CN106345458A - Mesoporous carbon-silicon dioxide complex loaded nano-palladium catalyst and synthesis method thereof - Google Patents
Mesoporous carbon-silicon dioxide complex loaded nano-palladium catalyst and synthesis method thereof Download PDFInfo
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- CN106345458A CN106345458A CN201610711837.6A CN201610711837A CN106345458A CN 106345458 A CN106345458 A CN 106345458A CN 201610711837 A CN201610711837 A CN 201610711837A CN 106345458 A CN106345458 A CN 106345458A
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 69
- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- VSTOHTVURMFCGL-UHFFFAOYSA-N [C].O=[Si]=O Chemical compound [C].O=[Si]=O VSTOHTVURMFCGL-UHFFFAOYSA-N 0.000 title abstract 3
- 238000001308 synthesis method Methods 0.000 title abstract 3
- 239000000243 solution Substances 0.000 claims abstract description 96
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 73
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 72
- 239000010703 silicon Substances 0.000 claims abstract description 72
- 239000004094 surface-active agent Substances 0.000 claims abstract description 44
- 239000002253 acid Substances 0.000 claims abstract description 30
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 22
- 239000007787 solid Substances 0.000 claims abstract description 22
- 239000003960 organic solvent Substances 0.000 claims abstract description 21
- 239000002243 precursor Substances 0.000 claims abstract description 15
- 238000003837 high-temperature calcination Methods 0.000 claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 13
- 239000002105 nanoparticle Substances 0.000 claims abstract description 13
- 150000002940 palladium Chemical class 0.000 claims abstract description 13
- 238000000034 method Methods 0.000 claims abstract description 12
- 239000011148 porous material Substances 0.000 claims abstract description 10
- 239000012266 salt solution Substances 0.000 claims abstract description 7
- 229910052751 metal Inorganic materials 0.000 claims abstract description 6
- 239000002184 metal Substances 0.000 claims abstract description 6
- 239000002245 particle Substances 0.000 claims abstract description 4
- 238000000605 extraction Methods 0.000 claims description 35
- 239000000377 silicon dioxide Substances 0.000 claims description 35
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 35
- 238000006243 chemical reaction Methods 0.000 claims description 27
- 239000002736 nonionic surfactant Substances 0.000 claims description 21
- -1 poly(ethylene oxide) Polymers 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 18
- 238000010189 synthetic method Methods 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 16
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 claims description 15
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 15
- 229920001568 phenolic resin Polymers 0.000 claims description 15
- 239000005011 phenolic resin Substances 0.000 claims description 15
- 238000010992 reflux Methods 0.000 claims description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 238000001354 calcination Methods 0.000 claims description 13
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 12
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 11
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 9
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 8
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 8
- 239000012279 sodium borohydride Substances 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 7
- 239000012298 atmosphere Substances 0.000 claims description 6
- 238000003763 carbonization Methods 0.000 claims description 6
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims description 6
- NBXZNTLFQLUFES-UHFFFAOYSA-N triethoxy(propyl)silane Chemical compound CCC[Si](OCC)(OCC)OCC NBXZNTLFQLUFES-UHFFFAOYSA-N 0.000 claims description 6
- 238000010792 warming Methods 0.000 claims description 6
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 5
- FDNAPBUWERUEDA-UHFFFAOYSA-N silicon tetrachloride Chemical compound Cl[Si](Cl)(Cl)Cl FDNAPBUWERUEDA-UHFFFAOYSA-N 0.000 claims description 5
- 229920001451 polypropylene glycol Polymers 0.000 claims description 4
- 229920000428 triblock copolymer Polymers 0.000 claims description 4
- 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 claims description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 3
- 239000000460 chlorine Substances 0.000 claims description 3
- 229910052801 chlorine Inorganic materials 0.000 claims description 3
- 229920000359 diblock copolymer Polymers 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 229910052717 sulfur Inorganic materials 0.000 claims description 3
- 239000011593 sulfur Substances 0.000 claims description 3
- XXZNHVPIQYYRCG-UHFFFAOYSA-N trihydroxy(propoxy)silane Chemical compound CCCO[Si](O)(O)O XXZNHVPIQYYRCG-UHFFFAOYSA-N 0.000 claims description 3
- YUYCVXFAYWRXLS-UHFFFAOYSA-N trimethoxysilane Chemical compound CO[SiH](OC)OC YUYCVXFAYWRXLS-UHFFFAOYSA-N 0.000 claims description 3
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 claims description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 claims 1
- 239000011261 inert gas Substances 0.000 claims 1
- 230000001590 oxidative effect Effects 0.000 claims 1
- YGCZTXZTJXYWCO-UHFFFAOYSA-N 3-phenylpropanal Chemical compound O=CCCC1=CC=CC=C1 YGCZTXZTJXYWCO-UHFFFAOYSA-N 0.000 abstract description 9
- KJPRLNWUNMBNBZ-QPJJXVBHSA-N (E)-cinnamaldehyde Chemical compound O=C\C=C\C1=CC=CC=C1 KJPRLNWUNMBNBZ-QPJJXVBHSA-N 0.000 abstract description 5
- 238000005984 hydrogenation reaction Methods 0.000 abstract description 3
- 239000012736 aqueous medium Substances 0.000 abstract description 2
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 238000002360 preparation method Methods 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 abstract 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 27
- 239000000463 material Substances 0.000 description 26
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 17
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 9
- 239000000376 reactant Substances 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- 238000002441 X-ray diffraction Methods 0.000 description 8
- 238000003786 synthesis reaction Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 238000001291 vacuum drying Methods 0.000 description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 6
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- 239000013335 mesoporous material Substances 0.000 description 6
- 229910052756 noble gas Inorganic materials 0.000 description 6
- 150000002835 noble gases Chemical class 0.000 description 6
- 229920000642 polymer Polymers 0.000 description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 6
- 238000013019 agitation Methods 0.000 description 5
