CN105727949A - Method for one-step preparing noble metal/SiO2 nano-composite particle - Google Patents
Method for one-step preparing noble metal/SiO2 nano-composite particle Download PDFInfo
- Publication number
- CN105727949A CN105727949A CN201610066026.5A CN201610066026A CN105727949A CN 105727949 A CN105727949 A CN 105727949A CN 201610066026 A CN201610066026 A CN 201610066026A CN 105727949 A CN105727949 A CN 105727949A
- Authority
- CN
- China
- Prior art keywords
- noble metal
- nano
- metal salt
- siloxanes
- containing amino
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 77
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 56
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 53
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 48
- 229910052681 coesite Inorganic materials 0.000 title claims abstract description 47
- 229910052906 cristobalite Inorganic materials 0.000 title claims abstract description 47
- 229910052682 stishovite Inorganic materials 0.000 title claims abstract description 47
- 229910052905 tridymite Inorganic materials 0.000 title claims abstract description 47
- 238000000034 method Methods 0.000 title claims abstract description 31
- 239000002114 nanocomposite Substances 0.000 title abstract description 6
- 235000012239 silicon dioxide Nutrition 0.000 title abstract 4
- -1 alkoxy silane Chemical compound 0.000 claims abstract description 48
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 40
- 150000003839 salts Chemical class 0.000 claims abstract description 38
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 26
- 239000000243 solution Substances 0.000 claims abstract description 25
- 239000002798 polar solvent Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 16
- 238000006722 reduction reaction Methods 0.000 claims abstract description 15
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims abstract description 10
- 239000000203 mixture Substances 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 229910000077 silane Inorganic materials 0.000 claims abstract 2
- 239000010970 precious metal Substances 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002082 metal nanoparticle Substances 0.000 claims description 14
- CMXPERZAMAQXSF-UHFFFAOYSA-M sodium;1,4-bis(2-ethylhexoxy)-1,4-dioxobutane-2-sulfonate;1,8-dihydroxyanthracene-9,10-dione Chemical compound [Na+].O=C1C2=CC=CC(O)=C2C(=O)C2=C1C=CC=C2O.CCCCC(CC)COC(=O)CC(S([O-])(=O)=O)C(=O)OCC(CC)CCCC CMXPERZAMAQXSF-UHFFFAOYSA-M 0.000 claims description 14
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 13
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 12
- 229910052700 potassium Inorganic materials 0.000 claims description 12
- 239000011591 potassium Substances 0.000 claims description 12
- 238000013329 compounding Methods 0.000 claims description 10
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 9
- 239000000126 substance Substances 0.000 claims description 9
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 8
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 8
- 239000003495 polar organic solvent Substances 0.000 claims description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 5
- 229920001400 block copolymer Polymers 0.000 claims description 5
- 230000002209 hydrophobic effect Effects 0.000 claims description 5
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 5
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 claims description 4
- 239000003002 pH adjusting agent Substances 0.000 claims description 4
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 4
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 3
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910021529 ammonia Inorganic materials 0.000 claims description 3
- 239000004202 carbamide Substances 0.000 claims description 3
- 235000013877 carbamide Nutrition 0.000 claims description 3
- 239000003638 chemical reducing agent Substances 0.000 claims description 3
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- 229910052710 silicon Inorganic materials 0.000 claims description 3
- 239000010703 silicon Substances 0.000 claims description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- YQBSAGGAIMKCAJ-UHFFFAOYSA-N [Au].CP(C)C.[Cl] Chemical compound [Au].CP(C)C.[Cl] YQBSAGGAIMKCAJ-UHFFFAOYSA-N 0.000 claims description 2
- 150000004996 alkyl benzenes Chemical class 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 229910021538 borax Inorganic materials 0.000 claims description 2
- 230000031709 bromination Effects 0.000 claims description 2
- 238000005893 bromination reaction Methods 0.000 claims description 2
- 150000001924 cycloalkanes Chemical class 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 239000003960 organic solvent Substances 0.000 claims description 2
- 239000001301 oxygen Substances 0.000 claims description 2
- 229910052760 oxygen Inorganic materials 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 235000010339 sodium tetraborate Nutrition 0.000 claims description 2
- SDKPSXWGRWWLKR-UHFFFAOYSA-M sodium;9,10-dioxoanthracene-1-sulfonate Chemical compound [Na+].O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)[O-] SDKPSXWGRWWLKR-UHFFFAOYSA-M 0.000 claims description 2
- 239000001117 sulphuric acid Substances 0.000 claims description 2
- 235000011149 sulphuric acid Nutrition 0.000 claims description 2
- BSVBQGMMJUBVOD-UHFFFAOYSA-N trisodium borate Chemical compound [Na+].[Na+].[Na+].[O-]B([O-])[O-] BSVBQGMMJUBVOD-UHFFFAOYSA-N 0.000 claims description 2
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims 1
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 claims 1
- 125000002015 acyclic group Chemical group 0.000 claims 1
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims 1
- 238000003980 solgel method Methods 0.000 abstract description 11
- KPUWHANPEXNPJT-UHFFFAOYSA-N disiloxane Chemical class [SiH3]O[SiH3] KPUWHANPEXNPJT-UHFFFAOYSA-N 0.000 abstract 3
- 239000000839 emulsion Substances 0.000 abstract 2
- 239000012454 non-polar solvent Substances 0.000 abstract 1
- 239000010931 gold Substances 0.000 description 21
- 239000002105 nanoparticle Substances 0.000 description 18
- 238000006555 catalytic reaction Methods 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 11
- 230000000694 effects Effects 0.000 description 11
- 239000002539 nanocarrier Substances 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 9
- 239000010944 silver (metal) Substances 0.000 description 9
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 239000006185 dispersion Substances 0.000 description 7
