CN105727949B - One step of one kind prepares noble metal/SiO2The method of nano-complex particle - Google Patents
One step of one kind prepares noble metal/SiO2The method of nano-complex particle Download PDFInfo
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- CN105727949B CN105727949B CN201610066026.5A CN201610066026A CN105727949B CN 105727949 B CN105727949 B CN 105727949B CN 201610066026 A CN201610066026 A CN 201610066026A CN 105727949 B CN105727949 B CN 105727949B
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- precious metal
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- 239000002245 particle Substances 0.000 title claims abstract description 74
- 229910000510 noble metal Inorganic materials 0.000 title claims abstract description 45
- 238000000034 method Methods 0.000 title claims abstract description 32
- -1 siloxanes Chemical class 0.000 claims abstract description 50
- 150000003839 salts Chemical class 0.000 claims abstract description 43
- 239000003995 emulsifying agent Substances 0.000 claims abstract description 42
- 239000010970 precious metal Substances 0.000 claims abstract description 41
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052681 coesite Inorganic materials 0.000 claims abstract description 36
- 229910052906 cristobalite Inorganic materials 0.000 claims abstract description 36
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 36
- 229910052682 stishovite Inorganic materials 0.000 claims abstract description 36
- 229910052905 tridymite Inorganic materials 0.000 claims abstract description 36
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims abstract description 27
- 239000000243 solution Substances 0.000 claims abstract description 23
- 239000002798 polar solvent Substances 0.000 claims abstract description 21
- 239000002082 metal nanoparticle Substances 0.000 claims abstract description 14
- 239000012454 non-polar solvent Substances 0.000 claims abstract description 13
- 238000013329 compounding Methods 0.000 claims abstract description 11
- 238000006722 reduction reaction Methods 0.000 claims abstract description 11
- 238000003980 solgel method Methods 0.000 claims abstract description 11
- 239000005416 organic matter Substances 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 239000012266 salt solution Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- 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
- 238000010438 heat treatment Methods 0.000 claims description 11
- 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
- 239000007788 liquid Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- 239000003795 chemical substances by application Substances 0.000 claims description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 7
- 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
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 6
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-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
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 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
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 3
- 150000001335 aliphatic alkanes Chemical class 0.000 claims description 3
- 239000004202 carbamide Substances 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
- 239000003002 pH adjusting agent Substances 0.000 claims description 3
- 239000002904 solvent Substances 0.000 claims description 3
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-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
- 125000002015 acyclic group Chemical group 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
- 239000000908 ammonium hydroxide Substances 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
- 238000004945 emulsification Methods 0.000 claims description 2
- 235000019441 ethanol Nutrition 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- CLSUSRZJUQMOHH-UHFFFAOYSA-L platinum dichloride Chemical compound Cl[Pt]Cl CLSUSRZJUQMOHH-UHFFFAOYSA-L 0.000 claims description 2
- 229910001494 silver tetrafluoroborate Inorganic materials 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 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
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 claims 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims 1
- OBNDGIHQAIXEAO-UHFFFAOYSA-N [O].[Si] Chemical compound [O].[Si] OBNDGIHQAIXEAO-UHFFFAOYSA-N 0.000 claims 1
- 229910021529 ammonia Inorganic materials 0.000 claims 1
- 239000006071 cream Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 description 23
- 239000010931 gold Substances 0.000 description 23
- 239000002105 nanoparticle Substances 0.000 description 18
- 239000003054 catalyst Substances 0.000 description 10
- 239000002539 nanocarrier Substances 0.000 description 10
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 239000010944 silver (metal) Substances 0.000 description 9
- 239000011324 bead Substances 0.000 description 8
- 238000006555 catalytic reaction Methods 0.000 description 8
- DCAYPVUWAIABOU-UHFFFAOYSA-N hexadecane Chemical compound CCCCCCCCCCCCCCCC DCAYPVUWAIABOU-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 6
- 239000006185 dispersion Substances 0.000 description 6
- 238000002474 experimental method Methods 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
- 239000000084 colloidal system Substances 0.000 description 5
- 229910052737 gold Inorganic materials 0.000 description 5
- 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 5
- 239000002243 precursor Substances 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
- 235000013339 cereals Nutrition 0.000 description 4
- 230000003247 decreasing effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 241000209094 Oryza Species 0.000 description 3
- 235000007164 Oryza sativa Nutrition 0.000 description 3
- 239000002253 acid Substances 0.000 description 3
- 230000009881 electrostatic interaction Effects 0.000 description 3
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 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
- 125000004123 n-propyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])* 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
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 3
- 229920000867 polyelectrolyte Polymers 0.000 description 3
- 229920000642 polymer Polymers 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 235000009566 rice Nutrition 0.000 description 3
- 239000003381 stabilizer 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
- 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
- 230000008859 change Effects 0.000 description 2
