CN114990683A - Graphene coating stainless steel array microporous fiber and preparation method thereof - Google Patents
Graphene coating stainless steel array microporous fiber and preparation method thereof Download PDFInfo
- Publication number
- CN114990683A CN114990683A CN202210633205.8A CN202210633205A CN114990683A CN 114990683 A CN114990683 A CN 114990683A CN 202210633205 A CN202210633205 A CN 202210633205A CN 114990683 A CN114990683 A CN 114990683A
- Authority
- CN
- China
- Prior art keywords
- stainless steel
- fiber
- graphene
- ssf
- coated
- 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.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25F—PROCESSES FOR THE ELECTROLYTIC REMOVAL OF MATERIALS FROM OBJECTS; APPARATUS THEREFOR
- C25F3/00—Electrolytic etching or polishing
- C25F3/02—Etching
- C25F3/06—Etching of iron or steel
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/04—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D only coatings of inorganic non-metallic material
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention provides a graphene coating stainless steel array microporous fiber and a preparation method thereof, wherein (1) the surface of the stainless steel fiber is clean; (2) etching the end of the stainless steel fiber in an electrochemical etching system; (3) immersing the pretreated stainless steel fiber into a coupling agent/MeOH mixed solution, and then drying in an oven to obtain SSF-NH 2; (4) then soaking SSF-NH2 into the graphene oxide dispersion liquid, and then drying at room temperature; (5) repeating the two steps (3) and (4) for multiple times to obtain a uniform coating; (6) and deoxidizing the graphene oxide coated fiber to obtain the SSF coated by the graphene oxide, namely SSF-GF. The invention adopts the four-electrode metal etching device to generate compact array micropores on the surface of the stainless steel fiber, so as to provide more anchor points for reaction, ensure that the coating material can be chemically bonded in the micropores, further improve the durability of the coating and reduce the friction loss. And a chemical bonding method is adopted, and the stability of the chemical bond is utilized to enhance the stability of the graphene coating.
Description
Technical Field
The invention provides a graphene coating stainless steel array microporous fiber and a preparation method thereof, and belongs to the technical field of sewage treatment.
Background
Persistent Organic Pollutants (POPs) in the environment are substances that are synthesized by humans, have persistence, bioaccumulation, biotoxicity, and are capable of long-distance migration. These substances are also referred to as "new environmental pollutants" because they are found relatively late in the environment. POPs have the following four characteristics: (1) high toxicity: POPs have serious influence on the operation condition and health condition of organisms to generate carcinogenic, teratogenic and mutagenic effects; (2) durability: mainly reflects the degradation difficulty and the degradation degree of the substance in nature, and the characteristic is one of important reasons for promoting the migration of persistent organic pollutants; (3) bioaccumulation properties: POPs have hydrophobic and lipophilic properties that make them more prone to accumulation in fatty substances, which over time increases the proportion of contaminating concentrations; (4) strong fluidity: POPs can migrate through evaporation in the atmosphere over long distances, leading to global pollution and spread.
Polycyclic Aromatic Hydrocarbons (PAHs) belong to POPs, have carcinogenic, teratogenic, mutagenic properties as well, and have been considered as a priority pollutant by the Environmental Protection Agency (EPA) and the World Health Organization (WHO) due to long-term retention of PAHs and potential harm to the environment and public health. However, due to the trace amount of polycyclic aromatic hydrocarbons and the complexity of environmental samples, determination of polycyclic aromatic hydrocarbons is often difficult. Therefore, the development of a high-efficiency pretreatment method for enriching and detecting trace polycyclic aromatic hydrocarbons is of great significance.
Solid-phase microextraction (SPME) SPME was proposed in 1990 by Pawliszyn and Arthur on the basis of SPE, and has received much attention because of its advantages of easy operation, no solvent, easy combination with GC, HPLC, MS, etc. This technique is a process based on repeated partitioning between the analyte and the coating material, with the analyte desorbing from the solvent and adsorbing to the coating. However, conventional silica fibers are fragile and have a short average service life, and therefore other materials have been explored in place of silica fibers, such as stainless steel wire (SSF), copper wire, titanium wire, platinum wire, silver wire, and the like.
