3O4@RF-Ni2+Magnetic core-shell structure nano material
Scanning electron microscope (SEM) photograph and transmission electron microscope picture are as shown in Figure 3.Fig. 3 a, b core-shell nano material Fe3O4@RF-Ni2+Shell thickness it is left for 7nm
It is right；Fig. 3 c, d core-shell nano material Fe3O4@RF-Ni2+Shell thickness for 10nm or so；Fig. 3 e, f core-shell nano material Fe3O4@
RF-Ni2+Shell thickness for 20nm or so.From the figure 3, it may be seen that with the increase of resorcinol and the amount of nickel salt, the phenolic aldehyde tree coated
The thickness of the cooperation nitride layer of fat and nickel salt is consequently increased.
Then by three seed nucleus shell nanometer material Fe obtained by above three group3O4@RF-Ni2+Forged in same as Example 1
Under the conditions of burning, core-shell nano material Fe is calcined to obtain3O4-Ni@C。
Coat the magnetic core-shell structure nano material Fe corresponding to the novolac resin layer of the doping nickel salt of different-thickness3O4-
Ni@C scanning electron microscope (SEM) photograph and transmission electron microscope picture is as shown in Figure 4.As shown in Figure 4, all Fe3O4- Ni@C core-shell nano materials are all in
Reveal coarse surface, and in TEM figures, there is dark part, these parts should be Fe3O4Acted on, formed with Ni
Alloy.
From above-mentioned experimental result, Fe3O4Microballoon is in the case where no silicon dioxide layer coats, direct coating-doping
There is the novolac resin layer of nickel salt, increase novolac resin layer thickness, to the Fe ultimately generated3O4The form of-Ni@C core-shell nano materials
With the improvement result very little of function.Therefore, in order to generate form and the excellent magnetic core-shell structure nano material of function, in Fe3O4
Microsphere surface coated silica protective layer be it is required, in conjunction with the embodiments 1 and embodiment 2 experimental result, be mainly reflected in：
First, protection of the silicon dioxide layer to ferroso-ferric oxide kernel, avoids oxidation；Second, the presence realization pair of silicon dioxide layer
The size of area load nickel particle and the Effective Regulation of density, it was demonstrated that the controllability of method.
Embodiment 4
Influence of the nickel content to nickel particle size and density
The present embodiment and the difference of embodiment 1 are that the amount of taking of resorcinol is 20mg, respectively with isophthalic two
The mol ratio of phenol and nickel salt is 1:0.25、1:4, the amount of corresponding nickel salt is taken, and corresponding Fe is prepared3O4@SiO2@C-Ni
Magnetic core-shell structure copolymer-shell structural nano material.
The Fe prepared under the molar ratio of different resorcinols and nickel salt3O4@SiO2@C-Ni magnetic core-shell structure copolymer-shell structure
Scanning electron microscope (SEM) photograph of the nano material under high low power lens is as shown in Figure 5.
As shown in Figure 5, the present embodiment prepares all Fe of gained3O4@SiO2@C-Ni magnetic core-shell structure copolymer-shell structural nano material
The overall appearance structure of material is good, and the metallic nickel granular size of area load is homogeneous, and metal nickel particle is in the magnetic core-shell structure copolymer-shell
Structure nano material surface good dispersion and homogeneous.
Contrasted from Fig. 5 and Fig. 1 h, i, Fe3O4@SiO2@C-Ni magnetic core-shell structure copolymer-shell structural nano material surface is born
Nickel particle amount, nickel particle particle size and the nickel particle distribution situation of load are with the change of resorcinol and the mol ratio of nickel salt
And change.
From Fig. 5 a, b and Fig. 1 h, i contrasts, the mol ratio of resorcinol and nickel salt is 1:When 0.25, rubbed with embodiment 1
You are than being 1:Compared when 1.85, nickel particle density is obvious small a lot, but mean particle size is still 5nm or so, and this two
Nickel particle size in the case of kind mol ratio is similar.
