CN110152730A - A kind of functional ordered mesopore Polymer-supported palladium catalyst and preparation method thereof - Google Patents
A kind of functional ordered mesopore Polymer-supported palladium catalyst and preparation method thereof Download PDFInfo
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- CN110152730A CN110152730A CN201910354120.4A CN201910354120A CN110152730A CN 110152730 A CN110152730 A CN 110152730A CN 201910354120 A CN201910354120 A CN 201910354120A CN 110152730 A CN110152730 A CN 110152730A
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- ordered mesopore
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 136
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 58
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 150000003242 quaternary ammonium salts Chemical class 0.000 claims abstract description 32
- 239000002131 composite material Substances 0.000 claims abstract description 21
- 239000000463 material Substances 0.000 claims abstract description 20
- 238000000034 method Methods 0.000 claims abstract description 13
- 239000002736 nonionic surfactant Substances 0.000 claims abstract description 11
- 229920005989 resin Polymers 0.000 claims abstract description 10
- 239000011347 resin Substances 0.000 claims abstract description 10
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005342 ion exchange Methods 0.000 claims abstract description 9
- 229910000077 silane Inorganic materials 0.000 claims abstract description 9
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000002904 solvent Substances 0.000 claims abstract description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 30
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 25
- 239000000377 silicon dioxide Substances 0.000 claims description 23
- 229910052757 nitrogen Inorganic materials 0.000 claims description 15
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 239000002861 polymer material Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 9
- 239000000203 mixture Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 8
- 229910052751 metal Inorganic materials 0.000 claims description 7
- 239000002184 metal Substances 0.000 claims description 7
- -1 polyethylene Polymers 0.000 claims description 6
- 229920000642 polymer Polymers 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 239000007822 coupling agent Substances 0.000 claims description 5
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000001257 hydrogen Substances 0.000 claims description 5
- 229910052739 hydrogen Inorganic materials 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- 239000003153 chemical reaction reagent Substances 0.000 claims description 4
- 229920003987 resole Polymers 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 3
- 229910003244 Na2PdCl4 Inorganic materials 0.000 claims description 2
- 230000000536 complexating effect Effects 0.000 claims description 2
- 125000004433 nitrogen atom Chemical group N* 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims 2
- 229920000573 polyethylene Polymers 0.000 claims 2
- 229920000428 triblock copolymer Polymers 0.000 claims 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 claims 1
- 238000005034 decoration Methods 0.000 claims 1
- 229920000359 diblock copolymer Polymers 0.000 claims 1
- 125000000524 functional group Chemical group 0.000 claims 1
- 239000007789 gas Substances 0.000 claims 1
- 229920001748 polybutylene Polymers 0.000 claims 1
- 229920001451 polypropylene glycol Polymers 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 claims 1
- 239000004094 surface-active agent Substances 0.000 claims 1
- 239000013335 mesoporous material Substances 0.000 abstract description 6
- VSTOHTVURMFCGL-UHFFFAOYSA-N [C].O=[Si]=O Chemical compound [C].O=[Si]=O VSTOHTVURMFCGL-UHFFFAOYSA-N 0.000 abstract description 4
- 238000001338 self-assembly Methods 0.000 abstract description 3
- 239000011521 glass Substances 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 7
- 229910052799 carbon Inorganic materials 0.000 description 7
- 229910052710 silicon Inorganic materials 0.000 description 7
- 239000010703 silicon Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 6
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 238000002474 experimental method Methods 0.000 description 6
- 238000007306 functionalization reaction Methods 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- UHEMFKHODNGGCH-UHFFFAOYSA-N 1-$l^{1}-azanylpropane Chemical compound CCC[N] UHEMFKHODNGGCH-UHFFFAOYSA-N 0.000 description 4
- 239000002253 acid Substances 0.000 description 4
- 239000012298 atmosphere Substances 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- 238000010792 warming Methods 0.000 description 4
- 238000005406 washing Methods 0.000 description 4
- KXGFMDJXCMQABM-UHFFFAOYSA-N 2-methoxy-6-methylphenol Chemical compound [CH]OC1=CC=CC([CH])=C1O KXGFMDJXCMQABM-UHFFFAOYSA-N 0.000 description 3
- YZCKVEUIGOORGS-OUBTZVSYSA-N Deuterium Chemical compound [2H] YZCKVEUIGOORGS-OUBTZVSYSA-N 0.000 description 3
- 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 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 125000000962 organic group Chemical group 0.000 description 3
- 229920001568 phenolic resin Polymers 0.000 description 3
- 239000005011 phenolic resin Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 229910052708 sodium Inorganic materials 0.000 description 3