Today, metal fibers are commonly used in two ways for solid phase micro-extraction. The first method is to use metal fiber as adsorbent and only use etching solution to change the surface structure of metal fiber and make new adsorption site. It has been studied to etch SS with hydrofluoric acid, forming a porous flower-like structure on its surface and generating high affinity for PAHs. The second approach considers the limitations of etching the fibers and uses physical or chemical methods to fix different coatings on the metal fibers, thereby expanding the application field of the metal fibers. Since a specific coating has excellent adsorption selectivity and excellent adsorption performance for a selected analyte, many materials have been applied to construct a coating having high adsorption capacity, such as porous polymer materials, molecularly imprinted polymer materials, carbon materials, metal organic framework materials, and the like.
Graphene, as a material with a honeycomb two-dimensional planar structure, has a wide application prospect in a plurality of fields such as sensors, lithium batteries, nano composite materials and the like due to excellent electronic, optical and mechanical properties. The graphene has the characteristics of large specific surface area, rich delocalized pi electrons and the like, so that the graphene has a large number of adsorption sites and generates strong pi-pi conjugation with aromatic compounds. In addition, the excellent thermal, chemical and mechanical stability makes graphene a durable SPME coating material. Graphene has been studied as an SPME coating material to detect residual drugs in water, showing good adsorption effect.
However, whether the coating is physically or chemically fixed to the metal fibers, repeated rubbing of the coating against the inner wall of the syringe during the experiment can cause the coating to peel off. It is therefore critical to develop a method for improving the durability and robustness of the fibers.
The manufacture of graphene coated fibers involves five processes (Zhang, s. -l.; Du, z.; Li, g. -k.layer-by-layer failure of chemical-bonded graphene coating for solid-phase microextraction [ J ]. anal. chem.,2011,83, 7531-. One tip (1.0 cm) thereof was immersed in acetone for 20 minutes to remove the protective polyimide layer. Subsequently, the fiber was immersed in a 1mol/L NaOH solution for 1h to expose the maximum amount of silanol, and finally washed thoroughly with water and dried. (b) The alkaline treated fiber is immersed in APTES solution for 12h at room temperature, and reacts with hydroxyl on the surface of the silica fiber to form Si-O-Si bonds. The fiber was then pulled out and immediately placed in an oven at 70 ℃ to complete the silanization reaction. (c) For coating, the alkylated fibers were inserted into a 0.2 wt% aqueous GO dispersion and held in a 70 ℃ water bath for 2 hours. It was then removed and dried in air to give a thin GO coating. The two operations (b) and (c) described above were repeated four times to obtain a uniform coating with a thickness of about 20 μm. (d) GO coated fiber was conditioned in a GC syringe for 2 hours at 60 ℃ under nitrogen. This aging process is essential to avoid the GO coating from peeling off the silica fibers during the subsequent reduction process. (e) The GO coated fibers were deoxygenated in distilled water mixture (10mL), hydrazine solution (35 wt% in water, 40 μ Ι _) and ammonia solution (28 wt% in water, 36 μ Ι _) were left at 70 ℃ for 18 hours to obtain graphene coated solid phase microextraction fibers.
The technical disadvantage is that the traditional quartz fiber is still used, but the traditional quartz fiber still has the disadvantages of fragility, insufficient chemical stability and thermal stability, and has limited use times and more limitation conditions.
Prior art (Chen, J. -M.; Zou, J.; Zeng, J. -B.; Song, X. -H.; Ji, J. -J.; Wang, Y. -R.; Ha, J.; Chen, X.preparation and evaluation of a graphene-coated solid-phase microextraction fiber, 2010,678,44-49.) the stock solution of G was filtered again and the PPD was removed by washing with acetone until the filtrate was colorless. The filter cake was redispersed in a 5mL plastic centrifuge tube with 2mL ethanol to form a concentrated G ethanol solution. The solution was centrifuged at 8000rpm for 10 minutes and the pellet was transferred to a 0.5mL plastic centrifuge tube. Before coating, the stainless steel wire (17cm) was washed successively with acetone, then methanol, and finally with distilled water in an ultrasonic generator for 5min each time, and then air-dried at room temperature. The coating was prepared by dipping the steel wire into a 0.5mL plastic centrifuge tube containing the G precipitate. Subsequently, the fibers were pulled out and dried in air for 30 seconds. This procedure was repeated until the thickness of the coating satisfied the requirements (6-8 m). The length of the G coating was controlled at 1.5cm by carefully scraping with a knife from the top. The new fibers were preheated in an oven at 100 ℃ for 24 hours and then further heated in a GC injection port at 240 ℃ under nitrogen for 30 minutes. The physical coating method ensures that the acting force between the material and the matrix is weaker, so the prepared coating is not firm, and has poor high temperature resistance and stability.
