CN104209106B - The Fe of 5-sulphosalicylic acid functionalization 3o 4magnetic nano-particle and synthetic method thereof and application - Google Patents
The Fe of 5-sulphosalicylic acid functionalization 3o 4magnetic nano-particle and synthetic method thereof and application Download PDFInfo
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- CN104209106B CN104209106B CN201410438856.7A CN201410438856A CN104209106B CN 104209106 B CN104209106 B CN 104209106B CN 201410438856 A CN201410438856 A CN 201410438856A CN 104209106 B CN104209106 B CN 104209106B
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- YCPXWRQRBFJBPZ-UHFFFAOYSA-N 5-sulfosalicylic acid Chemical compound OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O YCPXWRQRBFJBPZ-UHFFFAOYSA-N 0.000 title claims abstract description 26
- 238000007306 functionalization reaction Methods 0.000 title claims abstract description 7
- 238000010189 synthetic method Methods 0.000 title claims abstract description 6
- 239000002105 nanoparticle Substances 0.000 title description 4
- 239000002122 magnetic nanoparticle Substances 0.000 claims abstract description 97
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 17
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 claims description 63
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 38
- -1 5-sulfosalicyl chloride Chemical compound 0.000 claims description 36
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 29
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 26
- 229910052681 coesite Inorganic materials 0.000 claims description 25
- 229910052906 cristobalite Inorganic materials 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 25
- 229910052682 stishovite Inorganic materials 0.000 claims description 25
- 229910052905 tridymite Inorganic materials 0.000 claims description 25
- 238000001816 cooling Methods 0.000 claims description 24
- BHDKTFQBRFWJKR-UHFFFAOYSA-N 2-hydroxy-5-sulfobenzoic acid;dihydrate Chemical compound O.O.OC(=O)C1=CC(S(O)(=O)=O)=CC=C1O BHDKTFQBRFWJKR-UHFFFAOYSA-N 0.000 claims description 22
- 238000005406 washing Methods 0.000 claims description 22
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims description 20
- 238000000034 method Methods 0.000 claims description 18
- 238000001035 drying Methods 0.000 claims description 17
- FYSNRJHAOHDILO-UHFFFAOYSA-N thionyl chloride Chemical compound ClS(Cl)=O FYSNRJHAOHDILO-UHFFFAOYSA-N 0.000 claims description 17
- 238000002360 preparation method Methods 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- 238000001308 synthesis method Methods 0.000 claims description 14
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 13
- 239000011541 reaction mixture Substances 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- 238000001704 evaporation Methods 0.000 claims description 6
- 239000000376 reactant Substances 0.000 claims description 6
- 238000000975 co-precipitation Methods 0.000 claims description 5
- 230000001681 protective effect Effects 0.000 claims description 4
- 239000011248 coating agent Substances 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011669 selenium Substances 0.000 abstract description 48
- 239000002245 particle Substances 0.000 abstract description 14
- 125000003748 selenium group Chemical group *[Se]* 0.000 abstract description 10
- 238000011160 research Methods 0.000 abstract description 2
- 229910004298 SiO 2 Inorganic materials 0.000 abstract 1
- 150000001263 acyl chlorides Chemical class 0.000 abstract 1
- 239000006185 dispersion Substances 0.000 abstract 1
- 238000012838 magnetic nanoparticle method Methods 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 27
- 239000000523 sample Substances 0.000 description 26
- 238000009835 boiling Methods 0.000 description 25
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 20
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 18
- 235000013527 bean curd Nutrition 0.000 description 16
- 229910052711 selenium Inorganic materials 0.000 description 16
- RJFAYQIBOAGBLC-BYPYZUCNSA-N Selenium-L-methionine Chemical compound C[Se]CC[C@H](N)C(O)=O RJFAYQIBOAGBLC-BYPYZUCNSA-N 0.000 description 13
- RJFAYQIBOAGBLC-UHFFFAOYSA-N Selenomethionine Natural products C[Se]CCC(N)C(O)=O RJFAYQIBOAGBLC-UHFFFAOYSA-N 0.000 description 13
- 239000007788 liquid Substances 0.000 description 13
- 229960002718 selenomethionine Drugs 0.000 description 13
- 238000001179 sorption measurement Methods 0.000 description 13
- 238000004458 analytical method Methods 0.000 description 11
- 238000002474 experimental method Methods 0.000 description 11
- 239000002351 wastewater Substances 0.000 description 11
- 235000019441 ethanol Nutrition 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- IDGUHHHQCWSQLU-UHFFFAOYSA-N ethanol;hydrate Chemical compound O.CCO IDGUHHHQCWSQLU-UHFFFAOYSA-N 0.000 description 9
- 239000000203 mixture Substances 0.000 description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 8
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 8
- 235000011114 ammonium hydroxide Nutrition 0.000 description 8
- 238000001962 electrophoresis Methods 0.000 description 8
- 230000005415 magnetization Effects 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 125000003130 L-selenocysteinyl group Chemical group O=C([*])[C@@](N([H])[H])([H])C([H])([H])[Se][H] 0.000 description 7
- BUGBHKTXTAQXES-UHFFFAOYSA-N Selenium Chemical compound [Se] BUGBHKTXTAQXES-UHFFFAOYSA-N 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- JULROCUWKLNBSN-UHFFFAOYSA-N seleno-DL-cystine Natural products OC(=O)C(N)C[Se][Se]CC(N)C(O)=O JULROCUWKLNBSN-UHFFFAOYSA-N 0.000 description 7
- 238000000702 capillary electrophoresis-electrothermal atomic absorption spectrometry Methods 0.000 description 6
- 238000001514 detection method Methods 0.000 description 6
- 229910021577 Iron(II) chloride Inorganic materials 0.000 description 5
- 229910021536 Zeolite Inorganic materials 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 5
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 5
- 239000000839 emulsion Substances 0.000 description 5
- 238000002347 injection Methods 0.000 description 5
- 239000007924 injection Substances 0.000 description 5
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 description 5
- 239000003921 oil Substances 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 239000010457 zeolite Substances 0.000 description 5
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 229960000583 acetic acid Drugs 0.000 description 4
- 229910052786 argon Inorganic materials 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 239000012362 glacial acetic acid Substances 0.000 description 4
- 238000002329 infrared spectrum Methods 0.000 description 4
- 150000002505 iron Chemical class 0.000 description 4
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 description 4
- 239000011259 mixed solution Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 150000003839 salts Chemical class 0.000 description 4
- 239000011734 sodium Substances 0.000 description 4
- 239000012086 standard solution Substances 0.000 description 4
- 238000005303 weighing Methods 0.000 description 4
