CN102965101B - Material with surface-enhancement Raman scattering performance and catalytic activity, preparation method and application thereof - Google Patents
Material with surface-enhancement Raman scattering performance and catalytic activity, preparation method and application thereof Download PDFInfo
- Publication number
- CN102965101B CN102965101B CN201210494493.XA CN201210494493A CN102965101B CN 102965101 B CN102965101 B CN 102965101B CN 201210494493 A CN201210494493 A CN 201210494493A CN 102965101 B CN102965101 B CN 102965101B
- Authority
- CN
- China
- Prior art keywords
- polyacrylonitrile
- raman scattering
- silver
- enhanced raman
- mol
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Landscapes
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a material with surface-enhancement Raman scattering performance and catalytic activity, a preparation method and the application of the material. The material takes polyacrylonitrile as a carrier of electrostatic spinning; and the preparation method comprises the steps of: adding silver nitrate into N, N-dimethyl formamide solvent; preparing polyacrylonitrile/ silver nitrate nanofiber by the electrostatic spinning technology; reducing by sodium borohydride to obtain polyacrylonitrile/ silver nanofiber; then, putting the polyacrylonitrile/ silver nanofiber into boiled chloroauric acid solution; carrying out a replacement reaction to obtain a polyacrylonitrile fiber film loaded with gold-silver alloy nano particles; and carrying out aftertreatment on the film by saturated salt water and deionized water to obtain the material with better surface-enhancement Raman scattering performance and higher catalytic activity. The material can be used for monitoring the process of catalytic reaction in situ.
Description
Technical field
The present invention relates to a kind of material that has surface enhanced Raman scattering performance and catalytic activity concurrently and preparation method thereof, belong to macromolecular material, laser raman field, chemical analysis detection field.
Background technology
In recent years, a kind of Rough Metal Surface based on nanoscale or the special optical reinforcing effect of granular system receive much concern, and this surface enhanced effect can greatly improve the sensitivity of analyzing and testing.Metal nanoparticle internal freedom electronics regular motion and produce surface plasma body resonant vibration under the external electromagnetic field action of certain frequency, the surface plasma body resonant vibration of adjacent nanoparticle is coupled, between the nanoparticle of coupling, form " hot-zone ", thereby the electric field in this region strengthens greatly.Utilize this highfield effect, the raising that can make the efficiency of many two-phonon process obtain showing, as surface-enhanced Raman, surface strengthens fluorescence and surface strengthens infrared.The lip-deep Raman signal enhancing of noble metal is called as surface enhanced Raman scattering (Surface Enhanced Raman Scattering, SERS), incident laser acts on the metal substrate surface of certain surface roughness, the electromagnetic field producing obtains larger enhancing, and square being directly proportional of the intensity of Raman scattering and molecule optical electric field of living in, therefore increased greatly the probability that is adsorbed on surperficial molecule generation Raman scattering, the surperficial raman scattering intensity detecting has also improved greatly.For SERS analytical technology, the Raman base material of preparing high responsiveness is a very important research contents.
At present, the active substrate of SERS comprises the solid substrate of coarse metal electrode, metal-sol and metallic membrane covering etc.Electrostatic spinning is a kind of method simply and easily of preparing nano-scale fiber, and it is by high tension electrostatic field is added in polymers soln or melt, makes polymers soln or melt first form the conical drop of Taylor at jet hole place.The electric field drawing force producing when high voltage electric place has overcome after the surface tension of drop, this charged drop has formed injection stream, this injection stream is further stretched in electric field, include solvent constantly volatilizees simultaneously, finally arrive dash receiver with spirrillum, solidify and form the fibrefelt of non-woven fabrics shape or the works of other shape.Its outstanding advantage of nanofiber that adopts electrostatic spinning to prepare is its high-specific surface area, and therefore, in the time that it detects base material as SERS, its high-specific surface area can effectively increase the surface in contact with detection material, thereby increases substantially the sensitivity of detection.At present, adopt polymer nanofiber and metal nanoparticle blend more and obtain for the nanofiber of SERS base material.