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 6
- 239000011324 bead Substances 0.000 description 6
- 239000007788 liquid Substances 0.000 description 6
- 125000000740 n-pentyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 6
- 239000002243 precursor Substances 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 description 6
- 230000005540 biological transmission Effects 0.000 description 5
- 238000002474 experimental method Methods 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 4
- 238000009825 accumulation Methods 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 230000033228 biological regulation Effects 0.000 description 3
- 239000000084 colloidal system Substances 0.000 description 3
- 230000007423 decrease Effects 0.000 description 3
- 230000009881 electrostatic interaction Effects 0.000 description 3
- 229910052737 gold Inorganic materials 0.000 description 3
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 3
- 125000001972 isopentyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])C([H])([H])* 0.000 description 3
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 125000001971 neopentyl group Chemical group [H]C([*])([H])C(C([H])([H])[H])(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- 229920000867 polyelectrolyte Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000004064 recycling Methods 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 description 3
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 125000004103 aminoalkyl group Chemical group 0.000 description 2
- 229920013822 aminosilicone Polymers 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000009835 boiling Methods 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000004581 coalescence Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 235000011121 sodium hydroxide Nutrition 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 229920001213 Polysorbate 20 Polymers 0.000 description 1
- 229920001214 Polysorbate 60 Polymers 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 235000011054 acetic acid Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 210000000481 breast Anatomy 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000002091 cationic group Chemical group 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000000151 deposition Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- JKGITWJSGDFJKO-UHFFFAOYSA-N ethoxy(trihydroxy)silane Chemical compound CCO[Si](O)(O)O JKGITWJSGDFJKO-UHFFFAOYSA-N 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 235000011167 hydrochloric acid Nutrition 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000000877 morphologic effect Effects 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002077 nanosphere Substances 0.000 description 1
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000012188 paraffin wax Substances 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 235000011007 phosphoric acid Nutrition 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000000256 polyoxyethylene sorbitan monolaurate Substances 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 235000011118 potassium hydroxide Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 235000015598 salt intake Nutrition 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 235000017550 sodium carbonate Nutrition 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003981 vehicle Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/44—Palladium
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
-
- B01J35/50—
-
- B01J35/51—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
Abstract
The invention discloses a method for one-step preparing a noble metal/SiO2 nano-composite particle. The method comprises the following steps: (1) dissolving low hydrophilic-oleophylic equilibrium value emulgator in a non-polar solvent, thereby acquiring an emulgator solution; (2) dissolving the noble metal salt in the polar solvent, and then adjusting pH value to 2-6, adding the noble metal salt solution into the emulgator solution, and dispersing, thereby acquiring a reversal fine emulsion; (3) adding compounded alkoxy silane and an amino-containing siloxane mixture solution into the reversal fine emulsion, uniformly mixing, and then adjusting the temperature to 50-150 DEG C, reacting for 1h-5d, reducing the noble metal salt into the noble metal nanometer particle by the amino-containing siloxane in the co-sol gel process of the siloxane; and (4) drying the products acquired in the step (3), and then performing heat treatment under air atmosphere for removing the organic matters, thereby acquiring the noble metal/SiO2 nano-composite particle. The invention also provides an application of the prepared noble metal/SiO2 nano-composite particle in the p-nitrophenol reduction reaction.
Description
(1) technical field
The present invention relates to a kind of noble metal/SiO2The preparation method of nano-complex particle, obtained noble metal
/SiO2Nano-complex particle and application thereof, be specifically related to one and utilize anti-phase miniemulsion techniques, a step is easy,
Efficiently prepare noble metal/SiO that water dispersible is good, catalysis activity is high, circulation catalytic performance is excellent2Nano combined
The method of particle and obtained noble metal/SiO2Nano-complex particle and its in paranitrophenol reduction reaction
In application.
(2) background technology
Several nanometers are that an efficient nanometer of class is urged to the noble metal such as Au, Ag, Pt and Pd of tens nanometers
Formed material, can be used for being catalyzed numerous organic reaction.But undersized noble metal nano particles surface can be high, easily
Reunite, cause its catalytic performance and decline.For improving the colloidal stability of noble metal nano particles, Yi Zhongyou
The method of effect is the glue such as the substantial amounts of emulsifying agent of use, polymeric dispersant or the organic ligand with surface activity
Body stabilizer.But there is certain defect in the method: the avtive spot quilt on (1) noble metal nano particles surface
Deflocculant covers, and causes it to be catalyzed activity decrease；(2) noble metal nano particles surface covering rubber body is steady
After determining agent, reactant absorption and product take off the difficulty of analysis all to be increased；(3) noble metal nano of stable dispersion
Particle size is little, it is difficult to effectively separate from reaction system, causes its recycling poor.