- 241000196324 Embryophyta Species 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
- 239000007853 buffer solution Substances 0.000 description 3
- 239000003153 chemical reaction reagent Substances 0.000 description 3
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 125000000020 sulfo group Chemical group O=S(=O)([*])O[H] 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 2
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- RAHZWNYVWXNFOC-UHFFFAOYSA-N Sulphur dioxide Chemical compound O=S=O RAHZWNYVWXNFOC-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- 238000011088 calibration curve Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 239000012154 double-distilled water Substances 0.000 description 2
- 238000000921 elemental analysis Methods 0.000 description 2
- 125000000524 functional group Chemical group 0.000 description 2
- 239000003864 humus Substances 0.000 description 2
- 229910052739 hydrogen Inorganic materials 0.000 description 2
- 239000000696 magnetic material Substances 0.000 description 2
- 239000006249 magnetic particle Substances 0.000 description 2
- 230000005389 magnetism Effects 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 2
- 235000013336 milk Nutrition 0.000 description 2
- 239000008267 milk Substances 0.000 description 2
- 210000004080 milk Anatomy 0.000 description 2
- 238000002414 normal-phase solid-phase extraction Methods 0.000 description 2
- 239000008213 purified water Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 239000012488 sample solution Substances 0.000 description 2
- 229910052717 sulfur Inorganic materials 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 description 1
- QJZYHAIUNVAGQP-UHFFFAOYSA-N 3-nitrobicyclo[2.2.1]hept-5-ene-2,3-dicarboxylic acid Chemical compound C1C2C=CC1C(C(=O)O)C2(C(O)=O)[N+]([O-])=O QJZYHAIUNVAGQP-UHFFFAOYSA-N 0.000 description 1
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical group OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 description 1
- 229910017135 Fe—O Inorganic materials 0.000 description 1
- 229910021578 Iron(III) chloride Inorganic materials 0.000 description 1
- 229910019142 PO4 Inorganic materials 0.000 description 1
- 235000010627 Phaseolus vulgaris Nutrition 0.000 description 1
- 244000046052 Phaseolus vulgaris Species 0.000 description 1
- 229910006069 SO3H Inorganic materials 0.000 description 1
- 229910006124 SOCl2 Inorganic materials 0.000 description 1
- 229910018557 Si O Inorganic materials 0.000 description 1
- 229910008051 Si-OH Inorganic materials 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 229910006358 Si—OH Inorganic materials 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- YKTCYBDLFFGPQA-DKWTVANSSA-N [Se].[SeH]C[C@H](N)C(O)=O Chemical compound [Se].[SeH]C[C@H](N)C(O)=O YKTCYBDLFFGPQA-DKWTVANSSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 239000012491 analyte Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000000559 atomic spectroscopy Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000012490 blank solution Substances 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000005251 capillar electrophoresis Methods 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 229910002091 carbon monoxide Inorganic materials 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000012159 carrier gas Substances 0.000 description 1
- 230000003197 catalytic effect Effects 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
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 1
- 238000001287 electrothermal atomic absorption spectrometry Methods 0.000 description 1
- 238000010828 elution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- YQGOJNYOYNNSMM-UHFFFAOYSA-N eosin Chemical compound [Na+].OC(=O)C1=CC=CC=C1C1=C2C=C(Br)C(=O)C(Br)=C2OC2=C(Br)C(O)=C(Br)C=C21 YQGOJNYOYNNSMM-UHFFFAOYSA-N 0.000 description 1
- 235000019253 formic acid Nutrition 0.000 description 1
- 239000005350 fused silica glass Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 239000004021 humic acid Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 description 1
- WTFXARWRTYJXII-UHFFFAOYSA-N iron(2+);iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[Fe+2].[Fe+3].[Fe+3] WTFXARWRTYJXII-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229940031182 nanoparticles iron oxide Drugs 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JCXJVPUVTGWSNB-UHFFFAOYSA-N nitrogen dioxide Inorganic materials O=[N]=O JCXJVPUVTGWSNB-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229920000767 polyaniline Polymers 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 229940065287 selenium compound Drugs 0.000 description 1
- 150000003343 selenium compounds Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- LIVNPJMFVYWSIS-UHFFFAOYSA-N silicon monoxide Inorganic materials [Si-]#[O+] LIVNPJMFVYWSIS-UHFFFAOYSA-N 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000001488 sodium phosphate Substances 0.000 description 1
- 229910000162 sodium phosphate Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 239000006228 supernatant Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- RYFMWSXOAZQYPI-UHFFFAOYSA-K trisodium phosphate Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])([O-])=O RYFMWSXOAZQYPI-UHFFFAOYSA-K 0.000 description 1
- 239000012498 ultrapure water Substances 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229910006297 γ-Fe2O3 Inorganic materials 0.000 description 1
Landscapes
- Soft Magnetic Materials (AREA)
- Compounds Of Iron (AREA)
Abstract
The invention discloses a kind of Fe of 5-sulphosalicylic acid functionalization
3o
4magnetic nano-particle and synthetic method thereof and application.The Fe of described 5-sulphosalicylic acid functionalization
3o
4magnetic nano-particle by ethyl orthosilicate to Fe
3o
4magnetic nano-particle carries out coated, gained Fe
3o
4/ SiO
2magnetic nano-particle obtains with 5-sulfosalisylic acyl chloride reaction again.The synthetic method of particle of the present invention is simple, and synthesize the particle obtained spherical in shape, size uniform, good dispersion, has good suction-operated to Se form, for the Determination of Trace Selenium form in research environment water sample provides feasibility foundation.
Description
Technical Field
The invention relates to 5-sulfosalicylic acid functionalized Fe3O4Magnetic nano-particles and a synthetic method and application thereof, belonging to the technical field of nano-materialsA domain.
Background
Magnetic Particles (MPs) are generally composed of magnetic elements such as iron, nickel, cobalt and oxides thereof. Superparamagnetic iron oxide nanoparticles (Fe)3O4，γ-Fe2O3) As a new solid phase extraction adsorbent, it has attracted much attention in the field of atomic spectroscopy. Magnetic nanoparticles have the following advantages: the surface is easy to modify, the analyte is selectively adsorbed, and the biological compatibility is realized. Bare Fe3O4Easily aggregated and nonselective for matrix adsorption in complex samples, using SiO2Coated Fe3O4The nanoparticles avoid the change of magnetism caused by the oxidation of the particle surface, and provide the possibility for further chemical functionalization.