- 239000000460 chlorine Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 229920001038 ethylene copolymer Polymers 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 239000013067 intermediate product Substances 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 238000006053 organic reaction Methods 0.000 description 2
- 239000003960 organic solvent Substances 0.000 description 2
- 229910052763 palladium Inorganic materials 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 238000009938 salting Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 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
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 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
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000004103 aminoalkyl group Chemical group 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001721 carbon Chemical group 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
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 230000001276 controlling effect Effects 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
- 239000002270 dispersing agent Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000000839 emulsion Substances 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000006210 lotion Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 238000005457 optimization Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000006116 polymerization reaction Methods 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
- 238000006479 redox reaction Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 150000003376 silicon Chemical class 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000003892 spreading Methods 0.000 description 1
- 230000007480 spreading Effects 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
- 238000004627 transmission electron microscopy Methods 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 one steps of one kind to prepare noble metal/SiO2The method of nano-complex particle, the described method comprises the following steps: (1) emulsifier of low hydrophile-lipophile balance value being dissolved in nonpolar solvent, obtain emulsifier solution；(2) precious metal salt is dissolved in polar solvent, then pH value is transferred in the range of 2~6；Above-mentioned precious metal salt solution is added in emulsifier solution, is dispersed and obtains reverse phase miniemulsion；(3) tetraalkoxysilane and amino-containing siloxanes mixed liquor of compounding are added into reverse phase miniemulsion, the temperature was then adjusted to 50 DEG C~150 DEG C after mixing, react 1h~5d, while siloxanes carries out total sol-gel process, precious metal salt is reduced to noble metal nano particles by amino-containing siloxanes；(4) it is heat-treated in air atmosphere after drying the product that step (3) obtains to remove organic matter, obtains noble metal/SiO2Nano-complex particle.The present invention also provides noble metal/SiO obtained2Application of the nano-complex particle in 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/SiO2It receives
Rice compound particle and its application, and in particular to a kind of to utilize reverse phase miniemulsion techniques, a step is easy, efficiently prepares water dispersible
Noble metal/SiO good, catalytic activity is high, circulation catalytic performance is excellent2The method of nano-complex particle and your obtained gold
Category/SiO2Nano-complex particle and its application in p-nitrophenol reduction reaction.
(2) background technique
The noble metals such as several nanometers to more than ten nanometers Au, Ag, Pt and Pd are a kind of efficient nano catalytic material, energy
For being catalyzed numerous organic reactions.But the noble metal nano particles surface of small size can be high, easily reunites, causes its catalytic performance
Decline.For the colloidal stability for improving noble metal nano particles, a kind of effective method is using a large amount of emulsifier, polymer
Dispersing agent or organic ligand isocolloid stabilizer with surface-active.But this method haves the defects that certain: (1) noble metal is received
The active site on rice corpuscles surface is covered by colloid stabilizer, its catalytic activity is caused to decline；(2) noble metal nano particles surface
After covering colloid stabilizer, the difficulty of reactant absorption and the de- analysis of product increases；(3) the noble metal nano grain of stable dispersion
Sub- size is small, it is difficult to effectively separate from reaction system, cause its recycling poor.
Noble metal nano particles are carried on size on tens to hundreds of nanometers nano-carrier surface, can be improved simultaneously expensive
The performances such as colloidal stability, catalytic activity and the recycling of metal nanoparticle.It is born currently, having and being prepared using template
The report of load type noble metal nano catalyst.For example, Zhu et al. is first in alkaline solution, SiO is utilized2Particle and cationic
Au (III) and ethylene diamine complex [Au (en)2Cl3] between electrostatic interaction, formed Au salt/SiO2Nano-complex particle；?
Au salt is reduced to Au nanoparticle by heat treatment under the reducing atmosphere of hydrogen, then under oxygenous oxidizing atmosphere, heat treatment
Organic matter is removed, Au/SiO is made2Nano-composite catalyst [Appl.Catal., A 2007,326,89-99].Ballauff etc.
People first passes through the method to polystyrene nanospheres grafted cation polyelectrolyte, is prepared for spherical polyelectrolyte molecular brush；Again
In aqueous solution, using electrostatic interaction, by PtCl6 2-Ion load is on polyelectrolyte layer, then to system plus sodium borohydride,
By PtCl6 2-Reduction obtain the Pt nanoparticle of small size, be made Pt/ polymer nanocomposite compound particle [Langmuir2005,21,
12229-12234】。
It is noted that precious metal salt is first reduced to expensive when template prepares carried noble metal nano-complex particle
Metal nanoparticle, then noble metal nano particles are re-depositing on corresponding carrier, and combined efficiency is often lower.It is multiple to improve
Efficiency is closed, moditied processing need to be carried out to template or precious metal salt, to improve the interaction force of the two, this undoubtedly can additionally increase
Preparation step declines combined coefficient.Therefore, the system of easier, more efficient carried noble metal nano-complex particle is developed
The problem of Preparation Method is still the field urgent need to resolve.
