CN109900758A - A kind of silver/carbon nanotube composite material and its preparation method and application - Google Patents
A kind of silver/carbon nanotube composite material and its preparation method and application Download PDFInfo
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- 229910052709 silver Inorganic materials 0.000 title claims abstract description 72
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 71
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 71
- 239000004332 silver Substances 0.000 title claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 58
- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 229920001690 polydopamine Polymers 0.000 claims abstract description 52
- 239000002121 nanofiber Substances 0.000 claims abstract description 38
- 239000004793 Polystyrene Substances 0.000 claims abstract description 36
- 229920002223 polystyrene Polymers 0.000 claims abstract description 15
- 238000003763 carbonization Methods 0.000 claims abstract description 8
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- 239000000835 fiber Substances 0.000 claims abstract description 6
- 239000000446 fuel Substances 0.000 claims abstract description 4
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 69
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 23
- 230000004048 modification Effects 0.000 claims description 18
- 238000012986 modification Methods 0.000 claims description 18
- 239000000243 solution Substances 0.000 claims description 18
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 14
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 12
- 229960003638 dopamine Drugs 0.000 claims description 11
- QKNYBSVHEMOAJP-UHFFFAOYSA-N 2-amino-2-(hydroxymethyl)propane-1,3-diol;hydron;chloride Chemical compound Cl.OCC(N)(CO)CO QKNYBSVHEMOAJP-UHFFFAOYSA-N 0.000 claims description 7
- 238000010438 heat treatment Methods 0.000 claims description 7
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 5
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000005253 cladding Methods 0.000 claims description 2
- 230000014759 maintenance of location Effects 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 230000008569 process Effects 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000001291 vacuum drying Methods 0.000 claims description 2
- 238000010792 warming Methods 0.000 claims description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 12
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 5
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 abstract description 5
- 239000001257 hydrogen Substances 0.000 abstract description 5
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 5
- 239000010411 electrocatalyst Substances 0.000 abstract 1
- 238000005502 peroxidation Methods 0.000 abstract 1
- 238000001338 self-assembly Methods 0.000 abstract 1
- 239000000463 material Substances 0.000 description 24
- -1 carbon nano tube compound Chemical class 0.000 description 17
- 230000000052 comparative effect Effects 0.000 description 11
- 238000002441 X-ray diffraction Methods 0.000 description 9
- 229910052799 carbon Inorganic materials 0.000 description 9
- 230000003197 catalytic effect Effects 0.000 description 8
- 239000003575 carbonaceous material Substances 0.000 description 7
- 238000006277 sulfonation reaction Methods 0.000 description 6
- 239000012298 atmosphere Substances 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 101710134784 Agnoprotein Proteins 0.000 description 4
- 239000012901 Milli-Q water Substances 0.000 description 4
- 229920000557 Nafion® Polymers 0.000 description 4
- 238000005034 decoration Methods 0.000 description 4
- 238000011065 in-situ storage Methods 0.000 description 4
- 239000002082 metal nanoparticle Substances 0.000 description 4
- 239000008363 phosphate buffer Substances 0.000 description 4
- 239000002243 precursor Substances 0.000 description 4
- 230000008439 repair process Effects 0.000 description 4
- 238000002604 ultrasonography Methods 0.000 description 4
- 235000013339 cereals Nutrition 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 229960000935 dehydrated alcohol Drugs 0.000 description 2
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical compound Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 2
- 238000001548 drop coating Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 239000010931 gold Substances 0.000 description 2
- 239000005457 ice water Substances 0.000 description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N monobenzene Natural products C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 2
- 239000002070 nanowire Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229920002239 polyacrylonitrile Polymers 0.000 description 2
- 229920000767 polyaniline Polymers 0.000 description 2
- 229920000128 polypyrrole Polymers 0.000 description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 229920000877 Melamine resin Polymers 0.000 description 1