Common active functional groups for modifying the surface of magnetic nanoparticles in the prior art include: carboxyl (-COOH), amino (-NH)2) Hydroxyl (-OH), mercapto (-SH), etc., and furthermore, adsorption can be performed by utilizing a conjugated structure (e.g., polyaniline, etc.), a large surface area (e.g., C18, etc.), and micelle properties. At present, no research report on modification of magnetic nanoparticles by 5-sulfosalicylic acid exists, and no report on adsorption of magnetic nanoparticles modified by 5-sulfosalicylic acid on selenium ions exists.
Disclosure of Invention
The invention aims to solve the technical problem of providing 5-sulfosalicylic acid functionalized Fe3O4Magnetic nanoparticles and a synthesis method and application thereof. 5-sulfosalicylic acid functionalized Fe synthesized by the method of the invention3O4The magnetic nano particles are spherical, have uniform size and good dispersity, and have good adsorption effect on the selenium form.
The 5-sulfosalicylic acid functionalized Fe of the invention3O4The magnetic nano-particle has the following structural formula:
wherein,represents Fe3O4Magnetic nanoparticles.
The 5-sulfosalicylic acid functionalized Fe of the invention3O4The synthetic method of the magnetic nano-particles comprises the following steps: firstly adopting coprecipitation method to prepare Fe3O4Magnetic nanoparticles, followed by Fe with tetraethoxysilane3O4Coating the magnetic nano particles to obtain Fe3O4/SiO2Magnetic nanoparticles, Fe obtained3O4/SiO2The magnetic nano particles react with 5-sulfosalicyl chloride to obtain the 5-sulfosalicylic acid functionalized Fe3O4Magnetic nanoparticles; the 5-sulfosalicyl chloride is prepared by the reaction of dihydrate 5-sulfosalicylic acid and excessive thionyl chloride in the presence of catalyst formamide.
More specifically, 5-sulfosalicylic acid functionalized Fe3O4The synthesis method of the magnetic nanoparticles specifically comprises the following steps:
1)Fe3O4preparation of magnetic nanoparticles
Preparing Fe by adopting a coprecipitation method3O4Magnetic nanoparticles;
2)Fe3O4/SiO2preparation of magnetic nanoparticles
Taking Fe3O4The magnetic nano-particles are placed in alcohol/water solution, ethyl orthosilicate is added after ultrasonic dispersion,under the protection atmosphere, adjusting the pH value of the solution to be 4-5 or 9-10, stirring and reacting for 1-16 h at 70-90 ℃, separating the reaction mixture by using an external magnetic field, washing and drying to obtain Fe3O4/SiO2Magnetic nanoparticles;
3)Fe3O4/SiO2sulfo functionalization of magnetic nanoparticles
3.1) adding excessive thionyl chloride into dihydrate 5-sulfosalicylic acid, adding a catalyst formamide, reacting at 100-120 ℃ for 5-12 h, cooling reactants, and evaporating excessive thionyl chloride to obtain 5-sulfosalicyl chloride;
3.2) taking Fe3O4/SiO2Placing magnetic nanoparticles and excessive 5-sulfosalicyl chloride into a reaction container, adding pyridine serving as a catalyst, stirring and reacting at the temperature of 0-10 ℃ for 12-24 hours, separating a reaction mixture by using an external magnetic field, washing and drying to obtain 5-sulfosalicylic acid functionalized Fe3O4Magnetic nanoparticles.
In the step 1) of the synthesis method, the Fe is prepared by adopting a coprecipitation method3O4The steps of magnetic nanoparticles are the same as those of the prior art, and preferably include the following steps: according to Fe3+:Fe2+Weighing FeCl at a ratio of 1.3 to 2:13·6H2O and FeCl2·4H2Placing O into a reaction container, adding deoxygenated water to dissolve the O, heating to 60-90 ℃ under a protective atmosphere, adding ammonia water to adjust the pH value to 9-10, reacting for 30-120 min under a heat preservation condition, separating a reaction mixture by using an external magnetic field, washing and drying to obtain Fe3O4Magnetic nanoparticles. The amount of the deoxidized water is usually calculated by 50-150 mL of deoxidized water per 0.01mol of iron salt (including ferrous salt and ferric salt).
In step 2) of the above synthesis method, the alcohol in the alcohol/water solution is glycerol or ethanol, and the volume ratio of the alcohol to the water is preferably 0.6-1.5: 1, the alcohol/water solution is generally used in an amount of 1gFe3O4For magnetic nanoparticles50-100 mL of alcohol/water solution. In the step, the time of ultrasonic dispersion is the same as that of the prior art, and is usually 10-50 min; the adding amount of the tetraethoxysilane after ultrasonic dispersion is the same as that of the prior art, and Fe is preferably controlled3O4The mass-volume ratio of the magnetic nanoparticles to the tetraethoxysilane is as follows: 1 g: 2-5 ml. After adding tetraethoxysilane, adjusting the pH of the solution to be 4-5 or 9-10, and then reacting to obtain Fe3O4/SiO2Magnetic nanoparticles, and Fe obtained by adjusting the pH of the solution to 4-5 or 9-10 and then reacting3O4/SiO2The magnetic nanoparticles have almost no difference in properties and performances; in general, the pH of the solution is adjusted to 4 to 5 with a weak acid, such as glacial acetic acid or formic acid; and (3) adjusting the pH value of the solution to 9-10 by using weak base, such as ammonia water or sodium bicarbonate.
In step 3.1) of the above synthesis method, the molar ratio of 5-sulfosalicylic acid dihydrate to thionyl chloride is usually 1: 25 to 72. The amount of the catalyst formamide is usually 20-55% of the molar amount of the 5-sulfosalicylic acid dihydrate. The reaction is usually carried out under oil bath conditions, and it is preferable to add several kinds of zeolite to the reaction system in order to avoid bumping during the reaction.
In step 3.2) of the above synthesis method, Fe3O4/SiO2The mass ratio of magnetic nanoparticles to 5-sulfosalicyl chloride is typically 1: 3 to 6. The catalyst pyridine is anhydrous pyridine, and specifically, the pyridine is dehydrated according to the conventional method; the anhydrous pyridine is usually used in an amount of Fe3O4/SiO25-10% of the mass of the magnetic nanoparticles. The reaction is typically carried out under ice bath conditions.
In the synthesis method, the used water can be water which does not bring other impurities into the reaction system, such as sub-boiling water, double distilled water, deionized water, purified water and the like; the protective atmosphere can be nitrogen, argon, helium and other protective atmospheres; the washing is usually carried out by alternately washing with water (which can be sub-boiling water, double-distilled water, deionized water, purified water and the like as mentioned above) and absolute ethyl alcohol; the drying is usually carried out under vacuum.