The prior art also comprises:
(1) treating the stainless steel fiber: selecting 304 stainless steel fibers, and grinding the stainless steel fibers by using phosphated silica sand paper; before electrochemical treatment, the mixture is treated in an organic solvent, washed by deionized water and finally dried by nitrogen airflow;
(2) and (3) building an etching device: in the electrolyte, performing electrochemical treatment on the stainless steel fibers by using a four-electrode electrochemical cell platinum counter electrode; the center is stainless steel fiber, and the periphery is three platinum electrodes in a stable triangular structure; the three platinum electrodes are connected with the cathode of a power supply to be protected, the stainless steel fiber is connected with the anode of the power supply to be etched, and the voltage and the polarization time of an external power supply are adjusted until the stainless steel fiber with the orderly arranged fish scale-shaped structure is prepared;
(3) chemical corrosion of lattice microporous metal wires: the method comprises the steps of flushing the stainless steel fiber with deionized water for a plurality of times, washing off organic matters remained on the surface of the stainless steel fiber, putting the stainless steel fiber into 35-45% hydrofluoric acid at room temperature for corrosion, fixing the stainless steel fiber in the corrosion process to ensure uniform corrosion, and then putting the stainless steel fiber into a gas chromatograph for drying for 3.5-4.5 hours under the protection of nitrogen.
The method only adopts the stainless steel fiber matrix to be treated to prepare the SPME fiber, and has insufficient extraction effect and specific adsorption effect on the analyte.
Disclosure of Invention
The invention provides a graphene coating stainless steel array microporous fiber and a preparation method thereof, and solves the following technical problems:
(1) the traditional quartz fiber is fragile and poor in durability, is replaced by stainless steel fiber, overcomes the fragile problem of the traditional fiber, and is high in durability of the metal matrix.
(2) Stainless steel fibers are indicated as being smoother with fewer reaction sites. A four-electrode metal etching device is adopted to enable the surface of the stainless steel fiber to generate compact array micropores, and more anchor points are provided for reaction.
(3) The traditional graphene coating mostly adopts a physical coating method, and the durability is poor. And a chemical bonding method is adopted, and the stability of the chemical bond is utilized to enhance the stability of the graphene coating.
The specific technical scheme is as follows:
the preparation method of the graphene-coated stainless steel array microporous fiber comprises the following steps:
(1) firstly, polishing stainless steel fibers to be smooth by using sand paper, then respectively removing organic matters on the surfaces of the stainless steel fibers in methanol and acetone by ultrasonic waves, then washing the stainless steel fibers by using ultrapure water, and drying the stainless steel fibers under nitrogen;
(2) etching the end of the stainless steel fiber in an electrochemical etching system;
after etching, washing the substrate with ultrapure water and drying the substrate in an oven, soaking the etched tail end in NaOH solution, washing the immersed tail end with ultrapure water and drying the immersed tail end in the oven;
(3) immersing the pretreated stainless steel fiber into a coupling agent/MeOH mixed solution, and drying in an oven to obtain the amino-functionalized SSF (single-stranded fibers), namely SSF-NH 2 ；
The coupling agent is APTES, and other coupling agents can also be adopted.
(4) Then adding SSF-NH 2 Immersing the graphene oxide into the graphene oxide dispersion liquid, and then drying the graphene oxide dispersion liquid at room temperature;
(5) repeating the two steps (3) and (4) for multiple times to obtain a uniform coating;
(6) deoxidizing the graphene oxide coated fiber in a mixed solution of ultrapure water, hydrazine hydrate and ammonium hydroxide to obtain the graphene coated SSF (single stranded fiber), namely SSF-GF.