- 239000011734 sodium Substances 0.000 description 3
- QDRKDTQENPPHOJ-UHFFFAOYSA-N sodium ethoxide Chemical compound [Na+].CC[O-] QDRKDTQENPPHOJ-UHFFFAOYSA-N 0.000 description 3
- KGYLMXMMQNTWEM-UHFFFAOYSA-J tetrachloropalladium Chemical compound Cl[Pd](Cl)(Cl)Cl KGYLMXMMQNTWEM-UHFFFAOYSA-J 0.000 description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 229920001296 polysiloxane Polymers 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000006443 Buchwald-Hartwig cross coupling reaction Methods 0.000 description 1
- 239000005046 Chlorosilane Substances 0.000 description 1
- 238000003477 Sonogashira cross-coupling reaction Methods 0.000 description 1
- CVWONAYPVZHJFE-UHFFFAOYSA-N [C+4].[O-2].[O-2].[Ti+4].[Si+4] Chemical compound [C+4].[O-2].[O-2].[Ti+4].[Si+4] CVWONAYPVZHJFE-UHFFFAOYSA-N 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000009903 catalytic hydrogenation reaction Methods 0.000 description 1
- KOPOQZFJUQMUML-UHFFFAOYSA-N chlorosilane Chemical compound Cl[SiH3] KOPOQZFJUQMUML-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 238000006482 condensation reaction Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 238000007172 homogeneous catalysis Methods 0.000 description 1
- 230000007062 hydrolysis Effects 0.000 description 1
- 238000006460 hydrolysis reaction Methods 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 239000006193 liquid solution Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000000696 nitrogen adsorption--desorption isotherm Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229920003986 novolac Polymers 0.000 description 1
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- HZBAVWLZSLOCFR-UHFFFAOYSA-N oxosilane Chemical compound [SiH2]=O HZBAVWLZSLOCFR-UHFFFAOYSA-N 0.000 description 1
- 238000006068 polycondensation reaction Methods 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
- 230000007306 turnover Effects 0.000 description 1
- 238000005292 vacuum distillation Methods 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000002023 wood Substances 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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- B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
- B01J20/26—Synthetic macromolecular compounds
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- B01J20/28—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties
- B01J20/28054—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof characterised by their form or physical properties characterised by their surface properties or porosity
- B01J20/28057—Surface area, e.g. B.E.T specific surface area
- B01J20/28061—Surface area, e.g. B.E.T specific surface area being in the range 100-500 m2/g
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- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28071—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being less than 0.5 ml/g
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- B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
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- B01J20/28069—Pore volume, e.g. total pore volume, mesopore volume, micropore volume
- B01J20/28073—Pore volume, e.g. total pore volume, mesopore volume, micropore volume being in the range 0.5-1.0 ml/g
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- B01J20/28078—Pore diameter
- B01J20/28083—Pore diameter being in the range 2-50 nm, i.e. mesopores
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
- B01J31/063—Polymers comprising a characteristic microstructure
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- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/61—Surface area
- B01J35/615—100-500 m2/g
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- B01J35/635—0.5-1.0 ml/g
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- B01J35/64—Pore diameter
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
- B01J37/0018—Addition of a binding agent or of material, later completely removed among others as result of heat treatment, leaching or washing,(e.g. forming of pores; protective layer, desintegrating by heat)
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- B01J37/16—Reducing
- B01J37/18—Reducing with gases containing free hydrogen
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- B01J37/30—Ion-exchange
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Abstract
The present invention relates to a kind of functional ordered mesopore Polymer-supported palladium catalysts and preparation method thereof.The catalyst has two-dimentional six side's mesoscopic structures, organic functional mass contg higher (0.5wt%~3wt%), large specific surface area (310~370m2/ g), Kong Rong great (0.4~0.6cm3/ g), aperture it is uniform (3~12nm), palladium mass content be 1-3wt%, palladium partial size be 2-4nm.Preparation method are as follows: using nonionic surfactant as template, water-soluble resin is presoma, and tetraethyl orthosilicate is inorganic silane, using method carbon-silicon dioxide composite material MCSiO synthesising mesoporous first of solvent volatilization self assembly2- 46, short chain quaternary ammonium salt TPTAC is then grafted onto carrier MCSiO using rear grafting2On -46, Pd is finally supported on to the surface of mesoporous material using ion-exchange.Operation of the present invention is simple, at low cost, prepares resulting materials and has broad application prospects in industrial circle.