5-sulfosalicylic acid functionalized Fe synthesized by the method3O4The magnetic nanoparticles have the particle size of 10-15 nm, are spherical, and have uniform size and good dispersibility.
The invention also includes the sulfo-functionalized Fe described above3O4Application of magnetic nanoparticles in adsorption separation of selenium form, specifically to Se (VI), Se (IV), SeMet (selenomethionine) and SeCys2The adsorption effect of the four forms of selenium (selenocysteine) is better, and the adsorption effect of Se (IV) is the best. During adsorption, pH value of a selenium ion-containing or seleno-containing liquid sample is adjusted to be 1-5 (preferably pH value is 3-5, more preferably pH value is 4), and then sulfo-functionalized Fe is added3O4The magnetic nano particles are adsorbed, and the adsorption time is more than or equal to 4min, so that a better effect can be achieved, and the optimal control time is 5 min. When the total concentration of selenium ions in the liquid sample containing selenium ions or selenium compounds is less than or equal to 20 ng.mL-1Then, under the above conditions (pH 4 of the liquid sample to be measured, adsorption time 5min), Fe was sulfo-functionalized3O4When the addition amount of the magnetic nanoparticles is 10mg, selenium ions in the sample can be completely adsorbed. If the adsorbed selenium ions need to be analyzed to determine the concentration of the selenium ions in the sample, particularly, Fe with the selenium ions adsorbed and functionalized by sulfo groups is analyzed3O4Magnetic nanoparticles are placed in a container, Na is added2CO3Carrying out ultrasonic elution on the solution, wherein the ultrasonic time is more than or equal to 3min, preferably 4min, and then collecting supernate to carry out detection on the selenium content; the Na is2CO3The concentration of the solution is preferably 0.1-2.0 mol/L.
Still further, the present invention provides sulfo-functionalized Fe3O4The magnetic nano-particles are applied to selenium form analysis and trace selenium detection in a liquid sample. The detection limit of the trace selenium in the liquid sample is 0.17-0.54 ng/mL.
Compared with the prior art, the invention provides sulfo-functionalized Fe modified by 5-sulfosalicyl chloride3O4The magnetic nanoparticles are simple in synthesis method, and the synthesized particles are spherical, uniform in size, good in dispersity and good in selenium form adsorption effect.
Drawings
FIG. 1 is an infrared spectrum of the magnetic nanoparticles of MNPs, SMNPs and SSA-SMNPs prepared in example 1, wherein a is the infrared spectrum of the magnetic nanoparticles of MNPs, b is the infrared spectrum of the magnetic nanoparticles of SMNPs, and c is the infrared spectrum of the magnetic nanoparticles of SSA-SMNPs;
FIG. 2 is an XRD pattern of magnetic nanoparticles of SSA-SMNPs prepared in example 1 of the present invention;
FIG. 3 is a TEM image of SSA-SMNPs magnetic nanoparticles prepared in example 1 of the present invention;
FIG. 4 is a magnetic hysteresis loop of SSA-SMNPs magnetic nanoparticles prepared in example 1 of the present invention;
FIG. 5 shows the SSA-SMNPs magnetic nanoparticles prepared in example 1 of the present invention under the condition of no magnetic field and in the presence of magnetic field, wherein a represents the state of the SSA-SMNPs magnetic nanoparticles under the condition of no magnetic field, and b represents the state of the SSA-SMNPs magnetic nanoparticles under the condition of magnetic field;
FIGS. 6 to 9 show the mixed standard solutions (Se (VI), Se (IV) SeMet and SeCys, respectively2All concentrations of (2) were 5 ng. mL-1) Se (VI), Se (IV), SeMet and SeCys2The working curve of (a);
FIG. 10 is an electrophoretogram of CE-ETAAS for measuring selenium form in mixed standard solution, humus emulsion and humus waste water sample, wherein A is 5 ng-mL concentration-1Se (VI), Se (IV) SeMet and SeCys2Electrophorogram of the mixed standard solution of (1); b is an electrophoretogram of a fermented bean curd wastewater sample; c is 4ng/mL-1Se(VI)、3ng·mL-1Se(IV)、2ng·mL-1SeMet、2ng·mL-1SeCys2And an electrophoretogram of a mixed solution of a fermented bean curd wastewater sample; d is an electrophoretogram of the humic acid emulsion; e is 6ng·mL-1Se(VI)、4ng·mL-1Se(IV)、3ng·mL-1SeMet、4ng·mL-1SeCys2And electrophoretogram of mixed solution of humic emulsion sample.
Detailed Description
The present invention is further illustrated by the following specific examples, but the present invention is not limited to these examples.
In the following examples, the MNPs represent Fe3O4Magnetic nanoparticles, the SMNPs representing Fe3O4/SiO2Magnetic nanoparticles, said SSA-SMNPs representing 5-sulfosalicylic acid functionalized Fe3O4Magnetic nanoparticles.
Example 1
1)Fe3O4Preparation of Magnetic Nanoparticles (MNPs)
4.7300gFeCl is accurately weighed3·6H2O and 1.9881gFeCl2·4H2O(Fe3+:Fe2+Dissolving the mixture in 200mL of deoxygenated water (deoxygenated sub-boiling water) for 10min by ultrasonic treatment, transferring the mixture into a 500mL three-necked flask, stirring the mixture at 85 ℃ for 30min at 800rpm under the protection of nitrogen, rapidly adding 20mL of 25-28% ammonia water, immediately blackening the solution (the pH of the solution is 9.5 at the moment), and curing the solution for 30 min. The reaction mixture was cooled to room temperature, separated by an external magnetic field, washed alternately 3 times with sub-boiling water and anhydrous ethanol, dried at 70 ℃ under vacuum, and cooled to obtain MNPs.
2)Fe3O4/SiO2Preparation of magnetic nanoparticles (SMNPs)
Dissolving the MNPs2g prepared in the above manner in 200mL of glycerol and sub-boiling water (1:1, v/v), ultrasonically dispersing for 30min, adding 10mL of TEOS (the adding amount of TEOS is calculated by adding 1g of MNPs into 5mL of TEOS), transferring into a 500mL three-neck flask, protecting with nitrogen, adjusting pH to 4.5 with glacial acetic acid, stirring and reacting at 90 ℃ for 2h at 800rpm, cooling the reaction mixture to room temperature, separating with an external magnetic field, alternately washing with sub-boiling water and anhydrous ethanol for 3 times, drying at 70 ℃ in vacuum, and cooling to obtain SMNPs.
