CN105921162A - Short-duct mesoporous nanosphere, preparation method thereof, bifunctional catalyst and preparation method thereof - Google Patents
Short-duct mesoporous nanosphere, preparation method thereof, bifunctional catalyst and preparation method thereof Download PDFInfo
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- CN105921162A CN105921162A CN201610325437.1A CN201610325437A CN105921162A CN 105921162 A CN105921162 A CN 105921162A CN 201610325437 A CN201610325437 A CN 201610325437A CN 105921162 A CN105921162 A CN 105921162A
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- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 33
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 23
- 239000002077 nanosphere Substances 0.000 title abstract description 6
- 238000006479 redox reaction Methods 0.000 claims abstract description 14
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims description 58
- 239000002102 nanobead Substances 0.000 claims description 47
- 238000006116 polymerization reaction Methods 0.000 claims description 36
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 28
- BXAVKNRWVKUTLY-UHFFFAOYSA-N 4-sulfanylphenol Chemical compound OC1=CC=C(S)C=C1 BXAVKNRWVKUTLY-UHFFFAOYSA-N 0.000 claims description 23
- 238000001354 calcination Methods 0.000 claims description 23
- 239000011347 resin Substances 0.000 claims description 16
- 229920005989 resin Polymers 0.000 claims description 16
- 239000004094 surface-active agent Substances 0.000 claims description 15
- 229920000642 polymer Polymers 0.000 claims description 14
- 150000001875 compounds Chemical class 0.000 claims description 12
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical group O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 10
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 10
- 239000000463 material Substances 0.000 claims description 10
- 230000032683 aging Effects 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- 239000010931 gold Substances 0.000 claims description 7
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 claims description 6
- 230000003197 catalytic effect Effects 0.000 claims description 6
- 238000006703 hydration reaction Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 208000011580 syndromic disease Diseases 0.000 claims description 2
- 230000000694 effects Effects 0.000 abstract description 8
- 239000011148 porous material Substances 0.000 abstract description 8
- 239000002253 acid Substances 0.000 abstract 1
- 238000011065 in-situ storage Methods 0.000 abstract 1
- 239000007788 liquid Substances 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 39
- 238000003756 stirring Methods 0.000 description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- 229960003742 phenol Drugs 0.000 description 15
- 239000007787 solid Substances 0.000 description 15
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 14
- 125000003396 thiol group Chemical group [H]S* 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000007864 aqueous solution Substances 0.000 description 9
- 238000006555 catalytic reaction Methods 0.000 description 8
- 238000000967 suction filtration Methods 0.000 description 8
- 229910052786 argon Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 239000003921 oil Substances 0.000 description 7
- 238000012360 testing method Methods 0.000 description 7
- 230000033228 biological regulation Effects 0.000 description 6
- 239000011324 bead Substances 0.000 description 5
- 238000010438 heat treatment Methods 0.000 description 5
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 4
- 238000001035 drying Methods 0.000 description 4
- 238000000034 method Methods 0.000 description 4
- 239000010453 quartz Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 239000002904 solvent Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 239000003377 acid catalyst Substances 0.000 description 3
- YYAPGCGSUOZSNQ-UHFFFAOYSA-K ethanol;trichlorogold Chemical compound CCO.Cl[Au](Cl)Cl YYAPGCGSUOZSNQ-UHFFFAOYSA-K 0.000 description 3
- 125000001967 indiganyl group Chemical group [H][In]([H])[*] 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 229910052717 sulfur Inorganic materials 0.000 description 3
- 239000011593 sulfur Substances 0.000 description 3
- RMVRSNDYEFQCLF-UHFFFAOYSA-N thiophenol Chemical compound SC1=CC=CC=C1 RMVRSNDYEFQCLF-UHFFFAOYSA-N 0.000 description 3
- 238000010792 warming Methods 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- -1 hydroxyl sulphur Phenol Chemical compound 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 description 2
- VMKYTRPNOVFCGZ-UHFFFAOYSA-N 2-sulfanylphenol Chemical compound OC1=CC=CC=C1S VMKYTRPNOVFCGZ-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- 239000005864 Sulphur Substances 0.000 description 1
- 150000001335 aliphatic alkanes Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000003111 delayed effect Effects 0.000 description 1
- 239000003989 dielectric material Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 239000008236 heating water Substances 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical class [H]* 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002954 polymerization reaction product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 239000000523 sample Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- KKCBUQHMOMHUOY-UHFFFAOYSA-N sodium oxide Chemical compound [O-2].[Na+].[Na+] KKCBUQHMOMHUOY-UHFFFAOYSA-N 0.000 description 1
- 229910001948 sodium oxide Inorganic materials 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 238000004804 winding Methods 0.000 description 1
Classifications
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
- B01J35/51—Spheres
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- 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
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/63—Pore volume
- B01J35/633—Pore volume less than 0.5 ml/g
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
- B01J35/64—Pore diameter
- B01J35/647—2-50 nm
-
- 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
- B01J37/084—Decomposition of carbon-containing compounds into carbon
-
- 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
- B01J37/16—Reducing
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
- C07C45/26—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by hydration of carbon-to-carbon triple bonds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Crystallography & Structural Chemistry (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Composite Materials (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
- Phenolic Resins Or Amino Resins (AREA)
Abstract
The invention provides a preparation method of a short-duct mesoporous nanosphere. The obtained short-duct mesoporous nanosphere has very high sulfydryl content. Experimental results of embodiments show that the sulfydryl content can be highest to 0.67 mmol/g. In addition, the experimental results of the embodiments also show that the obtained short-duct mesoporous nanosphere is of a body centered cubic structure and has good degree of order, the sylfydryl content can be highest to 0.67 mmol/g, the specific surface area is 110 m<2>/g or above, and the pore size is about 5.0 nm. The invention further provides a preparation method of a bifunctional catalyst. The mixed liquid of the obtained short-duct mesoporous nanosphere and a chloroauric acid solution is subjected to in-situ redox reaction, and the bifunctional catalyst is obtained. The experimental results of the embodiments show that the obtained catalyst has good catalyzing activity.