Reverse phase miniemulsion system is a kind of heterogeneous reaction using nonpolar solvent as continuous phase, polar droplet for dispersed phase
System [Nanoscale2013,5,10093-10107].In reverse phase miniemulsion reaction system, pass through polar vinyl monomer
The chemically or physically methods such as polymerization reaction, colloidal sol-gel process of inorganic precursors, polymer phase separation, can easily prepare
Miscellaneous hydrophilic nano particle or nano-complex particle.The technology is to prepare hydrophilic inorganic nano-particle or nanometer multiple
Also there is very important application in terms of closing particle.For example, before Germany Landfester professor seminar once utilized hydrophilic inorganic
Colloidal sol-the gel process for driving object is prepared for SiO2、TiO2And CeO2Equal nanoparticles [Chem.Mater.2008,20,5768-
5780；Chem. Mater.2009,21,5088-5098；Nanotechnology 2011,22,135606].This seminar is logical
It crosses to reverse phase miniemulsion reaction system introducing precious metal salt and is prepared for one in conjunction with colloidal sol-gel process of inorganic precursors
A little nano-complex particles of the column containing precious metal salt；It recycles reduction reaction to convert noble metal nano particles for precious metal salt, makes
Must there are photocatalytic activity or the active Ag/TiO of chemical catalysis2、Au/TiO2、Pd/SiO2And Au/SiO2Equal nano-complex particles
[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 this method is that: (1) type, form, pore structure and specific surface of inorganic carrier
Product etc. can be regulated and controled by the types of inorganic precursors, colloidal sol-gel process condition；(2) kind of noble metal nano particles
Class can be regulated and controled by the type of precious metal salt, and because precious metal salt in polar solvent biggish solubility, noble metal nano
The content of particle can regulate and control in a wider scope；(3) precious metal salt is converted into noble metal nano grain in nano-complex particle
Son, therefore the utilization rate of precious metal salt is high.But note that it is assumed that the above method need to first prepare precious metal salt/inorganic carrier nanometer
Then compound particle converts noble metal nano particles for metal salt by reduction reaction again, noble metal/without airborne is made in two steps
Body nano-complex particle.
The present invention is directed to be further simplified above-mentioned preparation process, intend in reverse phase miniemulsion reaction system, is matched by experiment
The optimization design of side and reaction process, so that the reduction reaction of colloidal sol-gel process of inorganic precursors and precious metal salt is simultaneously
It carries out, noble metal/SiO is directly made in a step2Nano-complex particle, the material have important application value in catalytic field.
(3) summary of the invention
The purpose of the present invention is to provide one kind by reverse phase miniemulsion reaction technology, and a step simply, efficiently prepares shape
Noble metal/SiO that looks are special, water dispersible is excellent, catalytic performance is good2The method of nano-complex particle and according to party's legal system
Noble metal/the SiO obtained2Nano-complex particle and its application in p-nitrophenol reduction reaction.
The technical solution adopted by the present invention is that:
One step of one kind prepares noble metal/SiO2The method of nano-complex particle, the described method comprises the following steps:
(1) emulsifier of low hydrophilic-lipophilic balance (HLB) (HLB) value is dissolved in nonpolar solvent, wherein emulsifier quality dosage
It is the 0.1%~20% of nonpolar solvent quality, obtains emulsifier solution；The emulsifier of the low hlb be selected from it is following at least
It is a kind of: this Pan's series emulsifier, twain series emulsifier, OP-10, the block copolymer emulsification being made of hydrophilic and hydrophobic section
Agent；
(2) precious metal salt is dissolved in polar solvent, wherein the ratio between precious metal salt and the quality dosage of polar solvent are
0.001~1:1, then pH value is transferred in the range of 2~6 with pH adjusting agent；Then above-mentioned precious metal salt solution is added to step
(1) in emulsifier solution made from, controlling the ratio between quality dosage of nonpolar solvent and polar solvent is 2~50:1, is dispersed
Obtain reverse phase miniemulsion；The precious metal salt is selected from following at least one: gold chloride, bromination gold salt, chlorine (trimethyl-phosphine) gold, chlorine
Sub- palladium acid potassium, palladium acetate, silver nitrate, silver tetrafluoroborate, potassium chloroplatinate, platinum chloride；The polar solvent is water or water and pole
Property organic solvent mixed solvent, wherein the ratio between quality dosage of polar organic solvent and water be 0~50:1；The pH is adjusted
Agent is selected from following at least one: hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, urea, sodium hydroxide, potassium hydroxide, sodium carbonate, bicarbonate
Sodium, Boratex, ammonium hydroxide；
(3) tetraalkoxysilane and amino-containing siloxanes of compounding are added in the reverse phase miniemulsion obtained to step (2)
Mixed liquor, the tetraalkoxysilane of compounding and the mass fraction of amino-containing siloxanes in amino-containing siloxanes mixed liquor are
5%~95%, the mole dosage of the tetraalkoxysilane of compounding and amino-containing siloxanes mixed liquor and water in reverse phase miniemulsion
The ratio between be 0.1~4:1, and to be used to restore in mixed system the amino-containing siloxanes of reducing agent of precious metal salt with it is expensive
The ratio between mole dosage of metal salt is 2~200:1；After mixing the temperature was then adjusted to 50 DEG C~150 DEG C, 1h~5d is reacted,
While siloxanes carries out total sol-gel process, precious metal salt is reduced to noble metal nano grain by amino-containing siloxanes
Son；
(4) it is put into Muffle furnace after drying the product that step (3) obtains, with 2 DEG C of min-1~30 DEG C of min-1Liter
Warm rate rises to 200 DEG C~800 DEG C, and 10min~10h is heat-treated under air atmosphere and removes organic matter, obtains noble metal/SiO2It receives
Rice compound particle.