- 239000011521 glass Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 238000006116 polymerization reaction Methods 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 229940117916 cinnamic aldehyde Drugs 0.000 description 4
- KJPRLNWUNMBNBZ-UHFFFAOYSA-N cinnamic aldehyde Natural products O=CC=CC1=CC=CC=C1 KJPRLNWUNMBNBZ-UHFFFAOYSA-N 0.000 description 4
- 239000000284 extract Substances 0.000 description 4
- ZWINLZAYDMUOAE-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-(2-hexadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical group CCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO ZWINLZAYDMUOAE-UHFFFAOYSA-N 0.000 description 3
- HNUQMTZUNUBOLQ-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-(2-octadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO HNUQMTZUNUBOLQ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- AXMVYSVVTMKQSL-UHFFFAOYSA-N UNPD142122 Natural products OC1=CC=C(C=CC=O)C=C1O AXMVYSVVTMKQSL-UHFFFAOYSA-N 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 239000012535 impurity Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000010926 purge Methods 0.000 description 3
- 239000002210 silicon-based material Substances 0.000 description 3
- 238000013022 venting Methods 0.000 description 3
- JKXYOQDLERSFPT-UHFFFAOYSA-N 2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-[2-(2-octadecoxyethoxy)ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethoxy]ethanol Chemical compound CCCCCCCCCCCCCCCCCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO JKXYOQDLERSFPT-UHFFFAOYSA-N 0.000 description 2
- DCQBZYNUSLHVJC-UHFFFAOYSA-N 3-triethoxysilylpropane-1-thiol Chemical group CCO[Si](OCC)(OCC)CCCS DCQBZYNUSLHVJC-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 235000013339 cereals Nutrition 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 238000009396 hybridization Methods 0.000 description 2
- UKVIEHSSVKSQBA-UHFFFAOYSA-N methane;palladium Chemical compound C.[Pd] UKVIEHSSVKSQBA-UHFFFAOYSA-N 0.000 description 2
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000001338 self-assembly Methods 0.000 description 2
- 125000003396 thiol group Chemical group [H]S* 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 125000001309 chloro group Chemical group Cl* 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- CWAFVXWRGIEBPL-UHFFFAOYSA-N ethoxysilane Chemical compound CCO[SiH3] CWAFVXWRGIEBPL-UHFFFAOYSA-N 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 239000010931 gold Substances 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 125000000962 organic group Chemical group 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920003987 resole Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229910052814 silicon oxide Inorganic materials 0.000 description 1
- 238000000935 solvent evaporation Methods 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 238000005292 vacuum distillation Methods 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
- B01J23/40—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
-
- B01J35/393—
-
- B01J35/50—
-
- B01J35/617—
-
- B01J35/635—
-
- B01J35/647—
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
- B01J37/086—Decomposition of an organometallic compound, a metal complex or a metal salt of a carboxylic acid
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/62—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by hydrogenation of carbon-to-carbon double or triple bonds
Abstract
The invention relates to a mesoporous carbon-silicon dioxide complex loaded nano-palladium catalyst and a synthesis method thereof. The specific surface area of the catalyst is 400 to 700 m<2>/g, the pore volume is 0.30 to 0.90 cm<3>/g, the pore diameter is 4.0 to 7.0 nm, the percentage content of metal Pd is 1 to 10 wt%, and the particle size of Pd nanoparticles is 3.0 to 8.0 nm. During preparation, a surfactant is dissolved into an organic solvent to obtain a solution A; a silicon source is added into an acid solution and prehydrolysis is conducted to obtain a solution B; the solution A and the solution B are mixed and stirred uniformly, then a soluble carbon source is added, and the organic solvent is volatilized to obtain a carrier precursor; and the carrier precursor and a palladium salt solution containing a reducing agent are mixed and fixed, solid is remained, and high-temperature calcination is conducted to obtain the catalyst. Compared with the prior art, the mesoporous carbon-silicon dioxide complex loaded nano-palladium catalyst and the synthesis method thereof have the advantages that the method is simple to operate and low in cost; and the catalyst can be applied to aqueous medium catalysis of cinnamyl aldehyde selective hydrogenation reduction reaction to produce 3-benzenepropanal, and has a good application prospect.
Description
Technical field
The invention belongs to mesoporous material preparing technical field, it is related to a kind of catalyst and its synthetic method, especially relates to
A kind of mesoporous carbon-silica complex loaded nanometer palladium catalyst and its synthetic method.
Background technology
Palladium catalyst is a kind of important catalyst for hydrogenation, extensively should be produced in organic synthesiss and fine chemicals
In.Palladium carbon is extensive applicable industry catalyst.But due to material with carbon element originally as the adhesion between inert carrier, and palladium relatively
Weak, in course of reaction, catalyst haves such problems as Metal Palladium loss, reunion, easy poisoning and deactivation.Therefore, study a kind of structure steady
Fixed, low cost palladium catalyst replaces traditional palladium-carbon catalyst significant.
Ordered mesoporous material has a higher specific surface area, larger pore volume, homogeneous aperture, can be widely applied to
The fields such as absorption, catalysis and separation.Palladium nano-particles are stablized for carrier with ordered mesoporous material, can be above-mentioned not with effectively solving
Foot, its development has caused extensive concern.Loading palladium nano-particles for carrier by back loading mode with ordered mesoporous material is
Prepare a kind of traditional method of metallic catalyst.But the method has obvious limitation, for example, back loading process easily causes carrier
Structural deterioration；Palladium nano-particles are easily enriched with aperture, the engagement capacity of palladium avtive spot and adsorbed material in impact duct；Carry
Between body and palladium, adhesion is weak, leads to that metal particle size is larger, skewness, is easy to run off in course of reaction.Synthesize organic work(
The hybridization mesoporous material of energyization can in hole surface and duct space functionalization, combination stronger between functional group and palladium makees
With disperseing during catalyst high temperature cabonization, stablize palladium species, final catalyst has palladium nano-particles and highly divides
Stability scattered, that size is less and higher.