Description
Technical field
The invention belongs to mesoporous material preparation technical fields, are related to a kind of functional ordered mesopore Polymer-supported palladium chtalyst
Agent and preparation method thereof.
Background technique
There are many type of palladium-containing catalyst, are applied to the reaction such as catalytic hydrogenation and catalysis oxidation in petrochemical industry mostly.?
Phase palladium chtalyst is in such as Heck, Stille, Suzuki, the various couplings of Sonogashira and Buchwald-Hartwig reaction
Huge association, this catalyst reaction rate with higher and higher turnover number (TON) are had been obtained in reaction, but
It is that homogeneous catalysis has and is difficult to recycle or at least there are problems that catalyst recycling, application homogeneous Pd catalysis is even in the industry
When connection reaction, it is necessary to overcome these problems.In order to realize the high recyclability and reusability of catalyst, it usually needs one is easy to
The carrier of catalyst is recycled from reaction medium, various types of solid carriers have been used to load nano particle, such as mesoporous material
Material, polymer, metal oxide (SiO2, TiO2, ZrO2, Al2O3), metal organic frame, graphene and carbon nanotube etc..Its
In, heterogeneous Pd catalysis is a selection well.Zaidi, R seminar report the display of solid carrier Pt-supported catalyst than equal
The higher activity of phase catalyst, it may be possible to because of their high stability.Therefore a kind of high recyclability, reusable is researched and developed
The heterogeneous palladium catalyst of property is of great significance.
The mesoporous material of functionalization has many advantages, such as large specific surface area, and high stability and aperture are uniform, in catalysis, inhales
Many fields such as attached, separation and light, electricity, magnetic have important application value.It can use two methods and obtain Jie of functionalization
Porous materials: 1) being grafted to inorganic silicon dioxide material surface for organic group using grafting, utilizes organic oxosilane ((R ' O)3SiR), chlorosilane (ClSiR3) or silazane (HN (SiR3)3) largely condensation reaction occurs for existing silicone hydroxyl with hole surface
And realize functionalization；2) it is combined with machine silane and inorganic silane using cocondensation is legal, the legal i.e. one-step synthesis of cocondensation, is with end
Hold the estersil (RO) containing organic group3Si-R is to mix silicon source with inorganic estersil (ethyl orthosilicate/methyl orthosilicate), and hydrolysis is altogether
Polycondensation forms functional mesoporous material.The interaction force of simple carbon-silica supports and noble metal is very weak, utilizes
Catalyst made from traditional synthesis mode can generally be faced with that metal particle size is larger, is unevenly distributed, is easy to reunite, reacting
The problems such as being easy to run off in journey.The present invention is modified with quaternary ammonium salt on the surface in mesoporous carbon-silica composite material duct, is recycled
Ion-exchange supported palladium, the quaternary ammonium salt in material cannot be only used for ion exchange supported palladium, and former using nitrogen in quaternary ammonium salt
Palladium can be fixed in material duct by son well with the coordination of palladium, can solve in subsequent reactions the reunion of metal and
Losing issue.
In view of the above-mentioned problems, the present invention has synthesized quaternary ammonium salt modification ordered mesoporous polymer using the polynary method assembled altogether
Loaded palladium catalyst, the hybrid material of functionalization have six side's mesoscopic structure of two dimension of high-sequential, have adjustable organic official
It can mass contg (0.5wt%~3wt%)；Higher specific surface area (310~370m2/g)；Big pore volume (0.4~0.6cm3/
g)；Uniform aperture (3~12nm).Synthesis step is simple and easy to operate, lower cost, has good industrialized production and answers
Use prospect.
Summary of the invention
It is negative it is an object of the invention to synthesize a kind of functional ordered mesopore polymer with high recyclability, high-sequential
Carried palladium catalyst and preparation method thereof.
Technical solution are as follows: a kind of functional ordered mesopore Polymer-supported palladium catalyst, the ordered mesoporous polymer
Loaded palladium catalyst is the polymer material containing resin and silane, has the ordered mesostructure of two-dimentional six sides, organic functional
Mass contg is 0.5wt%~3wt%；Specific surface area is 310~370m2/g；0.4~0.6cm of Kong Rongwei3/g；Aperture be 3~
12nm；The mass percentage of metal Pd is 1-3wt%, and the partial size of palladium particle is 2-4nm.