3) 5-sulfosalicylic acid functionalized Fe3O4Preparation of magnetic nanoparticles (SSA-SMNPs)
3.1) weigh 2.5g SSA (5-sulfosalicylic acid dihydrate) into a 100mL three-necked flask, add 3 grains of zeolite, add 40mL of LOCl2And formamide accounting for 24 percent of the molar amount of the SSA, reacting for 7 hours at 110 ℃ in an oil bath, cooling reactants to room temperature, and evaporating excessive SOCl at 55 ℃ by using a rotary evaporator2To obtain light brown oily substance, namely 5-sulfosalicyl chloride. Through result characterization, the structural formula of the 5-sulfosalicyl chloride is determined as follows:
3.2) taking the mass ratio of SMNPs prepared in the step (A) to excessive 5-sulfosalicyl chloride (the mass ratio of the SMNPs to the 5-sulfosalicyl chloride is 1: 3) and (2) placing the mixture into a reaction solution container, adding anhydrous pyridine with the mass equivalent to 5% of SMNPs, stirring and reacting for 24 hours at the temperature of 5-10 ℃, separating through an external magnetic field, alternately washing for 3 times by using sub-boiling water and anhydrous ethanol, drying at the temperature of 70 ℃ in vacuum, and cooling to obtain SSA-SMNPs. The synthetic route of the SSA-SMNPs is as follows:
the SSA-SMNPs prepared in the above way are characterized:
1. FT-IR spectroscopy
Characterization of SSA-SMNPs by FT-IR spectroscopy confirmed the bonding of Si-OH and sulfo groups to Fe3O4The surface of the magnetic nanoparticles. Infrared profiles for MNPs, SMNPs and SSA-SMNPs are shown in FIG. 1. In MNPs, 586cm-1The peak at (A) is a characteristic absorption peak of Fe-O. Fe3O4the-OH on the surface of the particle can be reacted with SiO2Bonding to prevent Fe3O4Oxidized and provide a platform for further grafting of functional groups. In SMNPs, 1080.12cm-1The peak at (A) is the stretching vibration of Si-O, which shows SiO2Successfully bonded to Fe3O4A surface. In SSA-SMNPs, 1670cm-1The position is C ═ O stretching vibration, carbonyl is conjugated with benzene ring, and absorption shifts to low frequency. 1431.54cm-1Is provided with benzene ring skeleton vibration[27]The presence of a benzene ring is indicated. 1160cm-1Peak is-SO3H stretching vibration absorption peak. Indicating that the SSA is successfully bonded to the surface of the SMNPs magnetic nanoparticles.
2. Elemental analysis
Elemental analysis is an analysis to identify the elements present in a compound and their content. Carbon, hydrogen, nitrogen and sulfur in the measured substances are respectively converted into carbon dioxide, water vapor, nitrogen and sulfur dioxide after catalytic oxidation-reduction. The oxygen in the substance to be tested is pyrolyzed to obtain carbon monoxide. Under the drive of carrier gas, the mixed gas is effectively separated after passing through a chromatographic column, and all components are sequentially measured by an element analyzer TCD detector. In the experiment, C, S, H element in SSA-SMNPs particles is subjected to element analysis, so that the C content is 6.86%, and the S content is 2.618%. The molar ratio of C to S was found to be 7:1 by calculation, indicating successful grafting of sulfosalicylic acid to SiO2And synthesizing sulfo-functionalized SSA-SMNPs magnetic nanoparticles on the coated MNPs.
3. XRD analysis
X-ray diffraction (XRD) is an effective method to study the microstructure of crystalline and certain amorphous materials. The XRD patterns of the SSA-SMNPs magnetic nanoparticles prepared in the above examples are shown in FIG. 2Shown in the figure. As can be seen from the figure, SSA-SMNPs show diffraction peaks at 2 theta of 30.38 degrees, 35.70 degrees, 43.28 degrees, 53.86 degrees, 57.36 degrees and 62.86 degrees, corresponding to cubic phases of Fe respectively3O4The (220), (311), (400), (422), (511) and (440) crystal planes of (a). With standard Fe3O4The crystal data are consistent (JCPDSNo. 65-3107). The peak position of each diffraction peak is basically unchanged, which shows that the surface is coated with SiO2Fe is not changed in the process of functionalizing sulfonic acid group3O4Spinel structure of the nanoparticles. SSA-SMNPs magnetic nanoparticle patterns were analyzed by the software Jade5.0 and the average particle size of SSA-SMNPs was estimated to be 10.9 nm.
4. TEM analysis
The size and morphology of the particles can be directly obtained by Transmission Electron Microscopy (TEM). TEM images of the SSA-SMNPs magnetic nanoparticles prepared in the above examples are shown in FIG. 3. As can be seen, the SSA-SMNPs prepared by the method have the average particle size of about 10.9nm, uniform size, spherical shape and good dispersibility. By coating with SiO2And sulfo group functionalization, so that the agglomeration among the magnetic nanoparticles is improved, the dispersity of the magnetic nanoparticles is improved, and the chemical stability of the magnetic nanoparticles is enhanced.
5. VSM analysis
The hysteresis loop reflects the response capability of the magnetic material to the change of the magnetic field and is an important curve for characterizing the characteristics of the magnetic material. The magnetic properties of the SSA-SMNPs prepared in the above examples were investigated using a Vibrating Sample Magnetometer (VSM), and the hysteresis loop thereof is shown in FIG. 4. The hysteresis loop of SSA-SMNPs measured at 300K is shown in the figure, and the saturation magnetization of SSA-SMNPs is 69.4emu g-1. In the magnetization process, the magnetization intensity of the SSA-SMNPs is rapidly increased along with the increase of the intensity of an external magnetic field and rapidly reaches saturation, and when the intensity of the external magnetic field is weakened, the magnetization intensity of the SSA-SMNPs returns along the original magnetization path and is in a reversible S shape without any hysteresis loop, which indicates that the SSA-SMNPs have no remanence phenomenon and coercive force at 300K and have good superparamagnetism. FIG. 5 shows the shape of the magnetic nanoparticles SSA-SMNPs prepared in the above-mentioned examples under the condition of no magnetic field and magnetic fieldAnd (b) the state of the SSA-SMNPs magnetic nanoparticles in the presence of a magnetic field. Under the action of an external magnetic field, the SSA-SMNPs are adsorbed on one side of the magnetic field of the bottle wall, which also shows that the SSA-SMNPs have good magnetism.