From Fig. 5 c, d and Fig. 1 h, i contrasts, the mol ratio of resorcinol and nickel salt is 1:When 4, with 1 mole of embodiment
Than for 1:Compared when 2, nickel particle, which starts to reunite, becomes big, and grain density also reduces.
As the above analysis, the mol ratio of resorcinol and nickel salt is 1:When 1.85, the density and particle diameter of nickel particle, phase
For 1:0.25、1:4, it is in Optimal State.
Therefore, can be by adjusting the mol ratio of resorcinol and nickel salt to Fe3O4@SiO2@C-Ni magnetic core-shell structure copolymer-shell knot
The nickel particle size that the surface of structure nano material is loaded is regulated and controled with density.
Embodiment 5
Influence of the sintering temperature to nickel particle size and density
The Fe for taking three parts of same amount of embodiments 1 to prepare3O4@SiO2@RF-Ni2+Core-shell structure copolymer-shell structural nano material, respectively
It is calcined 5 hours in 400 DEG C, 500 DEG C and 600 DEG C insulations under nitrogen protection, three parts of Fe of gained3O4@SiO2@C-Ni magnetic cores-
Shell-shell structural nano material is designated as C/Ni-400, C/Ni-500 and C/Ni-600 respectively, their SEM (ESEM) and TEM
(transmission electron microscope) is as shown in Figure 6.
The average grain diameter for the nickel particle that sintering temperature generates when being 400 DEG C is 4.28 ± 0.042nm, sintering temperature 500
DEG C when the average grain diameter of nickel particle that generates be 4.92 ± 0.22nm, the nickel particle that sintering temperature generates when being 600 DEG C is averaged
Particle diameter is 7.16 ± 0.031nm, with the rise of sintering temperature, Fe3O4@SiO2@C-Ni magnetic core-shell structure copolymer-shell structural nano material
The particle diameter of the nickel particle loaded becomes larger with temperature rise, and density also changes.
As shown in fig. 6, the nickel particle size that is generated when being 400 DEG C of sintering temperature is similar when with sintering temperature being 500 DEG C,
Close to 5nm, but the nickel particle density of gained core-shell structure copolymer-shell structural nano material load is not so good as 500 DEG C during 400 DEG C of sintering temperature.
And when sintering temperature is upgraded to 600 DEG C, nickel particle has been reunited because sintering temperature is higher, and nickel particle particle diameter is by relative low temperature
When 5nm increase to 7nm, and nickel particle density also reduces.Therefore, 500 DEG C of gained core-shell structure copolymer-shell structural nano materials of sintering temperature
Nickel particle and density be superior to 400 DEG C and 600 DEG C of sintering temperature, sintering temperature can effectively control nickel particle size with it is close
Degree.
Embodiment 6
Catalytic performance is examined or check：
(1) C/Ni-400, C/Ni-500 and C/Ni-600 sample for taking 0.5mg embodiments 5 to prepare respectively are placed in 4mL concentration
For in the 0.1mmol/L p-nitrophenol aqueous solution, then by 5mg NaBH4Rapidly join in p-nitrophenyl phenol solution, use UV
UV spectrophotometer measuring p-nitrophenol concentration changes with time, and testing result is shown in Fig. 7 to Fig. 9.
Fig. 7 is the dynamic purple that the C/Ni-400 samples generated under 400 DEG C of sintering temperatures are catalyzed p-nitrophenol reduction reaction
Outer microphotohram, be followed successively by 0 from top to bottom, 4,8,12,16,20,24min when ultra-violet absorption spectrum, it is seen then that by C/Ni-
The time of 400 samples catalysis p-nitrophenol reduction reaction is 24min.
Fig. 8 is the dynamic purple that the C/Ni-500 samples generated under 500 DEG C of sintering temperatures are catalyzed p-nitrophenol reduction reaction
Outer microphotohram, be followed successively by 0 from top to bottom, 1,2,3min when ultra-violet absorption spectrum, it is seen then that be catalyzed by C/Ni-500 samples
The time of p-nitrophenol reduction reaction is 3min.
