CN106268961A - The preparation method and applications of Ag/PAM/PPy/GO composite - Google Patents
The preparation method and applications of Ag/PAM/PPy/GO composite Download PDFInfo
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- CN106268961A CN106268961A CN201610902517.9A CN201610902517A CN106268961A CN 106268961 A CN106268961 A CN 106268961A CN 201610902517 A CN201610902517 A CN 201610902517A CN 106268961 A CN106268961 A CN 106268961A
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- ppy
- graphene oxide
- polypyrrole
- pam
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- 239000002131 composite material Substances 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 229920000128 polypyrrole Polymers 0.000 claims abstract description 131
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 61
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 54
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims abstract description 21
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000003054 catalyst Substances 0.000 claims abstract description 12
- OWXJKYNZGFSVRC-NSCUHMNNSA-N (e)-1-chloroprop-1-ene Chemical compound C\C=C\Cl OWXJKYNZGFSVRC-NSCUHMNNSA-N 0.000 claims abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 10
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 10
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims abstract description 8
- 239000000178 monomer Substances 0.000 claims abstract description 8
- 238000011065 in-situ storage Methods 0.000 claims abstract description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000001257 hydrogen Substances 0.000 claims abstract description 4
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 4
- 239000003999 initiator Substances 0.000 claims abstract description 4
- 239000000203 mixture Substances 0.000 claims abstract description 4
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 4
- 238000006467 substitution reaction Methods 0.000 claims abstract description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 claims abstract description 4
- 229920002554 vinyl polymer Polymers 0.000 claims abstract description 4
- 230000001960 triggered effect Effects 0.000 claims abstract description 3
- 229920002401 polyacrylamide Polymers 0.000 claims description 75
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 claims description 27
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 18
- 239000002055 nanoplate Substances 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 9
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 8
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 6
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 6
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 5
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- 229910002804 graphite Inorganic materials 0.000 claims description 4
- 239000010439 graphite Substances 0.000 claims description 4
- 229910052757 nitrogen Inorganic materials 0.000 claims description 4
- 230000003647 oxidation Effects 0.000 claims description 4
- 238000007254 oxidation reaction Methods 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 3
- 150000001336 alkenes Chemical class 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 239000005457 ice water Substances 0.000 claims description 3
- 238000011068 loading method Methods 0.000 claims description 3
- 230000007935 neutral effect Effects 0.000 claims description 3
- 239000012286 potassium permanganate Substances 0.000 claims description 3
- 235000010344 sodium nitrate Nutrition 0.000 claims description 3
- 239000004317 sodium nitrate Substances 0.000 claims description 3
- 239000001117 sulphuric acid Substances 0.000 claims description 3
- 235000011149 sulphuric acid Nutrition 0.000 claims description 3
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 claims description 2
- 239000004575 stone Substances 0.000 claims description 2
- ZHNUHDYFZUAESO-UHFFFAOYSA-N Formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 claims 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 125000000636 p-nitrophenyl group Chemical group [H]C1=C([H])C(=C([H])C([H])=C1*)[N+]([O-])=O 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000003638 chemical reducing agent Substances 0.000 abstract description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 22
- 235000013339 cereals Nutrition 0.000 description 17
- PLIKAWJENQZMHA-UHFFFAOYSA-N 4-aminophenol Chemical compound NC1=CC=C(O)C=C1 PLIKAWJENQZMHA-UHFFFAOYSA-N 0.000 description 9
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 229910052709 silver Inorganic materials 0.000 description 5
- 239000004332 silver Substances 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical compound [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000002135 nanosheet Substances 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 238000001291 vacuum drying Methods 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- ATHHXGZTWNVVOU-UHFFFAOYSA-N N-methylformamide Chemical compound CNC=O ATHHXGZTWNVVOU-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 238000002835 absorbance Methods 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000002322 conducting polymer Substances 0.000 description 2