Content of the invention
The purpose of the present invention is exactly that palladium is received in order to overcome the defect of above-mentioned prior art presence to provide a kind of high-sequential
Rice grain particle diameter distribution is homogeneous, the mesoporous carbon-silica complex loaded nanometer palladium catalyst of stable performance.
It is a further object of the present invention to provide a kind of step is simple, controllability is good, low cost, it is easy to accomplish extensive
The synthetic method of the mesoporous carbon-silica complex loaded nanometer palladium catalyst producing.
The purpose of the present invention can be achieved through the following technical solutions:
Mesoporous carbon-silica complex loaded nanometer palladium catalyst, this catalyst has orderly two dimension six side Jie and sees
Structure, specific surface area is 400-700m2/ g, pore volume is 0.30-0.90cm3/ g, aperture is 4.0-7.0nm, and the percentage of metal pd contains
Measure as 1-10wt%, the particle diameter of pd nano-particle is 3.0-8.0nm.
The synthetic method of mesoporous carbon-silica complex loaded nanometer palladium catalyst, the method specifically includes following step
Rapid:
(1) surfactant is dissolved in organic solvent, obtained solution a；
(2) silicon source is added in acid solution, through prehydrolysis, obtained solution b；
(3) solution a is mixed with solution b, stir, controlling reaction temperature is 20-40 DEG C, the response time is 0.5-2
Hour, add the carbon source of solubility, react 10 minutes -6 hours at 20-40 DEG C, organic solvent is volatilized, obtains in the middle of solid
Thing；
(4) solid intermediate is carried out low temperature thermosetting reaction, reaction temperature is 80-120 DEG C, the response time is that 12-36 is little
When, after question response terminates, use acid solution reflux extraction, in order to remove surfactant, prepared support precursor；
(5) support precursor is mixed with the palladium salt solution containing reducing agent, filter, retain solid, then at noble gases
High-temperature calcination under atmosphere, through carbonization, reduction, that is, is obtained mesoporous carbon-silica complex loaded nanometer palladium catalyst.
Surfactant described in step (1) is nonionic surfactant, and this nonionic surfactant is in solution a
Weight/mass percentage composition be 0.5-25%, preferably 10-25%.
Described organic solvent includes c1-c4Alcohols, benzene, toluene, oxolane, chloroform, in dichloromethane or ether
One or more.
Preferably, described c1-c4Alcohols include methanol, ethanol, normal propyl alcohol or n-butyl alcohol.
Described organic solvent is preferably oxolane, ethanol or ether.
Described nonionic surfactant includes poly(ethylene oxide)-poly(propylene oxide) triblock copolymer or alkane-poly-
One of oxirane diblock copolymer or two kinds.
Described poly(ethylene oxide)-poly(propylene oxide) triblock copolymer or alkane-poly(ethylene oxide) diblock copolymer,
Its formula can use cah2a+1eob、eocpodeocRepresent, wherein a numerical range is 10-18, b numerical range is 5-25, c numerical value
Scope is 5-135, and d numerical range is 25-135.
Preferably, described nonionic surfactant is selected from brij56 (c16h33eo10)、brij76(c18h37eo10)、
brij78(c16h33eo20)、p123(eo20po70eo20)、f127(eo106po70eo106) or f108 (eo132po50eo132) in one
Plant or several.Above surfactant can obtain from basf or sigma-aldrich.
In silicon source described in step (2), silicon and the mol ratio of water in acid solution are 1:2-10, the solubility described in step (3)
The mol ratio of carbon source and silicon source be 0.1-0.6:1.
Described silicon source is mixed for 0-5:1 with organic silicon source in molar ratio by inorganic silicon source, and described organic
Silicon source is 10-53:1 with the mol ratio of surfactant.
Preferably, described silicon source is mixed for 0.5-5:1 with organic silicon source in molar ratio by inorganic silicon source.
Described inorganic silicon source includes one of tetraethyl orthosilicate, methyl silicate, Silicon chloride. or positive silicic acid propyl ester
Or multiple, described organic silicon source is organic silicon source of sulfur-bearing, including 3-mercaptopropyi trimethoxy silane, 3- mercaptopropyi three
One of Ethoxysilane, double (triethoxy propyl silane) tetrasulfide or double (triethoxy propyl silane) disulphide
Or it is multiple.
The carbon source of the solubility described in step (3) is the phenolic resin of 200-5000 for relative molecular mass, step (4) institute
The reducing agent stated includes one of sodium borohydride or potassium borohydride or two kinds, and described palladium salt includes chlorine palladium acid sodium or Palladous chloride.
One of or two kinds.
Preferably, described phenolic resin is resol.
Described acid solution is the hydrochloric acid solution of 0.1-0.5mol/l for molar concentration.
The condition of the acid solution reflux extraction described in step (4) is: using the sulphuric acid for 40-60% for the weight/mass percentage composition
Solution reflux extraction, removes surfactant, controls extraction temperature to be 80-100 DEG C, and extraction time is 12-48 hour；
The condition of the high-temperature calcination described in step (5) is: control heating rate is 1-5 DEG C/min, is warming up to 350-900
DEG C, calcining at constant temperature 2-5 hour.
Described noble gases are nitrogen or argon.
The present invention utilizes solvent evaporation induced self-assembly technology, is structure directing agent using surfactant, using organic
Silicon source and inorganic silicon source and soluble resin (i.e. carbon source) carry out the mesoporous high score of self assembly with nonionic surfactant
Sub- polymer, then through reflux extraction or low temperature calcination, obtain organic group functionized ordered mesoporous polymer material；Then pass through
The method of back loading introduces Metal Palladium in this material.Specifically, for example, the present invention with phenolic resin as carbon source, 3- sulfydryl
Propyl trimethoxy silicane is originated for organo-functional group, and tetraethyl orthosilicate is inorganic silicon source, poly(ethylene oxide)-poly(propylene oxide) three
Block copolymer is template, prepares mercapto-functionalized ordered mesoporous polymer-silicon oxide by the method for polynary assembling altogether multiple
Condensation material, is further loaded to pd on mesoporous polymer using pd-s coordination, receives through high-temperature calcination in-situ reducing pd
Rice grain obtains mesoporous carbon-silica complex loaded nanometer palladium catalyst.
