CN109225326A - The preparation method of composite catalyst based on polypyrrole and Carbon foam load gold nano line - Google Patents
The preparation method of composite catalyst based on polypyrrole and Carbon foam load gold nano line Download PDFInfo
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- CN109225326A CN109225326A CN201811072777.3A CN201811072777A CN109225326A CN 109225326 A CN109225326 A CN 109225326A CN 201811072777 A CN201811072777 A CN 201811072777A CN 109225326 A CN109225326 A CN 109225326A
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- polypyrrole
- carbon foam
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- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 52
- 239000010931 gold Substances 0.000 title claims abstract description 47
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 229910052737 gold Inorganic materials 0.000 title claims abstract description 32
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 title claims abstract description 32
- 239000003054 catalyst Substances 0.000 title claims abstract description 27
- 239000002131 composite material Substances 0.000 title claims abstract description 11
- 238000002360 preparation method Methods 0.000 title claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 22
- 239000006260 foam Substances 0.000 claims abstract description 19
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 14
- 239000003610 charcoal Substances 0.000 claims abstract description 14
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000004033 plastic Substances 0.000 claims abstract description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 39
- 239000000243 solution Substances 0.000 claims description 26
- 235000019441 ethanol Nutrition 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 19
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 claims description 16
- 238000003756 stirring Methods 0.000 claims description 16
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- 238000010521 absorption reaction Methods 0.000 claims description 10
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 9
- 239000001257 hydrogen Substances 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 238000010438 heat treatment Methods 0.000 claims description 8
- 235000010323 ascorbic acid Nutrition 0.000 claims description 7
- 229960005070 ascorbic acid Drugs 0.000 claims description 7
- 239000011668 ascorbic acid Substances 0.000 claims description 7
- 239000012153 distilled water Substances 0.000 claims description 7
- 239000012046 mixed solvent Substances 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 150000003233 pyrroles Chemical class 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 238000010792 warming Methods 0.000 claims description 7
- LMJXSOYPAOSIPZ-UHFFFAOYSA-N 4-sulfanylbenzoic acid Chemical compound OC(=O)C1=CC=C(S)C=C1 LMJXSOYPAOSIPZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000005457 ice water Substances 0.000 claims description 5
- DWAQJAXMDSEUJJ-UHFFFAOYSA-M Sodium bisulfite Chemical compound [Na+].OS([O-])=O DWAQJAXMDSEUJJ-UHFFFAOYSA-M 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 235000010267 sodium hydrogen sulphite Nutrition 0.000 claims description 4
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 2
- 239000001307 helium Substances 0.000 claims description 2
- 229910052734 helium Inorganic materials 0.000 claims description 2
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 2
- 238000004321 preservation Methods 0.000 claims description 2
- 238000002791 soaking Methods 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims 2
- 206010011224 Cough Diseases 0.000 claims 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 14
- 238000004227 thermal cracking Methods 0.000 abstract description 3
- 239000003638 chemical reducing agent Substances 0.000 abstract description 2
- 238000011049 filling Methods 0.000 abstract description 2
- 238000011065 in-situ storage Methods 0.000 abstract description 2
- 238000006116 polymerization reaction Methods 0.000 abstract description 2
- 238000006722 reduction reaction Methods 0.000 abstract description 2
- 239000002105 nanoparticle Substances 0.000 description 13
- 238000006555 catalytic reaction Methods 0.000 description 11
- 238000002371 ultraviolet--visible spectrum Methods 0.000 description 9
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 description 5
- 229910004042 HAuCl4 Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 229910001870 ammonium persulfate Inorganic materials 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000011259 mixed solution Substances 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 206010013786 Dry skin Diseases 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000010276 construction Methods 0.000 description 2
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 description 2
- 239000003063 flame retardant Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 229910052961 molybdenite Inorganic materials 0.000 description 2
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 230000003075 superhydrophobic effect Effects 0.000 description 2
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 1
- 239000011165 3D composite Substances 0.000 description 1