Description
Technical field
The present invention relates to technical field of function materials, particularly relate to a kind of short-bore road meso-porous nano bead and
Preparation method and bifunctional catalyst and preparation method thereof.
Background technology
Meso-porous nano bead due to have relatively short-bore road, ball size strong at Nano grade, surface hydrophobic,
High surface, high mechanical properties, it is easily-synthesized and a series of advantages such as low cost increasingly cause the pass of people
Note.Meso-porous nano bead can be applied separating, adsorbs, is catalyzed, dielectric material and biology sensor etc.
Technical field.
The little ball material of meso-porous nano comprises mesoporous silicon sphere, mesopore metal oxide nanosphere and mesoporous carbon spheres etc..
Zhao Dongyuan academician seminar has synthesized a kind of mesoporous height with body-centered cubic structure by hydrothermal synthesis method
Molecule nano bead, and by modulation phenol and the mol ratio of water, can obtain ball size, aperture big
The most regulatable little mesoporous polymer nanometer bead, wherein the size of meso-porous nano bead can be from 20nm
It is tuned to 140nm.Compared with the mesoporous material of long duct, the nanometer bead of this kind of meso-hole structure has regular
Pattern, short-bore road, aperture be relatively larger than the features such as long duct, be more beneficial for reactant and catalytic active site
Contact, thus improve reaction catalysis activity.
In order to improve absorption property, it will usually modify the functional groups such as sulfydryl at meso-porous nano bead material surface
Thus improve clearance and the selectivity of heavy metal ion.The little ball material of meso-porous nano of high sulfhydryl content
(SH-MPN) have that high surface, big pore volume, duct be regular and heat endurance advantages of higher, show relatively
Good absorption property.
But, meso-porous nano bead material function used in the market is more single, there are no about short
The report of the little ball material of meso-porous nano of duct-high sulfhydryl content.
Summary of the invention
It is an object of the invention to provide a kind of short-bore road meso-porous nano bead and preparation method thereof with difunctional
Catalyst and preparation method thereof, the meso-porous nano bead and the one that obtain a kind of short-bore Dao-high sulfhydryl content are high
The function catalyst of catalytic efficiency.
In order to realize foregoing invention purpose, the present invention provides techniques below scheme:
The invention provides the preparation method of a kind of short-bore road meso-porous nano bead, comprise the following steps:
Carry out adding heat fusing by the mixture of thiohydroquinone and phenol, obtain fused mass；
Described fused mass and alkaline compound solution are mixed, obtains alkaline mixt；
By described alkaline mixt and formaldehyde hybrid reaction, obtain mercapto-functionalized resin；
Described mercapto-functionalized resin and surfactant are carried out the first hot polymerization reaction, described surface-active
Agent is PEO-PPOX-PEO；
The product of described first hot polymerization reaction is mixed with Part I water and carries out the second hot polymerization reaction, obtain
Hot polymerization system；
Described hot polymerization system and Part II water are mixed and is aged, obtain polymer；
Described polymer is calcined under an inert atmosphere, obtains short-bore road meso-porous nano bead.
Preferably, the mass ratio of described thiohydroquinone and phenol is (2～5): (1～6)；
The mass concentration of described alkaline compound solution is 0.01～0.5mol/L；
The quality of described thiohydroquinone and the volume ratio of alkaline compound solution are
(0.2～0.5) g:(10～20) mL；
Described formaldehyde is formalin；
The mass concentration of described formalin is 35～40%；
The quality of described thiohydroquinone and the mass ratio of formalin are (0.2～0.5) g:(0.35～1.2) g.
Preferably, the temperature adding heat fusing described in is 60～80 DEG C.
Preferably, described surfactant is surfactant solution；
The mass ratio of described thiohydroquinone and surfactant is (0.2～0.5): (0.5～1.5)；
The mass ratio of thiohydroquinone and Part I water is (0.2～0.5): (40～60)；
The volume ratio of described hot polymerization system and Part II water is (15～20): (50～60).
Preferably, the temperature of described first hot polymerization reaction is 60～70 DEG C；
The time of described first hot polymerization reaction is 1～3 hour；
The temperature of described second hot polymerization reaction is 60～70 DEG C；
The time of described second hot polymerization reaction is 16～18 hours；
The temperature of described ageing is 120～140 DEG C；
The time of described ageing is 20～28 hours.