Noble metal nano particles is carried on size on the nano-carrier surface of tens to hundreds of nanometers, can be simultaneously
Improve the performances such as the colloidal stability of noble metal nano particles, catalysis activity and recycling.At present,
There is the report utilizing template to prepare carried noble metal nanocatalyst.Such as, Zhu et al. is first molten in alkalescence
In liquid, utilize SiO2Particle and cationic Au (III) and ethylene diamine complex [Au (en)2Cl3Between]
Electrostatic interaction, forms Au salt/SiO2Nano-complex particle；Heat treatment under the reducing atmosphere of hydrogen
Au salt is reduced to Au nanoparticle, then under oxygenous oxidizing atmosphere, heat treatment removes Organic substance,
Prepare Au/SiO2Nano-composite catalyst [Appl.Catal., A 2007,326,89-99].Ballauff et al. is first
By the method to polystyrene nanospheres grafted cation polyelectrolyte, it is prepared for spherical polyelectrolyte molecule
Brush；The most in aqueous, utilize electrostatic interaction, by PtCl6 2-Ion load is on polyelectrolyte layer, with backward
System adds sodium borohydride, by PtCl6 2-Reduction obtains undersized Pt nanoparticle, prepares Pt/ polymer nanocomposite
Compound particle [Langmuir2005,21,12229-12234].
During it is noted that template prepares carried noble metal nano-complex particle, precious metal salt is first gone back
Originally being noble metal nano particles, then noble metal nano particles is re-depositing on corresponding carrier, combined efficiency
The most relatively low.For improving combined efficiency, template or precious metal salt need to be carried out moditied processing, improve both
Interaction force, this can additionally increase preparation process undoubtedly, make combined coefficient decline.Therefore, exploitation is more
The preparation method of easy, more efficient carried noble metal nano-complex particle, is still this field and needs solution badly
Problem.
Anti-phase miniemulsion system be with non-polar solven as continuous phase, a polar droplet class as dispersion phase non-all
Phase reaction system [Nanoscale2013,5,10093-10107].In anti-phase miniemulsion reaction system, logical
Cross the polyreaction of polar vinyl monomer, the sol-gel process of inorganic precursors, polymer phase separation
Deng chemically or physically method, miscellaneous hydrophilic nano particle or nano-complex particle can be prepared easily.
This technology also has very important application in terms of preparing hydrophilic inorganic nano-particle or nano-complex particle.
Such as, Germany Landfester professor seminar once utilized the sol-gel process system of hydrophilic inorganic precursors
For SiO2、TiO2And CeO2Deng nanoparticle [Chem.Mater.2008,20,5768-5780；Chem.
Mater.2009,21,5088-5098；Nanotechnology 2011,22,135606】.This seminar by
Anti-phase miniemulsion reaction system introduces precious metal salt, in conjunction with the sol-gel process of inorganic precursors, system
For some row nano-complex particles containing precious metal salt；Precious metal salt is converted into expensive by recycling reduction reaction
Metal nanoparticle, prepares and has photocatalytic activity or the Ag/TiO of chemical catalysis activity2、Au/TiO2、Pd/SiO2
And Au/SiO2Deng nano-complex particle [J.Colloid Interface Sci.2014,435,51-58；Colloid
Polym.Sci.2015,293,277-288；Langmuir 2015,31,4341-4350；Colloids Surf.,A
2016,489,223-233；Chinese invention patent 2015, ZL201310409136.3].The advantage of the method exists
In: type, form, pore structure and the specific surface area etc. of (1) inorganic carrier can pass through inorganic precursors
Type, sol-gel process condition regulates and controls；(2) your gold is the kind of noble metal nano particles can pass through
Belong to the type regulation and control of salt, and because of the dissolubility bigger in polar solvent of precious metal salt, noble metal nano grain
The content of son can regulate and control in wider scope；(3) your gold precious metal salt is converted in nano-complex particle
Belonging to nanoparticle, therefore the utilization rate of precious metal salt is high.But note that it is assumed that said method need to first be prepared expensive
Slaine/inorganic carrier nano-complex particle, is converted into noble metal by reduction reaction by slaine the most again and receives
Rice corpuscles, two steps prepare noble metal/inorganic carrier nano-complex particle.
It is contemplated that simplify above-mentioned preparation process further, intend in anti-phase miniemulsion reaction system, pass through
The optimization design of experimental formula and reaction process so that the sol-gel process of inorganic precursors and noble metal
The reduction reaction of salt is carried out simultaneously, and a step directly prepares noble metal/SiO2Nano-complex particle, this material is being urged
There is important using value in change field.
(3) summary of the invention
It is an object of the invention to provide a kind of by anti-phase miniemulsion reaction technology, a step is simply, efficiently
Prepare noble metal/SiO that pattern is special, water dispersible is excellent, catalytic performance is good2The method of nano-complex particle
And according to the method prepare noble metal/SiO2Nano-complex particle and its in paranitrophenol reduction reaction
Application.