- JAJIPIAHCFBEPI-UHFFFAOYSA-N 9,10-dioxoanthracene-1-sulfonic acid Chemical compound O=C1C2=CC=CC=C2C(=O)C2=C1C=CC=C2S(=O)(=O)O JAJIPIAHCFBEPI-UHFFFAOYSA-N 0.000 description 1
- 239000004640 Melamine resin Substances 0.000 description 1
- 238000005452 bending Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012620 biological material Substances 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000009841 combustion method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 229960003638 dopamine Drugs 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 125000004433 nitrogen atom Chemical group N* 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N phenol group Chemical group C1(=CC=CC=C1)O ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 229920001187 thermosetting polymer Polymers 0.000 description 1
- -1 thiol modified melamine Chemical class 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
- 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
- B01J31/069—Hybrid organic-inorganic polymers, e.g. silica derivatized with organic groups
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—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
- 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
- B01J35/56—Foraminous structures having flow-through passages or channels, e.g. grids or three-dimensional monoliths
-
- 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
-
- 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
- B01J37/02—Impregnation, coating or precipitation
- B01J37/0201—Impregnation
-
- 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
- B01J37/06—Washing
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Physics & Mathematics (AREA)
- Thermal Sciences (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a kind of preparation methods of composite catalyst based on polypyrrole and Carbon foam load gold nano line, using melamine foamed plastic as template, the porous foam charcoal with certain form and elasticity is obtained by the method for a step thermal cracking, the complex carrier of polypyrrole filling is prepared by in-situ polymerization again, finally by chemical reduction method load gold nano line, to obtain a kind of novel load gold nano line catalyst based on porous foam charcoal.Catalyst produced by the present invention has both the physical aspect structure of three-dimensional foam charcoal simultaneously, and has the catalytic activity of gold, can be used as the catalyst of p-nitrophenol in water removal, has good catalytic effect.
Description
Technical field
The present invention relates to a kind of preparation methods of composite catalyst based on polypyrrole and Carbon foam load gold nano line, belong to
In composite catalyzing technical field.
Background technique
First Carbon foam is made to be pyrolyzed thermosetting phenolic early in early 1960s Walter Ford, steeps so far
Foam charcoal has had the developing history of decades.Carbon foam refers to that the one kind being made of hole bubble with interconnected hole steep that wall has
The light porous material of low-density, the three-dimensional open pores network structure of multiple dimensioned hole.This special construction causes Carbon foam both to have
Have the traditional performance of charcoal, there are also conductive, thermally conductive, high-intensitive, corrosion-resistant, density is small, chemical property is stable etc. good physics and
Chemical property.The excellent properties of Carbon foam make it heat exchange, heat transfer, catalyst carrier, gas absorption, filter device,
Before the high-tech areas such as biomaterial highlight unique status, therefore it has wide application in chemical industry, ship, aerospace industry
Scape.
Polymeric foamed material, such as melamine foamed plastic, can for prepare in large quantity three-dimensional porous Carbon Materials provide it is non-
Often good template.Traditional Carbon foam preparation method is to carry out charing preparation again by modifying and decorating, such as dopamine and 12
Perfluorinated thiol modified melamine resin foam can prepare super-hydrophobic flame-retardant sponge.But it needs to use in above-mentioned modifying process
A large amount of modifying agent and nonaqueous solvents, thus limit its industrialized production.Recently, Wang etc. is directly existed using one-step method
The direct available plasticity carbon foam of thermal cracking melamine foamed plastic at 400 DEG C, or can be made by toluene auxiliary combustion method
For super-hydrophobic fire-retardant carbon deposit foam sponge, supported catalyst causes the extensive concern of people on three-dimensional porous material.Park
Deng by MoS2It loads on microcellular carbon foam/N doped graphene carrier and prepares CF-NG@MoS2Composite catalyst, this uniqueness
3D composite construction make its show enhancing HER catalytic activity.As far as we know, most of work at present are devoted to develop
Three-dimensional porous electrocatalysis material there is the organic catalytic reaction of significant application value but seldom to study actual industrial production.
Summary of the invention
The purpose of the present invention is to overcome above-mentioned the deficiencies in the prior art.