- 229920001940 conductive polymer Polymers 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- CPJSUEIXXCENMM-UHFFFAOYSA-N phenacetin Chemical compound CCOC1=CC=C(NC(C)=O)C=C1 CPJSUEIXXCENMM-UHFFFAOYSA-N 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 230000036962 time dependent Effects 0.000 description 2
- LLYXJBROWQDVMI-UHFFFAOYSA-N 2-chloro-4-nitrotoluene Chemical compound CC1=CC=C([N+]([O-])=O)C=C1Cl LLYXJBROWQDVMI-UHFFFAOYSA-N 0.000 description 1
- WXQDFOGZIYLEGP-UHFFFAOYSA-N C(C(C)C)#N.C(C(C)C)#N.[N] Chemical compound C(C(C)C)#N.C(C(C)C)#N.[N] WXQDFOGZIYLEGP-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 241000519995 Stachys sylvatica Species 0.000 description 1
- 229910021536 Zeolite Inorganic materials 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 125000003368 amide group Chemical group 0.000 description 1
- 230000000202 analgesic effect Effects 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
- RRTCFFFUTAGOSG-UHFFFAOYSA-N benzene;phenol Chemical compound C1=CC=CC=C1.OC1=CC=CC=C1 RRTCFFFUTAGOSG-UHFFFAOYSA-N 0.000 description 1
- KVNRLNFWIYMESJ-UHFFFAOYSA-N butyronitrile Chemical compound CCCC#N KVNRLNFWIYMESJ-UHFFFAOYSA-N 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000000118 hair dye Substances 0.000 description 1
- 238000006197 hydroboration reaction Methods 0.000 description 1
- 229920001477 hydrophilic polymer Polymers 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 125000000449 nitro group Chemical group [O-][N+](*)=O 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229960005489 paracetamol Drugs 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229960003893 phenacetin Drugs 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 230000001568 sexual effect Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000010457 zeolite Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/28—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of the platinum group metals, iron group metals or copper
-
- 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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/38—Organic compounds containing nitrogen
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Inorganic Chemistry (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses the preparation method of a kind of Ag/PAM/PPy/GO composite, including: 1) first with hummer method, synthesis graphene oxide, polypyrrole/graphene oxide is obtained by hydrogen bond and graphene oxide combination with polypyrrole, again chloropropene is connected in polypyrrole/surface of graphene oxide by substitution reaction, obtains intermediate A；Again with acrylamide as monomer, azodiisobutyronitrile is initiator, acrylamide triggered in intermediate A surface generation vinyl polymerization reaction, obtains PAM/PPy/GO；2) by PAM/PPy/GO and AgNO3Solution mix homogeneously, with sodium borohydride as reducing agent, at PAM/PPy/GO surface in situ reduction Ag+, obtain Ag/PAM/PPy/GO.Solve the problem easily reunited of Nano silver grain, and utilize the synergism of Nano silver grain and PAM/PPy/GO composite to add the catalytic efficiency of catalyst.
Description
Technical field
The invention belongs to the field of chemical synthesis, more particularly to the preparation method of a kind of Ag/PAM/PPy/GO composite
And the catalysis reduction to paranitrophenol (4-NP).
Background technology
In recent years, along with the development of nanosecond science and technology, noble metal nano particles because of its electronic device, optical material, medicine,
The excellent properties of the aspects such as waste water process, catalyst and receive significant attention.And Nano silver grain has than other metals because of it
The cheapest cost is especially paid close attention to.In order to prevent Nano silver grain from reuniting and improving its performance, typically by silver nanoparticle
Particulate load is on carrier, such as activated carbon, CNT, zeolite, silicon dioxide, aluminium oxide and polymer etc..
Paranitrophenol is the pollutant in a kind of trade waste and agricultural effluent, and its reduzate polyamino benzene
Phenol then toxicity is the least.Further, para-aminophenol still produces analgesic and the weight of febrifuge such as acetaminophen and Phenacetin
Wanting intermediate, in addition, it is also widely used in the classes of agents such as developing agent, corrosion inhibitor, preservative, hair dye.Therefore, will
Paranitrophenol is reduced into para-aminophenol critically important meaning.
Summary of the invention
It is an object of the invention to prepare a kind of Ag/PAM/PPy/GO composite, solve the easily reunion of Nano silver grain
Problem, and utilize the synergism of Nano silver grain and PAM/PPy/GO composite to add the catalytic efficiency of catalyst.