Fig. 9 is the dynamic purple that the C/Ni-600 samples generated under 600 DEG C of sintering temperatures are catalyzed p-nitrophenol reduction reaction
Outer microphotohram, be followed successively by 0 from top to bottom, 2,4,6,8,10,12min when ultra-violet absorption spectrum, it is seen then that by C/Ni-600
The time of sample catalysis p-nitrophenol reduction reaction is 12min.
From Fig. 7 to Fig. 9, catalyst C/Ni-500 catalytic activity is better than C/Ni-400 and C/Ni-600, can be at 3 points
Catalytic reaction is completed in clock, catalyst C/Ni-500 is the Fe prepared under 500 DEG C of sintering temperatures3O4@SiO2@C-Ni magnetic cores-
Shell-shell structural nano material, from the experimental result of embodiment 5, the size of the nickel metallic particles of nano-material surface load
And density, the Fe prepared better than 400 DEG C and under 600 DEG C of sintering temperatures3O4@SiO2@C-Ni magnetic core-shell structure copolymer-shell structural nano material
Material.The pattern of catalyst influences the activity of catalyst.
(2) the feasibility checking of catalytic reaction：When adding 5mg sodium borohydrides in the p-nitrophenyl phenol solution to 9mL, to nitre
Base phenol solution is changed into glassy yellow from light yellow, and the ultraviolet absorption peak of p-nitrophenol is immediately that 317nm is advanced to by wavelength
It is the ultraviolet absorption peak of intermediate product at 400nm, at 400nm；When solution becomes colorless, p-nitrophenyl phenol solution has been reduced to
P-aminophenyl phenol solution, its ultraviolet absorption peak is at wavelength 295nm, the change of ultraviolet absorption peak such as Figure 10 institutes in course of reaction
Show.
(3) by Fe after catalysis terminates3O4@SiO2@C-Ni magnetic core-shell structure copolymer-shell structural nano material centrifuge washing, Ran Houzhen
Sky is dried, and circulates the reduction reaction for being catalyzed p-nitrophenol, to examine or check the activity of its recycling, refers to Figure 11.By scheming
11 it is recognized that while by 5 recyclings, the Fe of the invention prepared3O4@SiO2@C-Ni magnetic core-shell structure copolymer-shell structural nano material
Still there is obvious catalytic activity.
(4) compared with catalyst, the amount of sodium borohydride is very big, and the amount of sodium borohydride can be considered as not in catalytic process
Become, to weigh, therefore, the speed constant of catalytic reaction meets first-rate dynamics, can be by first-rate dynamics formula ln
(C/C0)=- kt is calculated.Wherein k is speed constant, and t is the reaction time, C0It is the initial concentration of matched somebody with somebody p-nitrophenol solution, C
The p-nitrophenol concentration for being t for the reaction time.But the amount of the nickel particle loaded by different catalysts is different, therefore,
Rate constants k can not represent the activity of catalyst.Therefore activity constant κ need to be introduced and (be defined as speed constant and catalyst
Mass ratio) catalyst activity is judged.
It is separately added into ln (C/C in the catalytic reaction of 0.5mg C/Ni-400, C/Ni-500 and C/Ni-600 catalyst0) with
Time t linear relationship chart is as shown in figure 12.
Add C/C in the catalytic reaction of 0.5mg C/Ni-500 catalyst0With ln (C/C0) with graph of a relation such as Figure 13 of time
It is shown.
Wherein, C/Ni-400, C/Ni-500 and C/Ni-600 rate constants k are respectively 5.9 × 10-3、21.7×10- 3and 18.6×10-3s-1, activity constant κ is respectively 0.142mg–1s–1、0.523mg–1s–1and 0.449mg–1s–1.By ICP numbers
According to understanding, the load capacity of nickel is 82.8 μ g/mg.Wherein, shown by table 1 it is catalyst prepared by the present invention and other reports
The reaction rate of middle catalyst and the contrast of activity constant.