Wherein, etching is carried out at 25V for 120 seconds in the step (2);
the electrochemical etching system is used for carrying out electrochemical treatment on the stainless steel fiber by using a four-electrode electrochemical cell in electrolyte, the center of the electrochemical etching system is the stainless steel fiber, three platinum electrodes distributed in an equilateral triangle structure are arranged on the periphery of the electrochemical etching system, and the distance between each platinum electrode and the stainless steel fiber is equal; the three platinum electrodes are connected with the negative electrode of the power supply, and the stainless steel fiber is connected with the positive electrode of the power supply;
the electrolyte is a mixture of anhydrous glycol and perchloric acid, and the v/v of the anhydrous glycol and the perchloric acid is 9: 1.
The electrolyte can be replaced, and comprises aqua regia, HF and the like, so that the surface of the stainless steel fiber can generate a rough surface structure to improve the specific surface area, and the coating is favorably carried out.
Preferably, the v/v of APTES/MeOH in step (3) is 2: 8; the immersion is carried out for 8h at 50 ℃.
In the step (4), the concentration of the graphene oxide dispersion liquid is 0.2 wt%, the temperature is 70 ℃, and the immersion time is 2 hours.
In the step (6), the deoxidation time is 18 hours, the temperature is 70 ℃, and the proportion of ultrapure water, hydrazine hydrate and ammonium hydroxide is as follows: 10ml, 40. mu.L, 36. mu.L.
The invention has the beneficial effects that:
(1) the stainless steel fiber is adopted to overcome the problem that the traditional fiber is fragile, the metal matrix has high durability, and the physical, chemical and thermal stability are excellent, so that the high-temperature condition of the GC gasification chamber can be met.
(2) The four-electrode metal etching device is adopted to enable the surface of the stainless steel fiber to generate compact array micropores, so that more anchor points are provided for reaction, the coating material can be chemically bonded in the micropores, the durability of the coating is improved, and the friction loss is reduced.
(3) And a chemical bonding method is adopted, and the stability of the chemical bond is utilized to enhance the stability of the graphene coating.
Drawings
FIG. 1 is a schematic diagram of an electrochemical etching system of the present invention;
FIG. 2(a) is an SEM image of SSF of an example at a magnification of 200;
FIG. 2(b) is an SEM image of SSF of the example at 50000 magnification;
FIG. 2(c) is an SEM image of the etched SSF of the example, at 200 magnification;
FIG. 2(d) is an SEM image of the etched SSF of the example at 50000 magnification;
FIG. 2(e) is an SEM image of SSF-GFs of the example, at 300 magnification;
FIG. 2(f) is an SEM image of SSF-GFs of the example, at 5000 magnification.
Detailed Description
The specific technical scheme of the invention is described by combining the embodiment.
The preparation method of the graphene-coated stainless steel array microporous fiber comprises the following steps:
(1) firstly, polishing 304 stainless steel fibers to be smooth by using sand paper, then respectively carrying out ultrasonic treatment in methanol and acetone for 10min to remove organic matters on the surfaces, then lightly washing thoroughly by using ultrapure water, and drying under nitrogen;
(2) the end of the stainless steel fiber was etched in an electrochemical etching system at 25V for 120 seconds;
as shown in fig. 1, in the electrochemical etching system, in order to perform electrochemical treatment on stainless steel fibers by using a four-electrode electrochemical cell in an electrolyte, the center of the electrochemical etching system is stainless steel fibers, three platinum electrodes distributed in an equilateral triangle structure are arranged on the periphery of the electrochemical etching system, and the distance between each platinum electrode and the stainless steel fibers is equal; the three platinum electrodes are connected with the negative electrode of the power supply to be protected, and the stainless steel fiber is connected with the positive electrode of the power supply to be etched.
The electrolyte is a mixture of anhydrous glycol and perchloric acid, and the v/v of the anhydrous glycol and the perchloric acid is 9: 1.