Compared with prior art, the invention has the characteristics that:
1) the mercapto-functionalized hybridization mesoporous material of present invention synthesis can introduce a large amount of mercaptos in hole surface and duct space
Base, using stronger combination between mercapto groups and palladium, can disperse during catalyst high temperature cabonization, stablize gold thing
Kind, acquisition palladium nano-particles high degree of dispersion, the palladium catalyst that size is less and stability is high；
2) present invention utilizes sulfydryl and palladium coordination back loading palladium nano-particles, and the mesoporous carbon-silica of synthesis is multiple
Fit loaded nanometer palladium catalyst has two dimension six side's mesoscopic structure of high-sequential, metal pd content height (1-10wt%), pd
Nanoparticle size little (3.0-8.0nm), the big (400-700m of specific surface area2/ g), the big (0.30-0.90cm of pore volume3/ g), aperture
Homogeneous (4.0-7.0nm)；
3) present invention is simple to operate, low cost, and it is anti-that catalyst can be used for aqueous medium spirit catalytic of cinnamaldehyde selective hydrogenation reduction
3-phenylpropion aldehyde should be generated, there is good application prospect.
Brief description
Fig. 1 is characteristic x-ray diffraction (xrd) spectrogram of the polymer earth silicon material prepared by embodiment 3；
Fig. 2 is the nitrogen adsorption-desorption isotherm figure of the polymer earth silicon material material prepared by embodiment 3；
Fig. 3 is the characteristic x-ray diffraction of the mesoporous carbon-silica material load palladium catalyst prepared by embodiment 4
(xrd) spectrogram；
Fig. 4 is the transmission electron microscope of mesoporous carbon-silica material load palladium catalyst prepared by embodiment 4
(tem) figure；
Fig. 5 is the characteristic x-ray diffraction of the mesoporous carbon-silica material load palladium catalyst prepared by embodiment 5
(xrd) spectrogram；
Fig. 6 is the characteristic x-ray diffraction of the mesoporous carbon-silica material load palladium catalyst prepared by embodiment 6
(xrd) spectrogram.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention
Premised on implemented, give detailed embodiment and specific operating process, but protection scope of the present invention be not limited to
Following embodiments.For example, ethanol or ether can with methanol, normal propyl alcohol, n-butyl alcohol, oxolane, benzene, toluene, chloroform or
Dichloromethane replaces；Surfactant is p123 (eo20po70eo20) it is also possible to brij76 (c18h37eo10)brij56
(c16h33eo10)、f127(eo106po70eo106) or f108 (eo132po50eo132) replace.Above-mentioned surfactant can from basf or
Sigma-aldrich obtains.
Embodiment 1
The preparation of novolak resin precursor liquid solution.6.0g phenol is put in three-neck flask, 50 DEG C of heating in water bath are so as to be in
Transparency liquid；Prepare the sodium hydroxide solution 3.70g that mass percent is 20%, slowly instill in this liquid.After 10 minutes, plus
Enter formalin 15.0g that weight/mass percentage composition is 37%, 90 DEG C are flowed back 1 hour, are cooled to room temperature, adjust ph to neutrality.?
Vacuum distillation under the conditions of 45～50 DEG C, acquisition residue is target product phenolic resin.After being cooled to room temperature, it is made into quality respectively
Percentage concentration is the ethanol of phenolic resin performed polymer of 20～45wt% or diethyl ether solution is standby.
Embodiment 2
At 40～60 DEG C, the f127 surfactant of 2.0g is dissolved in 10.0g ethanol solution, subsequent Deca mass fraction
For 36.5% hydrochloric acid solution 1.0g, stir prehydrolysis 1 hour, then sequentially add 1.4g tetraethyl orthosilicate, the organic silicon source of 0.6g
With the phenolic resin of synthesis in 20wt% embodiment 1, magnetic agitation 4 hours.Obtain water white settled solution.Will be above-mentioned molten
Liquid is uniformly layered on glass culture dish surface, places 2 hours, afterwards, temperature is risen to 100 DEG C of hot polymerizations 24 hours under room temperature, takes out
Flaxen transparent membrane is scraped, i.e. preformed material.
Embodiment 3
At 40～60 DEG C, the f127 surfactant of 2.0g is dissolved in 10.0g ethanol solution, subsequent Deca mass fraction
For 36.5% hydrochloric acid solution 1.0g, stir prehydrolysis 1 hour, then sequentially add 1.4g tetraethyl orthosilicate, the organic silicon source of 0.6g
With the phenolic resin of synthesis in 20wt% embodiment 1, magnetic agitation 4 hours.Obtain water white settled solution.Will be above-mentioned molten
Liquid is uniformly layered on glass culture dish surface, places 2 hours, afterwards, temperature is risen to 100 DEG C of hot polymerizations 24 hours under room temperature, takes out
Flaxen transparent membrane is scraped, i.e. preformed material.
Preformed material is removed surfactant in 24 hours with sulfuric acid solution stirring extraction by 90 DEG C, extracts two to four times, takes out
Filter, is then dried overnight in 80 DEG C of vacuum drying ovens.
The material obtaining is polymer earth silicon material.This material has the structure (space group of two-dimentional six sides
P6mm), aperture 7.2nm, pore volume is 0.63cm3/ g, specific surface area 326m2/g.
Its characteristic x-ray diffraction (xrd) collection of illustrative plates is as shown in Figure 1.
Its nitrogen adsorption-desorption isotherm figure is as shown in Figure 2.