To achieve these goals, the technical solution used in the present invention is:
The preparation method of a kind of Ag/PAM/PPy/GO composite, comprises the following steps:
1) first with hummer method, graphene oxide GO is synthesized, afterwards with polypyrrole by hydrogen bond and graphene oxide
GO combines and obtains polypyrrole/graphene oxide PPy/GO, then by substitution reaction, chloropropene is connected on polypyrrole/graphene oxide
On PPy/GO surface, obtain intermediate A；Again with acrylamide as monomer, azodiisobutyronitrile is initiator, acrylamide triggered
There is vinyl polymerization reaction in intermediate A surface, obtains acrylamide/polypyrrole/graphene oxide composite nano-grade sheet；
2) by acrylamide/polypyrrole/graphene oxide composite nano-grade sheet and AgNO3Solution mix homogeneously, with hydroboration
Sodium is reducing agent, at PAM/PPy/GO surface in situ reduction Ag+, obtain load Nano silver grain polyacrylamide/polypyrrole/
Graphene oxide composite nano-grade sheet Ag/PAM/PPy/GO.
Described preparation method, step 1) specifically include,
1.1) synthesis graphene oxide, adds the there-necked flask being positioned in ice-water bath and filling sulphuric acid by graphite and sodium nitrate
In, it is slowly added to potassium permanganate after stirring, after 32～38 DEG C are reacted 30-40 minute, standing at room temperature 5-6 days；Then use
Warm water dilutes, and dropping hydrogen peroxide to solution is glassy yellow, and centrifuge washing, to neutral, be dried, obtain graphene oxide GO；
1.2) synthesis polypyrrole/graphene oxide PPy/GO, joins deionization by graphene oxide GO and pyrrole monomer
In water, ultrasonic disperse, add iron chloride, continue ultrasonic 30-40 minute, product deionized water and ethanol centrifuge washing, put
Enter 50-60 DEG C to be vacuum dried 24 hours, obtain polypyrrole/graphene oxide PPy/GO；
1.3) synthetic intermediate A, is scattered in N-N bis-by chloropropene, potassium hydroxide and polypyrrole/graphene oxide PPy/GO
In methylformamide DMF, 60-70 DEG C of backflow 24-30h, with water and ethanol centrifuge washing, it is dried, obtains intermediate A；
1.4) synthesis polyacrylamide/polypyrrole/graphene oxide composite nano-grade sheet PAM/PPy/GO, respectively by intermediate
A, acrylamide monomer and azodiisobutyronitrile ultrasonic disperse are in ethanol, and under nitrogen protection, 70-80 DEG C is refluxed 6-7 hour,
Afterwards with deionized water and ethanol centrifuge washing, after 50 DEG C are vacuum dried 24 hours, obtain polyacrylamide/polypyrrole/oxidation stone
Ink alkene composite nano plate.
Described preparation method, step 1.2) mol ratio of polypyrrole PPy and iron chloride is 1:3；Polypyrrole/graphite oxide
Alkene PPy/GO and chloropropene mass ratio are 3:5.
Described preparation method, step 1.4) mass ratio of acrylamide AM and intermediate A is 1:5.
Described preparation method, step 2) AgNO3Matter with acrylamide/polypyrrole/graphene oxide composite nano-grade sheet
Amount ratio is 2:1.
Ag/PAM/PPy/GO composite prepared by a kind of described method is being catalyzed reduction paranitrophenol as catalyst
Application on 4-NP.
Described application, joins newly configured sodium borohydride solution in paranitrophenol aqueous solution, obtains mixed liquor A；
Join in mixed liquor A with Ag/PAM/PPy/GO composite for catalyst, catalysis reduction paranitrophenol.
The mol ratio of described application, paranitrophenol and sodium borohydride is 1:100-150.
The invention has the beneficial effects as follows:
The preparation method and applications of the present invention a kind of Ag/PAM/PPy/GO composite.The technical scheme is that
The surface of polyacrylamide/polypyrrole/graphene oxide (PAM/PPy/GO) composite nano plate uses in-situ reducing Ag+Method
Obtain Ag/PAM/PPy/GO nano composite material.Concrete grammar is as follows: first synthesize polypyrrole/stannic oxide/graphene nano sheet
(PPy/GO), then it is connected on PPy/GO surface by substitution reaction with chloropropene, then with acrylamide (AM) as monomer, even
Nitrogen bis-isobutyronitrile (AIBN) is initiator, causes vinyl polymerization anti-on chloropropene/polypyrrole/stannic oxide/graphene nano sheet surface
Should, obtain polyacrylamide/polypyrrole/graphene oxide (PAM/PPy/GO) composite nano plate；Finally, by PAM/PPy/GO with
Certain density AgNO3Solution mix homogeneously, with sodium borohydride (NaBH4) it is reducing agent, reduce at PAM/PPy/GO surface in situ
Ag+, obtain loading the polyacrylamide/polypyrrole/stannic oxide/graphene nano sheet (Ag/PAM/PPy/GO) of Nano silver grain.This
Invention is that to utilize polyacrylamide/polypyrrole/graphene oxide composite nano-grade sheet be backing material, and Nano silver grain is combined
A kind of composite come, and the catalysis reduction being catalyst paranitrophenol (4-NP) with Ag/PAM/PPy/GO composite
Performance is studied.