The technical solution used in the present invention is:
An a kind of step prepares noble metal/SiO2The method of nano-complex particle, said method comprising the steps of:
(1) emulsifying agent of low hydrophilic-lipophilic balance (HLB) (HLB) value is dissolved in non-polar solven, wherein emulsifying agent
Quality consumption is the 0.1%～20% of non-polar solven quality, obtains emulsifier solution；Described low hlb
Emulsifying agent selected from following at least one: this Pan's series emulsifying agent, twain series emulsifier, OP-10, by hydrophilic
Block copolymer emulsif iotaer with hydrophobic section composition；
(2) precious metal salt is dissolved in polar solvent, wherein precious metal salt and the quality consumption of polar solvent
Ratio be 0.001～1:1, then by pH adjusting agent, pH value is transferred in the range of 2～6；Then by above-mentioned expensive
Metal salt solution is added in the emulsifier solution that step (1) prepares, and controls non-polar solven and polar solvent
The ratio of quality consumption is 2～50:1, is dispersed through obtaining anti-phase miniemulsion；Described precious metal salt selected from following at least
A kind of: gold chloride, bromination gold salt, chlorine (trimethyl-phosphine) gold, potassium chloropalladite, palladium, silver nitrate, four
Silver fluoborate, potassium chloroplatinate, platinum chloride；Described polar solvent is the mixed of water or water and polar organic solvent
Bonding solvent, wherein polar organic solvent is 0～50:1 with the ratio of the quality consumption of water；Described pH adjusting agent
Selected from following at least one: hydrochloric acid, sulphuric acid, acetic acid, phosphoric acid, carbamide, sodium hydroxide, potassium hydroxide,
Sodium carbonate, sodium bicarbonate, sodium borate, ammonia；
(3) in the anti-phase miniemulsion that step (2) obtains, compounding tetraalkoxysilane is added and containing amino
Siloxanes mixed liquor, silicon containing amino in compounding tetraalkoxysilane and siloxanes mixed liquor containing amino
The mass fraction of oxygen alkane is 5%～95%, compounding tetraalkoxysilane and the siloxanes mixed liquor containing amino with
In anti-phase miniemulsion, the ratio of the mole dosage of water is 0.1～4:1, and makes be used in mixed system reducing
The reducing agent of the precious metal salt siloxanes containing amino is 2～200:1 with the ratio of the mole dosage of precious metal salt；Mixed
After closing uniformly, temperature is regulated to 50 DEG C～150 DEG C, react 1h～5d, carry out common sol-gel mistake at siloxanes
While journey, precious metal salt is reduced to noble metal nano particles by the siloxanes containing amino；
(4) product that step (3) obtains is put in Muffle furnace after drying, with 2 DEG C of min-1～30 DEG C of min-1
Heating rate rise to 200 DEG C～800 DEG C, under air atmosphere heat treatment 10min～10h remove Organic substance,
To noble metal/SiO2Nano-complex particle.
In step of the present invention (1), emulsifying agent has low hlb, and wherein this Pan's series emulsifying agent can be
The group of one or more in Si Pan-85, Si Pan-80, Si Pan-65, Si Pan-60, Si Pan-40 or Si Pan-20
Close；Twain series emulsifier can be the one in tween 80, Tween-60, Tween-40 or tween 20 or several
The combination planted；The block copolymer emulsif iotaer being made up of hydrophilic and hydrophobic section is preferably with butene-ethylene copolymer
For block copolymer P (the E/B)-PEO that hydrophobic section, polyoxyethylene are hydrophilic section.In view of system stability,
Prioritizing selection HLB value is low and has an emulsifying agent founding more greatly structure stablizing effect, therefore the breast of described low hlb
Agent is preferably the mixture of more than one of following or two of which: this Pan's series emulsifying agent (more preferably this
Pan-80, Si Pan-85), with OP-10, butene-ethylene copolymer as hydrophobic section, polyoxyethylene is as hydrophilic section
Block copolymer emulsif iotaer P (E/B)-PEO.The quality consumption of emulsifying agent is preferably non-polar solven quality
1%～18%.
In step of the present invention (1), described non-polar solven be selected from following at least one: the fat of C6～C20
Fat race linear paraffin, the cycloalkane of C6～C20, alkylbenzene containing 1～3 C1～C4 alkyl.Consider
Higher reaction temperature, hexadecane that the preferred boiling point of non-polar solven is higher or the carbon number isomery more than 10
Alkane, such as isoparM (mixture of C12～C16 alkane, Exxon Mobil).
In step of the present invention (2), it is contemplated that being smoothed out of the sol-gel process of siloxanes, polarity is molten
Agent must contain a certain amount of water, and in view of the useful load of precious metal salt and drop size and the control of distribution,
Polar solvent then also can add a certain amount of polar organic solvent；Therefore polar solvent selects water or water and polarity
The mixed solvent of organic solvent.Wherein polar organic solvent can be dimethyl sulfoxide, dimethylformamide,
One or more mixing in ethylene glycol, ethanol, oxolane.In view of higher reaction temperature,
Dimethyl sulfoxide that the preferred boiling point of polar organic solvent is higher, dimethylformamide, ethylene glycol etc..
In step of the present invention (2), consider cost and the catalytic performance of catalyst, precious metal salt and polarity
The ratio preferably 0.005～0.3:1 of the quality consumption of solvent.
In step of the present invention (2), consider production efficiency and system stability, non-polar solven and pole
The optimal proportion of property solvent quality consumption is 2.5～45:1.