In addition, metal nanoparticle can be used as catalyzer under alkaline condition nitro compound reducing, a series of organic chemical reactionses of catalysis by wide coverage wide coverage.Bimetal nano particles is because two kinds of metals are in the synergistic effect aspect promotion molecular absorption and activation, and the catalytic activity showing is often better than the catalytic activity of single metal.At present, have the material of surface-enhanced Raman effects and catalytic activity concurrently actually rare simultaneously.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of surface enhanced Raman substrate material of in-situ monitoring catalytic process, and the feature of this material is existing higher surface-enhanced Raman effects, has again good catalytic activity simultaneously.The signal reinforced effects of this material is good, and detection sensitivity is high, and catalytic activity is high, good stability, and preparation method is simple.
The technical solution adopted in the present invention is to provide a kind of material that has surface enhanced Raman scattering performance and catalytic activity concurrently, described material is loaded with gold-silver alloy nanoparticles at polyacrylonitrile fibre film surface, in described gold-silver alloy nanoparticles, gold: the mol ratio 1:3～2:3 of silver; Described material is dividing a period of the day from 11 p.m. to 1 a.m with rhodamine 6G as being detected, and the minimal detectable concentration of its surface-enhanced Raman is 10
-11mol/L; In the reaction that described material is p-aminophenol at p-NP by sodium borohydride reduction, its reaction rate constant is 5.4 × 10
-3/ sec～5.6 × 10
-3/ sec.。
The Fibre diameter of described polyacrylonitrile fibre film is 200～400nm.
Prepare a kind of method that has surface enhanced Raman scattering performance and catalytically active material concurrently as above, comprise the steps:
A. be that 11.0～13.0% polyacrylonitrile dissolve in solvent N, dinethylformamide by massfraction, then to add massfraction be 2.0～2.2% presoma Silver Nitrate, obtain mixing solutions;
B. the mixing solutions obtaining is adopted to high-voltage electrostatic spinning technique, prepare polyacrylonitrile/Silver Nitrate nano-fiber film;
C. nano-fiber film step b being obtained is soaked in the sodium borohydride solution that concentration is 0.01mol/L～0.02mol/L, through the reduction reaction of 20-30s, obtains polyacrylonitrile/silver nanoparticle fiber membrane;
D. it is 2.0 × 10 that nano-fiber film step c being obtained is soaked in concentration
-4mol/L～1.0 × 10
-3in the chlorauric acid solution of the boiling of mol/L, after replacement(metathesis)reaction 10～20s, remove by product Silver Nitrate through saturated sodium chloride washings, obtain a kind of surface enhanced Raman scattering substrate material that is loaded with gold-silver alloy nanoparticles at polyacrylonitrile fibre film surface.
The processing condition of described high-voltage electrostatic spinning are voltage 7～8KV, and receiving screen distance is 10～12cm.
A kind of material that has surface enhanced Raman scattering performance and catalytic activity concurrently as above, is applied to in-situ monitoring catalytic reaction process.
Technical solution of the present invention is directly to generate Nano silver grain in fiber surface original position, and prepare a series of surfaces and be loaded with the conjugated fibre of gold-silver alloy nanoparticles by the replacement(metathesis)reaction between Nano silver grain and hydrochloro-auric acid, the existing higher surface-enhanced Raman effects of this conjugated fibre, has again good catalytic reaction activity simultaneously concurrently.It is better that the conjugated fibre of this reinforced effects specific surface in a fiber surface load load Nano silver grain is wanted, and shows better catalytic performance simultaneously.The electrum nanofiber that is loaded with of being prepared by electrostatic spinning in the present invention has high-specific surface area, better at the electrum particle stability of fiber surface, can be used as the surface enhanced Raman substrate material of in-situ monitoring catalytic process.
Owing to having implemented technique scheme, compared with prior art, the obvious advantage of the present invention is:
1,, when electrospun fibers detects base material as SERS, its high-specific surface area can effectively increase the surface in contact with detection molecules, thereby increases substantially the sensitivity of detection.
2, the method that tradition is prepared the composite nano fiber of nanoparticle and polymkeric substance adopts the method for blend more, and nanoparticle dense degree is inadequate, cannot produce surface enhanced effect required " hot-zone ".The gold-silver alloy nanoparticles that this programme adopts the method for in-situ reducing to obtain is intensive, even in polyacrylonitrile fibre surface arrangement, can strengthen the Raman signal of analyte, realizes high-sensitivity detection.
3, adopt the fiber that is loaded with gold-silver alloy nanoparticles as surface Raman enhancement substrate, its reinforced effects is better than the substrate that is loaded with single component silver, the wider general employing of its applicable wavelengths.