Polyacrylamide/polypyrrole/graphene oxide composite nano-grade sheet combine hydrophilic polymer, conducting polymer and
The advantage of graphene oxide, has good electron transport ability, high-specific surface area and excellent hydrophilicity, is load silver granuel
The good carrier of son.It is carrier loaded Nano silver grain with PAM/PPy/GO composite nano plate, has the advantage that and effectively prevent
Nano silver grain is reunited, and makes it be evenly distributed on carrier surface；The hydrophilic that polyacrylamide has can make catalyst good
Be scattered in aqueous solution, and amide groups can by the more paranitrophenol of adsorption by hydrogen bond thus improve its catalytic efficiency；
PAM/PPy/GO composite nano plate is because it is compounded with conducting polymer thus has good electron transport ability, and then is conducive to
The catalysis reduction of paranitrophenol；
Due to the fact that, with PAM/PPy/GO composite nano plate as carrier, Ag/PAM/PPy/GO composite is to nitro
The reduction of phenol has more excellent catalytic performance, and its reaction rate constant is up to 3.38 × 10-2/ sec, shows Ag/PAM/
PPy/GO composite nano plate can be used for being catalyzed reduction paranitrophenol as good, stable catalyst.
Accompanying drawing explanation
Fig. 1 a is the scanning electron microscope (SEM) photograph of Ag/PAM/PPy/GO.
Fig. 1 b is the transmission electron microscope picture of Ag/PAM/PPy/GO.
Fig. 2 is the XRD analysis figure of Ag/PAM/PPy/GO (a) and Ag/PAM/PPy/GO (b) respectively
Fig. 3 is the EDS figure of Ag/PAM/PPy/GO
Fig. 4 is the ultraviolet-visible spectrogram of paranitrophenol
Fig. 5 is ln (A/A0) time history plot
Detailed description of the invention
The preparation of embodiment 1Ag/PAM/PPy/GO composite
1) synthesis polyacrylamide/polypyrrole/graphene oxide composite nano-grade sheet (PAM/PPy/GO)
1.1) synthesis graphene oxide (GO)
Graphene oxide is synthesized by hummer method, first, adds 67.5mL concentrated sulphuric acid, be placed in 250mL there-necked flask
In ice-water bath, then in there-necked flask, add 2g graphite and 1.6g sodium nitrate, be slowly added to 9g potassium permanganate after stirring, then
There-necked flask is placed in oil bath pan, and after 32～38 DEG C are reacted half an hour, room temperature stands 5 days.Then dilute with 560mL warm water,
Dropping hydrogen peroxide (30%) is glassy yellow to solution.Finally, with deionized water centrifuge washing to neutral, vacuum drying oven is put into
50 DEG C are dried 24 hours, obtain graphene oxide (GO).
1.2) synthesis polypyrrole/graphene oxide (PPy/GO)
0.1g GO and 0.1g pyrrole monomer being joined in the flask filling 50mL deionized water respectively, ultrasonic disperse is equal
Even, the rear addition ultrasonic 30min of 0.6g iron chloride, product deionized water and ethanol centrifuge washing 2～3 times, 50 DEG C of vacuum drying
24 hours, obtain polypyrrole/graphene oxide (PPy/GO).
1.3) synthetic intermediate A (PPy/GO-CH2=CH2)
Respectively 90mg polypyrrole/graphene oxide (PPy/GO), 0.15g potassium hydroxide and 0.15g chloropropene are joined
In 75mLDMF, ultrasonic disperse；Be placed in oil bath pan 60 DEG C and reflux 24 hours；The most respectively by deionized water and washing with alcohol 2
～3 times, 50 DEG C are vacuum dried 24 hours, obtain intermediate A.
1.4) synthesis of PAM/PPy/GO
Respectively by 50mg intermediate A (PPy/GO-CH2=CH2), 250mg acrylamide (AM) monomer and 5mg azo two different
Butyronitrile AIBN ultrasonic disperse in 150mL ethanol, be placed on oil bath pan, under nitrogen protection, 80 DEG C are refluxed 6 hours, finally use
Deionized water and ethanol centrifuge washing 2～3 times, after 50 DEG C of vacuum drying 24 hours, obtain polyacrylamide/polypyrrole/oxidation
Graphene composite nano plate (PAM/PPy/GO).