Embodiment 4
At 40～60 DEG C, the f127 surfactant of 2.5g is dissolved in 10.0g ethanol solution, subsequent Deca mass fraction
For 36.5% hydrochloric acid solution 1.0g, stir prehydrolysis 1 hour, then sequentially add 1.8g tetraethyl orthosilicate, the organic silicon source of 0.7g
With the phenolic resin of synthesis in 20wt% embodiment 1, magnetic agitation 4 hours.Obtain water white settled solution.Will be above-mentioned molten
Liquid is uniformly layered on glass culture dish surface, places 2 hours, afterwards, temperature is risen to 100 DEG C of hot polymerizations 24 hours under room temperature, takes out
Flaxen transparent membrane is scraped, i.e. preformed material.
Preformed material is removed surfactant in 24 hours with sulfuric acid solution stirring extraction by 90 DEG C, extracts two to four times, takes out
Filter, is then dried overnight in 80 DEG C of vacuum drying ovens.
Weigh the above-mentioned solid sample of 0.4g to be placed in moderate beaker, add 3.4ml palladium solution (1g/100ml).Sealing
Place it in constant temperature oscillator, shake uniformly under room temperature.It is proportionally added into sodium borohydride solution after taking-up, continuously add constant temperature
Half an hour is shaken up in agitator.Then take out and be placed on indoor solvent flashing, after solvent is evaporated completely, be placed in 80 in vacuum drying oven
DEG C slough the moisture and other absorption impurity in sample surfaces.Then this sample is placed in calcining in tube furnace, 600 DEG C of calcinings 2
Hour.
The material obtaining is mesoporous carbon-silica material load palladium catalyst.There is the structure (space of two-dimentional six sides
Group p6mm), aperture 6.3nm, pore volume is 0.67cm3/ g, specific surface area 629m2/ g, the load capacity of palladium is 2wt%, pd nano-particle
A size of 4nm.
Its characteristic x-ray diffraction (xrd) collection of illustrative plates is as shown in Figure 3.
Its transmission electron microscope figure (tem) is as shown in Figure 4.
15mg palladium catalyst agent is placed in 25ml autoclave, thereto cinnamic aldehyde (0.52g, 4mmol) successively,
10ml water is as solvent.Tighten reactor, be passed through hydrogen into it, (hydrogen after processing for 6 times through overshoot-venting body purge process
Pressure reach 0.8mpa), finally control autoclave in pressure be 1mpa (room temperature pressure), then reactor is placed in
Under oil bath environment, rise high-temperature to 120 DEG C of beginning stirring reactions.After reaction terminates, it is cooled to room temperature, add in reactant liquor
The reactant liquor of residual and catalyst on 5ml alcohol flushing kettle.With gas chromatograph, reactant liquor is analyzed, obtains 3-phenylpropion aldehyde
Yield be 80%.
Embodiment 5
At 40～60 DEG C, the f127 surfactant of 2.0g is dissolved in 10.0g ethanol solution, subsequent Deca mass fraction
For 36.5% hydrochloric acid solution 1.0g, stir prehydrolysis 1 hour, then sequentially add 1.4g tetraethyl orthosilicate, the organic silicon source of 0.6g
With the phenolic resin of synthesis in 20wt% embodiment 1, magnetic agitation 4 hours.Obtain water white settled solution.Will be above-mentioned molten
Liquid is uniformly layered on glass culture dish surface, places 2 hours, afterwards, temperature is risen to 100 DEG C of hot polymerizations 24 hours under room temperature, takes out
Flaxen transparent membrane is scraped, i.e. preformed material.
Preformed material is removed surfactant in 24 hours with sulfuric acid solution stirring extraction by 90 DEG C, extracts two to four times, takes out
Filter, is then dried overnight in 80 DEG C of vacuum drying ovens.
Weigh the above-mentioned solid sample of 0.4g to be placed in moderate beaker, add the palladium solution (1g/100ml) of 1.4ml.Envelope
Mouth places it in constant temperature oscillator, shakes uniformly under room temperature.It is proportionally added into sodium borohydride solution after taking-up, continuously add perseverance
Half an hour is shaken up in warm agitator.Then take out and be placed on indoor solvent flashing, after solvent is evaporated completely, be placed in vacuum drying oven
Slough the moisture and other absorption impurity in sample surfaces for 80 DEG C.Then this sample is placed in calcining in tube furnace, 600 DEG C of calcinings
2 hours.
The material obtaining is mesoporous carbon-silica material load palladium catalyst.There is the structure (space of two-dimentional six sides
Group p6mm), aperture 4.3nm, pore volume is 0.47cm3/ g, specific surface area 429m2/ g, the load capacity of palladium is 4wt%, pd nano-particle
A size of 5nm, its characteristic x-ray diffraction (xrd) collection of illustrative plates is as shown in Figure 5.
15mg palladium catalyst is placed in 25ml autoclave, thereto cinnamic aldehyde (0.52g, 4mmol), 10ml successively
Water is as solvent.Tighten reactor, be passed through hydrogen into it, (the pressure of hydrogen after processing for 6 times through overshoot-venting body purge process
Reach by force 0.8mpa), finally control the pressure in autoclave to be 1mpa (room temperature pressure), then reactor is placed in oil bath
Under environment, rise high-temperature to 120 DEG C of beginning stirring reactions.After reaction terminates, it is cooled to room temperature, add 5ml's in reactant liquor
The reactant liquor of residual and catalyst on alcohol flushing kettle.With gas chromatograph, reactant liquor is analyzed, obtains 3-phenylpropion aldehyde
Yield is 87%.
Embodiment 6
At 40～60 DEG C, the f127 surfactant of 3.0g is dissolved in 12.0g ethanol solution, subsequent Deca mass fraction
For 36.5% hydrochloric acid solution 2.0g, stir prehydrolysis 1 hour, then sequentially add 3.4g tetraethyl orthosilicate, the organic silicon source of 0.9g
With the phenolic resin of synthesis in 20wt% embodiment 1, magnetic agitation 4 hours.Obtain water white settled solution.Will be above-mentioned molten
Liquid is uniformly layered on glass culture dish surface, places 2 hours, afterwards, temperature is risen to 100 DEG C of hot polymerizations 24 hours under room temperature, takes out
Flaxen transparent membrane is scraped, i.e. preformed material.