To realize above goal of the invention, the present invention provides a kind of compound based on polypyrrole and Carbon foam load gold nano line
The preparation method of catalyst, includes the following steps:
(1) melamine foamed plastic is cut into suitable size, is cleaned by ultrasonic 3 times with ethyl alcohol and distilled water respectively, it is dry to perseverance
Weight；
(2) above-mentioned melamine foamed plastic is placed into the tube furnace for being mixed with the mixed atmosphere of hydrogen and nitrogen, with constant
Heating rate be warming up to certain temperature and keep the temperature a period of time, then room temperature is down to constant rate of temperature fall, being made has one
The porous foam charcoal of the state that shapes and elasticity；
(3) above-mentioned porous foam charcoal is immersed in pyrroles's aqueous solution the stirring under ice-water bath and absorbs a period of time, then
Addition NaHSO3 aqueous solution continues absorption stirring and is placed on refrigerator standing for a period of time, after taking-up embathes 3 times with deionized water, sets
Enter vacuum drying in vacuum oven and obtains polypyrrole/Carbon foam support C F@PPy；
(4) CF PPy is put into the in the mixed solvent of the second alcohol and water of the solution containing aminopropyl triethoxysilane, is stirred
For a period of time, taking-up is embathed 3 times with deionized water, is then placed in previously prepared Au seed solution and is adsorbed a period of time
Afterwards, taking-up is embathed 3 times with deionized water, be finally putting by 4- mercaptobenzoic acid solution, gold chloride and ascorbic acid solution by
It in the good growth-promoting media of proportional arrangement, is embathed 3 times with deionized water after reaction, drying is based in merging vacuum oven
Polypyrrole/Carbon foam load gold nano line composite catalyst CF@PPy.AuNWs.
Further, in the step (2), hydrogen and helium volume ratio are 1:4~1:15.
Further, in the step (2), the speed of heating is 5 DEG C/min~50 DEG C/min, and the temperature range of heat preservation is
300~1000 DEG C.
Further, in the step (2), soaking time is 1h~8h.
Further, in the step (3), the concentration of pyrroles's aqueous solution is 5 0mM~200mM, NaHSO3 aqueous solution
Concentration is 0.05M~0.2M.
Further, in the step (3), absorption mixing time be 10min~120min, refrigerator time of repose be 4h~
24h。
Further, in the step (3), vacuum drying temperature is 20 DEG C~100 DEG C, and drying time is 6h~48h.
Further, in the step (4), the concentration of aminopropyl triethoxysilane (APTES) is 2~10mM, ethyl alcohol
Ratio with water is 1:2~2:1.
Further, in the step (4), mixing time is 10min~120min, and adsorption time is in Au seed solution
4h~120h.
Further, in the step (4), the ethanol solution concentration of 4- mercaptobenzoic acid is 0.5~10mM in growth-promoting media,
Aqueous solution of chloraurate concentration is 1~20mM, and aqueous ascorbic acid concentration is 1~50mM.
Further, in the step (4), the dip time in growth-promoting media is 10~30min.
Further, in the step (4), vacuum drying temperature is 70 DEG C~100 DEG C, and drying time is 6h~48h.
Compared with prior art, the beneficial effects of the present invention are:
The present invention is using polypyrrole/Carbon foam rich in nitrogen-atoms as skeleton, negative by oriented growth using gold salt as presoma
Load prepares new catalyst.Above-mentioned three-dimensional porous polypyrrole/Carbon foam load gold nano line catalyst, passes through p-nitrophenol
Model catalysis reaction, finds it with good catalytic activity.And compared to traditional handicraft, preparation is simple, and time-consuming is few, cost
Low, pollution-free, catalytic activity is good, has good industrial prospect.
It is disclosed by the invention using melamine foamed plastic as template, by a step thermal cracking preparation have certain form and elasticity
Porous foam charcoal, then by in-situ polymerization prepare polypyrrole filling complex carrier, finally by chemical reduction method gold-supported
Nano wire, to obtain a kind of novel load gold nano line catalyst based on porous foam charcoal.This new catalyst is same
When have both the physical aspect structure of three-dimensional foam charcoal, and there is the catalytic activity of gold.It is anti-by the model catalysis of p-nitrophenol
It answers, finds it with good catalytic activity.This composite catalyst not only has certain theoretical value, also has wide
Application value.