2) polyacrylamide/polypyrrole/graphene oxide composite nano-grade sheet (Ag/PAM/ of synthesis load Nano silver grain
PPy/GO)
Take 20mg PAM/PPy/GO composite nano plate to join in 8mL deionized water, be slowly added to what 1mL configured
The silver nitrate solution of 17.6mM, stirs 3 hours, is then slowly added into 0.2M sodium borohydride (NaBH newly configured for 1mL4) solution,
Stirring 12 hours, finally with deionized water and ethanol centrifuge washing 2～3 times, 50 DEG C are vacuum dried 24 hours, obtain loading silver and receive
The polyacrylamide of rice corpuscles/polypyrrole/graphene oxide composite nano-grade sheet (Ag/PAM/PPy/GO).
Testing result
Fig. 1 a is that the polyacrylamide/polypyrrole/graphene oxide of the load Nano silver grain of embodiment 1 preparation is compound to be received
The scanning electron microscope (SEM) photograph of rice sheet Ag/PAM/PPy/GO, shows in figure that the Ag/PAM/PPy/GO of synthesis is laminated structure, and surface has very
Many folds, to provide higher specific surface area, surface also has many small white spots, is Nano silver grain；And Fig. 1 b is Ag/
The transmission electron microscope picture of PAM/PPy/GO, can substantially be found to have Nano silver grain from figure has and is distributed the most uniformly.Permissible
Well proving the method by in-situ reducing, Nano silver grain the most successfully loads to the surface of PAM/PPy/GO nanometer sheet.
Fig. 2 is the XRD analysis figure of PAM/PPy/GO (a) and Ag/PAM/PPy/GO (b) respectively, and (a) is that PAM/PPy/GO receives
The XRD figure of mitron, as can be seen from the figure only has a wide cutting edge of a knife or a sword at 2 θ=25.4 °, shows the non-of PAM/PPy/GO nanometer sheet
Crystalline structure.XRD curve (b) of Ag/PAM/PPy/GO, at 38.7 °, 44.7 °, occurs in that four diffraction at 65.1 ° and 77.9 °
Peak, (111) of the most corresponding Nano silver grain cubic system, (200), (220), (311) crystal face, this illustrates that face-centered cubic is tied
The silver metal nanoparticles of structure successful deposition is on the surface of PAM/PPy/GO composite nano plate.According to Scherrer formula
Calculating, the mean diameter of golden nanometer particle is about about 20nm, and SEM spectrogram 1 (a) of this and Ag/PAM/PPy/GO presents
Result is similar.Also demonstrated by the sign of XRD and be implicitly present in nano grain of silver in the Ag/PAM/PPy/GO complex of synthesis
Son.
Fig. 3 is the EDS figure of Ag/PAM/PPy/GO.It can be seen that carbon in figure, nitrogen, oxygen, the existence of these several elements of silver and
The content of these several elements is the highest, proves that Nano silver grain has successfully been loaded to the surface of complex by us further.
Embodiment 2Ag/PAM/PPy/GO composite is to paranitrophenol (4-NP) catalytic Quality Research
(1) method: paranitrophenol is carried out catalysis also with the Ag/PAM/PPy/GO composite of embodiment 1 preparation
Former.
Take the Ag/PAM/PPy/GO complex that 0.4mg is dried, join the sodium borohydride solution of 10mM newly configured for 4mL
In, it being uniformly dispersed, rear addition 1 paranitrophenol aqueous solution newly configured for microlitre 0.4M also starts timing, uses purple at interval of 30s
Outer visible spectrophotometer measures absorbance.
(2) test result
Fig. 4 presents along with the carrying out of reaction, the time dependent ultra-violet absorption spectrum of absorbance.It may be seen that
At 400nm, the absworption peak of paranitrophenol (4-NP) reduces in time, and after 2.5min, the absworption peak of paranitrophenol is several
Disappear；Meanwhile, at 295nm the absworption peak of the reduzate para-aminophenol (4-AP) of paranitrophenol (4-NP) with
Reaction to carry out and occur, show that paranitrophenol successfully and has rapidly been reduced into para-aminophenol.