Further, the organo-functional group is organosilan, and the organosilan stablizes palladium as complexing reagents.
It further, can be fine by Pd using the coordination of nitrogen-atoms in quaternary ammonium salt and Pd containing short chain quaternary ammonium salt
Ground is fixed in material duct, prevents metal Pd reunion from growing up and being lost.
The present invention also provides the preparation method of above-mentioned material, preparation method includes the following steps:
(1) using nonionic surfactant as template, water-soluble resin is presoma, and tetraethyl orthosilicate is inorganic silicon
Alkane synthesizes to obtain mesoporous carbon-silica composite material MCSiO using the method for solvent volatilization self assembly2-46；
(2) short chain quaternary ammonium salt TPTAC is grafted by mesoporous carbon-silica composite material MCSiO using rear grafting2-
Functional ordered mesopore polymer material P-TPTAC-MCSiO is made on 462-46；
(3) using the coordination of the channel surfaces quaternary ammonium salt of the functional ordered mesopore polymer material, by metal
Pd is immobilized on the surface of the functional ordered mesopore polymer material, and functional ordered mesopore Polymer-supported palladium is prepared
Catalyst Pd/TPTAC-MCSiO2-46。
Further, the nonionic surfactant is selected from C12H25EO23、C16H33EO10、C18H37EO10、
EO20PO70EO20、EO106PO70EO106、EO132PO50EO132One of or more than one mixtures, it is preferred that it is total for three block
Polymers F127 (molecular formula are as follows: EO106PO70EO106)。
Further, the soluble resin is resol, and molecular weight is 200~500.
Further, the step (1) specifically: nonionic surfactant is dissolved in organic solvent, is added appropriate
0.2mol/L hydrochloric acid reacts 0.5-1 hours at 35-45 DEG C, using inorganic silane ethyl orthosilicate as silicon source, water-soluble resin
As carbon source, continuation is reacted 1-3 hours at 35-45 DEG C；Then reaction solution is equably coated in glass dish surface, after the completion will
Glass dish is put in baking oven to volatilize 6-8 hours at 35-45 DEG C, is warming up to 100 DEG C of hot polymerizations 20-25 hours；By cooling glass
Ware takes out from baking oven, scrapes surface covering, carbon-silicon dioxide composite material as-made sample is obtained, then in nitrogen atmosphere
It is lower that as-made sample is calcined to 4-6 hour at 330-360 DEG C, mesoporous carbon-silica composite material MCSiO is made2-
46。
Further, the mass concentration of the nonionic surfactant is 9.05wt%, and the dosage of silicon source and carbon source is rubbed
You are than being 0.4:1.
Further, short chain quaternary ammonium salt TPTAC described in the step (2) is nitrogen position-trimethyl silicon substrate propyl-nitrogen, nitrogen,
Nitrogen position-trimethyl ammonium chloride (50wt%), molecular formula are as follows: C9H24ClNO3Si。
Further, rear grafting described in the step (2), is using TPTAC as coupling agent, to mesoporous carbon-titanium dioxide
Silicon composite carries out quaternary ammonium salt modification, concrete operations are as follows: it is multiple successively to weigh mesoporous carbon-silica obtained in step (1)
Condensation material MCSiO2- 46 and toluene set in a round bottom flask, stir half an hour after be added TPTAC (wherein dosage mass ratio is inorganic
Silane: organosilan=1:1.2) it sets in a round bottom flask, it is stirred at room temperature 11-12 hours, then reflux 6 is small at 353K
When, it is washed respectively for several times with toluene and ethyl alcohol, middle drying of dropping a hint, that is, the P-TPTAC- of quaternary ammonium salt modification is prepared
MCSiO2-46。
Further, the step (3) uses ion-exchange supported palladium, concrete operations are as follows: by TPTAC-MCSiO2-46
With the source Pd (Na2PdCl4) it is dissolved in organic solvent, then stir 10-12 hours at room temperature.Mixture is filtered, deionized water washing
For several times, it is put in 50 DEG C of vacuum drying ovens to be dried overnight, (the volume H under 20% atmosphere of hydrogen of the material after drying2:N2=1:4), in
It is carried out in tube furnace hydrogen reducing 2-3 hours (temperature is 200 DEG C), obtains functional ordered mesopore Polymer-supported palladium chtalyst
Agent is named as Pd/TPTAC-MCSiO2-46。
The invention has the characteristics that:
1) present invention is prepared for carbon-silica nanometer composite wood of high-sequential using the method for solvent volatilization self assembly
Material；After the completion of inorganic material preparation, organic group is introduced into mesoporous material by the interaction with surface group, it is
Using organosilan and hole surface, largely existing silicone hydroxyl occurs condensation and realizes functionalization；Finally utilize ion exchange
Then final functional ordered mesopore Polymer-supported palladium catalyst is made with hydrogen reduction method in method supported palladium.