Detailed description of the invention
Fig. 1 is the SEM figure of the three-dimensional porous foams charcoal (CF) in embodiment 1.
Fig. 2 is the SEM figure of polypyrrole/Carbon foam (CF@PPy) in embodiment 3.
Fig. 3 is the SEM figure of polypyrrole/Carbon foam load gold nano line (CF@PPy@AuNWs) in embodiment 5.
Fig. 4 is the UV-Vis absorption spectrum that the CF in embodiment 1 adsorbs gold nanoparticle catalyzed p-nitrophenol.
Fig. 5 is the UV-Vis absorption spectrum that CF PPy in embodiment 3 adsorbs gold nanoparticle catalyzed p-nitrophenol.
Fig. 6 is the UV-Vis absorption spectrum of the CF@PPy@Au nano particle catalysis p-nitrophenol in embodiment 4.
Fig. 7 is the UV-Vis absorption spectrum of the CF@PPy@AuNWs catalysis p-nitrophenol in embodiment 5.
Specific embodiment
The present invention will be further explained below with reference to the attached drawings and specific examples.
Embodiment 1
(1) ethyl alcohol and distilled water melamine foamed plastic is used respectively to be cleaned by ultrasonic 3 times, it is dry to constant weight.It is then placed into
It is mixed in the tube furnace of the mixed atmosphere of hydrogen and nitrogen (V1/V2=1:9), is warming up to 600 with the heating rate of 10 DEG C/min
DEG C and keep the temperature 2h, then be down to room temperature.Fig. 1 is the SEM figure of three-dimensional porous foams charcoal in the present embodiment, and skeleton diameter is about 3.5 μ
m.In addition, the space between skeleton makes greatly Carbon foam foam have very high porosity very much, major part is to hand between skeleton
The structure of fork, this structure can occur bending and deformation when foam is by stress, so that foam has extraordinary elasticity.
(2) take the APTES solution of 12 μ L in the 10mL in the mixed solvent of second alcohol and water, ultrasonic vibration 3min is put into 5mg's
Carbon foam, stirring 30min taking-up are washed with water 3 times.Then the APTES CF modified is put into the Au seed solution of 1mL and is adsorbed
For 24 hours, deionized water is embathed 3 times, is placed in 75 DEG C of dry 8h in vacuum oven.
(3) in the deionized water of 2.5mL, the ice NaBH4 of the 4-NP and 200 μ L, 0.1mM of 200 μ L, 1.0mM is added, so
After above-mentioned catalyst is added, catalytic reaction process is monitored by UV-Vis.Fig. 4 is the UV-Vis absorption spectrum in the present embodiment.
Fig. 4 is the UV-Vis absorption spectrum that CF adsorbs gold nanoparticle catalyzed p-nitrophenol in the present embodiment.P-nitrophenol amount base
Originally interior in 12min to be held essentially constant, it can thus be appreciated that CF adsorbs Au nanoparticle catalyst poor catalytic activity.
Embodiment 2
(1) ethyl alcohol and distilled water melamine foamed plastic is used respectively to be cleaned by ultrasonic 3 times, it is dry to constant weight.It is then placed into
It is mixed in the tube furnace of the mixed atmosphere of hydrogen and nitrogen (V1/V2=1:9), is warming up to 600 with the heating rate of 10 DEG C/min
DEG C and keep the temperature 2h, then be down to room temperature.
(2) take the APTES solution of 12 μ L in the 10mL in the mixed solvent of second alcohol and water, ultrasonic vibration 3min is put into 5mg's
Carbon foam, stirring 30min taking-up are washed with water 3 times.Then the APTES CF modified is put into the Au seed solution of 1mL and is adsorbed
For 24 hours, deionized water is embathed 3 times, is placed in 75 DEG C of dryings in vacuum oven.
(3) Carbon foam for adsorbing gold seeds is added in ethanol/water (2:1) mixed solution, 34 μ L is added, 50mM's
HAuCl4 aqueous solution, the ascorbic acid solution of 205 μ L, 20mM stand reaction 0.5h.Taking-up is embathed 3 times with deionized water, is placed in
Vacuum oven, 75 DEG C of dry 8h.