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 230000000844 anti-bacterial 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
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000872 buffer Substances 0.000 description 1
- 229940075397 calomel Drugs 0.000 description 1
- 239000003990 capacitor Substances 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 1
- 150000002978 peroxides Chemical class 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 239000010944 silver (metal) Substances 0.000 description 1
- 239000011343 solid material Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
本发明涉及一种银/碳纳米管复合材料及其制备方法和应用，将聚多巴胺和银纳米颗粒包覆在聚苯乙烯纳米纤维表面，采用层层自主装调节银/聚多巴胺厚度，利用高温碳化直接去除聚苯乙烯纤维模板制得。本发明制备方法简单易行，反应条件温和，银纳米颗粒分布均匀，制备出的银/碳纳米管复合材料富氮多孔，管壁厚度可控，该复合材料是制备活性电催化剂用于过氧化氢电化学传感器，燃料电池催化剂领域表现出良好的前途。
The invention relates to a silver/carbon nanotube composite material and a preparation method and application thereof. Polydopamine and silver nanoparticles are coated on the surface of polystyrene nanofibers, the thickness of silver/polydopamine is adjusted by layer-by-layer self-assembly, and high temperature is utilized. Carbonization directly removes the polystyrene fiber template. The preparation method of the invention is simple and feasible, the reaction conditions are mild, the silver nanoparticles are uniformly distributed, the prepared silver/carbon nanotube composite material is nitrogen-rich and porous, and the thickness of the tube wall is controllable, and the composite material is used for preparing active electrocatalysts for peroxidation. The fields of hydrogen electrochemical sensors and fuel cell catalysts show good promise.
Description
Technical field
The invention belongs to technical field of composite materials, in particular to a kind of silver/carbon nanotube composite material and its preparation side
Method and application.
Background technique
Carbon material is formed due to its excellent performance, such as excellent chemical stability, big surface area, high electric conductivity
For attractive catalysis material.It can be very by noble metal nano particles (for example, Ag, Au, Pt, Pd etc.) modified carbon material
Big degree improves catalytic performance.In these noble metal nano particles, Nano silver grain (AgNPs) is because of its high catalytic activity, valence
Lattice are cheap, the excellent properties of thermal conductivity and electric conductivity and receive significant attention.The silver nano-grain of high degree of dispersion can mention significantly
The catalytic performance of high material.However, silver nano-grain is easy to reunite, electro-chemical activity is caused to decline.It is first in order to improve this problem
First Nano silver grain is uniformly fixed on carbon materials material precursor, silver is then directly obtained by the carbonization of carbon materials material precursor
Modified by nano particles carbon material, carbon materials material precursor include polyaniline (PANI), polypyrrole (PPy), melamine, poly-dopamine
(PDA), polyvinylpyrrolidone (PVP) and polyacrylonitrile (PAN) etc..
In these precursors, research is used for biosensor, catalyst, adsorbent, antibacterial to poly-dopamine (PDA) extensively
Agent, the various applications such as capacitor.Dopamine (DA) autohemagglutination merging can show excellent adhesion property in alkaline solution,
It can spontaneously be attached on the surface of various solid materials.Further, since the reducing power of poly-dopamine itself, can with it is more
Metal ion species act on and obtain metal nanoparticle.Poly-dopamine is due to containing a large amount of amine functional group and adjacent benzene two simultaneously
Phenol, poly-dopamine can easily be carbonized into the graphitized carbon of N doping, and electronic conductivity and catalytic activity can be improved in this.
The poly-dopamine of load silver, gold etc. has been reported that more, but the load of metallic particles and the thickness of poly-dopamine are at present only with difference
Growth time and concentration adjust, frequently result in growth cycle it is too long caused by metal nanoparticle reunion (One-step
hydrothermal green synthesis of silver nanoparticle-carbon nanotube reduced-
graphene oxide composite and its application as hydrogen peroxide sensor,
Sens.Actuator B-Chem.,208(2015)389-398.)。
Summary of the invention
Technical problem to be solved by the invention is to provide a kind of silver/carbon nanotube composite material and preparation method and answer
With not only overcoming that silver nano-grain is not strong in conjunction with carbon material and the defects of be unevenly distributed, and pipe thickness also can be obtained can
The silver/carbon nanotube composite material of tune, at the same by poly-dopamine carbonization high-specific surface area can be obtained, the carbon of porous, rich nitrogen is received
Mitron.