After etching, washing the substrate with ultrapure water and drying the substrate in an oven, immersing the etched tail end into a 5mmol NaOH solution for soaking for 10min, washing the etched tail end with ultrapure water and drying the washed tail end in the oven for 1 h;
(3) immersing the pretreated stainless steel fiber into APTES/MeOH mixed solution at 50 ℃ for 8h, and drying in an oven for 1h to obtain amino functionalized SSF (single-stranded chain fertilizing factor) -NH 2 (ii) a APTES/MeOH has a v/v of 2: 8;
(4) then adding SSF-NH 2 Immersing the graphene oxide into graphene oxide dispersion liquid at 70 ℃ for 2 hours, and then drying the graphene oxide dispersion liquid at room temperature for 12 hours; the concentration of the graphene oxide dispersion was 0.2 wt%;
(5) repeating the two steps (3) and (4) for a plurality of times to obtain a uniform coating;
(6) deoxidizing the graphene oxide coated fiber in a mixed solution of ultrapure water at 70 ℃, hydrazine hydrate and ammonia hydroxide for 18 hours to obtain graphene coated SSF (single stranded fiber) namely SSF-GF; the proportion of the ultrapure water, the hydrazine hydrate and the ammonium hydroxide is as follows: 10ml, 40. mu.L, 36. mu.L.
Fig. 2(a) to 2(f) are SEM images of SSF at magnification of 200 × and 50000 ×; SEM images of etched SSF at 200 x and 50000 x magnification; SEM images of SSF-GFs at 300X and 5000X magnifications.
Table 1: analytical Properties of SSF-GF on PAHs solid phase microextraction
Table 2: analysis result for determining PAHs in water sample
nd＝Not detected
The above-mentioned embodiments only express several embodiments of the present invention, and the description thereof is more specific and detailed, but not construed as limiting the scope of the invention. It should be noted that, for a person skilled in the art, several variations and modifications can be made without departing from the inventive concept, which falls within the scope of the present invention. Therefore, the protection scope of the present patent shall be subject to the appended claims.
Claims (7)
1. The preparation method of the graphene-coated stainless steel array microporous fiber is characterized by comprising the following steps:
(1) firstly, polishing stainless steel fibers to be smooth by using abrasive paper, then respectively removing organic matters on the surfaces of the stainless steel fibers in methanol and acetone by using ultrasonic waves, then washing the stainless steel fibers by using ultrapure water, and drying the stainless steel fibers under nitrogen;
(2) etching the end of the stainless steel fiber in an electrochemical etching system;
after etching, washing the substrate with ultrapure water and drying the substrate in an oven, soaking the etched tail end in NaOH solution, washing the immersed tail end with ultrapure water and drying the immersed tail end in the oven;
(3) immersing the pretreated stainless steel fiber into a coupling agent/MeOH mixed solution, and drying in an oven to obtain the amino-functionalized SSF (single-stranded fibers), namely SSF-NH 2 ；
(4) Then adding SSF-NH 2 Immersing the graphene oxide into the graphene oxide dispersion liquid, and then drying the graphene oxide dispersion liquid at room temperature;
(5) repeating the two steps (3) and (4) for a plurality of times to obtain a uniform coating;
(6) deoxidizing the graphene oxide coated fiber in a mixed solution of ultrapure water, hydrazine hydrate and ammonium hydroxide to obtain SSF (graphene coated fiber), namely SSF-GF.
2. The method for preparing microporous graphene coated stainless steel array fibers according to claim 1, wherein the step (2) is carried out at 25V for 120 seconds;
the electrochemical etching system is used for carrying out electrochemical treatment on the stainless steel fiber by using a four-electrode electrochemical cell in electrolyte, the center of the electrochemical etching system is the stainless steel fiber, three platinum electrodes distributed in an equilateral triangle structure are arranged on the periphery of the electrochemical etching system, and the distance between each platinum electrode and the stainless steel fiber is equal; the three platinum electrodes are connected with the negative electrode of the power supply, and the stainless steel fiber is connected with the positive electrode of the power supply.
3. The method for preparing the graphene-coated stainless steel array microporous fiber according to claim 2, wherein the electrolyte is a mixture of anhydrous ethylene glycol and perchloric acid, and v/v of the anhydrous ethylene glycol and the perchloric acid is 9: 1.