In step (1) of the present invention, emulsifier have low hlb, wherein this Pan's series emulsifier can be Si Pan -85, this
The combination of one or more of Pan -80, Si Pan -65, Si Pan -60, Si Pan -40 or Si Pan -20；Twain series emulsifier can be with
It is the combination of one or more of Tween-80, Tween-60, Tween-40 or Tween-20；It is made of hydrophilic and hydrophobic section embedding
Section copolymer emulsifier is preferably the block copolymer P of hydrophilic section by hydrophobic section, polyoxyethylene of butene-ethylene copolymer
(E/B)-PEO.It is preferential to select HLB value low and emulsifier with larger vertical structure stablizing effect in view of system stability, therefore institute
The emulsifier for stating low hlb is preferably one of following or in which two or more mixture: this Pan's series emulsifier is (more preferably
Si Pan -80, Si Pan -85), using OP-10, butene-ethylene copolymer as hydrophobic section, polyoxyethylene be the block copolymer of hydrophilic section
Emulsifier P (E/B)-PEO.The quality dosage of emulsifier is preferably the 1%~18% of nonpolar solvent quality.
In step (1) of the present invention, the nonpolar solvent can be selected from following at least one: the acyclic straight of C6~C20
Alkane, the cycloalkane of C6~C20, the alkylbenzene containing 1~3 C1~C4 alkyl.In view of higher reaction temperature, nonpolarity is molten
The higher hexadecane of the preferred boiling point of agent or carbon atom number are greater than 10 isoparaffin, for example, isoparM (C12~C16 alkane it is mixed
Close object, Exxon Mobil).
In step (2) of the present invention, it is contemplated that colloidal sol-gel process of siloxanes is gone on smoothly, and must be contained in polar solvent
A certain amount of water, and in view of the useful load of precious metal salt and drop size and the control of distribution, then can also it add in polar solvent
Add a certain amount of polar organic solvent；Therefore polar solvent selects the mixed solvent of water or water and polar organic solvent.Wherein polarity
Organic solvent can be one or more of dimethyl sulfoxide, dimethylformamide, ethylene glycol, ethyl alcohol, tetrahydrofuran
Mixing.In view of higher reaction temperature, the higher dimethyl sulfoxide of the preferred boiling point of polar organic solvent, dimethyl formyl
Amine, ethylene glycol etc..
In step (2) of the present invention, the cost and catalytic performance of catalyst, the matter of precious metal salt and polar solvent are comprehensively considered
Measure the ratio between dosage preferably 0.005~0.3:1.
In step (2) of the present invention, production efficiency and system stability, nonpolar solvent and polar solvent matter are comprehensively considered
The optimal proportion for measuring dosage is 2.5~45:1.
In step (3) of the present invention, shown in the structure of the tetraalkoxysilane such as formula (I), the amino-containing siloxanes
Structure such as formula (II) such as show:
In formula (I): R1~R4For the alkyl for respectively standing alone as C1~C5, such as methyl, ethyl, n-propyl, isopropyl, positive fourth
Base, isobutyl group, tert-butyl, n-pentyl, n-pentyl, isopentyl, sec-amyl, tertiary pentyl, neopentyl；In view of reactant at
This, the tetraalkoxy siloxanes is more preferably ethyl orthosilicate or methyl orthosilicate；
In formula (II): R5~R7For the alkyl for respectively standing alone as C1~C5, such as methyl, ethyl, n-propyl, isopropyl, positive fourth
Base, isobutyl group, tert-butyl, n-pentyl, n-pentyl, isopentyl, sec-amyl, tertiary pentyl, neopentyl；R8For the amino alkane of C1~C5
Base, the i.e. alkyl of C1~C5 (such as methyl, ethyl, n-propyl, isopropyl, normal-butyl, isobutyl group, tert-butyl, n-pentyl, positive penta
Base, isopentyl, sec-amyl, tertiary pentyl, neopentyl etc.) replaced by an amino；In view of inorganic carrier form and pore structure
Regulation and cost, the amino-containing further preferred 3- aminopropyl triethoxysilane of siloxanes.In the present invention, compounding
In tetraalkoxysilane and amino-containing siloxanes mixed liquor, the mass fraction of amino-containing siloxanes is preferably 10%~
95%.