A kind of silver/carbon nanotube composite material of the invention, is coated on polystyrene for poly-dopamine and silver nano-grain
Nanofiber surface, use autonomous adjustment section silver/poly-dopamine thickness layer by layer directly remove polystyrene fibre using high temperature cabonization
Template is tieed up to be made.
In tubular construction, surface richness nitrogen is porous, and pipe thickness is controllable for the silver/carbon nanotube composite material.
The diameter of the sulfonated polystyrene nanofiber is 100-800nm, preferably 200-300nm.
The partial size of the silver nano-grain is 4-8nm.
The silver/carbon nanotube composite material pipe thickness is 30-100nm.
The poly-dopamine and the cladding number of plies of silver nano-grain are >=1 layer, preferably 1-3 layers, most preferably 2 layers.
The present invention also provides the preparation methods of above-mentioned silver/carbon nanotube composite material, comprising:
(1) sulfonated polystyrene nanofiber is immersed in dopamine solution and is reacted, obtain poly-dopamine modification through washing
Polystyrene nano fiber；
(2) styroflex that poly-dopamine made from step (1) is modified is impregnated in silver nitrate solution, then water
It washes, be dried in vacuo, obtain silver nano-grain/poly-dopamine modification polystyrene nano fiber；
(3) step (1) and (2) is repeated, obtains different layers of silver nano-grains/poly-dopamine modification polystyrene and receives
Rice fiber, carbonization treatment obtain silver/carbon nanotube composite material.
Dopamine solution is to contain 0.5-10mg/mL, the preferably 10mM of the dopamine of 2-3mg/mL in the step (1)
The aqueous solution of Tris-HCl, pH=8.5.
The technological parameter reacted in the step (1) are as follows: reaction temperature is 20-30 DEG C, reaction time 1-24h.
The concentration of silver nitrate solution is 0.1-50mg/mL in the step (2).
The time impregnated in the step (2) is 0.5-20h.
The process conditions of carbonization treatment in the step (3) are as follows: in nitrogen atmosphere, from room temperature with heating rate 2-10
DEG C/min, preferably 5 DEG C/min, it is warming up to 500-1200 DEG C, preferably 800 DEG C, retention time 30-120min, preferably 60min.
The present invention still further provides above-mentioned silver/carbon nanotube composite material in hydrogen peroxide electrochemical sensor or combustion
Expect the application in cell catalyst field.
Polystyrene nano fiber after sulfonation is soaked in dopamine solution by the present invention, and poly-dopamine autohemagglutination is wrapped in
Polystyrene nano fiber surface；It immerses in silver nitrate solution afterwards, using the reproducibility of poly-dopamine itself, in its surface in situ
Restore silver nano-grain；Step is appealed repeatedly, and high temperature cabonization, number of plies difference obtain different tube walls to multilayer film under an inert gas
The silver/carbon nanotube composite material of thickness.Silver nano-grain is evenly distributed, the silver/carbon nanotube composite material richness nitrogen prepared
Porous, pipe thickness is controllable, which is to prepare active elctro-catalyst for hydrogen peroxide electrochemical sensor, fuel electricity
Pond catalyst field shows good future.
Beneficial effect
(1) mentality of designing of the present invention is ingenious, and poly-dopamine and silver nano-grain are coated on polystyrene nano fiber table
Face directly removes styroflex template using high temperature cabonization, obtains silver/carbon nanotube composite material.Present invention preparation side
Method is simple and easy, and reaction process is mild, environmentally friendly, easily operated, is a kind of Green Chemistry preparation method.
(2) silver/carbon nanotube prepared by the present invention, surface silver nano-grain are evenly distributed, and have high-specific surface area, porous
, tubular structure rich in nitrogen；The present invention can be adjusted by the number of plies that control poly-dopamine and silver nano-grain independently fill layer by layer
Control the pipe thickness of silver/carbon nanotube.
(3) silver/carbon nanotube composite material prepared by the present invention is used for hydrogen peroxide electrochemical sensor and fuel cell
Catalyst has high catalytic performance.