Preferably, described calcining is to be incubated 1～3 hour under the first calcining heat successively, in the second calcining
At a temperature of be incubated 5～10 hours；
Described first calcining heat is 90～110 DEG C；
Described second calcining heat is 340～360 DEG C.
Present invention also offers the short-bore road meso-porous nano bead that above-mentioned preparation method obtains, its specific surface area
More than or equal to 110m2/ g, aperture diameter is 4～6nm.
The preparation method of a kind of bifunctional catalyst of the present invention, comprises the following steps:
According to the preparation method described in claim 1～6 any one, prepare short-bore road meso-porous nano
Bead；
Described short-bore road meso-porous nano bead and gold chloride are carried out redox reaction under solution system,
Obtain bifunctional catalyst；
Described gold chloride is chlorauric acid solution；
The substance withdrawl syndrome of described chlorauric acid solution is 7～10mmol/L；
The ratio of the amount of the material of the S in described short-bore road meso-porous nano bead and the Au in gold chloride is
(1～3): 1.
Preferably, the temperature of described redox reaction is-5～0 DEG C；
The time of described redox reaction is 20～30 hours.
The bifunctional catalyst that the preparation method preferably stated obtains, this catalyst is
Au-SH/SO3H-MPN, the catalytic rate to phenylacetylene hydration reaction is 81%.
The invention provides the preparation method of a kind of short-bore road meso-porous nano bead, the present invention will be to hydroxyl sulphur
Phenol and phenol obtain mercapto-functionalized resin under the catalysis of formaldehyde；Described mercapto-functionalized resin is through overheated
Gather, be aged and calcining obtains short-bore road meso-porous nano bead.Test result indicate that of embodiment, the present invention
The sulfhydryl content of the short-bore road meso-porous nano bead obtained reaches as high as 0.67mmol/g, and specific surface area all exists
110m2/ more than g, and pore size is at about 5.0nm.
Present invention also offers the preparation method of a kind of bifunctional catalyst, the short-bore road present invention obtained
The mixed liquor of meso-porous nano bead and chlorauric acid solution carries out redox reaction, obtains bifunctional catalyst.
Test result indicate that of embodiment, the catalyst obtained is respectively provided with and is preferably catalyzed activity, and catalytic rate is the highest
79% can be reached.
Accompanying drawing explanation
Fig. 1 is the flow chart that the present invention prepares short-bore road meso-porous nano bead；
Fig. 2 is the XRD diffraction pattern of the SH-MPN that the embodiment of the present invention 1～3 obtains；
Fig. 3 is the XPS figure of the SH-MPN that the embodiment of the present invention 1～3 obtains；
Fig. 4 is the N of the SH-MPN that the embodiment of the present invention 1～3 obtains2Inhale de--attached thermoisopleth；
Fig. 5 is the graph of pore diameter distribution of the SH-MPN that the embodiment of the present invention 1～3 obtains；
Fig. 6 is the SEM figure of the SH-MPN that the embodiment of the present invention 1～3 obtains.
Detailed description of the invention
The invention provides the preparation method of a kind of short-bore road meso-porous nano bead, comprise the following steps:
Carry out adding heat fusing by the mixture of thiohydroquinone and phenol, obtain fused mass；
Described fused mass and alkaline compound solution are mixed, obtains alkaline mixt；
By described alkaline mixt and formaldehyde hybrid reaction, obtain mercapto-functionalized resin；
Described mercapto-functionalized resin and surfactant are carried out the first hot polymerization reaction；
The product of described first hot polymerization reaction is mixed with Part I water and carries out the second hot polymerization reaction, obtain
Hot polymerization system；
Described hot polymerization system and Part II water are mixed and is aged, obtain polymer；
Described polymer is calcined under an inert atmosphere, obtains short-bore road meso-porous nano bead.
The mixture of thiohydroquinone and phenol is carried out adding heat fusing by the present invention, obtains fused mass.This
Inventing the source to described thiohydroquinone and phenol and do not have particular/special requirement, concrete can be to hydroxyl
Benzenethiol and the commercially available prod of phenol.In the present invention, described thiohydroquinone and the mass ratio of phenol
It is preferably (2～5): (1～6), is preferably (3～4.5): (2～5), more preferably (3.5～4.2): (3～4).
In the present invention, the temperature adding heat fusing is preferably 60～80 DEG C, more preferably 65～75 DEG C, optimum
Elect 68～72 DEG C as.The present invention does not has particular/special requirement to the described time adding heat fusing, it is possible to by para hydroxybenzene
The mixture of thiophenol and phenol melts.The described detailed description of the invention adding heat fusing is not had by the present invention
Particular/special requirement, concrete can be heating water bath or oil bath heating.
After obtaining described fused mass, described fused mass and alkaline compound solution are mixed by the present invention,
To alkaline mixt.In the present invention, described alkali compounds is preferably hydroxide, more preferably hydrogen
Sodium oxide molybdena or potassium hydroxide.