2) six side's of two dimension that functional ordered mesopore polymer material prepared by the present invention has height orderly is mesoporous
Structure also has the larger (310~370m of specific surface area2/ g), Kong Rong great (0.4~0.6cm3/ g), pore-size distribution it is uniform (3~
12nm) the features such as, has organo-functional group abundant (0.5wt%~3wt%).It can be used as adsorbent, handle a huge sum of money in waste water
Belong to ion etc.；Also catalyst carrier or catalyst be can be used as, organic synthesis is applied to, before there is wide application in industrial circle
Scape.
3) functional ordered mesopore polymer material of the invention has good characteristic, and preparation method of the invention
There is the advantages that easy to operate, equipment requirement simplicity, cheap compared with traditional organic group functionized process.
Detailed description of the invention
After Fig. 1 is the prepared carbon-silica supports with two-dimentional six side's p6mm structures of embodiment 1, modifies quaternary ammonium salt
Carbon-silica supports, quaternary ammonium salt modify the nitrogen adsorption desorption isothermal curve statistical chart of carrier loaded palladium rear catalyst.
After Fig. 2 is the prepared carbon-silica supports with two-dimentional six side's p6mm structures of embodiment 1, modifies quaternary ammonium salt
Carbon-silica supports, quaternary ammonium salt modify the pore-size distribution statistical chart of carrier loaded palladium rear catalyst.
After Fig. 3 is the prepared carbon-silica supports with two-dimentional six side's p6mm structures of embodiment 1, modifies quaternary ammonium salt
Carbon-silica supports, quaternary ammonium salt modify the small angle statistics spectrogram of XRD of carrier loaded palladium rear catalyst.
Fig. 4 is that the prepared quaternary ammonium salt with two-dimentional six side's p6mm structures of embodiment 1 modifies carrier loaded palladium rear catalyst
XRD wide-angle count spectrogram.
Fig. 5 is that the prepared quaternary ammonium salt with two-dimentional six side's p6mm structures of embodiment 1 modifies carrier loaded palladium rear catalyst
TEM figure.
Specific embodiment
Below with reference to embodiment, the present invention is described in further detail and completely, it is clear that described embodiment is this
Invention a part of the embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art exist
Every other embodiment obtained under the premise of creative work is not made, shall fall within the protection scope of the present invention.
Specific experiment step or condition person are not specified in embodiment, according to the literature in the art described routine experiment
The operation of step or condition can carry out.Reagents or instruments used without specified manufacturer, being can be by commercially available acquisition
Conventional reagent product.Wherein the molecular weight of resol is 200 < Mw < 500.
Embodiment 1
The synthesis of novolak resin precursor liquid solution.Its synthetic method is as follows: the phenol for weighing 16g is put in clean round bottom and burns
Bottle, is put in 45 DEG C of water-baths and heats；After phenol dissolution, the mass fraction that 3.40g is slowly added dropwise into reaction solution is 20%
Sodium hydroxide solution；Continue after ten minutes, the sodium hydroxide solution that 28.32g mass fraction is 37% to be added dropwise wait react；It adjusts
Water-saving bath temperature is 70 DEG C, is flowed back after about 1 hour at this temperature, reaction solution is cooled to room temperature；With 2mol/L dilute hydrochloric acid
After adjusting solution PH to neutrality, vacuum distillation removing moisture；It is finally configured to 20% ethanol solution, centrifuging and taking supernatant is standby
With.Gained supernatant is resol (abbreviation PF), is a kind of oligomeric resin of solubility.
The preparation method of functional ordered mesopore Polymer-supported palladium catalyst, the specific steps are as follows:
1) it takes 1.6g nonionic surfactant F127 to be dissolved in 8.0g ethyl alcohol, the 0.2mol/L hydrochloric acid of 1.0g is added.