Detailed description of the invention
Fig. 1 is the preparation process schematic diagram of the silver/carbon nanotube composite material of 1-3 of the embodiment of the present invention；
Fig. 2 is the polystyrene nano fiber (A) in the embodiment of the present invention 1, and silver/poly-dopamine modification polystyrene is received
Rice fiber (B), the scanning electron microscope (SEM) photograph of silver/carbon nanotube composite nano materials (C)；
Fig. 3 is prepared by different layers of silver/carbon nanotube composite materials of 1-3 of embodiment of the present invention preparation and comparative example 1
Carbon nano-tube material plane and cross-sectional scans electron microscope；
Fig. 4 is the transmission electron microscope picture of silver/carbon nanotube composite material prepared by the embodiment of the present invention 2；
Fig. 5 is the silver/carbon nanotube composite material scanning electron microscope (SEM) photograph of differential responses time prepared by comparative example 2 of the present invention；
Fig. 6 is prepared by different layers of silver/carbon nanotube composite materials of 1-3 of embodiment of the present invention preparation and comparative example 1
Carbon nano-tube material XRD spectra；
Fig. 7 is the nitrogen adsorption desorption figure of silver/carbon nanotube composite material prepared by the embodiment of the present invention 2；
Fig. 8 is the XPS figure of the N1s of silver/carbon nanotube composite material prepared by the embodiment of the present invention 2；
Fig. 9 is that silver/carbon nanotube composite material modified electrode prepared by the embodiment of the present invention 2 is containing various concentration peroxide
Change the linear graph (B) of the cyclic voltammogram (A) and concentration and electric current in the phosphate buffer of hydrogen；
Figure 10 is bare electrode and carbon nano tube modified electrode prepared by comparative example 1 of the present invention, silver/carbon prepared by embodiment 2
Cyclic voltammogram of the nanometer tube composite materials modified electrode in oxygen-saturated phosphate buffer.
Specific embodiment
Present invention will be further explained below with reference to specific examples.It should be understood that these embodiments are merely to illustrate the present invention
Rather than it limits the scope of the invention.In addition, it should also be understood that, after reading the content taught by the present invention, those skilled in the art
Member can make various changes or modifications the present invention, and such equivalent forms equally fall within the application the appended claims and limited
Range.
Dopamine (J&K Scientific Ltd) is used in the embodiment of the present invention；Use μ-AUTOLAB-III electrochemistry
Work station carries out electro-chemical test in conventional three-electrode system.
Embodiment 1
(1) the PS nanofiber after sulfonation is immersed into the water-soluble of 10mM Tris-HCl, pH=8.5 containing 2mg/mL DA
20h is reacted in liquid.After reaction, in order to remove nonadherent PDA, nanofiber is thoroughly washed for several times with ultrapure water, PDA is obtained and repairs
The PS nanofiber of decorations.
(2) the PS nanofiber of the PDA modification obtained step (1) immerses the AgNO of 10mg/mL3It is reacted in solution
1.5h is put into vacuum oven dry 8h at 50 DEG C afterwards for several times with milli-Q water, obtains the PS Nanowire of Ag/PDA modification
Dimension.
(3) sample that step (2) obtains is transferred in tube furnace, under the atmosphere of nitrogen, with the heating speed of 5 DEG C/min
Degree rises to 800 DEG C, retains 1h, is carbonized, obtains Ag/ carbon nano tube compound material, be denoted as 1-AgNPs-NCNTs.
The scanning electron microscope (SEM) photograph of PS nanofiber is as shown in Figure 2 A in the present embodiment, and the PS nanofiber of Ag/PDA modification is swept
Retouch that electron microscope is as shown in Figure 2 B, the scanning electron microscope (SEM) photograph of Ag/ carbon nano tube compound material is as shown in Figure 2 C, and plane and section are swept
Electron microscope is retouched respectively as shown in Fig. 3 B and B', it is known that Ag/ carbon nano tube compound material it is of uniform size, have a degree of collapse
It collapses.