4, bimetal nano particles is because two kinds of metals are in the synergistic effect aspect promotion molecular absorption and activation, and the fiber that is loaded with gold-silver alloy nanoparticles has good catalytic performance, and can reuse.
5, composite nano-fiber film has SERS activity and catalytic performance concurrently simultaneously, by detecting the variation of the surface enhanced Raman scattering signal in catalytic process, with in-situ monitoring catalytic reaction process.
Brief description of the drawings
Fig. 1 is scanning electron microscope (SEM) and transmission electron microscope (TEM) figure of polyacrylonitrile/electrum nanofiber of preparing by the embodiment of the present invention 1 technical scheme;
Fig. 2 is that the polyacrylonitrile/electrum nanofiber preparing by the present invention is 10 to concentration
-7～10
-11the SERS spectrogram of mol/L rhodamine 6G;
Fig. 3 is that the polyacrylonitrile/electrum nanofiber preparing by the present invention is 10 to concentration
-11the SERS spectrogram and 10 of mol/L rhodamine 6G
-4the Raman spectrogram of mol/L rhodamine 6G solution;
Fig. 4 is under polyacrylonitrile/electrum nanofiber katalysis of preparing of the present invention, and p-NP calculates ln (A by the time dependent uv atlas of sodium borohydride reduction and by 400nm place ultraviolet absorption value
t/ A
0) with respect to the graph of a relation of time;
Fig. 5 is polyacrylonitrile/electrum nanofiber of preparing by the present invention SERS spectrogram in p-Nitrobenzenethiol reduction reaction process.
Embodiment
Below in conjunction with drawings and Examples, technical solution of the present invention is further elaborated.
Embodiment 1:
The polyacrylonitrile powder of 0.587g is dissolved in the N, dinethylformamide (DMF) solvent of 4.200g, and 40 DEG C of temperature of reaction, are stirred to PAN and are dissolved in completely in DMF, and solution is down to after room temperature, adds wherein 0.100g Silver Nitrate solid, is sufficiently uniformly dissolved.Above-mentioned solution is injected in the spinning solution container of electrostatic spinning machine, spinning temperature is room temperature, and the output voltage of high-voltage power supply is 7kV, distance 12cm between receiving screen and spinning nozzle.Solution becomes droplet-like to tangle and forms taylor cone at rifle head, collects the upper adularescent tunica fibrosa of screen and exists.
The PAN/ Silver Nitrate nanofiber making is soaked in the sodium borohydride solution of 0.01mol/L and reduces, reaction times is 30s, fully rinse fiber with deionized water and remove unnecessary sodium borohydride, it is fully dry that fiber membrane is placed in vacuum drying oven, makes PAN/ silver nanoparticle fiber.
Concentration is respectively to 2.0 × 10
-4mol/L, 4.0 × 10
-4mol/L, 6.0 × 10
-4mol/L, 8.0 × 10
-4mol/L, 1.0 × 10
-3the chlorauric acid solution of mol/L is heated to boiling, and the PAN/ silver nanoparticle fiber membrane being fixed on wave carrier piece reacts 20s in chlorauric acid solution.After reaction finishes, use successively saturated aqueous common salt and deionized water rinsing fiber membrane, it is fully dry that film is placed in vacuum drying oven, makes PAN/ electrum nanofiber.
PAN/ electrum nanofiber is done to Analysis of Surface Topography, and referring to accompanying drawing 1, wherein, a figure is the scanning electron microscope (SEM) of the PAN/ electrum nanofiber prepared by the present embodiment technical scheme, and b figure is transmission electron microscope (TEM) figure; By seeing in figure, the diameter Distribution of PAN/ electrum nanofiber is in 200～400nm left and right, and the gold-silver alloy nanoparticles of fiber surface is densely distributed, even.
Referring to accompanying drawing 2, it is that the PAN/ electrum nanofiber of preparing by the present embodiment technical scheme is 10 to concentration
-7-10
-11the SERS spectrogram pair of mol/L rhodamine 6G, can see from spectrogram, the reinforcing effect of Raman is very strong, and minimal detectable concentration can reach 10
-11mol/L.
Referring to accompanying drawing 3, curve a is that the PAN/ electrum nanofiber of preparing by the present embodiment technical scheme is 10 to concentration
-11the SERS spectrogram of mol/L rhodamine 6G; Curve b is 10
-4the Raman spectrogram of mol/L rhodamine 6G solution can be seen from spectrogram, and composite nano-fiber film has very strong SERS effect, and sensitivity is higher.