In step of the present invention (3), shown in the structure of described tetraalkoxysilane such as formula (I), described containing amino
The structure such as formula (II) of siloxanes as shown:
In formula I: R1～R4For each standing alone as the alkyl of C1～C5, as methyl, ethyl, n-pro-pyl,
Isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-pentyl, isopentyl, sec-amyl, uncle penta
Base, neopentyl；In view of the cost of reactant, described tetraalkoxy siloxanes more preferably positive silicic acid
Ethyl ester or methyl silicate；
In formula (II): R5～R7For each standing alone as the alkyl of C1～C5, as methyl, ethyl, n-pro-pyl,
Isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-pentyl, isopentyl, sec-amyl, uncle penta
Base, neopentyl；R8For the alkyl of the aminoalkyl of C1～C5, i.e. C1～C5 (such as methyl, ethyl, just
Propyl group, isopropyl, normal-butyl, isobutyl group, the tert-butyl group, n-pentyl, n-pentyl, isopentyl, sec-amyl,
Tertiary pentyl, neopentyl etc.) replaced by an amino；In view of inorganic carrier form and pore structure regulation and control with
And cost, the described siloxanes containing amino further preferred 3-aminopropyl triethoxysilane.In the present invention,
In compounding tetraalkoxysilane and the siloxanes mixed liquor containing amino, the mass fraction of the siloxanes containing amino
It is preferably 10%～95%.
In step of the present invention (3), compounding tetraalkoxysilane with the siloxanes mixed liquor containing amino with anti-phase
The ratio preferably 0.2～2.5:1 of the mole dosage of water in miniemulsion；Siloxanes containing amino and precious metal salt mole
The ratio preferably 3～168:1 of consumption.
In step of the present invention (3), it is contemplated that being smoothed out of precious metal salt reduction reaction, the temperature of reaction system
Spend preferably 60 DEG C～120 DEG C.
In step of the present invention (4), it is contemplated that effectively remove the organic component in nano-complex particle and avoid
The situation such as particles sintering and golden nanometer particle coalescence during high-temperature heat treatment, heat treatment temperature preferably 250 DEG C～500 DEG C,
Preferred 0.5h～3h of heat treatment time.
About the present invention, inventor finds through further investigation, with the polar solvent of precious metal salt as dispersion phase,
The non-polar solution of low hlb emulsifying agent is continuous phase, can build anti-phase miniemulsion reaction system easily.
Inorganic precursors directly makes an addition in anti-phase miniemulsion, and it by dissolving and can migrate to polarity by the way of diffusion
Drop surface, contacts generation sol-gel process with water.In acid condition, in the sol-gel of siloxanes
Between product in polar solvent, have preferable dissolubility, therefore these intermediate products can enter drop internal.This
Outward, in acid condition, aminoalkyl such as aminopropyl positively charged ((CH2)3–NH3 +), therefore shape in drop
The silicon nucleus band positive electricity become, has preferable colloidal stability, and the internuclear coalescence of silicon is less, major part SiO2Granule
Son each growth.It is said that in general, comprise substantial amounts of SiO in granule2Small particles, after the reaction phase, by
In SiO2The size of small particles increases, and interparticle spacing reduces, and is packed together, and by further
Sol-gel process, forms the link of chemical bond, ultimately forms the spherical accumulation body that morphological stability is good.Ball
The form of shape accumulation body and structure can be regulated and controled by the proportioning of two class siloxanes, with the increasing of amino silicone content
Adding, particle changes to accumulation form from homogeneous spheroid, but when amino silicone content is higher, particle
Form can change to homogeneous spheroid from accumulation form again.The size of inorganic nano carrier is by the size of initial liquid drop
Determining, therefore the size of inorganic nano carrier can pass through emulsifier, precious metal salt consumption, polar solvent
Be conveniently adjusted with the ratio of non-polar solven, such as by reduce polar solvent and the ratio of non-polar solution,
Improve the method such as precious metal salt or emulsifier and can reduce drop size, and then reduce inorganic nano carrier
Size.
While siloxanes carries out sol-gel process, there is the siloxanes containing amino of certain reproducibility,
Such as 3-aminopropyl triethoxysilane, can exist precious metal salt with precious metal salt generation oxidation-reduction reaction
Drop interior in-situ reducing mutually is noble metal nano particles.Sol-gel process and precious metal salt with siloxanes
Completing of reduction reaction, a final step directly obtains noble metal/SiO2Nano-complex particle.Due to precious metal salt
Generally having higher dissolubility in polar solvent, therefore the useful load of precious metal salt can be in wider scope
Interior adjustment.