(4) in the deionized water of 2.5mL, 4-NP, the ice NaBH4 of the 0.1mM of 200 μ L of 200 μ L, 1.0mM is added, so
The catalyst of CF load gold nano particle after above-mentioned drying is added afterwards, monitors catalytic reaction process by UV-Vis.
Embodiment 3
(1) ethyl alcohol and distilled water melamine foamed plastic is used respectively to be cleaned by ultrasonic 3 times, it is dry to constant weight.It is then placed into
It is mixed in the tube furnace of the mixed atmosphere of hydrogen and nitrogen (V1/V2=1:9), is warming up to 600 with the heating rate of 10 DEG C/min
DEG C and keep the temperature 2h, then be down to room temperature.
(2) Carbon foam of 10mg is weighed, 6.62mL is immersed and contains in the aqueous solution of 144.2 μ L pyrroles, be placed in 0 DEG C of ice-water bath
Middle absorption stir about 30min.6.62mL is slowly added dropwise again, the ammonium persulfate aqueous solution of 0.18M continues to stir 30min, then set
12h is stood in 4 DEG C of refrigerators.Taking-up cleans up postposition 75 DEG C of dryings in a vacuum drying oven with clear water, obtains CF PPy.Fig. 2
It is the SEM figure of CF PPy in the present embodiment, it is seen that a large amount of spherical shape polypyrroles are attached on Carbon foam skeleton, and convex portion increases
The specific surface of total skeleton is added.
(3) take the APTES solution of 12 μ L in the 10mL in the mixed solvent of second alcohol and water, ultrasonic vibration 3min is put into 5mg's
CF@PPy, stirring 30min taking-up are washed with water 3 times.Then the APTES CF@PPy modified is put into the Au seed solution of 1mL
For 24 hours, deionized water is embathed 3 times for absorption.
(4) in the deionized water of 2.5mL, the ice NaBH4 of the 0.1mM of the 4-NP and 200 μ L of 200 μ L, 1.0mM is added,
Then the CF PPy after above-mentioned drying is added adsorbs Au nanoparticle catalyst, monitors catalytic reaction process by UV-Vis.Fig. 5
It is the UV-Vis absorption spectrum that CF PPy adsorbs gold nanoparticle in the present embodiment.P-nitrophenol fundamental reaction in 12min
Completely, it follows that the gold nanoparticle catalyzed activity of CF PPy absorption adsorbs gold nanoparticle better than CF.
Embodiment 4
(1) melamine bubble is cleaned by ultrasonic 3 times with ethyl alcohol and distilled water respectively, it is dry to constant weight.It is then placed into mixed
In the tube furnace for having the mixed atmosphere of hydrogen and nitrogen (V1/V2=1:9), 600 DEG C are warming up to the heating rate of 10 DEG C/min
And 2h is kept the temperature, then be down to room temperature.
(2) Carbon foam of 10mg is weighed, 6.62mL is immersed and contains in the aqueous solution of 144.2 μ L pyrroles, be placed in 0 DEG C of ice-water bath
Middle absorption stir about 30min.6.62mL is slowly added dropwise again, the ammonium persulfate aqueous solution of 0.18M continues to stir 30min, then set
12h is stood in 4 DEG C of refrigerators.Taking-up is cleaned up with clear water is placed on vacuum oven, and 75 DEG C of dry 8h obtain CF@PPy.
(3) take the APTES solution of 12 μ L in the 10mL in the mixed solvent of second alcohol and water, ultrasonic vibration 3min is put into 5mg's
CF@PPy, stirring 30min taking-up are washed with water 3 times.Then the CF@PPy of APTES is put into the Au seed solution of 1mL and is adsorbed
For 24 hours, deionized water is embathed 3 times.
(4) the CF PPy for adsorbing gold seeds is added in ethanol/water (2:1) mixed solution, 34 μ L is added, 50mM's
HAuCl4 aqueous solution, the ascorbic acid solution of 205 μ L, 20mM stand reaction 0.5h.Taking-up is embathed 3 times with deionized water, is placed in
Vacuum oven, 75 DEG C of dry 8h.