Example 2
1) Preparation of MNPs
According to Fe3+:Fe2+Accurately weighing FeCl in the ratio of the amounts of 2:13·6H2O and FeCl2·4H2And O, adding deoxygenated water (the deoxygenated water is deoxygenated sub-boiling water, the dosage of the deoxygenated water is calculated by using 100mL of deoxygenated water per 0.01mol of iron salt (including ferrous salt and ferric salt)), carrying out ultrasonic treatment for 5min, then transferring the mixture into a 500mL three-neck flask, stirring the mixture at a temperature of 70 ℃ for 10min at 1000rpm under the protection of nitrogen, quickly adding ammonia water (the concentration is 25%), adjusting the pH value of the solution to be 10, and curing the solution for 60 min. Cooling the reaction mixture to room temperature, separating by an external magnetic field, alternately washing for 3 times by using sub-boiling water and absolute ethyl alcohol, drying at 60 ℃ in vacuum, and cooling to obtain MNPs;
2) preparation of SMNPs
Dissolving the MNPs2g prepared in the above step into 200mL of ethanol and sub-boiling water (0.6:1, v/v), carrying out ultrasonic dispersion for 10min, adding TEOS (the adding amount of TEOS is calculated by adding 2mL of MNPs into 1g of MNPs), transferring into a 500mL three-neck flask, carrying out nitrogen protection, adjusting the pH to 5 by using glacial acetic acid, carrying out stirring reaction for 10h at the temperature of 80 ℃ at 800rpm, cooling the reaction mixture to room temperature, carrying out external magnetic field separation, alternately washing for 3 times by using sub-boiling water and absolute ethanol, drying at the temperature of 70 ℃ in vacuum, and cooling to obtain SMNPs;
3) preparation of SSA-SMNPs
3.1) 2.5g SSA (5-sulfosalicylic acid dihydrate) were weighed into a 100mL three-necked flask, 2 grains of zeolite were placed, and 50mL of LOCl were added2And formamide accounting for 40 percent of the molar amount of the SSA, reacting for 10 hours at 110 ℃ in an oil bath, cooling reactants to room temperature, and evaporating to remove by using a rotary evaporator at 70 DEG CExcess SOCl2To obtain 5-sulfosalicyl chloride;
3.2) taking the mass ratio of SMNPs prepared in the step (A) to excessive 5-sulfosalicyl chloride (the mass ratio of the SMNPs to the 5-sulfosalicyl chloride is 1: 5) and (2) placing the mixture into a reaction solution container, adding anhydrous pyridine with the mass equivalent to 10% of SMNPs, stirring and reacting for 18 hours at the temperature of 0-4 ℃, separating through an external magnetic field, alternately washing for 3 times by using sub-boiling water and anhydrous ethanol, drying at the temperature of 70 ℃ in vacuum, and cooling to obtain SSA-SMNPs.
The SSA-SMNPs obtained in this example had an average particle size of 12.4nm and a saturation magnetization of 70.1emu g at 300K-1。
Example 3
1) Preparation of MNPs
According to Fe3+:Fe2+Accurately weighing FeCl in the amount ratio of 1.3:13·6H2O and FeCl2·4H2And O, adding deoxygenated water (the deoxygenated water is deoxygenated sub-boiling water, the dosage of the deoxygenated water is calculated by 50mL of deoxygenated water per 0.01mol of iron salt (including ferrous salt and ferric salt)), carrying out ultrasonic treatment for 30min, then transferring into a 500mL three-neck flask, stirring at 1000rpm for 20min at 90 ℃ under the protection of nitrogen, rapidly adding ammonia water (the concentration is 28%) to adjust the pH value of the solution to 9, and curing for 120 min. Cooling the reaction mixture to room temperature, separating by an external magnetic field, alternately washing for 3 times by using sub-boiling water and absolute ethyl alcohol, drying at 60 ℃ in vacuum, and cooling to obtain MNPs;
2) preparation of SMNPs
Dissolving the MNPs3g prepared in the above step into 200mL of ethanol and sub-boiling water (1.5:1, v/v), carrying out ultrasonic dispersion for 50min, adding TEOS (the adding amount of TEOS is calculated by adding 3mL of MNPs into 1g of MNPs), transferring into a 500mL three-neck flask, carrying out nitrogen protection, adjusting the pH to 9 by using ammonia water, carrying out stirring reaction for 1h at the temperature of 70 ℃ at 1000rpm, cooling the reaction mixture to room temperature, carrying out external magnetic field separation, alternately washing for 3 times by using sub-boiling water and absolute ethanol, drying at the temperature of 60 ℃ in vacuum, and cooling to obtain SMNPs;
3) preparation of SSA-SMNPs
3.1) 2.5g SSA (5-sulfosalicylic acid dihydrate) were weighed into a 100mL three-necked flask, 2 grains of zeolite were placed, and 50mL of LOCl were added2And formamide accounting for 55 percent of the molar amount of the SSA, reacting for 10 hours at 100 ℃ in an oil bath, cooling reactants to room temperature, and evaporating excessive SOCl at 55 ℃ by using a rotary evaporator2To obtain 5-sulfosalicyl chloride;
3.2) taking the mass ratio of SMNPs prepared in the step (A) to excessive 5-sulfosalicyl chloride (the mass ratio of the SMNPs to the 5-sulfosalicyl chloride is 1: 6) placing the mixture into a reaction solution container, adding anhydrous pyridine with the mass equivalent to 8% of SMNPs, stirring and reacting for 12h at the temperature of 0 ℃, separating by an external magnetic field, alternately washing for 3 times by using sub-boiling water and anhydrous ethanol, drying at the temperature of 60 ℃ in vacuum, and cooling to obtain SSA-SMNPs.