In the present invention, the molar concentration of described alkaline compound solution is preferably 0.01～0.5mol/L, more
It is preferably 0.05～0.3mol/L, most preferably 0.1～0.2mol/L.In the present invention, described alkalescence chemical combination
Solvent in thing solution is preferably water.The present invention is suitable to the mixing of described fused mass and alkaline compound solution
Sequence does not has particular/special requirement, can mix in any order.
The alkaline mixt obtained preferably is stirred by the present invention so that alkaline mixt mixes more
Uniformly.The present invention does not has particular/special requirement to the concrete mode of described stirring, uses those skilled in the art institute
Known to agitating mode carry out.In the present invention, the time of described stirring is preferably 8～12 minutes,
Concrete can be 8 minutes, 9 minutes, 10 minutes, 11 minutes or 12 minutes.
In the present invention, the quality of described thiohydroquinone and the volume ratio of alkaline compound solution are preferred
For (0.2～0.5) g:(10～20) mL, more preferably (0.3～0.5) g:(12～18) mL, most preferably
0.402g:15mL。
After obtaining described alkaline mixt, the present invention by described alkaline mixt and formaldehyde hybrid reaction,
Obtain mercapto-functionalized resin.Formaldehyde is preferably mixed with described alkalescence by the present invention with the form of formalin
Thing hybrid reaction；The mass concentration of described formalin is preferably 35～40%, concrete can be 35%,
36%, 37%, 38% or 39%.In the present invention, the solvent in described formalin is preferably water.This
Invent the order by merging to described alkaline mixt and formalin and there is no particular/special requirement, can be according to arbitrarily
Order mix.
The mixture of described alkaline mixt and formaldehyde is preferably stirred by the present invention.The present invention is to described
The concrete mode of stirring does not has particular/special requirement, uses agitating mode well-known to those skilled in the art to carry out
?.In the present invention, the time of described stirring is preferably 50～70 minutes, more preferably 55～65 points
Clock, most preferably 58～62 minutes.In the present invention, the speed of described stirring is preferably 300～380rpm,
More preferably 320～360rpm, most preferably 330～350rpm.
In the present invention, the quality of described thiohydroquinone and the mass ratio of formalin are preferably
(0.2～0.4) g:(0.35～1.2) g, more preferably (0.25～0.35) g:(0.55～1) g, most preferably
(0.28～0.3) g:(0.7～0.9) g.
After obtaining described mercapto-functionalized resin, described mercapto-functionalized resin and surface are lived by the present invention
Property agent carries out the first hot polymerization reaction, and described surfactant is PEO-PPOX-polycyclic oxygen second
Alkane (F127).In the present invention, the weight average of described PEO-PPOX-PEO divides
Son amount preferably 12000～13000, more preferably 12300～12800, most preferably 12500～12600.
In the present invention, described surfactant is preferably surfactant solution, described surfactant
Solvent in solution is preferably water；The concentration of described surfactant solution is preferably 0.025～0.15g/mL,
More preferably 0.05～0.12g/mL, most preferably 0.07～0.1g/mL.
In the present invention, the mass ratio of described thiohydroquinone and surfactant is
(0.2～0.5): (0.5～1.5), more preferably (0.2～0.4): (0.7～1.3), most preferably 0.3:(0.8～1).
In the present invention, the temperature of described first hot polymerization reaction is preferably 60～70 DEG C, more preferably
63～68 DEG C, most preferably 65～66 DEG C；The time of described first hot polymerization reaction is preferably 1～3 hour, tool
Body can be 1 hour, 2 hours or 3 hours.
The present invention described first hot polymerization reaction after, by described first hot polymerization reaction product and first
Divide water mixing to carry out the second hot polymerization reaction, obtain hot polymerization system.In the present invention, thiohydroquinone and
The mass ratio of Part I water is preferably (0.2～0.5): (40～60), more preferably (0.2～0.5): (45～55),
It is preferably 0.402:50.
In the present invention, the temperature of described second hot polymerization reaction is preferably 60～70 DEG C, more preferably
63～68 DEG C, most preferably 65～66 DEG C；The time of described second hot polymerization reaction is preferably 16～18 hours,
Concrete can be 16 hours, 17 hours or 18 hours.
After obtaining described hot polymerization system, described hot polymerization system and Part II water are mixed into by the present invention
Row ageing, obtains polymer.In the present invention, the volume ratio of described hot polymerization system and Part II water is excellent
Elect as (15～20): (50～60), more preferably (17～18): (54～58), most preferably 17.7:56.
In the present invention, the temperature of described ageing is preferably 120～140 DEG C, more preferably 125～135 DEG C,
Most preferably 130～132 DEG C；The time of described ageing is preferably 20～28 hours, more preferably 22～26
Hour, most preferably 24～25 hours.
Product after described ageing is preferably centrifuged by the present invention, obtains solid polymer.The present invention couple
Described centrifugal concrete operation does not has particular/special requirement, uses centrifugal behaviour well-known to those skilled in the art
Make to carry out.
Described solid polymer is preferably washed by the present invention.In the present invention, wash used by described washing
Wash agent and be preferably ethanol and/or water.The present invention does not has particular/special requirement to the concrete operation of described washing, adopts
Carry out with washing operation well-known to those skilled in the art.