In step (3) of the present invention, the tetraalkoxysilane of compounding and amino-containing siloxanes mixed liquor and reverse phase miniemulsion
The ratio between mole dosage of middle water preferably 0.2~2.5:1；The ratio between mole dosage of amino-containing siloxanes and precious metal salt preferably 3
~168:1.
In step (3) of the present invention, it is contemplated that precious metal salt reduction reaction is gone on smoothly, the temperature of reaction system preferably 60
DEG C~120 DEG C.
In step (4) of the present invention, it is contemplated that effectively remove the organic component in nano-complex particle and avoid high warm
Situations such as particles sintering and gold nanoparticle are gathered simultaneously when processing, preferably 250 DEG C~500 DEG C of heat treatment temperature, heat treatment time is excellent
Select 0.5h~3h.
About the present invention, inventor has found through further investigation, using the polar solvent of precious metal salt as dispersed phase, low hlb
The non-polar solution of emulsifier is continuous phase, can easily construct reverse phase miniemulsion reaction system.Inorganic precursors are directly added
It in reverse phase miniemulsion, can be migrated by way of dissolving and spreading to polarity droplet surface, it is solidifying that generation colloidal sol-is contacted with water
Glue process.In acid condition, the sol-gel intermediate product of siloxanes has preferable dissolubility in polar solvent, therefore
These intermediate products can enter drop internal.In addition, in acid condition, the positively charged (- (CH of aminoalkyl such as aminopropyl2)3–
NH3 +), therefore the silicon nucleus band positive electricity formed in drop, there are preferable colloidal stability, internuclear poly- and less, the major part of silicon
SiO2Small particles are respectively grown.In general, including a large amount of SiO in particle2Small particles, phase after the reaction, due to SiO2
The size of small particles increases, and interparticle spacing reduces, and is packed together, and by further sol-gel process, is formed
The link of chemical bond ultimately forms the good spherical accumulation body of morphological stability.The form and structure of spherical accumulation body can pass through two
The proportion of class siloxanes regulates and controls, and with the increase of amino silicone content, particle changes from uniform sphere to accumulation form, but works as
When amino silicone content is higher, the form of particle can change again from accumulation form to uniform sphere.The ruler of inorganic nano carrier
It is very little to be determined by the size of initial liquid drop, therefore the size of inorganic nano carrier can pass through emulsifier, precious metal salt dosage, pole
Property solvent and the ratio of nonpolar solvent be conveniently adjusted, for example the ratio by reducing polar solvent and non-polar solution, mention
The methods of high precious metal salt or emulsifier can reduce drop size, and then reduce the size of inorganic nano carrier.
While siloxanes carries out colloidal sol-gel process, the amino-containing siloxanes with certain reproducibility, such as
3- aminopropyl triethoxysilane can occur oxidation-reduction reaction with precious metal salt, precious metal salt is gone back in situ in drop phase
It originally is noble metal nano particles.With the sol-gel process of siloxanes and the completion of precious metal salt reduction reaction, a final step
Directly obtain noble metal/SiO2Nano-complex particle.Due to precious metal salt in polar solvent universal solubility with higher,
Therefore the useful load of precious metal salt can adjust in a wider scope.
Invention further provides noble metal/SiO according to made from the above method2Nano-complex particle and your gold
Category/SiO2Application of the nano-complex particle in p-nitrophenol reduction reaction.Further, reducing agent is NaBH4。
Compared with prior art, the beneficial effects are mainly reflected as follows: the present invention provides one kind by reverse phase it is thin
Emulsion technology, a step simply, efficiently prepare noble metal/SiO2The method of nano-complex particle.Your gold is the method for the present invention prepare
Category/SiO2The advantages of nano-complex particle, is: (1) passing through the adjusting of siloxanes compound proportion, be able to achieve inorganic nano carrier
The transformation of sphere is accumulated from uniform sphere to fine particle；(2) noble metal/SiO made of being accumulated as fine particle2It is nano combined
Particle surface is electrically charged, and there are stronger electrostatic interactions between particle, so that nano-complex particle has good water dispersible；(3)
Catalysis experiments show that the catalyst has high catalytic activity and excellent circulation catalytic capability.In addition, using proposed by the present invention
Technology can control size, size distribution and the pore structure of inorganic nano carrier, noble metal nano particles content, particle well
Size and crystallite dimension etc..Noble metal/SiO that the present invention obtains2Nano-complex particle is at organic reaction catalysis, vehicle exhaust
There is very high application value in the fields such as reason.
(4) Detailed description of the invention
Fig. 1 is 1 gained Au/SiO of embodiment2The transmission electron microscope picture of nano-complex particle.