Embodiment 2:
At 2mL 1 × 10
-4the sodium borohydride solution that adds 1mL 0.1mol/L in the p-nitrophenyl phenol solution of mol/L, is placed in mixing solutions by the composite fiber thin film obtaining in embodiment 1, fully stirs and detected rapidly every 3 minutes the uv atlas of solution.
Referring to accompanying drawing 4, a figure is that under the PAN/ electrum nanofiber katalysis of preparing by embodiment 1, p-NP is by the time dependent uv atlas of sodium borohydride reduction.From spectrogram, can see, within 15 minutes, the characteristic peak at p-NP 400nm place under alkaline condition reduces gradually, and the product p-aminophenol of reduction raises gradually at the characteristic peak at 300nm place.B figure calculates ln (A by the ultraviolet absorption value ultraviolet absorption value at 400nm place in a figure
t/ A
0) with respect to the graph of a relation of time, it is 5.52 × 10 that the single order straight line simulating obtains reaction rate constant
-3/ sec.Result shows under PAN/ electrum nanofiber exists, p-NP is by the reaction rate accelerates of sodium borohydride reduction, the gold-silver alloy nanoparticles of polyacrylonitrile fibre film surface has catalyzing cooperation effect, and the nanofiber of preparation has good catalytic activity.
Embodiment 3:
At 2mL 1 × 10
-4the sodium borohydride solution that adds 2mL 0.1mol/L in the p-Nitrobenzenethiol ethanolic soln of mol/L, is placed in mixing solutions by the composite fiber thin film obtaining in embodiment 1, fully stirring the surface-enhanced raman scattering signal every 5 minutes test compound fiber membranes.
Referring to accompanying drawing 5, curve a is that PAN/ electrum nanofiber is 10 to concentration
-4the SERS spectrogram of mol/L p-Nitrobenzenethiol; Curve b, c and e are respectively taking PAN/ electrum nanofiber as catalyzer, and p-Nitrobenzenethiol is that the reaction of p-aminophenyl thiophenol was carried out after 5 minutes by sodium borohydride reduction, detects the SERS spectrogram of PAN/ electrum nanofiber to reaction soln.From spectrogram, can see 1113cm
-1and 1346cm
-1the Raman scattering peak of place's nitro stretching vibration reduces gradually, and 1575
-1the Raman scattering peak position of place's phenyl ring ring internal vibration moves on to 1589cm
-1, above variation shows, p-Nitrobenzenethiol can finally be reduced to p-aminophenyl thiophenol.And intermediate product is at 1144 cm
-1, 1392cm
-1and 436cm
-1there is the Raman scattering peak of azo in place, shows to have generated 4,4'-'-dimercaprol azobenzene in reaction process, and the nanofiber of preparation can be applicable to in-situ monitoring catalytic reaction process.
Claims (4)
1. a material that has surface enhanced Raman scattering performance and catalytic activity concurrently, is characterized in that: be loaded with gold-silver alloy nanoparticles at polyacrylonitrile fibre film surface, and in described gold-silver alloy nanoparticles, gold: the mol ratio 1:3～2:3 of silver; Described material is dividing a period of the day from 11 p.m. to 1 a.m with rhodamine 6G as being detected, and the minimal detectable concentration of its surface-enhanced Raman is 10
-11mol/L; In the reaction that described material is p-aminophenol at p-NP by sodium borohydride reduction, its reaction rate constant is 5.4 × 10
-3/ sec～5.6 × 10
-3/ sec.
2. a kind of material that has surface enhanced Raman scattering performance and catalytic activity concurrently according to claim 1, is characterized in that: the Fibre diameter of described polyacrylonitrile fibre film is 200～400nm.
3. preparation a kind of method that has surface enhanced Raman scattering performance and catalytically active material concurrently as claimed in claim 1, is characterized in that comprising the steps:
A. be that 11.0～13.0% polyacrylonitrile dissolve in solvent N, dinethylformamide by massfraction, then to add massfraction be 2.0～2.2% presoma Silver Nitrate, obtain mixing solutions;
B. the mixing solutions obtaining is adopted to high-voltage electrostatic spinning technique, prepare polyacrylonitrile/Silver Nitrate nano-fiber film;
C. nano-fiber film step b being obtained is soaked in the sodium borohydride solution that concentration is 0.01mol/L～0.02mol/L, through the reduction reaction of 20-30s, obtains polyacrylonitrile/silver nanoparticle fiber membrane;
D. it is 2.0 × 10 that nano-fiber film step c being obtained is soaked in concentration
-4mol/L～1.0 × 10
-3in the chlorauric acid solution of the boiling of mol/L, after replacement(metathesis)reaction 10～20s, remove by product Silver Nitrate through saturated sodium chloride washings, obtain a kind of surface enhanced Raman scattering substrate material that is loaded with gold-silver alloy nanoparticles at polyacrylonitrile fibre film surface.