After described washing, described solid polymer is preferably dried by the present invention.The present invention is to described dry
Dry temperature and time does not has particular/special requirement, it is possible to the water of solid polymer surfaces and/or ethanol are dried
?.
After obtaining described polymer, described polymer is calcined by the present invention under an inert atmosphere,
To short-bore road meso-porous nano bead.In the present invention, described inert atmosphere is preferably argon gas.In the present invention
In, described calcining is preferably carried out in quartz boat.
In the present invention, described calcining is preferably and is incubated 1～3 hour under the first calcining heat successively,
It is incubated 5～10 hours under second calcining heat.In an embodiment of the present invention, the guarantor under described first calcining
The temperature time is 1 hour, 2 hours or 3 hours；Temperature retention time under described second calcining is 5 hours, 6
Hour, 7 hours, 8 hours, 9 hours or 10 hours.
In the present invention, described first calcining heat is preferably 90～110 DEG C, more preferably 95～105 DEG C,
Most preferably 98～100 DEG C；Described second calcining heat is preferably 340～360 DEG C, more preferably
345～355 DEG C, most preferably 348～350 DEG C K.
The present invention preferably rises to the first calcining heat with the first heating rate from room temperature, with the second heating rate
The second calcining heat is risen to from the first calcining heat.In the present invention, described first heating rate is preferably
1～3 DEG C/min, that concrete can be 1 DEG C/min, 2 DEG C/min or 3 DEG C/min；Described second heating rate
Being preferably 1～3 DEG C/min, that concrete can be 1 DEG C/min, 2 DEG C/min or 3 DEG C/min.
The present invention prepares the process of SH-MPN short-bore road meso-porous nano bead as it is shown in figure 1, Fig. 1 is this
The flow chart of invention preparation short-bore road meso-porous nano bead.
Present invention also offers the preparation method of a kind of bifunctional catalyst, comprise the following steps:
According to the preparation method of short-bore road meso-porous nano bead described in technique scheme, prepare short-bore
Road meso-porous nano bead；
Described short-bore road meso-porous nano bead and gold chloride are carried out redox reaction under solution system,
Obtain bifunctional catalyst.
After obtaining described short-bore road meso-porous nano bead, the present invention is by described short-bore road meso-porous nano bead
Under solution system, carry out redox reaction with gold chloride, obtain bifunctional catalyst.
In the present invention, described gold chloride is preferably chlorauric acid solution, the solvent in described chlorauric acid solution
It is preferably water, methyl alcohol, ethanol or propyl alcohol.In the present invention, the amount of the material of described chlorauric acid solution is dense
Degree is preferably 7～10mmol/L, concrete can be 7mmol/L, 8mmol/L, 9mmol/L or
10mmol/L。
In the present invention, the S in described short-bore road meso-porous nano bead and the mol ratio of the Au in gold chloride
Being preferably (1～3): 1, that concrete can be 1:1,1.5:1,2:1,2.5:1 or 3:1.
In the present invention, the temperature of described redox reaction is preferably-5～0 DEG C, concrete can be-5 DEG C,
-4 DEG C ,-3 DEG C ,-2 DEG C ,-1 or 0 DEG C；The time of described redox reaction is preferably 20～30 hours,
More preferably 22～28 hours, most preferably 24～26 hours.In the present invention, described redox is anti-
Should preferably carry out in recirculation cooler.
The present invention preferably carries out suction filtration to the bifunctional catalyst obtained.The present invention is concrete to described suction filtration
Embodiment does not has particular/special requirement, uses suction filtration well-known to those skilled in the art operation to carry out.
After described suction filtration, the solid that suction filtration is preferably obtained by the present invention with water and/or ethanol washs.
The present invention does not has particular/special requirement to the detailed description of the invention of described washing, uses those skilled in the art institute ripe
The washing operation known is carried out.
After described washing, described solid is preferably dried by the present invention, obtains Au-SH/SO3H-MPN
Bifunctional catalyst.In the present invention, described dry temperature is preferably 70～90 DEG C, more preferably
75～85 DEG C, most preferably 78～82 DEG C.In the present invention, to be preferably 20～28 little the described dry time
Time, more preferably 22～26 hours, most preferably 23～25 hours.In the present invention, described dry excellent
It is selected in drying box and carries out.
The invention provides the preparation method of a kind of short-bore road meso-porous nano bead, the present invention will be to hydroxyl sulphur
Phenol and phenol obtain mercapto-functionalized resin under the catalysis of formaldehyde；Described mercapto-functionalized resin is through overheated
Gather, be aged and calcining obtains short-bore road meso-porous nano bead.Test result indicate that of embodiment, the present invention
The sulfhydryl content of the short-bore road meso-porous nano bead obtained reaches as high as 0.67mmol/g, and specific surface area all exists
110m2/ more than g, and pore size is at about 5.0nm.
Present invention also offers the preparation method of a kind of bifunctional catalyst, the short-bore road present invention obtained
The mixed liquor of meso-porous nano bead and chlorauric acid solution carries out redox reaction, obtains bifunctional catalyst.
Test result indicate that of embodiment, the catalyst obtained is respectively provided with and is preferably catalyzed activity, and catalytic rate is the highest
79% can be reached.A kind of short-bore road meso-porous nano bead present invention provided below in conjunction with embodiment
The preparation of preparation and bifunctional catalyst is described in detail, but they can not be interpreted as this
The restriction of bright protection domain.