(5) in the deionized water of 2.5mL, the ice NaBH4 of the 0.1mM of the 4-NP and 200 μ L of 200 μ L, 1.0mM is added,
Then the CF@PPy load gold nano particle catalyst after above-mentioned drying is added, detects catalytic reaction process by UV-Vis.Fig. 6
It is the UV-Vis absorption spectrum of CF@PPy load gold nano particle-catalytic p-nitrophenol in this embodiment.P-nitrophenol exists
Fundamental reaction is complete when 16min, it follows that CF@PPy load gold nano particle-catalytic activity is preferably, and adsorbs with CF@PPy
Au nanoparticle catalyst catalytic activity is not much different.
Embodiment 5
(1) ethyl alcohol and distilled water melamine foamed plastic is used respectively to be cleaned by ultrasonic 3 times, it is dry to constant weight.It is then placed into
It is mixed in the tube furnace of the mixed atmosphere of hydrogen and nitrogen (V1/V2=1:9), is warming up to 600 with the heating rate of 10 DEG C/min
DEG C and keep the temperature 2h, then be down to room temperature.
(2) Carbon foam of 10mg is weighed, 6.62mL is immersed and contains in the aqueous solution of 144.2 μ L pyrroles, be placed in 0 DEG C of ice-water bath
Middle absorption stir about 30min.6.62mL is slowly added dropwise again, the ammonium persulfate aqueous solution of 0.18M continues to stir 30min, then set
12h is stood in 4 DEG C of refrigerators.Taking-up is cleaned up with clear water is placed on vacuum oven, and 75 DEG C of dry 8h obtain CF@PPy.
(3) it takes the APTES solution of 12 μ L in the 10mL in the mixed solvent of second alcohol and water, is put into the CF PPy of 5mg, stir
30min taking-up is washed with water 3 times.Then the APTES CF@PPy modified is put into the Au seed solution of 1mL and is adsorbed for 24 hours, go from
Sub- water logging is washed 3 times.
(4) the CF PPy for adsorbing gold seeds is added in ethanol/water (2:1) mixed solution, 110 μ L is added, 10mM's
The ascorbic acid solution of 4- mercaptobenzoic acid (4-MBA) solution, the HAuCl4 aqueous solution of 34 μ L, 50mM and 205 μ L, 20mM are quiet
Set reaction 0.5h.Taking-up is embathed 3 times with deionized water, is placed in vacuum oven, 75 DEG C of dry 8h.
(5) in the deionized water of 2.5mL, the ice NaBH4 of the 4-NP and 200 μ L, 0.1mM of 200 μ L, 1.0mM is added, so
CF@PPy load gold nano line catalyst after above-mentioned drying is added afterwards, detects catalytic reaction process by UV-Vis.Fig. 3 is this
The SEM of polypyrrole/Carbon foam load gold nano line (CF@PPy@AuNWs) in embodiment schemes, and Fig. 7 is CF@in the present embodiment
PPy load gold nano line is catalyzed the UV-Vis absorption spectrum of p-nitrophenol, p-nitrophenol fully reacting in 6min, catalysis
Activity is substantially better than above-mentioned all catalyst.
The research of the catalytic activity of the three-dimensional porous polypyrrole/Foam carbon composite material of load gold nano line of the present invention utilizes
The catalytic model of p-nitrophenol reacts, and catalytic performance is reinforced after discovery Carbon foam load polypyrrole, while loading Au nanometers
Particle can also reinforce its catalytic activity, and catalytic activity when loading Au nano wire is higher than load Au nanoparticle.
Taking the above-mentioned ideal embodiment according to the present invention as inspiration, through the above description, relevant staff is complete
Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention
Property range is not limited to the contents of the specification, it is necessary to which the technical scope thereof is determined according to the scope of the claim.