Invention further provides the noble metal/SiO prepared according to said method2Nano-complex particle and should
Noble metal/SiO2Nano-complex particle application in paranitrophenol reduction reaction.Further, reducing agent is
NaBH4。
Compared with prior art, the beneficial effects are mainly as follows: the invention provides one and pass through
Anti-phase miniemulsion techniques, a step prepares noble metal/SiO simply, efficiently2The method of nano-complex particle.This
Inventive method prepares noble metal/SiO2The advantage of nano-complex particle is: (1) passes through siloxanes compound proportion
Regulation, can realize inorganic nano carrier from homogeneous spheroid to fine particle pile up spheroid transformation；(2) by
Noble metal/SiO that fine particle is piled up2Nano-complex particle surface is electrically charged, exists stronger between particle
Electrostatic interaction so that nano-complex particle has good water dispersible；(3) Catalysis experiments shows this catalyst
There is the circulation catalytic capability that high catalysis is active and excellent.Additionally, utilize the technology that the present invention proposes, can be very
Control well the size of inorganic nano carrier, distribution of sizes and pore structure, noble metal nano particles content,
Particle size and crystallite dimension etc..Noble metal/SiO that the present invention obtains2Nano-complex particle organic reaction be catalyzed,
There is the highest using value in the fields such as vehicle maintenance service.
(4) accompanying drawing explanation
Fig. 1 is embodiment 1 gained Au/SiO2The transmission electron microscope picture of nano-complex particle.
Fig. 2 is embodiment 1 gained Au/SiO2The scanning electron microscope (SEM) photograph of nano-complex particle.
(5) detailed description of the invention
Below in conjunction with specific embodiment, the present invention is described further, but protection scope of the present invention is not
It is only limitted to this:
Embodiment 1:
Weigh emulsifying agent P (E/B)-PEO2.0g, be dissolved in 198g hexadecane, obtain emulsifier solution.This is embedding
Section copolymer preparation method see document [Macromolecules, 2001,34,4302-4304.Langmuir,
2003,19,4455-4459.】。
1g gold chloride is dissolved in the mixed solution of 1g water and 10g dimethyl sulfoxide composition, then uses 1mol L-1
Sodium hydrate aqueous solution by the pH regulator of saline solution to 4；Gained chlorauric acid solution joins mentioned emulsifier
In solution, with ultrasound wave, above-mentioned mixed liquor is disperseed, obtain stable anti-phase miniemulsion.
2.2g methyl silicate and 3.7g 3-aminopropyl triethoxysilane is added in above-mentioned anti-phase miniemulsion,
Temperature rises to 90 DEG C, reacts 24h, obtains Au/SiO2The dispersion liquid of nano-complex particle.Centrifugation, dry
Dry obtain Au/SiO2The dry powder of nano-complex particle, with 30 DEG C of min in Muffle furnace-1Heating rate heat up
To 500 DEG C of calcining 0.5h, remove Organic substance, prepare Au/SiO2Nano-complex particle.
X-ray diffraction test confirms that Au salt is successfully reduced to Au nanoparticle.Transmission and scanning electron
Microscope all shows that nano-complex particle has obvious packed structures, and Au nanoparticle is mainly distributed on compound
The surface of particle, wherein SiO2The number average bead diameter of nano-carrier is the number average bead diameter of 299nm, Au nanoparticle
For 9.0nm.With NaBH4The reaction of reduction paranitrophenol (p-NPH) is model reaction, tests Au/SiO2
The catalytic performance of nano-complex particle, found that the relative reaction rate constant k of this catalystrIt is 5.4
s-1·Au-mmol-1, embodied high catalysis activity；Repeat Catalysis experiments and show that this catalyst is reused
After 30 times, catalysis activity has no and is decreased obviously.krComputing formula be kr=Nka N pp M, wherein kappAnd NNMPoint
Wei apparent reaction rate constant and the mole of noble metal.
Embodiment 2:
Weigh emulsifying agent Si Pan-808.1g, be dissolved in 45g isoparaffin IsoparM (ExonMobil), obtain
Emulsifier solution.
0.1g silver nitrate is dissolved in 1g water, then uses 1mol L-1Aqueous solution of urea the pH of saline solution is adjusted
Joint is to 6；Gained silver nitrate solution joins in mentioned emulsifier solution, is disperseed by above-mentioned mixed liquor with ultrasound wave,
Obtain stable anti-phase miniemulsion.
3.0g tetraethyl orthosilicate and 0.4g 3-aminopropyl triethoxysilane is added in above-mentioned anti-phase miniemulsion,
Temperature rises to 60 DEG C, reacts 3d, obtains Ag/SiO2Nano-complex particle dispersion liquid.Centrifugation, be dried
Obtain Ag/SiO2The dry powder of nano-complex particle, with 15 DEG C of min in Muffle furnace-1Heating rate be warming up to
350 DEG C, calcine 2h, remove Organic substance, prepare Ag/SiO2Nano-complex particle.
X-ray diffraction test confirms that silver nitrate is successfully reduced to Ag nanoparticle.Transmission and scanning electron
Microscope all shows that nano-complex particle has obvious packed structures, and Ag nanoparticle is mainly distributed on compound
The surface of particle, wherein SiO2The number average bead diameter of nano-carrier is the number average bead diameter of 210nm, Ag nanoparticle
For 18nm.With NaBH4The reaction of reduction p-NPH is model reaction, tests Ag/SiO2Nano combined
The catalytic performance of particle, found that the relative reaction rate constant k of this catalystrFor 4.2s-1·Ag-mmol-1,
Embody high catalysis activity；After repetition Catalysis experiments shows that this catalyst reuses 30 times, catalysis is lived
Property has no and is decreased obviously.