Embodiment 1
Weigh 0.3g phenol respectively and 0.402g thiohydroquinone is placed in clean three-necked bottle, regulation
Oil bath temperature is 70 DEG C.After being heated to fusing, pour the 15ml 0.10mol/L NaOH aqueous solution into, stirring
After 10min, then it is added thereto to 2.1ml 37wt% formalin, and returns with the rotating speed of 340rpm
Stream 1.0h, prepares the mercapto-functionalized resin of low-molecular-weight.
Weigh 0.96g F127 as 15ml H2In O so that it is dissolve, obtain the F127 aqueous solution.Will
The 15ml F127 aqueous solution pours above-mentioned three-necked bottle into, and regulation oil bath temperature is 66 DEG C, adds after stirring 2h again
50ml water, continuing to keep temperature is 66 DEG C.During whole stirring, the color from light yellow of solution
Become orange, after continuing stirring 16h～18h, have a small amount of pale yellow precipitate to produce, stop reaction, stand
Dissolve to sediment, obtain orange settled solution.
Then 17.7ml gained solution and 56.0ml H are measured2O pours in reactor, is aged at 130 DEG C
After 24h, centrifuge washing is dried to obtain faint yellow solid.The faint yellow solid grind into powder obtained is gone to
In quartz boat, calcine under 350 DEG C of argon gas atmosphere.Tube furnace the most at room temperature leads to argon gas half an hour, so
After rise to 100 DEG C with the speed of 2 DEG C/min and keep 1h after, then 2 DEG C/min is warming up to 350 DEG C, protects
After holding 7h, obtain 50%-SH-MPN order mesoporous nanometer bead.
Embodiment 2
Weigh 0.3g phenol respectively and 0.2412g thiohydroquinone is placed in clean three-necked bottle, regulation
Oil bath temperature is 70 DEG C.After being heated to fusing, pour the 15ml 0.10mol/L NaOH aqueous solution into, stirring
After 10min, then it is added thereto to 2.1ml 37wt% formalin, and returns with the rotating speed of 340rpm
Stream 1.0h, prepares the mercapto-functionalized resin of low-molecular-weight.
Weigh 0.96g F127 as 15ml H2In O so that it is dissolve, obtain the F127 aqueous solution.Will
The 15ml F127 aqueous solution pours above-mentioned three-necked bottle into, and regulation oil bath temperature is 66 DEG C, adds after stirring 2h again
50ml water, continuing to keep temperature is 66 DEG C.During whole stirring, the color from light yellow of solution
Become orange, after continuing stirring 16h～18h, have a small amount of pale yellow precipitate to produce, stop reaction, stand
Dissolve to sediment, obtain orange settled solution.
Then 17.7ml gained solution and 56.0ml H are measured2O pours in reactor, is aged at 130 DEG C
After 24h, centrifuge washing is dried to obtain faint yellow solid.The faint yellow solid grind into powder obtained is gone to
In quartz boat, calcine under 350 DEG C of argon gas atmosphere.Tube furnace the most at room temperature leads to argon gas half an hour, so
After rise to 100 DEG C with the speed of 2 DEG C/min and keep 1h after, then 2 DEG C/min is warming up to 350 DEG C, protects
After holding 7h, obtain 30%-SH-MPN order mesoporous nanometer bead.
Embodiment 3
Weigh 0.3g phenol respectively and 0.1206g thiohydroquinone is placed in clean three-necked bottle, regulation
Oil bath temperature is 70 DEG C.After being heated to fusing, pour the 15ml 0.10mol/L NaOH aqueous solution into, stirring
After 10min, then it is added thereto to 2.1ml 37wt% formalin, and returns with the rotating speed of 340rpm
Stream 1.0h, prepares the mercapto-functionalized resin of low-molecular-weight.
Weigh 0.96g F127 as 15ml H2In O so that it is dissolve, obtain the F127 aqueous solution.Will
The 15ml F127 aqueous solution pours above-mentioned three-necked bottle into, and regulation oil bath temperature is 66 DEG C, adds after stirring 2h again
50ml water, continuing to keep temperature is 66 DEG C.During whole stirring, the color from light yellow of solution
Become orange, after continuing stirring 16h～18h, have a small amount of pale yellow precipitate to produce, stop reaction, stand
Dissolve to sediment, obtain orange settled solution.
Then 17.7ml gained solution and 56.0ml H are measured2O pours in reactor, is aged at 130 DEG C
After 24h, centrifuge washing is dried to obtain faint yellow solid.The faint yellow solid grind into powder obtained is gone to
In quartz boat, calcine under 350 DEG C of argon gas atmosphere.Tube furnace the most at room temperature leads to argon gas half an hour, so
After rise to 100 DEG C with the speed of 2 DEG C/min and keep 1h after, then 2 DEG C/min is warming up to 350 DEG C, protects
After holding 7h, obtain 15%-SH-MPN order mesoporous nanometer bead.