4. a kind of method that has surface enhanced Raman scattering performance and catalytically active material concurrently of preparing according to claim 2, is characterized in that: the processing condition of described high-voltage electrostatic spinning are voltage 7～8KV, and receiving screen distance is 10～12cm.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210494493.XA CN102965101B (en) | 2012-11-28 | 2012-11-28 | Material with surface-enhancement Raman scattering performance and catalytic activity, preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210494493.XA CN102965101B (en) | 2012-11-28 | 2012-11-28 | Material with surface-enhancement Raman scattering performance and catalytic activity, preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102965101A CN102965101A (en) | 2013-03-13 |
| CN102965101B true CN102965101B (en) | 2014-09-17 |
Family
ID=47795538
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210494493.XA Expired - Fee Related CN102965101B (en) | 2012-11-28 | 2012-11-28 | Material with surface-enhancement Raman scattering performance and catalytic activity, preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102965101B (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110102083A (en) * | 2019-05-30 | 2019-08-09 | 苏州大学 | Multi-functional water-oil separating material and its preparation method and application |
Families Citing this family (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103526539A (en) * | 2013-10-23 | 2014-01-22 | 东华大学 | Preparation method of functional gold-silver core-shell nanoparticle/electrostatic spun composite nano-fiber felt |
| CN104111246A (en) * | 2014-07-29 | 2014-10-22 | 苏州大学 | Sensing material for trace detection of heavy metal ions as well as preparation method and application of sensing material |
| CN104389110B (en) * | 2014-10-24 | 2017-08-25 | 中国人民大学 | Embed polyelectrolyte fibrofelt of zeroth order Nanoscale Iron and preparation method thereof |
| CN105784667B (en) * | 2014-12-22 | 2018-05-01 | 深圳先进技术研究院 | A kind of surface enhanced Raman scattering substrate and its preparation method and application |
| CN105002657A (en) * | 2015-03-26 | 2015-10-28 | 长春理工大学 | Porous polymer-Ag composite film serving as SERS substrate |
| CN106179497B (en) * | 2016-07-08 | 2019-04-09 | 上海电力学院 | A kind of preparation method of metal nanoparticles loaded nano-fiber composite film |
| CN107321383B (en) * | 2017-06-20 | 2020-08-28 | 桂林电子科技大学 | Nano-fiber-loaded cobalt-silver alloy material and preparation method and application thereof |
| CN109752360A (en) * | 2017-11-01 | 2019-05-14 | 南京理工大学 | The detection method of 2,4,6- trinitrotoluene |
| CN107976431B (en) * | 2017-11-23 | 2021-06-08 | 深圳大学 | Surface enhanced Raman substrate based on metal nanoparticles and preparation method thereof |
| CN109406486A (en) * | 2018-10-22 | 2019-03-01 | 福建师范大学 | A kind of insoluble fibre is the SERS substrate and preparation method thereof of template |
| CN111235874A (en) * | 2018-11-28 | 2020-06-05 | 南京理工大学 | Preparation method of polyvinyl alcohol/silver composite surface enhanced Raman substrate |
| CN114423894A (en) * | 2019-09-20 | 2022-04-29 | 富士胶片株式会社 | Nonwoven fabric, method for producing nonwoven fabric, and filter |
| CN110747435B (en) * | 2019-11-05 | 2021-03-30 | 清华大学 | Preparation method of nanogold thin film SERS substrate based on electrochemical coarsening |
| CN113509793A (en) * | 2020-04-09 | 2021-10-19 | 宁波方太厨具有限公司 | Preparation method of composite nanofiber filtering membrane for removing formaldehyde |
| CN115888818B (en) * | 2022-07-29 | 2024-04-02 | 南京工业大学 | Microfluidic electrostatic spinning in-situ growth flue gas denitration catalyst and preparation method and application thereof |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338459A (en) * | 2008-08-08 | 2009-01-07 | 东华大学 | Method for preparing organic and inorganic nanometer assorted fibre |
-
2012
- 2012-11-28 CN CN201210494493.XA patent/CN102965101B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101338459A (en) * | 2008-08-08 | 2009-01-07 | 东华大学 | Method for preparing organic and inorganic nanometer assorted fibre |
Non-Patent Citations (2)
| Title |
|---|