Fig. 2 is 1 gained Au/SiO of embodiment2The scanning electron microscope (SEM) photograph of nano-complex particle.
(5) specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This:
Embodiment 1:
Emulsifier P (E/B)-PEO2.0g is weighed, is dissolved in 198g hexadecane, obtains emulsifier solution.The block 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 1molL-1Hydrogen-oxygen
Change sodium water solution and the pH of salting liquid is adjusted to 4；Gained chlorauric acid solution is added in mentioned emulsifier solution, will with ultrasonic wave
Above-mentioned mixed liquor dispersion, obtains stable reverse phase miniemulsion.
2.2g methyl orthosilicate and 3.7g 3- aminopropyl triethoxysilane, temperature are added into above-mentioned reverse phase miniemulsion
90 DEG C are risen to, reaction for 24 hours, obtains Au/SiO2The dispersion liquid of nano-complex particle.It is centrifugated, is dried to obtain Au/SiO2Nanometer
The dry powder of compound particle, with 30 DEG C of min in Muffle furnace-1Heating rate be warming up to 500 DEG C of calcining 0.5h, remove organic
Au/SiO is made in object2Nano-complex particle.
X-ray diffraction test confirms that Au salt is successfully reduced to Au nanoparticle.Transmission and scanning electron microscope are equal
Showing that nano-complex particle has apparent packed structures, Au nanoparticle is mainly distributed on the surface of compound particle, wherein
SiO2The number average bead diameter of nano-carrier is 299nm, and the number average bead diameter of Au nanoparticle is 9.0nm.With NaBH4Restore p-nitrophenyl
The reaction of phenol (p-NPH) is model reaction, tests Au/SiO2The catalytic performance of nano-complex particle, as a result, it has been found that the catalysis
The relative reaction rate constant k of agentrFor 5.4 s-1·Au-mmol-1, embodied high catalytic activity；It is aobvious to repeat Catalysis experiments
After showing that the catalyst is reused 30 times, catalytic activity, which has no, to be decreased obviously.krCalculation formula be kr=Nka N pp M, wherein
kappAnd NNMThe respectively mole of apparent reaction rate constant and noble metal.
Embodiment 2:
Emulsifier Si Pan -808.1g is weighed, 45g isoparaffin IsoparM (ExonMobil) is dissolved in, it is molten to obtain emulsifier
Liquid.
0.1g silver nitrate is dissolved in 1g water, then uses 1molL-1Aqueous solution of urea the pH of salting liquid is adjusted to 6；Institute
It obtains silver nitrate solution to be added in mentioned emulsifier solution, above-mentioned mixed liquor is dispersed with ultrasonic wave, it is thin to obtain stable reverse phase
Lotion.
3.0g ethyl orthosilicate and 0.4g 3- aminopropyl triethoxysilane, temperature are added into above-mentioned reverse phase miniemulsion
60 DEG C are risen to, 3d is reacted, obtains Ag/SiO2Nano-complex particle dispersion liquid.It is centrifugated, is dried to obtain Ag/SiO2It is nano combined
The dry powder of particle, with 15 DEG C of min in Muffle furnace-1Heating rate be warming up to 350 DEG C, calcine 2h, remove organic matter, system
Obtain Ag/SiO2Nano-complex particle.
X-ray diffraction test confirms that silver nitrate is successfully reduced to Ag nanoparticle.Transmission and scanning electron microscope
Showing that nano-complex particle has apparent packed structures, Ag nanoparticle is mainly distributed on the surface of compound particle, wherein
SiO2The number average bead diameter of nano-carrier is 210nm, and the number average bead diameter of Ag nanoparticle is 18nm.With NaBH4Restore the anti-of p-NPH
It should be model reaction, test Ag/SiO2The catalytic performance of nano-complex particle, as a result, it has been found that the relative response speed of the catalyst
Rate constant krFor 4.2s-1·Ag-mmol-1, embodied high catalytic activity；It repeats Catalysis experiments and shows that the catalyst repeats to make
After 30 times, catalytic activity, which has no, to be decreased obviously.
Embodiment 3:
Emulsifier Si Pan -8513g and OP-1013g are weighed, 260g hexadecane is dissolved in, obtains emulsifier solution.
0.17g potassium chloroplatinate is dissolved in the mixed solution of 4g water and 30g dimethylformamide composition, then is used
0.5mol·L-1The pH of potassium chloroplatinate solution is adjusted to 3 by hydrochloric acid；Gained potassium chloroplatinate solution is added to mentioned emulsifier solution
In, above-mentioned mixed liquor is dispersed with ultrasonic wave, obtains stable reverse phase miniemulsion.