The SH-MPN that embodiment 1～3 is obtained by the present invention is detected, testing result such as Fig. 2～6 Hes
Shown in table 1.Wherein, Fig. 2 is the XRD diffraction pattern of the SH-MPN that the embodiment of the present invention 1～3 obtains,
Fig. 3 is the XPS figure of the SH-MPN that the embodiment of the present invention 1～3 obtains；Fig. 4 is the embodiment of the present invention 1～3
The N of the SH-MPN obtained2Inhale de--attached thermoisopleth；Fig. 5 is that the embodiment of the present invention 1～3 obtains
The graph of pore diameter distribution of SH-MPN；Fig. 6 is the SEM figure of the SH-MPN that the embodiment of the present invention 1～3 obtains.
As shown in Figure 2, the meso-hole structure of the SH-MPN that the present invention obtains is body-centered cubic structure, at 2 θ
Diffraction maximum at=0 °～0.9 ° and 2 θ=1.5 ° represents [110] and [211] face of body-centered cubic structure respectively；With
The increase of sulfhydryl content, the degree of order of mercapto-functionalized meso-porous nano bead reduces constantly.
From the figure 3, it may be seen that one absworption peak of appearance that the SH-MPN that obtains of the present invention is at 164.0eV,
Belong to-the sulphur of divalent.As shown in Figure 4, the SH-MPN that the present invention obtains is first kind adsorption desorption isothermal
Line, and have delayed winding and slight capillary condensation phenomenon, show with the presence of meso-hole structure.Can by Fig. 5
Knowing, the aperture of the SH-MPN material that the present invention obtains does not presents mountain valley shape distribution trend, all 0～5nm
Between.
In Fig. 6 a, b, c, d, e be respectively 15%-SH-MPN, 20%-SH-MPN, 30%-SH-MPN,
50%-SH-MPN and 100%-SH-MPs.It will be appreciated from fig. 6 that the different sulfhydryl contents that obtain of the present invention
SH-MPN presents regular spherical morphology, and the surface of ball also can be clearly seen the existence of mesopore orbit,
And the size of ball is all at about 150nm, and e figure is the SEM figure of long duct SH-MPs-H, with a,
B, c, d are contrary, are shaped as sheet, size heterogeneity, do not have regular pattern.
The structural parameters of the SH-MPN that table 1 obtains for the present embodiment and sulfur content data.
The structural parameters of SH-MPN and sulfur content data in table 1 embodiment 1～3
As shown in Table 1, the sulfhydryl content of the SH-MPN that the present invention obtains can reach 0.67mmol/g,
Specific surface area is all at 110m2/ more than g, and pore size is at about 5.0nm.
Embodiment 4
50%-SH-MPN and 8.0mmol/L gold chloride ethanol solution embodiment 1 obtained is placed in flask
In so that the mol ratio of S:Au is 1.5:1.0.Flask is placed in recirculation cooler, and regulates temperature
It it is 0 DEG C.After stirring 24h, solution stirring obtained carries out suction filtration, and fully washs with water and ethanol
After, it is placed in 80 DEG C of drying boxes and is dried 24h, thus prepare 50%-Au-SH/SO3H-MPN is difunctional solid
Body acid catalyst.The Au-SH/SO that table 2 obtains for the present embodiment3The structural parameters of H-MPN and gold content
Data.
Table 2Au-SH/SO3The structural parameters of H-MPN and sulfur content data
Embodiment 5
30%-SH-MPN and 8.0mmol/L gold chloride ethanol solution embodiment 2 obtained is placed in flask
In so that the mol ratio of S:Au is 1.5:1.0.Flask is placed in recirculation cooler, and regulates temperature
It it is 0 DEG C.After stirring 24h, solution stirring obtained carries out suction filtration, and fully washs with water and ethanol
After, it is placed in 80 DEG C of drying boxes and is dried 24h, thus prepare 30%-Au-SH/SO3H-MPN is difunctional solid
Body acid catalyst.
Embodiment 6
15%-SH-MPN and 8.0mmol/L gold chloride ethanol solution embodiment 3 obtained is placed in flask
In so that the mol ratio of S:Au is 1.5:1.0.Flask is placed in recirculation cooler, and regulates temperature
It it is 0 DEG C.After stirring 24h, solution stirring obtained carries out suction filtration, and fully washs with water and ethanol
After, it is placed in 80 DEG C of drying boxes and is dried 24h, thus prepare 15%-Au-SH/SO3H-MPN is difunctional solid
Body acid catalyst.
The Au-SH/SO that embodiment 4～6 is also obtained by the present invention3H-MPs catalysis phenylacetylene hydration reaction is made
Catalysis activity for probe reaction compares, and comparative result is as shown in table 3.
Au-SH/SO implemented by table 33H-MPN is catalyzed expression activitiy
As shown in Table 2, when catalyst feeds intake identical with catalysis time, three kinds of catalyst are respectively provided with preferably
Catalysis activity, but catalysis activity most preferably 50%-Au-SH/SO3H-MPN。
As seen from the above embodiment, the short-bore road meso-porous nano bead that the present invention obtains has the highest sulfydryl
Content, test result indicate that of embodiment, sulfhydryl content reaches as high as 0.67mmol/g.Additionally, embodiment
Experimental result it is also shown that the short-bore road meso-porous nano bead that the present invention obtains is body-centered cubic structure, tool
Having the preferable degree of order, sulfhydryl content can reach 0.67mmol/g, and specific surface area is all at 110m2/G with
On, and pore size is at about 5.0nm.