Preformed material is removed surfactant in 24 hours with sulfuric acid solution stirring extraction by 90 DEG C, extracts two to four times, takes out
Filter, is then dried overnight in 80 DEG C of vacuum drying ovens.
Weigh the above-mentioned solid sample of 0.4g to be placed in moderate beaker, add the palladium solution (1g/100ml) of 6.4ml.Envelope
Mouth places it in constant temperature oscillator, shakes uniformly under room temperature.It is proportionally added into sodium borohydride solution after taking-up, continuously add perseverance
Half an hour is shaken up in warm agitator.Then take out and be placed on indoor solvent flashing, after solvent is evaporated completely, be placed in vacuum drying oven
Slough the moisture and other absorption impurity in sample surfaces for 80 DEG C.Then this sample is placed in calcining in tube furnace, 600 DEG C of calcinings
2 hours.
The material obtaining is mesoporous carbon-silica material load palladium catalyst.There is the structure (space of two-dimentional six sides
Group p6mm), aperture 6.3nm, pore volume is 0.87cm3/ g, specific surface area 529m2/ g, the load capacity of palladium is 8wt%, pd nano-particle
A size of 8.0nm, its characteristic x-ray diffraction (xrd) collection of illustrative plates is as shown in Figure 6.
15mg palladium catalyst is placed in 25ml autoclave, thereto cinnamic aldehyde (0.52g, 4mmol), 10ml successively
Water is as solvent.Tighten reactor, be passed through hydrogen into it, (the pressure of hydrogen after processing for 6 times through overshoot-venting body purge process
Reach by force 0.8mpa), finally control the pressure in autoclave to be 1mpa (room temperature pressure), then reactor is placed in oil bath
Under environment, rise high-temperature to 120 DEG C of beginning stirring reactions.After reaction terminates, it is cooled to room temperature, add 5ml second in reactant liquor
Alcohol rinses the reactant liquor of residual and catalyst on kettle.With gas chromatograph, reactant liquor is analyzed, obtains the product of 3-phenylpropion aldehyde
Rate is 90%.
Embodiment 7
The synthetic method of the present embodiment mesoporous carbon-silica complex loaded nanometer palladium catalyst, specifically includes following
Step:
(1) surfactant is dissolved in organic solvent, obtained solution a；
(2) silicon source is added in acid solution, through prehydrolysis, obtained solution b；
(3) solution a is mixed with solution b, stir, controlling reaction temperature is 20 DEG C, the response time is 2 hours, then
Add the carbon source of solubility, react 6 hours at 20 DEG C, organic solvent is volatilized, obtains solid intermediate；
(4) solid intermediate is carried out low temperature thermosetting reaction, reaction temperature is 80 DEG C, the response time is 36 hours, treat anti-
After should terminating, use acid solution reflux extraction, in order to remove surfactant, prepared support precursor；
(5) support precursor is mixed with the palladium salt solution containing reducing agent, filter, retain solid, then at noble gases
High-temperature calcination under atmosphere, through carbonization, reduction, that is, is obtained mesoporous carbon-silica complex loaded nanometer palladium catalyst.
In step (1), surfactant is nonionic surfactant, and this nonionic surfactant is in solution a
Weight/mass percentage composition is 0.5%.
Organic solvent includes methanol, ethanol, normal propyl alcohol and oxolane, and nonionic surfactant is brij56
(c16h33eo10).
In step (2), in silicon source, silicon and the mol ratio of water in acid solution are 1:2, the carbon source of solubility and silicon in step (3)
The mol ratio in source is 0.1:1.
In the present embodiment, silicon source is mixed for 0.5:1 with organic silicon source in molar ratio by inorganic silicon source, and organosilicon
Source is 10:1 with the mol ratio of surfactant.Wherein, inorganic silicon source by tetraethyl orthosilicate with methyl silicate is in mass ratio
1:1 mixes, and organic silicon source is 3-mercaptopropyi trimethoxy silane.
In step (3), the phenolic resin that the carbon source of solubility is 200 for relative molecular mass, in step (4), reducing agent is
Potassium borohydride, palladium salt is chlorine palladium acid sodium.
In step (4), the condition of acid solution reflux extraction is: is returned using the sulfuric acid solution that weight/mass percentage composition is 40%
Stream extraction, removes surfactant, controls extraction temperature to be 80 DEG C, and extraction time is 48 hours；
In step (5), the condition of high-temperature calcination is: control heating rate is 1 DEG C/min, is warming up to 350 DEG C, calcining at constant temperature
5 hours.
Embodiment 8
The synthetic method of the present embodiment mesoporous carbon-silica complex loaded nanometer palladium catalyst, specifically includes following
Step:
(1) surfactant is dissolved in organic solvent, obtained solution a；
(2) silicon source is added in acid solution, through prehydrolysis, obtained solution b；
(3) solution a is mixed with solution b, stir, controlling reaction temperature is 32 DEG C, the response time is 1 hour, then
Add the carbon source of solubility, react 45 minutes at 35 DEG C, organic solvent is volatilized, obtains solid intermediate；
(4) solid intermediate is carried out low temperature thermosetting reaction, reaction temperature is 100 DEG C, the response time is 20 hours, treat anti-
After should terminating, use acid solution reflux extraction, in order to remove surfactant, prepared support precursor；
(5) support precursor is mixed with the palladium salt solution containing reducing agent, filter, retain solid, then at noble gases
High-temperature calcination under atmosphere, through carbonization, reduction, that is, is obtained mesoporous carbon-silica complex loaded nanometer palladium catalyst.
In step (1), surfactant is nonionic surfactant, and this nonionic surfactant is in solution a
Weight/mass percentage composition is 10%.
Organic solvent includes n-butyl alcohol, chloroform, dichloromethane, normal propyl alcohol and oxolane, and nonionic surfactant is
brij78(c16h33eo20) and p123 (eo20po70eo20)、f127(eo106po70eo106) mix for 1:1:2 in molar ratio.