The SSA-SMNPs obtained in this example had an average particle size of 11.5nm and a saturation magnetization of 71.2emu g at 300K-1。
Example 4
1) Preparation of MNPs
According to Fe3+:Fe2+Weighing FeCl accurately according to the ratio of the amount of the substances in the ratio of 1:13·6H2O and FeCl2·4H2And O, adding 150mL of deoxygenated water (the deoxygenated water is deoxygenated sub-boiling water, the dosage of the deoxygenated water is calculated by using 150mL of deoxygenated water per 0.01mol of iron salt (including ferrous salt and ferric salt)), carrying out ultrasonic treatment for 30min, then transferring into a 500mL three-neck flask, stirring at 1000rpm for 30min at 65 ℃ under the protection of argon, rapidly adding ammonia water to adjust the pH value of the solution to 10, and curing for 90 min. Cooling the reaction mixture to room temperature, separating by an external magnetic field, alternately washing for 3 times by using sub-boiling water and absolute ethyl alcohol, drying at 80 ℃ in vacuum, and cooling to obtain MNPs;
2) preparation of SMNPs
Dissolving the MNPs4g prepared in the above step into 200mL of ethanol and sub-boiling water (0.8:1, v/v), carrying out ultrasonic dispersion for 10min, adding TEOS (the adding amount of TEOS is calculated by adding 5mL of MNPs into 1g of MNPs), transferring into a 500mL three-neck flask, carrying out argon protection, adjusting the pH to 10 by using ammonia water, carrying out stirring reaction for 16h at the temperature of 70 ℃ at 1000rpm, cooling the reaction mixture to room temperature, separating by using an external magnetic field, alternately washing for 3 times by using sub-boiling water and absolute ethanol, drying at the temperature of 80 ℃ in vacuum, and cooling to obtain SMNPs;
3) preparation of SSA-SMNPs
3.1) 2.5g SSA (5-sulfosalicylic acid dihydrate) were weighed into a 100mL three-necked flask, 2 grains of zeolite were placed, and 30mL of LOCl were added2And formamide accounting for 30 percent of the molar amount of the SSA, reacting for 5 hours at 120 ℃ in an oil bath, cooling reactants to room temperature, and evaporating excessive SOCl at 55 ℃ by using a rotary evaporator2To obtain 5-sulfosalicyl chloride;
3.2) taking the mass ratio of SMNPs prepared in the step (A) to excessive 5-sulfosalicyl chloride (the mass ratio of the SMNPs to the 5-sulfosalicyl chloride is 1: 4) placing the mixture into a reaction solution container, adding anhydrous pyridine with the mass of 6% of SMNPs, stirring and reacting for 20 hours at the temperature of 5 ℃, separating by an external magnetic field, alternately washing 3 times by using sub-boiling water and anhydrous ethanol, drying at the temperature of 50 ℃ in vacuum, and cooling to obtain SSA-SMNPs.
The SSA-SMNPs obtained in this example had an average particle size of 10.2nm and a saturation magnetization of 75.1emu g at 300K-1。
Experimental example: the adsorption of the SSA-SMNPs magnetic nanoparticles prepared in example 1 on the selenium-containing liquid sample is measured by using a CE-ETAAS combined technology
1. Instruments and working conditions
TAS-986 atomic absorption spectrophotometer (beijing pros instrument ltd), selenium hollow cathode lamp (beijing eosin electron light source instrument ltd), spectrumtofft-IR infrared spectrometer (PerkinElmer), RigakuD/max2500/pc type X-ray powder diffractometer (japan science); MPMS-XL-7 superconducting quantum interference magnetic measurement system (Quantum design company, USA); JEM-2100 Transmission Electron microscope (Japan); PE2400II elemental analyzer (PerkinElmer); a sprayer device (see Talanta109(2013) 128-132, such as Dengbuyang); a rotor flow meter (Kodao instrument factory in Jiangyin city), an HV-303P1 high-voltage electrophoresis power supply (Tianjin Shenghuo science and technology Co., Ltd.), a fused silica quartz capillary tube (Jiangxing chromatograph company in Yongxi province), a DW-3 digital display stepless constant-speed stirrer (Yingyu Yushui instrument factory in Jiangyi city), and a SYZ-550 quartz high-purity water distiller (Jiangsu Qinhua glass instrument factory).
2. Reagent
FeCl2·4H2O、FeCl3·6H2O, Tetraethylorthosilicate (TEOS), ammonia, 5-sulfosalicylic acid dihydrate (SSA), NaOH, hydrochloric acid, and sodium phosphate (Na)3PO4·12H2O) and disodium hydrogen phosphate (Na)2HPO4·12H2O) (Xilongsu chemical Co., Ltd.), absolute ethanol, glacial acetic acid (Guangdong Guanghua science and technology Co., Ltd.), glycerol, Na2CO3(Shantou Guanghua chemical plant), thionyl chloride (SOCl)2Tianjin Selencheng Chemicals, Inc.), methanol (Shanghai reagent Co.), cetyltrimethylammonium bromide (CTAB, Hunan center for the development of chemical reagents).
The reagents used in the experiment are analytically pure; the experimental water was sub-boiling water.
3. Introduction of the sample
The volume of the injected sample is influenced by the sample injection time, the sample injection pressure, the sample property, the length of the capillary and the like, and in the experiment, the sample solution is introduced into the capillary by using the argon pressure of 0.04MPa, the sample injection time is 10s, and the sample injection volume is about 0.5 mu L. Pretreatment of a new molten silicon capillary: by CH3OH rinsing for 30min, then 0.1 mol.L-1Washing with NaOH for 40min, and washing with sub-boiling water for 10 min. Before each experiment, the sample was washed with buffer solution for 8 min. After the experiment is finished, 0.1 mol.L is used-1Washing with NaOH for 10min, and washing with sub-boiling water for 15 min. Before the experiment, all samples are subjected to ultrasonic treatment for 10min to remove air bubbles, so that the phenomenon of flow interruption in the electrophoresis process is prevented. In the experiment, use firstFilling the whole section of capillary with buffer solution, then injecting sample under pressure, replacing buffer solution after sample injection, and detecting by using ETAAS according to the working conditions shown in the following tables 1 and 2.
TABLE 1 working parameters of capillary electrophoresis and atomic absorption spectrometry
TABLE 2 electrothermal atom absorption temperature program
4. Sample pretreatment
The water samples measured in the experiment are taken from the fermented bean curd liquid and the fermented bean curd waste water of the same fermented bean curd factory in Guilin. Standing for one day after collection, filtering with filter paper, filtering with sand core funnel, and filtering with 0.45 μm filter membrane. The filtered solution is stored for later use.
5. Solid phase extraction process
10mL of the sample solution (i.e., the solution obtained after the filtration at the 4 th point) was added to a beaker, and the solution was filtered at 0.1 mol. L-1The HCl solution was adjusted to pH 4 and 10mg of the SSA-SMNPs magnetic nanoparticles prepared in example 1 were added. The mixed solution is ultrasonically adsorbed for 5min and separated by an external magnetic field. Then 0.5mLNa was added2CO3Solution (0.5 mol. L)-1) Eluting, subjecting the new mixed solution to ultrasound for 4min, separating with external magnetic field, collecting supernatant with PTEF tube, and measuring with CE-ETAAS for three times. The blank solution was prepared as above.