The XRD spectra of Ag/ carbon nano tube compound material made from the present embodiment is as shown in fig. 6, wherein X-ray diffraction is bent
Diffraction maximum at 2 θ=38.2 ° in line, 44.2 °, 64.4 °, 77.4 ° and 81.6 ° it is consistent with the standard diffraction peak of silver (JCPDS,
Number 04-0783), show silver ion by PDA in-situ reducing at silver nano-grain.
Embodiment 2
(1) the PS nanofiber after sulfonation is immersed into the water-soluble of 10mM Tris-HCl, pH=8.5 containing 2mg/mL DA
20h is reacted in liquid.After reaction, in order to remove nonadherent PDA, nanofiber is thoroughly washed for several times with ultrapure water, PDA is obtained and repairs
The PS nanofiber of decorations.
(2) the PS nanofiber of the PDA modification obtained step (1) immerses the AgNO of 10mg/mL3It is reacted in solution
1.5h, with milli-Q water for several times after, repeat immerse the same terms dopamine solution and silver nitrate solution in.It is put into after washing
Vacuum oven dry 8h at 50 DEG C, obtains the PS nanofiber of Ag/PDA modification.
(3) sample that step (2) obtains is transferred in tube furnace, under the atmosphere of nitrogen, with the heating speed of 5 DEG C/min
Degree rises to 800 DEG C, retains 1h, is carbonized, obtains Ag/ carbon nano tube compound material, be denoted as 2-AgNPs-NCNTs.
The scanning electron microscope (SEM) photograph of Ag/ carbon nano tube compound material made from the present embodiment such as Fig. 3 C (plane) and the section C'() institute
Show, it is known that Ag/ carbon nanotube sizes are uniform, and at uniform tubular structure, Ag/ carbon nanotube diameter is in 200-300nm, pipe thickness
In 40-60nm.
The transmission electron microscope picture of Ag/ carbon nano tube compound material made from the present embodiment, as shown in figure 4, showing silver nanoparticle
Grain is evenly distributed, and particle size is about 6nm.
The XRD spectra of Ag/ carbon nano tube compound material made from the present embodiment is as shown in fig. 6, wherein X-ray diffraction is bent
Diffraction maximum at 2 θ=38.2 ° in line, 44.2 °, 64.4 °, 77.4 ° and 81.6 ° it is consistent with the standard diffraction peak of silver (JCPDS,
Number 04-0783), show silver ion by PDA in-situ reducing at silver nano-grain.
Nitrogen adsorption desorption and the specific surface area size of Ag/ carbon nano tube compound material made from the present embodiment as shown in fig. 7,
Show that it is 245.1 that composite material specific surface area, which is made,.
The XPS spectrum figure of the N1s of Ag/ carbon nano tube compound material made from the present embodiment as shown in figure 8, N mainly with graphite
The form for changing N and pyridine N exists.
Ag/ carbon nanotube made from the present embodiment is dispersed in dehydrated alcohol (mass concentration 0.1mg/mL) and with carefully
Born of the same parents are crushed instrument and carry out ice-water bath ultrasound 30 minutes, and Nafion is then added, makes Nafion dispersion concentration 0.01%, continues ultrasound
It is allowed to be uniformly dispersed within 10 minutes.5 μ L drop coatings are drawn in glassy carbon electrode surface with microsyringe, and then naturally dry forms a film, and obtains
The glass-carbon electrode modified to Ag/ carbon nano tube compound material.
For the glass-carbon electrode carbon nano tube modified using Ag/ made from the present embodiment as working electrode, platinum filament is to satisfy to electrode
It is reference electrode with calomel electrode, three electrodes are inserted into 10mL phosphate buffer (PBS, pH=8,0.1mol/L), will be different dense
The hydrogen peroxide of degree is added in buffer, connects electrochemical workstation, carries out cyclic voltammetry scan, cyclic voltammogram (A) and dense
The linear graph (B) of degree and electric current is as shown in Figure 9, it is known that with the increase of concentration, corresponding electric current is successively increased, dense in 1 μM of -5mM
It spends in range into good linear relationship.