Claims (12)
1. the preparation method of the composite catalyst based on polypyrrole and Carbon foam load gold nano line, which is characterized in that including such as
Lower step:
(1) melamine foamed plastic is cut into suitable size, is cleaned by ultrasonic 3 times with ethyl alcohol and distilled water respectively, it is dry to constant weight；
(2) above-mentioned melamine foamed plastic is placed into the tube furnace for being mixed with the mixed atmosphere of hydrogen and nitrogen, with constant liter
Warm rate is warming up to certain temperature and keeps the temperature a period of time, then is down to room temperature with constant rate of temperature fall, and being made has a setting
The porous foam charcoal of state and elasticity；
(3) above-mentioned porous foam charcoal is immersed in pyrroles's aqueous solution the stirring under ice-water bath and absorbs a period of time, be then added
NaHSO3 aqueous solution continues absorption stirring and is placed on refrigerator standing for a period of time, and after taking-up embathes 3 times with deionized water, merging is true
Vacuum drying obtains polypyrrole/Carbon foam support C F@PPy in empty drying box；
(4) CF PPy is put into the in the mixed solvent of the second alcohol and water of the solution containing aminopropyl triethoxysilane, stirs one section
Time, taking-up are embathed 3 times with deionized water, are then placed in after adsorbing a period of time in previously prepared Au seed solution, are taken
It is embathed 3 times with deionized water out, is finally putting into and is matched in proportion by 4- mercaptobenzoic acid solution, gold chloride and ascorbic acid solution
It in the growth-promoting media set, is embathed 3 times with deionized water after reaction, drying is obtained based on poly- pyrrole in merging vacuum oven
Cough up/composite catalyst CF@the PPy.AuNWs of Carbon foam load gold nano line.
2. the method according to claim 1, wherein hydrogen and helium volume ratio are 1:4 in the step (2)
~1:15.
3. the method according to claim 1, wherein in the step (2), the speed of heating be 5 DEG C/min~
50 DEG C/min, the temperature range of heat preservation is 300~1000 DEG C.
4. the method according to claim 1, wherein soaking time is 1h~8h in the step (2).
5. the method according to claim 1, wherein the concentration of pyrroles's aqueous solution is 50mM in the step (3)
The concentration of~200mM, NaHSO3 aqueous solution is 0.05M~0.2M.
6. the method according to claim 1, wherein in the step (3), absorption mixing time be 10min~
120min, refrigerator time of repose are 4h~for 24 hours.
7. the method according to claim 1, wherein in the step (3), vacuum drying temperature is 20 DEG C~
100 DEG C, drying time is 6h~48h.
8. the method according to claim 1, wherein in the step (4), aminopropyl triethoxysilane
(APTES) concentration is 2~10mM, and the ratio of second alcohol and water is 1:2~2:1.
9. the method according to claim 1, wherein in the step (4), mixing time be 10min~
Adsorption time is 4h~120h in 120min, Au seed solution.
10. the method according to claim 1, wherein in the step (4), 4- mercaptobenzoic acid in growth-promoting media
Ethanol solution concentration be 0.5~10mM, aqueous solution of chloraurate concentration be 1~20mM, aqueous ascorbic acid concentration be 1~
50mM。
11. the method according to claim 1, wherein in the step (4), the dip time in growth-promoting media
For 10~30min.