In step (2), in silicon source, silicon and the mol ratio of water in acid solution are 1:6, the carbon source of solubility and silicon in step (3)
The mol ratio in source is 0.4:1.
In the present embodiment, silicon source is mixed for 2:1 with organic silicon source in molar ratio by inorganic silicon source, and organic silicon source
Mol ratio with surfactant is 40:1.Wherein, inorganic silicon source is mixed for 1:1 with positive silicic acid propyl ester in mass ratio by Silicon chloride.
Conjunction forms, and organic silicon source is double (triethoxy propyl silane) tetrasulfide.
In step (3), the phenolic resin that the carbon source of solubility is 500 for relative molecular mass, in step (4), reducing agent is
Sodium borohydride, palladium salt is Palladous chloride..
In step (4), the condition of acid solution reflux extraction is: is returned using the sulfuric acid solution that weight/mass percentage composition is 50%
Stream extraction, removes surfactant, controls extraction temperature to be 85 DEG C, and extraction time is 36 hours；
In step (5), the condition of high-temperature calcination is: control heating rate is 3 DEG C/min, is warming up to 450 DEG C, calcining at constant temperature
4 hours.
Embodiment 9
The synthetic method of the present embodiment mesoporous carbon-silica complex loaded nanometer palladium catalyst, specifically includes following
Step:
(1) surfactant is dissolved in organic solvent, obtained solution a；
(2) silicon source is added in acid solution, through prehydrolysis, obtained solution b；
(3) solution a is mixed with solution b, stirs, controlling reaction temperature is 40 DEG C, the response time is 0.5 hour,
Add the carbon source of solubility, react 10 minutes at 40 DEG C, organic solvent is volatilized, obtains solid intermediate；
(4) solid intermediate is carried out low temperature thermosetting reaction, reaction temperature is 120 DEG C, the response time is 12 hours, treat anti-
After should terminating, use acid solution reflux extraction, in order to remove surfactant, prepared support precursor；
(5) support precursor is mixed with the palladium salt solution containing reducing agent, filter, retain solid, then at noble gases
High-temperature calcination under atmosphere, through carbonization, reduction, that is, is obtained mesoporous carbon-silica complex loaded nanometer palladium catalyst.
In step (1), surfactant is nonionic surfactant, and this nonionic surfactant is in solution a
Weight/mass percentage composition is 25%.
Organic solvent includes toluene, chloroform, ethanol, normal propyl alcohol and oxolane, and nonionic surfactant is brij76
(c18h37eo10).
In step (2), in silicon and acid solution in silicon source, the mol ratio of water is 1:10, in step (3) carbon source of solubility with
The mol ratio of silicon source is 0.6:1.
In the present embodiment, silicon source is mixed for 5:1 with organic silicon source in molar ratio by inorganic silicon source, and organic silicon source
Mol ratio with surfactant is 53:1.Wherein, inorganic silicon source is mixed for 1:1 with methyl silicate in mass ratio by Silicon chloride.
Conjunction forms, and organic silicon source is 3- Mercaptopropyltriethoxysilane.
In step (3), the phenolic resin that the carbon source of solubility is 5000 for relative molecular mass, reducing agent in step (4)
For sodium borohydride, palladium salt is Palladous chloride..
In step (4), the condition of acid solution reflux extraction is: is returned using the sulfuric acid solution that weight/mass percentage composition is 60%
Stream extraction, removes surfactant, controls extraction temperature to be 100 DEG C, and extraction time is 12 hours；
In step (5), the condition of high-temperature calcination is: control heating rate is 5 DEG C/min, is warming up to 900 DEG C, calcining at constant temperature
2 hours.
Embodiment 10
The synthetic method of the present embodiment mesoporous carbon-silica complex loaded nanometer palladium catalyst, specifically includes following
Step:
(1) surfactant is dissolved in organic solvent, obtained solution a；
(2) silicon source is added in acid solution, through prehydrolysis, obtained solution b；
(3) solution a is mixed with solution b, stirs, controlling reaction temperature is 35 DEG C, the response time is 1.5 hours,
Add the carbon source of solubility, react 2 hours at 32 DEG C, organic solvent is volatilized, obtains solid intermediate；
(4) solid intermediate is carried out low temperature thermosetting reaction, reaction temperature is 85 DEG C, the response time is 30 hours, treat anti-
After should terminating, use acid solution reflux extraction, in order to remove surfactant, prepared support precursor；
(5) support precursor is mixed with the palladium salt solution containing reducing agent, filter, retain solid, then at noble gases
High-temperature calcination under atmosphere, through carbonization, reduction, that is, is obtained mesoporous carbon-silica complex loaded nanometer palladium catalyst.
In step (1), surfactant is nonionic surfactant, and this nonionic surfactant is in solution a
Weight/mass percentage composition is 16%.
Organic solvent includes toluene, chloroform, ethanol, normal propyl alcohol and oxolane, and nonionic surfactant is f108
(eo132po50eo132).
In step (2), in silicon source, silicon and the mol ratio of water in acid solution are 1:3, the carbon source of solubility and silicon in step (3)
The mol ratio in source is 0.3:1.
In the present embodiment, silicon source is mixed for 4:1 with organic silicon source in molar ratio by inorganic silicon source, and organic silicon source
Mol ratio with surfactant is 25:1.Wherein, inorganic silicon source is mixed for 1:1 with methyl silicate in mass ratio by Silicon chloride.
Conjunction forms, and disulphide is in molar ratio with double (triethoxy propyl silane) by 3- Mercaptopropyltriethoxysilane for organic silicon source
Mix for 1:1.
In step (3), the phenolic resin that the carbon source of solubility is 1000 for relative molecular mass, reducing agent in step (4)
For sodium borohydride, palladium salt is Palladous chloride..
In step (4), the condition of acid solution reflux extraction is: is returned using the sulfuric acid solution that weight/mass percentage composition is 55%
Stream extraction, removes surfactant, controls extraction temperature to be 90 DEG C, and extraction time is 24 hours；
In step (5), the condition of high-temperature calcination is: control heating rate is 2 DEG C/min, is warming up to 720 DEG C, calcining at constant temperature
3 hours.