Embodiment 3
(1) the PS nanofiber after sulfonation is immersed into the water-soluble of 10mM Tris-HCl, pH=8.5 containing 2mg/mL DA
20h is reacted in liquid.After reaction, in order to remove nonadherent PDA, nanofiber is thoroughly washed for several times with ultrapure water, PDA is obtained and repairs
The PS nanofiber of decorations.
(2) the PS nanofiber of the PDA modification obtained step (1) immerses the AgNO of 10mg/mL3It is reacted in solution
1.5h, with milli-Q water for several times after, be repeated twice immerse the same terms dopamine solution and silver nitrate solution in.After washing
It is put into vacuum oven dry 8h at 50 DEG C, obtains the PS nanofiber of Ag/PDA modification.
(3) sample that step (2) obtains is transferred in tube furnace, under the atmosphere of nitrogen, with the heating speed of 5 DEG C/min
Degree rises to 800 DEG C, retains 1h, is carbonized, obtains Ag/ carbon nano tube compound material, be denoted as 3-AgNPs-NCNTs.
The scanning electron microscope (SEM) photograph of Ag/ carbon nano tube compound material made from the present embodiment such as Fig. 3 D (plane) and the section D'() institute
Show, it is known that Ag/ carbon nanotube sizes are uniform, and at uniform tubular structure, tube diameters and tube wall thicken.
The XRD spectra of Ag/ carbon nano tube compound material made from the present embodiment is as shown in fig. 6, wherein X-ray diffraction is bent
Diffraction maximum at 2 θ=38.2 ° in line, 44.2 °, 64.4 °, 77.4 ° and 81.6 ° it is consistent with the standard diffraction peak of silver (JCPDS,
Number 04-0783), show silver ion by PDA in-situ reducing at silver nano-grain.
Comparative example 1
Control group of the invention, the preparation of the carbon nanotube for the silver nano-grain that undopes, comprising:
(1) the PS nanofiber after sulfonation is immersed into the water-soluble of 10mM Tris-HCl, pH=8.5 containing 2mg/mL DA
20h is reacted in liquid.After reaction, in order to remove nonadherent PDA, nanofiber is thoroughly washed for several times with ultrapure water, is put into vacuum
Drying box dry 8h at 50 DEG C, obtains the PS nanofiber of PDA modification.
(2) the PS nanofiber modified of PDA made from step (1) is transferred in tube furnace under the atmosphere of nitrogen with 5
DEG C/heating rate of min rises to 800 DEG C, retain 1h, is carbonized, obtains carbon nanotube, be denoted as NCNTs.
Scanning electron microscope (SEM) photograph such as Fig. 3 A (plane) and the section A'(of nanotube after the carbonization obtained of this comparative example) shown in, it is known that
Carbon nanotube sizes are uniform, there is a degree of collapsing.The XRD spectra of carbon nanotube made from this comparative example as shown in fig. 6, its
Diffraction maximum of the middle X-ray diffraction curve without containing silver.
Carbon nanotube made from this comparative example is dispersed in dehydrated alcohol (mass concentration 0.1mg/mL) and uses cell
Broken instrument carries out ice-water bath ultrasound 30 minutes, and Nafion is then added, makes Nafion dispersion concentration 0.01%, continues ultrasound 10
Minute is allowed to be uniformly dispersed.5 μ L drop coatings are drawn in glassy carbon electrode surface with microsyringe, and then naturally dry forms a film, and obtains
Carbon nano tube modified glass-carbon electrode.
Respectively by glass-carbon electrode NCNTs/GCE carbon nano tube modified made from bare electrode bare GCE, this comparative example, reality
The carbon nano tube modified glass-carbon electrode AgNPs-NCNTs/GCE of Ag/ made from example 2 is applied as working electrode, platinum filament be to electrode,
Saturated calomel electrode is reference electrode, and three electrodes are inserted into 10mL phosphate buffer (PBS, pH=8,0.1mol/L), full in oxygen
Cyclic voltammetry scan is carried out under the conditions of, the results are shown in Figure 10, however, be evident that: bare electrode is to hydrogen reduction catalytic effect very little；
Carbon nano tube modified electrode has certain catalytic effect to hydrogen reduction；Ag/ carbon nano tube modified electrode has well hydrogen reduction
Catalytic effect.