After reacting 1 hour at 40 DEG C, 2.08g ethyl orthosilicate is added as silicon source, 5.0g phenolic resin ethanol solution as carbon source,
Continuation is reacted 2 hours at 40 DEG C.Then reaction solution is uniformly coated in glass dish surface, glass dish is put in baking oven after the completion
In volatilize 6-8 hours at 40 DEG C, be warming up to 100 DEG C of hot polymerizations 24 hours.Cooling glass dish is taken out from baking oven, scrapes lower surface
Coating obtains carbon-silica composite material as-made sample.Then as-made sample is forged at 350 DEG C under nitrogen atmosphere
5 hours are burnt, resulting materials are named as MCSiO2-46。
2) rear grafting is used, with nitrogen position-trimethyl silicon substrate propyl-nitrogen, nitrogen, nitrogen position-trimethyl ammonium chloride (TPTAC) is
Coupling agent carries out quaternary ammonium salt modification to mesoporous carbon-silica composite material.Concrete operations are as follows: weighing 0.5g MCSiO2-
46, in round-bottomed flask, measure 50mL toluene and round-bottomed flask are added, add 5.0mL TPTAC.It is stirred at room temperature 12 hours, so
It flows back 6 hours at 353K afterwards.It is washed respectively for several times with toluene and ethyl alcohol, middle drying of dropping a hint.Obtain the P- of quaternary ammonium salt modification
TPTAC-MCSiO2-46。
3) using quaternary ammonium salt modified carbon-silicon dioxide composite material as carrier, sodium tetrachloropallate is palladium source, passes through ion exchange
Method supported palladium.Steps are as follows for specific experiment: weighing 0.2g P-TPTAC-MCSiO2- 46, in round-bottomed flask, are added 2.3g mass point
Then the tetrachloro-palladium acid sodium ethoxide solution that number is 0.25% stirs 12 hours at room temperature.Mixture is filtered, deionized water washing
For several times, 50 DEG C of vacuum drying ovens are put in be dried overnight.Material after drying (the volume H under 20% atmosphere of hydrogen2:N2=1:4), in
Reductase 12 hour, (temperature is 200 DEG C) was to get palladium catalyst is arrived in tube furnace, was named as Pd/TPTAC-MCSiO2-46。
Above-mentioned steps 1), 2), 3) in prepare resulting material, nitrogen adsorption-desorption isotherm figure is as shown in Fig. 1,
Graph of pore diameter distribution is as shown in Fig. 2, and distinctive X-ray diffraction (XRD) map is as shown in attached drawing 3-4, TEM phenogram such as 5 institute of attached drawing
Show.The Pd/TPTAC-MCSiO that can must be prepared by attached drawing interpretation of result2- 46 materials have two-dimentional hexagonal structure (space group
P6mm), aperture 8.6nm, Kong Rongwei 0.585cm3/ g, specific surface area 368m2/ g, palladium content 1wt%, palladium partial size are 3nm.
Embodiment 2
The preparation method of functional ordered mesopore Polymer-supported palladium catalyst, the specific steps are as follows:
1) it takes 1.5g nonionic surfactant F127 to be dissolved in 8.0g ethyl alcohol, the salt of the 0.2mol/L of 1.0g is added
Acid.After reacting 1 hour at 35 DEG C, 2.05g ethyl orthosilicate is added as silicon source, 5.17g phenolic resin ethanol solution conduct
Carbon source, continuation are reacted 2 hours at 35 DEG C.Then reaction solution is uniformly coated in glass dish surface, after the completion put glass dish
It volatilizees 6-8 hours at 30 DEG C in baking oven, is warming up to 100 DEG C of hot polymerizations 24 hours.Cooling glass dish is taken out from baking oven, is scraped
Following table finishing coat obtains carbon-silica composite material as-made sample.Then under nitrogen atmosphere by as-made sample 350
5 hours are calcined at DEG C, resulting materials are named as MCSiO2-46。
2) rear grafting is used, with nitrogen position-trimethyl silicon substrate propyl-nitrogen, nitrogen, nitrogen position-trimethyl ammonium chloride (TPTAC) is
Coupling agent carries out quaternary ammonium salt modification to mesoporous carbon-silicon dioxide composite material.Concrete operations are as follows: weighing 0.3g MCSiO2-
46, in round-bottomed flask, measure 40mL toluene and round-bottomed flask are added, add 4.0mL TPTAC.It is stirred at room temperature 11 hours, so
It flows back 6 hours at 353K afterwards.It is washed respectively for several times with toluene and ethyl alcohol, middle drying of dropping a hint.Obtain the P- of quaternary ammonium salt modification