Embodiment 3:
Weigh emulsifying agent Si Pan-8513g and OP-1013g, be dissolved in 260g hexadecane, obtain emulsifier solution.
0.17g potassium chloroplatinate is dissolved in the mixed solution of 4g water and 30g dimethylformamide composition, then uses
0.5mol·L-1Hydrochloric acid by the pH regulator of potassium chloroplatinate solution to 3；Gained potassium chloroplatinate solution joins above-mentioned
In emulsifier solution, with ultrasound wave, above-mentioned mixed liquor is disperseed, obtain stable anti-phase miniemulsion.
1g methyl silicate and 13g 3-aminopropyl triethoxysilane, temperature is added in above-mentioned anti-phase miniemulsion
Degree rises to 110 DEG C, reacts 6h, obtains Pt/SiO2Nano-complex particle dispersion liquid.Centrifugation, be dried
To Pt/SiO2The dry powder of nano-complex particle, with 5 DEG C of min in Muffle furnace-1Heating rate be warming up to
450 DEG C, calcine 1h, remove Organic substance, prepare Pt/SiO2Nano-complex particle.
X-ray diffraction test confirms that potassium chloroplatinate is successfully reduced to Pt nanoparticle.Transmission and scanning electricity
Sub-microscope all shows that nano-complex particle has obvious packed structures, and Pt nanoparticle is mainly distributed on multiple
Close the surface of particle, wherein SiO2The number average bead diameter of nano-carrier is the equal grain of number of 320nm, Pt nanoparticle
Footpath is 7.8nm.With NaBH4The reaction of reduction p-NPH is model reaction, tests Pt/SiO2Nano combined
The catalytic performance of particle, found that the relative reaction rate constant k of this catalystrFor 6.5s-1·Pt-mmol-1,
Embody high catalysis activity；After repetition Catalysis experiments shows that this catalyst reuses 30 times, catalysis is lived
Property has no and is decreased obviously.
Embodiment 4:
Weigh 8.6g Si Pan-80 and 8.6gOP-10 as emulsifying agent, be dissolved in 123g hexadecane, obtain emulsifying
Agent solution.
10.5g potassium chloropalladite is dissolved in the mixed solution of 1.5g water and 36g dimethylformamide composition, then
Use 0.5mol L-1Hydrochloric acid by the pH regulator of potassium chloropalladite solution to 3；Gained potassium chloropalladite solution adds
In mentioned emulsifier solution, with ultrasound wave, above-mentioned mixed liquor is disperseed, obtain stable anti-phase miniemulsion.
15g tetraethyl orthosilicate and 25g 3-aminopropyl triethoxysilane, temperature is added in above-mentioned anti-phase miniemulsion
Degree rises to 120 DEG C, reacts 5h, obtains Pd/SiO2Nano-complex particle dispersion liquid.Centrifugation, be dried
To Pd/SiO2The dry powder of nano-complex particle, with 30 DEG C of min in Muffle furnace-1Heating rate be warming up to 400 DEG C
Calcining 45min, removes Organic substance, prepares Pd/SiO2Nano-complex particle.
X-ray diffraction test confirms that potassium chloropalladite is successfully reduced to Pd nanoparticle.Transmission and scanning
Ultramicroscope all shows that nano-complex particle has obvious packed structures, and Pd nanoparticle is mainly distributed on
The surface of compound particle, wherein SiO2The number average bead diameter of nano-carrier is that the number of 275nm, Pd nanoparticle is equal
Particle diameter is 12nm.With NaBH4The reaction of reduction p-NPH is model reaction, tests Pd/SiO2Nanometer is multiple
Close the catalytic performance of particle, found that the relative reaction rate constant k of this catalystrFor 6.2s-1·Pd-mmol-1,
Embody high catalysis activity；After repetition Catalysis experiments shows that this catalyst reuses 30 times, catalysis is lived
Property has no and is decreased obviously.