1g methyl orthosilicate is added into above-mentioned reverse phase miniemulsion and 13g 3- aminopropyl triethoxysilane, temperature rise to
110 DEG C, 6h is reacted, Pt/SiO is obtained2Nano-complex particle dispersion liquid.It is centrifugated, is dried to obtain Pt/SiO2Nano combined grain
The dry powder of son, with 5 DEG C of min in Muffle furnace-1Heating rate be warming up to 450 DEG C, calcine 1h, remove organic matter, be made
Pt/SiO2Nano-complex particle.
X-ray diffraction test confirms that potassium chloroplatinate is successfully reduced to Pt nanoparticle.Transmission and scanning electron microscopy
Mirror shows that nano-complex particle has apparent packed structures, and Pt nanoparticle is mainly distributed on the surface of compound particle,
Middle SiO2The number average bead diameter of nano-carrier is 320nm, and the number average bead diameter of Pt nanoparticle is 7.8nm.With NaBH4Restore p-NPH's
Reaction is model reaction, tests Pt/SiO2The catalytic performance of nano-complex particle, as a result, it has been found that the relative response of the catalyst
Rate constants krFor 6.5s-1·Pt-mmol-1, embodied high catalytic activity；It repeats Catalysis experiments and shows that the catalyst repeats
After 30 times, catalytic activity, which has no, to be decreased obviously.
Embodiment 4:
8.6g Si Pan -80 and 8.6gOP-10 are weighed as emulsifier, 123g hexadecane is dissolved in, obtains emulsifier solution.
10.5g potassium chloropalladite is dissolved in the mixed solution of 1.5g water and 36g dimethylformamide composition, then is used
0.5mol·L-1The pH of potassium chloropalladite solution is adjusted to 3 by hydrochloric acid；Gained potassium chloropalladite solution is added to mentioned emulsifier
In solution, above-mentioned mixed liquor is dispersed with ultrasonic wave, obtains stable reverse phase miniemulsion.
15g ethyl orthosilicate and 25g 3- aminopropyl triethoxysilane, temperature liter are added into above-mentioned reverse phase miniemulsion
To 120 DEG C, 5h is reacted, Pd/SiO is obtained2Nano-complex particle dispersion liquid.It is centrifugated, is dried to obtain Pd/SiO2It is nano combined
The dry powder of particle, with 30 DEG C of min in Muffle furnace-1Heating rate be warming up to 400 DEG C of calcining 45min, remove organic matter, system
Obtain Pd/SiO2Nano-complex particle.
X-ray diffraction test confirms that potassium chloropalladite is successfully reduced to Pd nanoparticle.Transmission and scanning electron are aobvious
Micro mirror shows that nano-complex particle has apparent packed structures, and Pd nanoparticle is mainly distributed on the surface of compound particle,
Wherein SiO2The number average bead diameter of nano-carrier is 275nm, and the number average bead diameter of Pd nanoparticle is 12nm.With NaBH4Restore p-NPH
Reaction be model reaction, test Pd/SiO2The catalytic performance of nano-complex particle, as a result, it has been found that the catalyst is relatively anti-
Answer rate constants krFor 6.2s-1·Pd-mmol-1, embodied high catalytic activity；It repeats Catalysis experiments and shows the catalyst weight
Again using after 30 times, catalytic activity, which has no, to be decreased obviously.
Claims (10)
1. an a kind of step prepares noble metal/SiO2The method of nano-complex particle, the described method comprises the following steps:
(1) emulsifier of low hydrophile-lipophile balance value is dissolved in nonpolar solvent, wherein emulsifier quality dosage is that nonpolarity is molten
The 0.1%~20% of agent quality, obtains emulsifier solution；The emulsifier of the low hydrophile-lipophile balance value be selected from it is following at least
It is a kind of: this Pan's series emulsifier, twain series emulsifier, OP-10, the block copolymer emulsification being made of hydrophilic and hydrophobic section
Agent；
(2) precious metal salt is dissolved in polar solvent, wherein the mass ratio of precious metal salt and polar solvent is 0.001~1:1,
PH value is transferred in the range of 2~6 with pH adjusting agent again；Then above-mentioned precious metal salt solution is added to cream made from step (1)
In agent solution, the mass ratio for controlling nonpolar solvent and polar solvent is 2~50:1, is dispersed and obtains reverse phase miniemulsion；Institute
State precious metal salt be selected from following at least one: gold chloride, bromination gold salt, chlorine (trimethyl-phosphine) gold, potassium chloropalladite, palladium acetate,
Silver nitrate, silver tetrafluoroborate, potassium chloroplatinate, platinum chloride；The polar solvent is the mixing of water or water and polar organic solvent
Solvent, wherein the ratio between quality dosage of polar organic solvent and water is 0~50:1；The pH adjusting agent is selected from following at least one
Kind: hydrochloric acid, sulfuric acid, acetic acid, phosphoric acid, urea, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium bicarbonate, Boratex, ammonium hydroxide；
(3) tetraalkoxysilane that compounding is added in the reverse phase miniemulsion obtained to step (2) is mixed with amino-containing siloxanes
Liquid, in the tetraalkoxysilane of compounding and amino-containing siloxanes mixed liquor the mass fraction of amino-containing siloxanes be 5%~
95%, the tetraalkoxysilane of compounding and the ratio between the mole dosage of amino-containing siloxanes mixed liquor and water in reverse phase miniemulsion are
0.1~4:1, and make the amino-containing siloxanes of reducing agent that can be used to restore precious metal salt in mixed system and precious metal salt
The ratio between mole dosage be 2~200:1；After mixing the temperature was then adjusted to 50 DEG C~150 DEG C, 1h~5d is reacted, in silicon oxygen
While alkane carries out total sol-gel process, precious metal salt is reduced to noble metal nano particles by amino-containing siloxanes；
(4) it is put into Muffle furnace after drying the product that step (3) obtains, with 2 DEG C of min-1~30 DEG C of min-1Heating speed
Rate rises to 200 DEG C~800 DEG C, and 10min~10h is heat-treated under air atmosphere and removes organic matter, obtains noble metal/SiO2Nanometer is multiple
Close particle.