Claims (10)
1. mesoporous carbon-silica complex loaded nanometer palladium catalyst is it is characterised in that this catalyst has orderly two dimension
Six side's mesoscopic structures, specific surface area is 400-700m2/ g, pore volume is 0.30-0.90cm3/ g, aperture is 4.0-7.0nm, metal pd
Percentage composition be 1-10wt%, the particle diameter of pd nano-particle is 3.0-8.0nm.
2. the synthetic method of mesoporous carbon-silica complex loaded nanometer palladium catalyst as claimed in claim 1, its feature
It is, the method specifically includes following steps:
(1) surfactant is dissolved in organic solvent, obtained solution a；
(2) silicon source is added in acid solution, through prehydrolysis, obtained solution b；
(3) solution a is mixed with solution b, stirs, controlling reaction temperature is 20-40 DEG C, the response time is 0.5-2 hour,
Add the carbon source of solubility, react 10 minutes -6 hours at 20-40 DEG C, organic solvent is volatilized, obtains solid intermediate；
(4) solid intermediate is carried out low temperature thermosetting reaction, reaction temperature is 80-120 DEG C, the response time is 12-36 hour, treats
After reaction terminates, use acid solution reflux extraction, in order to remove surfactant, prepared support precursor；
(5) support precursor is mixed with the palladium salt solution containing reducing agent, filter, retain solid, then at atmosphere of inert gases
Lower high-temperature calcination, through carbonization, reduction, that is, is obtained mesoporous carbon-silica complex loaded nanometer palladium catalyst.
3. the synthetic method of mesoporous carbon-silica complex loaded nanometer palladium catalyst according to claim 2, it is special
Levy and be, the surfactant described in step (1) is nonionic surfactant, and this nonionic surfactant is in solution a
Weight/mass percentage composition be 0.5-25%, described organic solvent includes c1-c4Alcohols, benzene, toluene, oxolane, chloroform,
One or more of dichloromethane or ether.
4. the synthetic method of mesoporous carbon-silica complex loaded nanometer palladium catalyst according to claim 3, it is special
Levy and be, described nonionic surfactant includes poly(ethylene oxide)-poly(propylene oxide) triblock copolymer or alkane-polycyclic
One of oxidative ethane diblock copolymer or two kinds.
5. the synthetic method of mesoporous carbon-silica complex loaded nanometer palladium catalyst according to claim 4, it is special
Levy and be, described nonionic surfactant is c16h33eo10、c16h33eo20、c18h37eo10、eo20po70eo20、
eo106po70eo106、eo132po50eo132One or more of.
6. the synthetic method of mesoporous carbon-silica complex loaded nanometer palladium catalyst according to claim 2, it is special
Levy and be, in the silicon source described in step (2), silicon and the mol ratio of water in acid solution are 1:2-10, the solubility described in step (3)
The mol ratio of carbon source and silicon source be 0.1-0.6:1.
7. the synthetic method of mesoporous carbon-silica complex loaded nanometer palladium catalyst according to claim 6, it is special
Levy and be, described silicon source is mixed for 0-5:1 with organic silicon source in molar ratio by inorganic silicon source, and described organosilicon
Source is 10-53:1 with the mol ratio of surfactant.
8. the synthetic method of mesoporous carbon-silica complex loaded nanometer palladium catalyst according to claim 7, it is special
Levy and be, described inorganic silicon source include one of tetraethyl orthosilicate, methyl silicate, Silicon chloride. or positive silicic acid propyl ester or
Multiple, described organic silicon source is organic silicon source of sulfur-bearing, including 3-mercaptopropyi trimethoxy silane, 3- mercaptopropyi three second
One of TMOS, double (triethoxy propyl silane) tetrasulfide or double (triethoxy propyl silane) disulphide or
Multiple.
9. the synthetic method of mesoporous carbon-silica complex loaded nanometer palladium catalyst according to claim 2, it is special
Levy and be, the carbon source of the solubility described in step (3) is the phenolic resin of 200-5000 for relative molecular mass, step (4) institute
The reducing agent stated includes one of sodium borohydride or potassium borohydride or two kinds, and described palladium salt includes chlorine palladium acid sodium or Palladous chloride.
One of or two kinds.
10. the synthetic method of mesoporous carbon-silica complex loaded nanometer palladium catalyst according to claim 2, its
It is characterised by, the condition of the acid solution reflux extraction described in step (4) is: using the sulfur for 40-60% for the weight/mass percentage composition
Acid solution reflux extraction, removes surfactant, controls extraction temperature to be 80-100 DEG C, and extraction time is 12-48 hour；
The condition of the high-temperature calcination described in step (5) is: control heating rate is 1-5 DEG C/min, is warming up to 350-900 DEG C, permanent
Temperature calcining 2-5 hour.
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| CN108441652A (en) * | 2018-03-16 | 2018-08-24 | 沈阳师范大学 | A kind of preparation method of mesoporous germanium material |
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| CN108636455A (en) * | 2018-04-20 | 2018-10-12 | 北京工业大学 | It is a kind of using nucleocapsid MOF as the preparation and application of the carried noble metal base catalyst of reaction vessel |
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| CN110368923A (en) * | 2019-07-23 | 2019-10-25 | 龙净科杰环保技术（上海）有限公司 | A kind of mesoporous denitration of middle low temperature takes off dioxin catalyst and preparation method thereof |
| CN114797846A (en) * | 2022-05-24 | 2022-07-29 | 四川轻化工大学 | Catalyst for hydrodechlorination and preparation method thereof |
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Inventor after: Wan Ying Inventor after: Chen Shangjun Inventor after: Zhao Xiaorui Inventor after: Meng Li Inventor before: Chen Shangjun Inventor before: Meng Li Inventor before: Zhao Xiaorui Inventor before: Wan Ying |
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