Present invention also offers the preparation method of a kind of bifunctional catalyst, the short-bore road present invention obtained
The mixed liquor of meso-porous nano bead and chlorauric acid solution carries out redox reaction, obtains bifunctional catalyst.
Test result indicate that of embodiment, the catalyst obtained is respectively provided with and is preferably catalyzed activity.
The above is only the preferred embodiment of the present invention, it is noted that general for the art
For logical technical staff, under the premise without departing from the principles of the invention, it is also possible to make some improvement and profit
Decorations, these improvements and modifications also should be regarded as protection scope of the present invention.
Claims (10)
1. a preparation method for short-bore road meso-porous nano bead, comprises the following steps:
Carry out adding heat fusing by the mixture of thiohydroquinone and phenol, obtain fused mass；
Described fused mass and alkaline compound solution are mixed, obtains alkaline mixt；
By described alkaline mixt and formaldehyde hybrid reaction, obtain mercapto-functionalized resin；
Described mercapto-functionalized resin and surfactant are carried out the first hot polymerization reaction, described surface-active
Agent is PEO-PPOX-PEO；
The product of described first hot polymerization reaction is mixed with Part I water and carries out the second hot polymerization reaction, obtain
Hot polymerization system；
Described hot polymerization system and Part II water are mixed and is aged, obtain polymer；
Described polymer is calcined under an inert atmosphere, obtains short-bore road meso-porous nano bead.
Preparation method the most according to claim 1, it is characterised in that described thiohydroquinone and
The mass ratio of phenol is (2～5): (1～6)；
The mass concentration of described alkaline compound solution is 0.01～0.5mol/L；
The quality of described thiohydroquinone and the volume ratio of alkaline compound solution are
(0.2～0.5) g:(10～20) mL；
Described formaldehyde is formalin；
The mass concentration of described formalin is 35～40%；
The quality of described thiohydroquinone and the mass ratio of formalin are (0.2～0.5) g:(0.35～1.2) g.
Preparation method the most according to claim 1, it is characterised in that described in add the temperature of heat fusing
It it is 60～80 DEG C；
The temperature of described ageing is 120～140 DEG C；
The time of described ageing is 20～28 hours.
Preparation method the most according to claim 1, it is characterised in that described thiohydroquinone and
The mass ratio of surfactant is (0.2～0.5): (0.5～1.5)；
The mass ratio of thiohydroquinone and Part I water is (0.2～0.5): (40～60)；
The volume ratio of described hot polymerization system and Part II water is (15～20): (50～60).
Preparation method the most according to claim 1, it is characterised in that described first hot polymerization reaction
Temperature is 60～70 DEG C；
The time of described first hot polymerization reaction is 1～3 hour；
The temperature of described second hot polymerization reaction is 60～70 DEG C；
The time of described second hot polymerization reaction is 16～18 hours.
Preparation method the most according to claim 1, it is characterised in that described calcining is successively
It is incubated 1～3 hour under one calcining heat, under the second calcining heat, is incubated 5～10 hours；
Described first calcining heat is 90～110 DEG C；
Described second calcining heat is 340～360 DEG C.
7. the short-bore road meso-porous nano bead that the preparation method described in claim 1～6 any one obtains,
Its specific surface area is more than or equal to 110m2/ g, aperture diameter is 4～6nm.
8. a preparation method for bifunctional catalyst, comprises the following steps:
According to the preparation method described in claim 1～6 any one, prepare short-bore road meso-porous nano
Bead；
Described short-bore road meso-porous nano bead and gold chloride are carried out redox reaction under solution system,
Obtain bifunctional catalyst；
Described gold chloride is chlorauric acid solution；
The substance withdrawl syndrome of described chlorauric acid solution is 7～10mmol/L；
The ratio of the amount of the material of the S in described short-bore road meso-porous nano bead and the Au in gold chloride is
(1～3): 1.
Preparation method the most according to claim 8, it is characterised in that:
The temperature of described redox reaction is-5～0 DEG C；
The time of described redox reaction is 20～30 hours.
10. the bifunctional catalyst that the preparation method described in claim 8 or 9 obtains, this catalyst is
Au-SH/SO3H-MPN, the catalytic rate to phenylacetylene hydration reaction is 79%.
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| CN101745366A (en) * | 2010-01-29 | 2010-06-23 | 上海师范大学 | Mercapto-functionalized organic inorganic hybrid ordered mesoporous silicon material and preparation method thereof |
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| CN101745366A (en) * | 2010-01-29 | 2010-06-23 | 上海师范大学 | Mercapto-functionalized organic inorganic hybrid ordered mesoporous silicon material and preparation method thereof |
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| CN107245136A (en) * | 2017-05-13 | 2017-10-13 | 淮阴师范学院 | A kind of ordered mesoporous polymer material and its preparation method and application |
| CN107245136B (en) * | 2017-05-13 | 2019-01-25 | 淮阴师范学院 | A kind of ordered mesoporous polymer material and its preparation method and application |
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