2. the method as described in claim 1, it is characterised in that: in step (1), the nonpolar solvent is selected from following at least one
Kind: the acyclic straight alkane of C6~C20, the cycloalkane of C6~C20, the alkylbenzene containing 1~3 C1~C4 alkyl.
3. the method as described in claim 1, it is characterised in that: in step (2), polar organic solvent is dimethyl sulfoxide, two
The mixing of one or more of methylformamide, ethylene glycol, ethyl alcohol, tetrahydrofuran.
4. the method as described in claim 1, it is characterised in that: in step (3), the structure of the tetraalkoxysilane such as formula
(I) shown in, the structure such as formula (II) of the amino-containing siloxanes is such as shown:
In formula (I): R1~R4Respectively to stand alone as C1~C5Alkyl；
In formula (II): R5~R7Respectively to stand alone as C1~C5Alkyl；R8For C1~C5Aminoalkyl.
5. method as claimed in claim 4, it is characterised in that: the amino-containing siloxanes is 3- aminopropyl-triethoxy silicon
Alkane；The tetraalkoxysilane is ethyl orthosilicate or methyl orthosilicate.
6. the method as described in claim 1, it is characterised in that: in step (1), the quality dosage of emulsifier is nonpolar solvent
The 1%~18% of quality；In step (2), the ratio between quality dosage of precious metal salt and polar solvent is 0.005~0.3:1, non-pole
Property solvent and polar solvent quality dosage ratio be 2.5~45:1；In step (3), the tetraalkoxysilane of compounding with contain ammonia
In the siloxanes mixed liquor of base, the mass fraction of amino-containing siloxanes is 10%~90%, the tetraalkoxysilane of compounding with
The ratio between mole dosage of water is 0.2~2.5:1, amino-containing siloxanes in amino-containing siloxanes mixed liquor and reverse phase miniemulsion
It is 3~168:1 with the ratio between the mole dosage of precious metal salt.
7. the method as described in claim 1, it is characterised in that: in step (3), the temperature of reaction system is 60 DEG C~120 DEG C.
8. method as claimed in claim 1 or 7, it is characterised in that: in step (4), heat treatment temperature is 250 DEG C~500 DEG C,
Heat treatment time is 0.5h~3h.
9. noble metal/SiO made from the method according to claim 112Nano-complex particle.
10. noble metal/SiO as claimed in claim 92Application of the nano-complex particle in p-nitrophenol reduction reaction.
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| CN102436886A (en) * | 2011-12-14 | 2012-05-02 | 吉林大学 | Method for preparing gold-coated magnetic composite nanoparticles |
| CN103551146A (en) * | 2013-09-10 | 2014-02-05 | 杭州师范大学 | Precious metal-titanium dioxide nanocomposite particle preparation method |
| CN104858413A (en) * | 2014-02-21 | 2015-08-26 | 中国科学院大连化学物理研究所 | Preparation method of silicon-dioxide-carried precious metal nanoparticles |
| CN105153453A (en) * | 2015-07-01 | 2015-12-16 | 安徽大学 | Nano-copper/polymer hollow composite microsphere and preparation method thereof |
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| CN102436886A (en) * | 2011-12-14 | 2012-05-02 | 吉林大学 | Method for preparing gold-coated magnetic composite nanoparticles |
| CN103551146A (en) * | 2013-09-10 | 2014-02-05 | 杭州师范大学 | Precious metal-titanium dioxide nanocomposite particle preparation method |
| CN104858413A (en) * | 2014-02-21 | 2015-08-26 | 中国科学院大连化学物理研究所 | Preparation method of silicon-dioxide-carried precious metal nanoparticles |
| CN105153453A (en) * | 2015-07-01 | 2015-12-16 | 安徽大学 | Nano-copper/polymer hollow composite microsphere and preparation method thereof |
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