Claims (10)
1. a step prepares noble metal/SiO2The method of nano-complex particle, said method comprising the steps of:
(1) emulsifying agent of low hydrophile-lipophile balance value is dissolved in non-polar solven, wherein emulsifying agent quality consumption
For the 0.1%～20% of non-polar solven quality, obtain emulsifier solution；Described low hydrophile-lipophile balance value
Emulsifying agent selected from following at least one: this Pan's series emulsifying agent, twain series emulsifier, OP-10, by hydrophilic
Block copolymer emulsif iotaer with hydrophobic section composition；
(2) being dissolved in polar solvent by precious metal salt, wherein precious metal salt with the mass ratio of polar solvent is
0.001～1:1, then by pH adjusting agent, pH value is transferred in the range of 2～6；Then by above-mentioned precious metal salt
Solution is added in the emulsifier solution that step (1) prepares, and controls the mass ratio of non-polar solven and polar solvent
It is 2～50:1, is dispersed through obtaining anti-phase miniemulsion；Described precious metal salt selected from following at least one: gold chloride,
Bromination gold salt, chlorine (trimethyl-phosphine) gold, potassium chloropalladite, palladium, silver nitrate, silver tetrafluoroborate, chlorine platinum
Acid potassium, platinum chloride；Described polar solvent is water or water and the mixed solvent of polar organic solvent, Qi Zhongji
Property organic solvent is 0～50:1 with the ratio of the quality consumption of water；Described pH adjusting agent is selected from following at least one
Kind: hydrochloric acid, sulphuric acid, acetic acid, phosphoric acid, carbamide, sodium hydroxide, potassium hydroxide, sodium carbonate, bicarbonate
Sodium, sodium borate, ammonia；
(3) in the anti-phase miniemulsion that step (2) obtains, compounding tetraalkoxysilane is added and containing amino
Siloxanes mixed liquor, silicon containing amino in compounding tetraalkoxysilane and siloxanes mixed liquor containing amino
The mass fraction of oxygen alkane is 5%～95%, compounding tetraalkoxysilane and the siloxanes mixed liquor containing amino with
In anti-phase miniemulsion, the ratio of the mole dosage of water is 0.1～4:1, and makes be used in mixed system reducing
The reducing agent of the precious metal salt siloxanes containing amino is 2～200:1 with the ratio of the mole dosage of precious metal salt；Mixed
After closing uniformly, temperature is regulated to 50 DEG C～150 DEG C, react 1h～5d, carry out common sol-gel mistake at siloxanes
While journey, precious metal salt is reduced to noble metal nano particles by the siloxanes containing amino；
(4) product that step (3) obtains is put in Muffle furnace after drying, with 2 DEG C of min-1～30 DEG C of min-1
Heating rate rise to 200 DEG C～800 DEG C, under air atmosphere heat treatment 10min～10h remove Organic substance,
To noble metal/SiO2Nano-complex particle.
2. the method for claim 1, it is characterised in that: in step (1), described nonpolar molten
Agent be selected from following at least one: the acyclic straight alkane of C6～C20, the cycloalkane of C6～C20, contain
The alkylbenzene of 1～3 C1～C4 alkyl.
3. the method for claim 1, it is characterised in that: in step (2), polar organic solvent
It is one or more in dimethyl sulfoxide, dimethylformamide, ethylene glycol, ethanol, oxolane
Mixing.
4. the method for claim 1, it is characterised in that: in step (3), described tetraalkoxy
Shown in the structure of silane such as formula (I), the structure such as formula (II) of the described siloxanes containing amino is as shown:
In formula I: R1～R4For each standing alone as C1～C5Alkyl；
In formula (II): R5～R7For each standing alone as C1～C5Alkyl；R8For C1～C5Aminoalkyl.
5. method as claimed in claim 4, it is characterised in that: the described siloxanes containing amino is 3-ammonia third
Ethyl triethoxy silicane alkane；Described tetraalkoxy siloxanes is tetraethyl orthosilicate or methyl silicate.
6. the method for claim 1, it is characterised in that: in step (1), the quality of emulsifying agent
Consumption is the 1%～18% of non-polar solven quality；In step (2), precious metal salt and the quality of polar solvent
The ratio of consumption is 0.005～0.3:1, and the ratio of non-polar solven and polar solvent quality consumption is 2.5～45:1；
In step (3), in compounding tetraalkoxysilane and the siloxanes mixed liquor containing amino, the silica containing amino
The mass fraction of alkane is 10%～95%, and compounding tetraalkoxysilane and the siloxanes mixed liquor containing amino are with anti-
In phase miniemulsion, the ratio of the mole dosage of water is 0.2～2.5:1, siloxanes containing amino and precious metal salt mole
The ratio of consumption is 3～168:1.
7. the method for claim 1, it is characterised in that: in step (3), the temperature of reaction system
Degree is 60 DEG C～120 DEG C.
8. the method as described in claim 1 or 7, it is characterised in that: in step (4), heat treatment temperature
Degree is 250 DEG C～500 DEG C, and heat treatment time is 0.5h～3h.
Noble metal/SiO that method the most according to claim 1 prepares2Nano-complex particle.
10. noble metal/SiO as claimed in claim 92Nano-complex particle is at noble metal/SiO2Nano combined
Particle application in paranitrophenol reduction reaction.
Priority Applications (1)
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| CN109126784A (en) * | 2018-08-02 | 2019-01-04 | 福州大学 | A kind of metal nanoparticle/silica composite photo-catalyst of visible light-near infrared light response |
| CN110201655A (en) * | 2019-05-07 | 2019-09-06 | 浙江理工大学 | A kind of one-step method prepares hollow TiO2The method and application of nanosphere |
| CN114621782A (en) * | 2022-03-21 | 2022-06-14 | 中节能工程技术研究院有限公司 | Ultra-deep oxidation desulfurization reaction based on Pickering emulsion |
| CN115888698A (en) * | 2022-11-10 | 2023-04-04 | 西部金属材料股份有限公司 | Basalt fiber-loaded noble metal nano catalyst and preparation method thereof |
| CN115888698B (en) * | 2022-11-10 | 2024-04-30 | 西部金属材料股份有限公司 | Basalt fiber supported noble metal nano catalyst and preparation method thereof |
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| CN115888698A (en) * | 2022-11-10 | 2023-04-04 | 西部金属材料股份有限公司 | Basalt fiber-loaded noble metal nano catalyst and preparation method thereof |
| CN115888698B (en) * | 2022-11-10 | 2024-04-30 | 西部金属材料股份有限公司 | Basalt fiber supported noble metal nano catalyst and preparation method thereof |
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