| Surface-enhanced Raman scattering-active substrates of electrospun polyvinyl alcohol/gold-silver nanofibers;Xxiaofei Li et al;《Journal of Colloid and Interface Science》;20120607;第382卷;28-35 * |
| Xxiaofei Li et al.Surface-enhanced Raman scattering-active substrates of electrospun polyvinyl alcohol/gold-silver nanofibers.《Journal of Colloid and Interface Science》.2012,第382卷28-35. |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110102083A (en) * | 2019-05-30 | 2019-08-09 | 苏州大学 | Multi-functional water-oil separating material and its preparation method and application |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102965101A (en) | 2013-03-13 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102965101B (en) | Material with surface-enhancement Raman scattering performance and catalytic activity, preparation method and application thereof | |
| Zhao et al. | Electrospun TiO2 nanofelt surface-decorated with Ag nanoparticles as sensitive and UV-cleanable substrate for surface enhanced Raman scattering | |
| Ding et al. | Electrospun nanomaterials for ultrasensitive sensors | |
| Abd Razak et al. | A review of electrospun conductive polyaniline based nanofiber composites and blends: processing features, applications, and future directions | |
| Dong et al. | Synthesis and assembly of metal nanoparticles on electrospun poly (4-vinylpyridine) fibers and poly (4-vinylpyridine) composite fibers | |
| Li et al. | Direct fabrication of composite and ceramic hollow nanofibers by electrospinning | |
| Ramesh Kumar et al. | Nanofibers: effective generation by electrospinning and their applications | |
| Wang et al. | Glassy carbon electrode coated with polyaniline-functionalized carbon nanotubes for detection of trace lead in acetate solution | |
| Wang et al. | Polypyrrole-coated electrospun nanofibre membranes for recovery of Au (III) from aqueous solution | |
| Fu et al. | Preparation of polyaniline-encapsulated carbon/copper composite nanofibers for detection of polyphenol pollutant | |
| CN106423154B (en) | A kind of three-dimension flexible electrode or three-dimension flexible catalyst and their preparation and application | |
| CN103882623B (en) | A kind of Prussian blue/polyvinylidene fluoride composite nano fiber film and preparation method thereof | |
| CN105297286B (en) | A kind of preparation method of functional polyalkylene methyl methacrylate, cyclodextrin and carbon nano tube composite nanofiber membrane | |
| CN102600737A (en) | Method for modifying electrostatic spinning film filtering materials | |
| Amarjargal et al. | Facile in situ growth of highly monodispersed Ag nanoparticles on electrospun PU nanofiber membranes: flexible and high efficiency substrates for surface enhanced Raman scattering | |
| CN104090011B (en) | The preparation method of nanometer gold nanofiber function and service thing modified electrode | |
| CN101491835A (en) | Preparation method of heparin modified gold nano-particles | |
| Huang et al. | Electrospun nanofibers: from rational design, fabrication to electrochemical sensing applications | |
| Yasin et al. | Recycling nanofibers from polyethylene terephthalate waste using electrospinning technique | |
| CN105420832A (en) | High sensitivity temperature sensitive conductive composite fiber and preparation method thereof | |
| CN103143392B (en) | Method for preparing phenolic aldehyde amine (PAA)/polyvinyl acetate (PVA) nano-fiber felt containing Au dendrimer-stabilized nanoparticles (DSNPs) | |
| Khamforoush et al. | The influences of collector diameter, spinneret rotational speed, voltage, and polymer concentration on the degree of nanofibers alignment generated by electrocentrifugal spinning method: Modeling and optimization by response surface methodology | |
| Ahmed | Electrospinning for the manufacture of biosensor components: A mini‐review | |
| Xu et al. | Batch preparation of CuO/ZnO-loaded nanofiber membranes for photocatalytic degradation of organic dyes | |
| CN103243408B (en) | Preparation method of porous fiber with surface-enhanced Raman scattering effect |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20140917 Termination date: 20171128 |