TPTAC-MCSiO2-46。
3) using quaternary ammonium salt modified carbon-silicon dioxide composite material as carrier, sodium tetrachloropallate is palladium source, passes through ion exchange
Method supported palladium.Steps are as follows for specific experiment: weighing 0.2g P-TPTAC-MCSiO2- 46, in round-bottomed flask, are added 2.3g mass point
Then the tetrachloro-palladium acid sodium ethoxide solution that number is 0.25% stirs 12 hours at room temperature.Mixture is filtered, deionized water washing
For several times, 50 DEG C of vacuum drying ovens are put in be dried overnight.Material after drying (the volume H under 20% atmosphere of hydrogen2:N2=1:4), in
Reductase 12 hour, (temperature is 200 DEG C) was to get palladium catalyst is arrived in tube furnace, was named as Pd/TPTAC-MCSiO2-46。
Embodiment 3
The preparation method of functional ordered mesopore Polymer-supported palladium catalyst, the specific steps are as follows:
1) it takes 1.7g nonionic surfactant F127 to be dissolved in 8.5g ethyl alcohol, the 0.2mol/L hydrochloric acid of 1.0g is added.
After reacting 1 hour at 40 DEG C, 2.18g ethyl orthosilicate is added as silicon source, 5.0g phenolic resin ethanol solution as carbon source,
Continuation is reacted 2 hours at 40 DEG C.Then reaction solution is uniformly coated in glass dish surface, glass dish is put in baking oven after the completion
In volatilize 6-8 hours at 40 DEG C, be warming up to 100 DEG C of hot polymerizations 24 hours.Cooling glass dish is taken out from baking oven, scrapes lower surface
Coating obtains carbon-silica composite material as-made sample.Then as-made sample is forged at 350 DEG C under nitrogen atmosphere
5 hours are burnt, resulting materials are named as MCSiO2-46。
2) rear grafting is used, with nitrogen position-trimethyl silicon substrate propyl-nitrogen, nitrogen, nitrogen position-trimethyl ammonium chloride (TPTAC) is
Coupling agent carries out quaternary ammonium salt modification to mesoporous carbon-silicon dioxide composite material.Concrete operations are as follows: weighing 0.6g MCSiO2-
46, in round-bottomed flask, measure 55mL toluene and round-bottomed flask are added, add 6.0mL TPTAC.It is stirred at room temperature 12 hours, so
It flows back 6 hours at 353K afterwards.It is washed respectively for several times with toluene and ethyl alcohol, middle drying of dropping a hint.Obtain the P- of quaternary ammonium salt modification
TPTAC-MCSiO2-46。
3) using quaternary ammonium salt modified carbon-silicon dioxide composite material as carrier, sodium tetrachloropallate is palladium source, passes through ion exchange
Method supported palladium.Steps are as follows for specific experiment: weighing 0.2g P-TPTAC-MCSiO2- 46, in round-bottomed flask, are added 2.3g mass point
Then the tetrachloro-palladium acid sodium ethoxide solution that number is 0.25% stirs 12 hours at room temperature.Mixture is filtered, deionized water washing
For several times, 50 DEG C of vacuum drying ovens are put in be dried overnight.Material after drying (the volume H under 20% atmosphere of hydrogen2:N2=1:4), in
(temperature is 200 DEG C) is restored 3 hours in tube furnace to get palladium catalyst is arrived, and is named as Pd/TPTAC-MCSiO2-46。
The preferred embodiment of the present invention has been described in detail above.It should be appreciated that the ordinary skill of this field is without wound
The property made labour, which according to the present invention can conceive, makes many modifications and variations.Therefore, all technician in the art
Pass through the available technology of logical analysis, reasoning, or a limited experiment on the basis of existing technology under this invention's idea
Scheme, all should be within the scope of protection determined by the claims.
Claims (10)
1. a kind of functional ordered mesopore Polymer-supported palladium catalyst, which is characterized in that the ordered mesoporous polymer is negative
Carried palladium catalyst contains resin and silane, has the ordered mesostructure of two-dimentional six sides, organic functional mass contg be 0.5wt%~
3wt%；Specific surface area is 310~370m2/g；0.4~0.6cm of Kong Rongwei3/g；Aperture is 3~12nm；The quality hundred of metal Pd
Dividing content is 1-3wt%, and the partial size of palladium particle is 2-4nm.