6. Working curve, detection limit and repeatability
Under the experimental conditions shown in tables 1 and 2, the concentrations were 5 ng/mL-1Se (VI), Se (IV), SeMet and SeCys of2The mixed standard solution of (2) is measured 6 times in succession, whichRelative standard deviations (RSD, n ═ 6) were 2.2%, 0.7%, 2.5%, and 2.9%, respectively. Se (VI), Se (IV), SeMet and SeCys2The detection limits of (3. sigma., n. equals to 11) were 0.18, 0.17, 0.54 and 0.49 ng.mL, respectively-1. The linear range, the enrichment factor EF (EF ═ slope of the post-enrichment calibration curve/slope of the pre-enrichment calibration curve), and the linear correlation coefficient are shown in table 3, and the working curves are shown in fig. 6 to 10. The recycling is one of the important factors for evaluating the adsorptive material, and the SSA-SMNPs particles obtained by the experiment can be recycled for 3 times for carrying out quantitative recovery experiments.
TABLE 3 Linear Range and correlation coefficient (n ═ 6)
7. Sample analysis
Under the experimental conditions of the above tables 1 and 2, CE-ETAAS was used to treat Se (VI), Se (IV), SeMet and SeCys in wastewater and corrosive liquid discharged from a fermented bean curd plant2Selenium morphology was measured as shown in figure 10. Comparing the mixed standard electrophoresis (curve A in FIG. 10), it can be seen that Se (VI) and Se (IV) are present in the fermented bean curd wastewater, and the contents thereof are 3.83 ng/mL respectively-1And 2.62 ng. mL-1. The presence of Se (VI), Se (IV), SeMet and SeCys in the corrosive emulsion2Four forms of selenium with contents of 6.39 ng/mL respectively-1、4.08ng·mL-1、2.77ng·mL-1And 4 ng. mL-1. The content of inorganic selenium form in the fermented bean curd waste water or the fermented bean curd liquid is higher than the content of organic selenium form.
Under the experimental conditions of the above tables 1 and 2, Se (VI), Se (IV), SeMet and SeCys in the waste water and the fermented bean curd liquid are treated by CE-ETAAS method2And performing a standard recovery experiment to obtain a recovery rate range of 99.14-104.5% and an RSD range of 0.82-3.5%. The results are shown in tables 4 and 5.
TABLE 4 analysis results and recovery rates of Se (IV) and Se (VI) in waste liquid and emulsion of fermented bean curd (n ═ 6)
Water1 is waste Water of fermented bean curd plant; water2 is rotten milk.
TABLE 5 fermented bean curd waste water and SeMet and SeCys in fermented bean curd2Analysis results and recovery (n ═ 6)
Water1 is waste Water of fermented bean curd plant; water2 is rotten milk.
8. Conclusion
The SSA-SMNPs magnetic nanoparticles prepared by the method have good adsorption effect on selenium ions, and a method for analyzing the selenium form by CE-ETAAS combined analysis is established. The prepared SSA-SMNPs magnetic nano-particle pairs Se (VI), Se (IV), SeMet and SeCys2The enrichment factors of (1) are respectively 12, 18, 21 and 29, and the detection limit is 0.17-0.54 ng.mL-1. Applying the prepared SSA-SMNPs magnetic nanoparticles to Se (VI), Se (IV), SeMet and SeCys in fermented bean curd waste liquid and fermented bean curd liquid2And analysis shows a good effect. The SSA-SMNPs magnetic nanoparticles and the method provide a new analysis means for researching the trace selenium form in an environmental water sample.
Claims (5)
1, 5-sulfosalicylic acid functionalized Fe3O4The synthesis method of the magnetic nanoparticles is characterized by comprising the following steps: said 5-sulfosalicylic acid functionalized Fe3O4The structural formula of the magnetic nanoparticles is as follows:
wherein,represents Fe3O4Magnetic nanoparticles;
said 5-sulfosalicylic acid functionalized Fe3O4The synthetic method of the magnetic nano-particles comprises the following steps: firstly adopting coprecipitation method to prepare Fe3O4Magnetic nanoparticles, followed by Fe with tetraethoxysilane3O4Coating the magnetic nano particles to obtain Fe3O4/SiO2Magnetic nanoparticles, Fe obtained3O4/SiO2The magnetic nano particles react with 5-sulfosalicyl chloride to obtain the 5-sulfosalicylic acid functionalized Fe3O4Magnetic nanoparticles; the 5-sulfosalicyl chloride is prepared by the reaction of dihydrate 5-sulfosalicylic acid and excessive thionyl chloride in the presence of catalyst formamide.
2. The 5-sulfosalicylic acid functionalized Fe of claim 13O4The synthesis method of the magnetic nanoparticles is characterized by comprising the following steps: the method specifically comprises the following steps:
1)Fe3O4preparation of magnetic nanoparticles
Preparing Fe by adopting a coprecipitation method3O4Magnetic nanoparticles;
2)Fe3O4/SiO2preparation of magnetic nanoparticles
Taking Fe3O4Placing the magnetic nanoparticles in an alcohol/water solution, adding ethyl orthosilicate after ultrasonic dispersion, adjusting the pH of the solution to 4-5 or 9-10 under a protective atmosphere, stirring and reacting for 1-16 h at 70-90 ℃, separating the reaction mixture by using an external magnetic field, washing and drying to obtain Fe3O4/SiO2Magnetic nanoparticles;
3)Fe3O4/SiO2sulfo functionalization of magnetic nanoparticles
3.1) adding excessive thionyl chloride into dihydrate 5-sulfosalicylic acid, adding a catalyst formamide, reacting at 100-120 ℃ for 5-12 h, cooling reactants, and evaporating excessive thionyl chloride to obtain 5-sulfosalicyl chloride;
3.2) taking Fe3O4/SiO2Placing magnetic nanoparticles and excessive 5-sulfosalicyl chloride into a reaction container, adding pyridine serving as a catalyst, stirring and reacting at the temperature of 0-10 ℃ for 12-24 hours, separating a reaction mixture by using an external magnetic field, washing and drying to obtain 5-sulfosalicylic acid functionalized Fe3O4Magnetic nanoparticles.
3. The 5-sulfosalicylic acid functionalized Fe of claim 23O4The synthesis method of the magnetic nanoparticles is characterized by comprising the following steps: in the step 2), the alcohol in the alcohol/water solution is glycerol or ethanol, and the volume ratio of the alcohol to the water is 0.6-1.5: 1.
4. the 5-sulfosalicylic acid functionalized Fe of claim 23O4The synthesis method of the magnetic nanoparticles is characterized by comprising the following steps: in the step 3.1), the dosage of the catalyst formamide is 20-55% of the molar weight of the dihydrate 5-sulfosalicylic acid.
5. The 5-sulfosalicylic acid functionalized Fe of claim 23O4The synthesis method of the magnetic nanoparticles is characterized by comprising the following steps: in the step 3.2), the catalyst pyridine is anhydrous pyridine, and the dosage of the anhydrous pyridine is Fe3O4/SiO25-10% of the mass of the magnetic nanoparticles.
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