12. the method according to claim 1, wherein in the step (4), vacuum drying temperature is 70 DEG C~
100 DEG C, drying time is 6h~48h.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110350142A (en) * | 2019-06-28 | 2019-10-18 | 浙江大学 | The sodium electrode of integrated Porous Polypyrrole load and the preparation method of sulfur electrode |
| CN112403519A (en) * | 2020-12-09 | 2021-02-26 | 兰州大学 | Preparation method and application of COF-300/PPy/Au (G) nanoenzyme catalyst |
| CN112501651A (en) * | 2020-12-03 | 2021-03-16 | 南京工业大学 | Substrate-based gold nanowire and preparation method and application thereof |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1642635A (en) * | 2002-02-14 | 2005-07-20 | 孟山都技术公司 | Oxidation catalyst and process for its preparation and process for oxidation using it |
| CN1674329A (en) * | 2005-02-21 | 2005-09-28 | 武汉理工大学 | Electric catalyst with compound conducing high polymer modification one-dimensional nano carbon as carrier and preparation |
| CN102614933A (en) * | 2012-03-20 | 2012-08-01 | 南京大学 | Noble metal silver deposition-polypyrrole sensitization hollow titanium dioxide nano photocatalyst and preparation method thereof |
| CN103406152A (en) * | 2013-07-22 | 2013-11-27 | 曾适之 | Visible light responsive metal/organic semiconductor photocatalyst, its preparation method and application |
| CN103945966A (en) * | 2011-09-23 | 2014-07-23 | 南洋理工大学 | Methods for forming gold nanowires on a substrate and gold nanowires formed thereof |
| CN104030687A (en) * | 2014-04-28 | 2014-09-10 | 宁波东联密封件有限公司 | Silicon carbide ceramic and low temperature sintering method thereof |
| CN104841482A (en) * | 2015-04-01 | 2015-08-19 | 沈阳理工大学 | Polymer-modified nano precious metal catalyst and preparation method therefor |
| CN107952466A (en) * | 2017-12-27 | 2018-04-24 | 浙江大学台州研究院 | In methods of the h-BN as catalyst reduction p-nitrophenol for loading Au or Pd |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102617853B (en) * | 2012-03-27 | 2013-08-07 | 大连理工大学 | Preparation method of foamed porous graphene/polypyrrole composite oil absorption material |
-
2018
- 2018-09-14 CN CN202111114617.2A patent/CN113828354A/en active Pending
- 2018-09-14 CN CN201811072777.3A patent/CN109225326A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1642635A (en) * | 2002-02-14 | 2005-07-20 | 孟山都技术公司 | Oxidation catalyst and process for its preparation and process for oxidation using it |
| CN1674329A (en) * | 2005-02-21 | 2005-09-28 | 武汉理工大学 | Electric catalyst with compound conducing high polymer modification one-dimensional nano carbon as carrier and preparation |
| CN103945966A (en) * | 2011-09-23 | 2014-07-23 | 南洋理工大学 | Methods for forming gold nanowires on a substrate and gold nanowires formed thereof |
| CN102614933A (en) * | 2012-03-20 | 2012-08-01 | 南京大学 | Noble metal silver deposition-polypyrrole sensitization hollow titanium dioxide nano photocatalyst and preparation method thereof |
| CN103406152A (en) * | 2013-07-22 | 2013-11-27 | 曾适之 | Visible light responsive metal/organic semiconductor photocatalyst, its preparation method and application |
| CN104030687A (en) * | 2014-04-28 | 2014-09-10 | 宁波东联密封件有限公司 | Silicon carbide ceramic and low temperature sintering method thereof |
| CN104841482A (en) * | 2015-04-01 | 2015-08-19 | 沈阳理工大学 | Polymer-modified nano precious metal catalyst and preparation method therefor |
| CN107952466A (en) * | 2017-12-27 | 2018-04-24 | 浙江大学台州研究院 | In methods of the h-BN as catalyst reduction p-nitrophenol for loading Au or Pd |
Non-Patent Citations (3)
| Title |
|---|
| XIANG LIU ET.AL: ""Monolithic carbon foam-supported Au nanoparticles with excellent catalytic performance in a fixed-bed system"", 《NEWJ.CHEM.》 * |
| XUN SUN ET.AL: "One-pot fabrication of core-shell", 《SYNTHETIC METALS》 * |
| 蔡莉: "原位复合法制备聚吡咯/介孔TiO2及光催化性能", 《硅酸盐学报》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110350142A (en) * | 2019-06-28 | 2019-10-18 | 浙江大学 | The sodium electrode of integrated Porous Polypyrrole load and the preparation method of sulfur electrode |
| CN112501651A (en) * | 2020-12-03 | 2021-03-16 | 南京工业大学 | Substrate-based gold nanowire and preparation method and application thereof |
| CN112501651B (en) * | 2020-12-03 | 2022-07-29 | 南京工业大学 | Substrate-based gold nanowire and preparation method and application thereof |
| CN112403519A (en) * | 2020-12-09 | 2021-02-26 | 兰州大学 | Preparation method and application of COF-300/PPy/Au (G) nanoenzyme catalyst |
| CN112403519B (en) * | 2020-12-09 | 2021-11-16 | 兰州大学 | Preparation method and application of COF-300/PPy/Au (G) nanoenzyme catalyst |
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