2. functional ordered mesopore Polymer-supported palladium catalyst as described in claim 1, which is characterized in that the organic functional
Group is organosilan, and the organosilan stablizes palladium as complexing reagents.
3. functional ordered mesopore Polymer-supported palladium catalyst as claimed in claim 1 or 2, which is characterized in that contain short chain
Quaternary ammonium salt, Pd is fixed in material duct by nitrogen-atoms and Pd coordination in the short chain quaternary ammonium salt.
4. the preparation method of functional ordered mesopore Polymer-supported palladium catalyst as described in claim 1, which is characterized in that packet
Include following steps:
(1) using nonionic surfactant as template, water-soluble resin is presoma, and tetraethyl orthosilicate is inorganic silane,
It synthesizes to obtain mesoporous carbon-silica composite material MCSiO using solvent volatilization self-assembling method2-46；
(2) short chain quaternary ammonium salt TPTAC is grafted by mesoporous carbon-silica composite material MCSiO using rear grafting2It is made on -46
Obtain functional ordered mesopore polymer material P-TPTAC-MCSiO2-46；
(3) using the coordination of the short chain quaternary ammonium salt of channel surfaces of the functional ordered mesopore polymer material, by metal
Pd is immobilized on the surface of the functional ordered mesopore polymer material, and functional ordered mesopore Polymer-supported palladium is prepared
Catalyst Pd/TPTAC-MCSiO2-46。
5. the preparation method of functional ordered mesopore Polymer-supported palladium catalyst as claimed in claim 4, which is characterized in that institute
It is poly- selected from polyethylene oxide-polypropylene oxide, polyethylene oxide-polybutylene oxide, alkane-to state nonionic surfactant
One of ethylene oxide diblock or triblock copolymer surfactant or more than one mixtures；General formula is CaH2a+ 1EOb、EOcPOdEOc、EOcBOdEOc、EOcBOd、EOcPOd, wherein a=10~18, b=5~25；C=5~135, d=25~
135, it is preferred that be triblock copolymer F127.
6. the preparation method of functional ordered mesopore Polymer-supported palladium catalyst, feature exist as described in claim 4 or 5
In the nonionic surfactant is selected from C12H25EO23、C16H33EO10、C18H37EO10、EO20PO70EO20、EO106PO70EO106、
EO132PO50EO132One of or more than one mixtures.
7. the preparation method of functional ordered mesopore Polymer-supported palladium catalyst as claimed in claim 4, which is characterized in that institute
Stating soluble resin is resol, and molecular weight is 200~500.
8. the preparation method of functional ordered mesopore Polymer-supported palladium catalyst as claimed in claim 4, which is characterized in that step
Suddenly rear grafting described in (2) is to carry out quaternary ammonium salt using TPTAC as coupling agent to mesoporous carbon-silica composite material and repair
Decorations, concrete operations are as follows: weigh mesoporous carbon-silica composite material MCSiO obtained in step (1)2- 46 and toluene be placed in circle
In the flask of bottom, TPTAC is added after stirring half an hour, wherein dosage quality is than inorganic silane: organosilan 1:1.2, in room temperature
Then lower stirring 11-12 hours flows back 6 hours at 353K, is washed respectively for several times with toluene and ethyl alcohol, middle drying of dropping a hint,
The P-TPTAC-MCSiO of quaternary ammonium salt modification is prepared2-46。
9. the preparation method of functional ordered mesopore polymer material as claimed in claim 4, which is characterized in that the step
(3) ion-exchange supported palladium, concrete operations are as follows: by P-TPTAC-MCSiO are used2- 46 are dissolved in organic solvent with palladium source, then
It stirs 10-12 hours at room temperature, mixture is filtered, deionized water is washed for several times, and it is dried to be put in 40-50 DEG C of vacuum drying oven
Night.
10. the preparation method of functional ordered mesopore polymer material as claimed in claim 9, which is characterized in that the palladium source
For Na2PdCl4, the reduction reaction conditions are as follows: in the mixed gas that hydrogen and nitrogen volume ratio are 1:4, controlled in tube furnace
Temperature processed is 200 DEG C, is carried out hydrogen reducing 2 hours.
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