4. The method for preparing the graphene-coated stainless steel array microporous fiber according to claim 1, wherein in the step (3), the coupling agent is APTES, and v/v of APTES/MeOH is 2: 8; the immersion is carried out for 8h at 50 ℃.
5. The preparation method of the graphene-coated stainless steel array microporous fiber according to claim 1, wherein in the step (4), the concentration of the graphene oxide dispersion liquid is 0.2 wt%, the temperature is 70 ℃, and the immersion time is 2 h.
6. The preparation method of the graphene-coated stainless steel array microporous fiber according to claim 1, wherein the deoxygenation time in the step (6) is 18 hours, the temperature is 70 ℃, and the proportion of ultrapure water, hydrazine hydrate and ammonia hydroxide is as follows: 10ml, 40. mu.L, 36. mu.L.
7. Graphene-coated stainless steel array microporous fiber obtained by the preparation method according to any one of claims 1 to 6.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210633205.8A CN114990683A (en) | 2022-06-06 | 2022-06-06 | Graphene coating stainless steel array microporous fiber and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210633205.8A CN114990683A (en) | 2022-06-06 | 2022-06-06 | Graphene coating stainless steel array microporous fiber and preparation method thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114990683A true CN114990683A (en) | 2022-09-02 |
Family
ID=83033355
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210633205.8A Pending CN114990683A (en) | 2022-06-06 | 2022-06-06 | Graphene coating stainless steel array microporous fiber and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114990683A (en) |
Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103083942A (en) * | 2013-02-05 | 2013-05-08 | 漳州师范学院 | Preparation method of solid phase micro-extraction adsorption coat based on SiO2 bonded graphene |
| CN103127919A (en) * | 2013-03-19 | 2013-06-05 | 北京师范大学 | Method for preparing titanium-based graphene coating for solid phase microextraction |
| US20140322518A1 (en) * | 2013-04-24 | 2014-10-30 | Raymond S. Addleman | Porous multi-component material for the capture and separation of species of interest |
| WO2015127792A1 (en) * | 2014-02-28 | 2015-09-03 | 天津工业大学 | Method for preparing oil-absorbing hollow fiber porous membrane |
| US20160153094A1 (en) * | 2014-12-01 | 2016-06-02 | Anish Tuteja | Salt Based Etching of Metals and Alloys for Fabricating Superhydrophobic and Superoleophobic Surfaces |
| CN106367710A (en) * | 2016-08-31 | 2017-02-01 | 中山大学惠州研究院 | Preparation method of abrasion-resistant coating of stainless steel base material |
| CN106475076A (en) * | 2015-09-02 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of preparation method of the solid-phase micro-extraction fibre that graphene oxide is modified |
| CN106622183A (en) * | 2016-11-15 | 2017-05-10 | 沈阳师范大学 | Novel solid-phase microextraction fiber preparation method and solid-phase microextraction fiber |
| CN106823461A (en) * | 2017-02-28 | 2017-06-13 | 甘肃政法学院 | A kind of preparation method of functionalization graphene coating probe and SPME handle |
| CN106835258A (en) * | 2016-12-15 | 2017-06-13 | 华北电力大学（保定） | A kind of dot matrix type etches the preparation method and applications of stainless steel fibre |
| CN106861600A (en) * | 2016-12-15 | 2017-06-20 | 华北电力大学（保定） | A kind of preparation method and applications of new etching stainless steel fibre |
| US20170254732A1 (en) * | 2016-03-02 | 2017-09-07 | Janusz Boleslaw Pawliszyn | Solid phase microextraction coating |
| US20180134561A1 (en) * | 2016-11-11 | 2018-05-17 | Shin-Etsu Chemical Co., Ltd. | Method of manufacturing graphene film and method of manufacturing pellicle using the same |