Fig. 5 is ln (A/A0) time dependent curve.It may be seen that ln (A/A0) and the time present good line
Sexual relationship, thus we can calculate the reaction rate constant of reaction and can reach 3.38 × 10-2/sec.It can be said that
Bright, Ag/PAM/PPy/GO composite nano plate can as catalysis reduction paranitrophenol excellent catalyst, and its catalytic performance and
Catalytic active phase is higher compared with the catalyst invented.
Claims (8)
1. the preparation method of an Ag/PAM/PPy/GO composite, it is characterised in that comprise the following steps:
1) first with hummer method, synthesize graphene oxide GO, tied by hydrogen bond and graphene oxide GO with polypyrrole afterwards
Conjunction obtains polypyrrole/graphene oxide PPy/GO, then by substitution reaction, chloropropene is connected on polypyrrole/graphene oxide PPy/
On GO surface, obtain intermediate A；Again with acrylamide as monomer, azodiisobutyronitrile is initiator, acrylamide triggered in centre
There is vinyl polymerization reaction in body A surface, obtains acrylamide/polypyrrole/graphene oxide composite nano-grade sheet；
2) by acrylamide/polypyrrole/graphene oxide composite nano-grade sheet and AgNO3Solution mix homogeneously, with sodium borohydride for also
Former dose, at PAM/PPy/GO surface in situ reduction Ag+, obtain loading the polyacrylamide/polypyrrole/oxidation stone of Nano silver grain
Ink alkene composite nano plate Ag/PAM/PPy/GO.
Preparation method the most according to claim 1, it is characterised in that: step 1) specifically include,
1.1) synthesis graphene oxide, adds graphite and sodium nitrate in the there-necked flask being positioned in ice-water bath and filling sulphuric acid, stirs
It is slowly added to potassium permanganate after mixing uniformly, after 32～38 DEG C are reacted 30-40 minute, standing at room temperature 5-6 days；Then dilute with warm water
Releasing, dropping hydrogen peroxide to solution is glassy yellow, and centrifuge washing, to neutral, be dried, obtain graphene oxide GO；
1.2) synthesis polypyrrole/graphene oxide PPy/GO, joins in deionized water by graphene oxide GO and pyrrole monomer,
Ultrasonic disperse, adds iron chloride, continues ultrasonic 30-40 minute, and product deionized water and ethanol centrifuge washing put into 50-
60 DEG C are vacuum dried 24 hours, obtain polypyrrole/graphene oxide PPy/GO；
1.3) synthetic intermediate A, is scattered in N-N dimethyl by chloropropene, potassium hydroxide and polypyrrole/graphene oxide PPy/GO
In Methanamide DMF, 60-70 DEG C of backflow 24-30h, with water and ethanol centrifuge washing, it is dried, obtains intermediate A；
1.4) synthesis polyacrylamide/polypyrrole/graphene oxide composite nano-grade sheet PAM/PPy/GO, respectively by intermediate A, third
Acrylamide monomer and azodiisobutyronitrile ultrasonic disperse are in ethanol, and under nitrogen protection, 70-80 DEG C is refluxed 6-7 hour, finally use
Deionized water and ethanol centrifuge washing, after 50 DEG C are vacuum dried 24 hours, obtain polyacrylamide/polypyrrole/graphene oxide
Composite nano plate.
Preparation method the most according to claim 2, it is characterised in that: step 1.2) polypyrrole PPy and iron chloride mole
Ratio is 1:3；Polypyrrole/graphene oxide PPy/GO and chloropropene mass ratio are 3:5.
Preparation method the most according to claim 1, it is characterised in that: step 1.4) acrylamide AM and the matter of intermediate A
Amount ratio is 1:5.
Preparation method the most according to claim 1, it is characterised in that: step 2) AgNO3With acrylamide/polypyrrole/oxidation
The mass ratio of Graphene composite nano plate is 2:1.
6. the Ag/PAM/PPy/GO composite that prepared by a method as described in claim 1-5 is as catalyst in catalysis also
Application on former paranitrophenol 4-NP.
Application the most according to claim 6, it is characterised in that newly configured sodium borohydride solution is joined p-nitrophenyl
In phenol aqueous solution, obtain mixed liquor A；Join in mixed liquor A with Ag/PAM/PPy/GO composite for catalyst, catalysis reduction
Paranitrophenol.
Application the most according to claim 7, it is characterised in that: the mol ratio of paranitrophenol and sodium borohydride is 1:100-
150。
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