From Fig. 8, Figure 10, Figure 11, Figure 13 and table 1：Magnetic core-shell structure copolymer-shell structural nano material prepared by the present invention has
P-nitrophenol catalysis is reduced to para-aminophenol by effect, and catalytic action is obvious, can within 3 minutes quick catalysis to nitre
The reduction reaction of base phenol, still there is notable catalytic activity after recycling.
Table 1
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Claims (10)
1. load the magnetic core-shell nano composite material of nickel particle, it is characterised in that the load including magnetic core, coated magnetic core
The carbonization shell of nickel particle and the silicon dioxide layer for being coated on magnetic core between the shell that is carbonized.
2. the magnetic core-shell nano composite material of load nickel particle according to claim 1, it is characterised in that magnetic core is
Fe3O4Magnetic core, Co Fe2O4Magnetic core, Fe2O3Magnetic core or FeO magnetic cores.
3. the magnetic core-shell nano composite material of load nickel particle according to claim 1, it is characterised in that magnetic karyosome
Footpath is 110~180nm, and nickel particle particle diameter is 4~7.5nm, and the thickness of silicon dioxide layer is 7~30nm.
4. the preparation method of the magnetic core-shell nano composite material of any one of claims 1 to 3 load nickel particle, including following step
Suddenly：
1) magnetic core of coated silica layer is scattered in alkaline alcohol-water system, adds the synthesis phenolic aldehyde tree for being mixed with nickel salt
The precursor solution of fat, reaction obtain coating the magnetic core of novolac resin layer, novolac resin layer doping nickel ion；
2) magnetic core for coating novolac resin layer is incubated roasting in inert gas, obtains loading the magnetic core-shell nanometer of nickel particle
Composite.
5. preparation method according to claim 4, it is characterised in that step 1), coat the alkalescence used in novolac resin layer
Alcohol-water system is made up of ethanol, water and ammoniacal liquor, wherein, the concentration of ethanol is 0.6~0.75g/mL, the concentration of ammonia for 16~
25mg/mL。
6. preparation method according to claim 4, it is characterised in that step 1) the synthesis phenolic aldehyde tree for being mixed with nickel salt
The Adding Way of the precursor solution of fat is, under stirring, the mixed solution of nickel salt and resorcinol is first added dropwise, then add
Enter formaldehyde, the mass ratio of magnetic core and resorcinol is 5~20：1, the mol ratio of nickel salt and resorcinol is 0.25~4：1, nickel
Salt is nickel sulfate, nickel nitrate, nickel acetate or nickel halogenide.
7. preparation method according to claim 4, it is characterised in that step 1), the reaction system added after precursor solution
In, the content of Resorcino is 0.20~0.70mg/mL.
8. preparation method according to claim 4, it is characterised in that the magnetic core of step 1) the coated silica layer
Preparation method is that first magnetic core is scattered in alkaline alcohol-water system, adds positive esters of silicon acis；Positive esters of silicon acis is tetraethyl orthosilicate
Or butyl silicate, the mass ratio of positive esters of silicon acis and magnetic core is 0.8~5：1；Alkaline alcohol-water system is by ethanol, water and ammoniacal liquor
Composition, wherein, the concentration of ethanol is 0.7~0.75g/mL, and the concentration of ammonia is 20~22mg/mL.
9. preparation method according to claim 4, it is characterised in that the insulation roasting condition of step 2) is nitrogen or lazy
Property gas condition under, after being warming up to 450~550 DEG C with 8~12 DEG C/min heating rate, insulation roasting 4~6 hours.
10. load the magnetic core-shell nano composite material of nickel particle prepare be catalyzed fragrant nitro compound reduction catalyst or
Application in terms of protein adsorbent.
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Application publication date: 20171110 |