Comparative example 2
Control group of the invention, the preparation of the Ag/ carbon nano tube compound material of differential responses time, comprising:
(1) the PS nanofiber after sulfonation is immersed into the water-soluble of 10mM Tris-HCl, pH=8.5 containing 2mg/mL DA
40h is reacted in liquid.After reaction, in order to remove nonadherent PDA, nanofiber is thoroughly washed for several times with ultrapure water, PDA is obtained and repairs
The PS nanofiber of decorations.
(2) the PS nanofiber of the modification of PDA made from step (1) is immersed to the AgNO of 10mg/mL3It is reacted in solution
4.5h is put into vacuum oven dry 8h at 50 DEG C afterwards for several times with milli-Q water, obtains the PS Nanowire of Ag/PDA modification
Dimension.
(3) sample made from step (2) is transferred in tube furnace, under the atmosphere of nitrogen, with the heating speed of 5 DEG C/min
Degree rises to 800 DEG C, retains 1h, is carbonized, obtains Ag/ carbon nano tube compound material.
The scanning electron microscope (SEM) photograph of Ag/ carbon nano tube compound material made from this comparative example, as shown in Figure 5, it is known that Ag/ carbon nanometer
Pipe is reunited seriously, and silver nano-grain size is larger.
Claims (10)
1. a kind of silver/carbon nanotube composite material, it is characterised in that: poly-dopamine and silver nano-grain are coated on polystyrene
Nanofiber surface, use autonomous adjustment section silver/poly-dopamine thickness layer by layer directly remove polystyrene fibre using high temperature cabonization
Template is tieed up to be made.
2. silver/carbon nanotube composite material according to claim 1, it is characterised in that: the sulfonated polystyrene nanometer
The diameter of fiber is 100-800nm；The partial size of the silver nano-grain is 4-8nm；The silver/carbon nanotube composite material tube wall
With a thickness of 30-100nm.
3. silver/carbon nanotube composite material according to claim 1, it is characterised in that: the poly-dopamine and silver nanoparticle
The cladding number of plies of particle is >=1 layer.
4. a kind of preparation method of any silver/carbon nanotube composite material as described in claim 1-3, comprising:
(1) sulfonated polystyrene nanofiber is immersed in dopamine solution and is reacted, obtain the poly- of poly-dopamine modification through washing
Styrene nanofiber；
(2) styroflex that poly-dopamine made from step (1) is modified is impregnated in silver nitrate solution, then wash,
Vacuum drying obtains silver nano-grain/poly-dopamine modification polystyrene nano fiber；
(3) step (1) and (2) is repeated, it is fine obtains different layers of silver nano-grains/poly-dopamine modification pipe/polyhenylethylene nano
Dimension, carbonization treatment obtain silver/carbon nanotube composite material.
5. the preparation method according to claim 4, it is characterised in that: in the step (1) dopamine solution be containing
The aqueous solution of the 10mM Tris-HCl, pH=8.5 of the dopamine of 0.5-10mg/mL.
6. the preparation method according to claim 4, it is characterised in that: the technological parameter reacted in the step (1) are as follows: anti-
Answering temperature is 20-30 DEG C, reaction time 1-24h.
7. the preparation method according to claim 4, it is characterised in that: the concentration of silver nitrate solution is in the step (2)
0.1-50mg/mL。
8. the preparation method according to claim 4, it is characterised in that: the time impregnated in the step (2) is 0.5-
20h。
9. the preparation method according to claim 4, it is characterised in that: the process conditions of carbonization treatment in the step (3)
Are as follows: in nitrogen atmosphere, from room temperature with 2-10 DEG C/min of heating rate, it is warming up to 500-1200 DEG C, retention time 30-
120min。
10. silver/carbon nanotube composite material described in claim 1 is in hydrogen peroxide electrochemical sensor or fuel cell catalyst
Application in agent field.
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