| CN108242341A (en) * | 2017-12-21 | 2018-07-03 | 华北电力大学 | A kind of preparation of multifunctional graphite vinyl sill and its application in terms of ultracapacitor and water process |
| CN108774879A (en) * | 2018-07-06 | 2018-11-09 | 东华大学 | A kind of preparation method of graphene coated conductive fiber |
| CN109281156A (en) * | 2018-07-19 | 2019-01-29 | 中国科学院宁波材料技术与工程研究所 | A kind of high stability, electrolyte-resistant etching conductive fiber and preparation method thereof |
| CN110292915A (en) * | 2019-07-19 | 2019-10-01 | 华中师范大学 | Surface molecule print graphene entirety fiber and its preparation method and application |
| CN111569848A (en) * | 2020-06-15 | 2020-08-25 | 甘肃政法大学 | Preparation method of solid-phase micro-extraction fiber with reduced graphene oxide as coating material |
-
2022
- 2022-06-06 CN CN202210633205.8A patent/CN114990683A/en active Pending
Patent Citations (18)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103083942A (en) * | 2013-02-05 | 2013-05-08 | 漳州师范学院 | Preparation method of solid phase micro-extraction adsorption coat based on SiO2 bonded graphene |
| CN103127919A (en) * | 2013-03-19 | 2013-06-05 | 北京师范大学 | Method for preparing titanium-based graphene coating for solid phase microextraction |
| US20140322518A1 (en) * | 2013-04-24 | 2014-10-30 | Raymond S. Addleman | Porous multi-component material for the capture and separation of species of interest |
| WO2015127792A1 (en) * | 2014-02-28 | 2015-09-03 | 天津工业大学 | Method for preparing oil-absorbing hollow fiber porous membrane |
| US20160153094A1 (en) * | 2014-12-01 | 2016-06-02 | Anish Tuteja | Salt Based Etching of Metals and Alloys for Fabricating Superhydrophobic and Superoleophobic Surfaces |
| CN106475076A (en) * | 2015-09-02 | 2017-03-08 | 中国石油化工股份有限公司 | A kind of preparation method of the solid-phase micro-extraction fibre that graphene oxide is modified |
| US20170254732A1 (en) * | 2016-03-02 | 2017-09-07 | Janusz Boleslaw Pawliszyn | Solid phase microextraction coating |
| CN106367710A (en) * | 2016-08-31 | 2017-02-01 | 中山大学惠州研究院 | Preparation method of abrasion-resistant coating of stainless steel base material |
| US20180134561A1 (en) * | 2016-11-11 | 2018-05-17 | Shin-Etsu Chemical Co., Ltd. | Method of manufacturing graphene film and method of manufacturing pellicle using the same |
| CN106622183A (en) * | 2016-11-15 | 2017-05-10 | 沈阳师范大学 | Novel solid-phase microextraction fiber preparation method and solid-phase microextraction fiber |
| CN106835258A (en) * | 2016-12-15 | 2017-06-13 | 华北电力大学（保定） | A kind of dot matrix type etches the preparation method and applications of stainless steel fibre |
| CN106861600A (en) * | 2016-12-15 | 2017-06-20 | 华北电力大学（保定） | A kind of preparation method and applications of new etching stainless steel fibre |
| CN106823461A (en) * | 2017-02-28 | 2017-06-13 | 甘肃政法学院 | A kind of preparation method of functionalization graphene coating probe and SPME handle |
| CN108242341A (en) * | 2017-12-21 | 2018-07-03 | 华北电力大学 | A kind of preparation of multifunctional graphite vinyl sill and its application in terms of ultracapacitor and water process |
| CN108774879A (en) * | 2018-07-06 | 2018-11-09 | 东华大学 | A kind of preparation method of graphene coated conductive fiber |
| CN109281156A (en) * | 2018-07-19 | 2019-01-29 | 中国科学院宁波材料技术与工程研究所 | A kind of high stability, electrolyte-resistant etching conductive fiber and preparation method thereof |
| CN110292915A (en) * | 2019-07-19 | 2019-10-01 | 华中师范大学 | Surface molecule print graphene entirety fiber and its preparation method and application |
| CN111569848A (en) * | 2020-06-15 | 2020-08-25 | 甘肃政法大学 | Preparation method of solid-phase micro-extraction fiber with reduced graphene oxide as coating material |
Non-Patent Citations (4)
| Title |
|---|
| 刘乐浩;莫金珊;李美成;赵廷凯;李铁虎;王大为;: "纳米颗粒的自组装及其在锂离子电池中的应用", 材料工程 * |
| 姚伟宣;张素玲;: "碳纳米材料固相微萃取涂层的制备及应用", 广东化工 * |
| 徐赫;张龙;周家孝;马一涛;罗斌;张素玲;: "石墨烯在固相微萃取中的应用研究", 化学工程师 * |
| 李悦;刘全亨;龙安应;: "原位自组装石墨烯固相微萃取探头的制备及其在水体苯系物分析中的应用", 分析测试学报 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Yantasee et al. | Simultaneous detection of cadmium, copper, and lead using a carbon paste electrode modified with carbamoylphosphonic acid self-assembled monolayer on mesoporous silica (SAMMS) | |
| Smith et al. | Polyaniline-gold nanocomposite system | |
| Stozhko et al. | Modified carbon-containing electrodes in stripping voltammetry of metals: Part I. Glassy carbon and carbon paste electrodes | |
| Bagheri et al. | Fabrication of a novel electrochemical sensing platform based on a core–shell nano-structured/molecularly imprinted polymer for sensitive and selective determination of ephedrine | |
| CN101832965B (en) | Laccase biosensor based on magnetic carbon nano tube and chitosan/silicon dioxide gel and preparation method and application thereof | |
| Wang et al. | A simultaneous and sensitive determination of hydroquinone and catechol at anodically pretreated screen-printed carbon electrodes | |
| JP2005172769A (en) | Electrochemical measuring electrode | |
| Zhao et al. | Selectively electrochemical determination of chloramphenicol in aqueous solution using molecularly imprinted polymer-carbon nanotubes-gold nanoparticles modified electrode | |
| Li et al. | Electrochemical detection of ractopamine based on a molecularly imprinted poly-o-phenylenediamine/gold nanoparticle–ionic liquid–graphene film modified glass carbon electrode | |
| KR101608584B1 (en) | Graphene thin film obtained from electrochemical reduction of hydroxyl groupenriched graphene oxide and method for detecting uric acid using the same | |
| Behzadi et al. | Electropolymerization of carbon nanotubes/poly-ortho-aminophenol nanocomposite on a stainless steel fiber for the solid-phase microextraction of phthalate esters | |
| CN105907844A (en) | Electrochemical DNA biosensor based on three-dimensional graphene-dendritic nanogold, and preparation method thereof | |
| Mardani et al. | Preparation of molecularly imprinted magnetic graphene oxide-gold nanocomposite and its application to the design of electrochemical sensor for determination of epinephrine | |
| Abolghasemi et al. | Preparation and evaluation of a layered double hydroxide film on a nanoporous anodic aluminum oxide/aluminum wire as a highly thermal-resistant solid-phase microextraction fiber | |
| Maeda et al. | Surface improvement of glassy carbon electrode anodized in triethylene glycol and its application to electrochemical HPLC analysis of protein-containing samples | |
| CN114990683A (en) | Graphene coating stainless steel array microporous fiber and preparation method thereof | |
| Ma et al. | Voltammetric determination of trace Zn (II) in seawater on a poly (sodium 4-styrenesulfonate)/wrinkled reduced graphene oxide composite modified electrode | |
| RU2645131C1 (en) | Production process of a sorption material | |
| CN112858428B (en) | Electrochemical sensor for detecting bisphenol A and bisphenol S based on covalent organic framework modified graphite core electrode | |
| Nikolenko et al. | Atomic force microscopy and X-ray photoelectron spectroscopy study of chitosan-carbon fiber materials | |
| Wang et al. | An effective gold nanotubes electrode for amperometric biosensor | |
| CN112326753B (en) | Preparation method and application of triclosan molecular imprinting membrane electrochemical sensor | |
| CN115343338A (en) | FeOOH/CC and nitrite electrochemical sensor and application thereof | |
| Pacheco-Fernández et al. | Metallic coatings in solid-phase microextraction: environmental applications | |
| Jiahong et al. | Methionine–Au Nanoparticle Modified Glassy Carbon Electrode: a Novel Platform for Electrochemical Detection of Hydroquinone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |