CN110562956A - Preparation method and application of ordered mesoporous carbon nanofiber array material - Google Patents
Preparation method and application of ordered mesoporous carbon nanofiber array material Download PDFInfo
- Publication number
- CN110562956A CN110562956A CN201910830068.5A CN201910830068A CN110562956A CN 110562956 A CN110562956 A CN 110562956A CN 201910830068 A CN201910830068 A CN 201910830068A CN 110562956 A CN110562956 A CN 110562956A
- Authority
- CN
- China
- Prior art keywords
- mesoporous carbon
- carbon nanofiber
- nanofiber array
- ordered mesoporous
- preparation
- 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
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
the invention relates to a preparation method of an ordered mesoporous carbon nanofiber array material and application of the ordered mesoporous carbon nanofiber array material in the aspect of electrochemical sensing analysis of malachite green. Discloses a preparation method of an ordered mesoporous carbon nanofiber array by using crab shells as a carbon source and calcining the crab shells in a nitrogen atmosphere. The preparation method is simple, low in energy consumption, cheap and easily available in raw materials, and the method for producing the functional material by utilizing the environmental wastes conforms to the national advocated for garbage classification and recycling. The prepared ordered mesoporous carbon nanofiber array material is used for electrochemical sensing analysis of malachite green, and rapid, sensitive and high-selectivity detection of the malachite green is realized.
Description
Technical Field
The invention belongs to the technical field of carbon material preparation and electrochemical analysis, and particularly relates to a preparation method of an ordered mesoporous carbon nanofiber array material and application of the ordered mesoporous carbon nanofiber array material in a malachite green electrochemical sensor.
Background
Malachite green is a cationic triphenylmethane dye, widely used in cotton, wool, silk, paper, jute and other industries because it has antibacterial, bactericidal and antiprotozoal effects, and also is used as a banned additive by lawless persons in the fish farming industry, with serious negative effects on public health and environment [ SACARA, NAIRI V, SALIS A, et al. At present, the common methods for detecting malachite green mainly include High Performance Liquid Chromatography (HPLC), Molecularly Imprinted Microspheres (MIMs), Surface Enhanced Raman Spectroscopy (SERS), and the like. The traditional instrument method has the defects of complex pretreatment, expensive instrument and corresponding matching cost, incapability of simultaneously detecting parallel samples in a large scale, incapability of being used for field analysis and the like. The electrochemical sensing analysis has the advantages of low cost, simple instrument, high reaction speed, high sensitivity and the like, and is widely applied to actual detection. Unfortunately, conventional electrodes, such as Glassy Carbon Electrodes (GCEs), have a large overpotential and are easily poisoned by products generated in the electrochemical process. Therefore, it is important to explore new substrate materials to improve sensitivity and widen the detection range.
Mesoporous carbon materials have a wide range of applications in a variety of fields due to their good properties. High specific surface area, high porosity, making it useful as an adsorbent and a gas storage device; the controllable pore structure, surface property and high mechanical stability can be used as a catalyst carrier, a super capacitor and a catalyst; good electrical and thermal conductivity, so that the material can be used as a super capacitor, an electrode material and the like. Although the preparation based on the carbon material has many successful precedent, the method is simple, convenient and quick, has low cost, and still lacks a preparation method for producing energy materials by recycling environmental wastes. Waste has received a great deal of attention as a source of carbon materials in terms of serious environmental problems.
Disclosure of Invention
The invention aims to provide a preparation method and application of an ordered mesoporous carbon nanofiber array material. The obtained carbon material has an oversized specific surface and good conductivity, and can be used as an electrode modification material of a malachite green electrochemical sensor. The method has the advantages of high sensitivity, strong selectivity and the like in the detection of the malachite green.
The invention provides a preparation method of an ordered mesoporous carbon nanofiber array material, which comprises the following specific steps:
(1) Calcining the crab shell in the air at a low temperature to remove organic protein and chitin in the crab shell;
(2) Grinding the product obtained in the step (1) into powder in a mortar to obtain crab shell powder;
(3) And (3) demolding the crab shell powder obtained in the step (2) by adopting a method of self-assembling a hard template and a surfactant, and then calcining at high temperature under the protection of nitrogen to obtain the ordered mesoporous carbon nanofiber array material.
In the present invention, the low-temperature calcination temperature in step (1) is 300 ℃ to 400 ℃.
In the invention, in the step (3), the hard template is soluble phenolic resin, and the surfactant is a triblock copolymer P123.
In the invention, the high-temperature calcination temperature in the step (3) is 800 ℃ to 1500 ℃.
The ordered mesoporous carbon nanofiber array material prepared by the preparation method disclosed by the invention is applied to the electrochemical sensing analysis aspect of malachite green. The method comprises the following specific steps: grinding ordered mesoporous carbon nanofiber array materials into fine powder, uniformly dispersing the fine powder in a mixed solution consisting of water, ethanol and Nafion to obtain a suspension, modifying the surface of a glassy carbon electrode with the suspension, baking the suspension by using an infrared lamp, and then adopting a Differential Pulse Voltammetry (DPV) method to obtain a product with the glassy carbon electrode modified by the mesoporous carbon nanofiber array materials as a working electrode, a platinum wire as a counter electrode and a saturated calomel electrode as a reference electrode at the temperature of 0.05M H2SO4malachite green was detected in solution.
In the present invention, in the mixed solution of water, ethanol and Nafion, 800. mu.L of water, 180. mu.L of ethanol and 20. mu.L of Nafion are added.
In the invention, the aperture of the carbon material is larger than 50 nm and the carbon material is in a fiber array shape, namely, the carbon material is called a mesoporous carbon nanofiber array. The specific surface area of the carbon material was 1200 m2 g-1。
In the present invention, the XRD pattern of the prepared material showed characteristic peaks of carbon at 22.9 ° and 43.6 °.
In the invention, the detection parameters of the differential pulse voltammetry are as follows: amplitude of 50 mV, pulse period of 0.5 s, standing time of 2 s, accumulation time of 500 s, and start-stop potential of 0- + 1.0V.
In the present invention, the + 0.53V in the differential pulse voltammogram is the characteristic oxidation peak of malachite green.
In the invention, the added interferents are: na (Na)+，Mg2+，Cu2+，Ca2+，SO42-，Cl-，NO3-And Violet (CV).
The invention has the beneficial effects that: the carbon material with good conductivity and large specific surface area is prepared by recycling domestic waste and garbage by a simple method at low cost and low energy consumption. The prepared material is successfully applied to electrochemical sensing of malachite green.
drawings
FIG. 1 is SEM (A, B) and TEM images of mesoporous carbon nanofiber arrays (C, D).
FIG. 2 shows BET (A) and XRD (B) patterns of mesoporous carbon nanofiber arrays.
Fig. 3 is a DPV graph (a) and a linear graph (B) of the mesoporous carbon nanofiber array material as a modified electrode for detecting malachite green. Wherein the DPV curves corresponding to 0.1. mu.M, 0.45. mu.M, 0.7. mu.M, 1.2. mu.M, 1.7. mu.M, 2.2. mu.M, 4.68. mu.M, 7.16. mu.M, 12.13. mu.M and 22.07. mu.M malachite green are shown in the diagram (A) from bottom to top, respectively.
FIG. 4 is an anti-interference diagram of detection of malachite green by using mesoporous carbon nanofiber array materials as modified electrodes.
FIG. 5 is a flow chart of the present invention.
Detailed Description
In order to make the technical solutions of the present invention better understood by those skilled in the art, the present invention is further described below with reference to examples, but the present invention is not limited thereto.
The experimental methods used in the following examples are all conventional methods unless otherwise specified. Materials, reagents, etc. used in the examples described below, e.g. wuteIn particular, they are commercially available. The starting materials for the reaction used in the following examples of the present invention are commercially available analytically pure potassium chloride, potassium ferricyanide, potassium ferrocyanide, malachite green, violet, etc. Electrolyte solution in performance test is 0.05M H2SO4Solution, the experiments were all performed at ambient temperature.
In the following examples, the morphology of the prepared mesoporous carbon nanofiber array material was observed by using a JSM-6390 Scanning Electron Microscope (SEM) and a JEOL2011 Transmission Electron Microscope (TEM) in japan, and the electron beam acceleration voltage was 200 kV. XRD was measured using a Bruker model D8X-ray diffractometer (XRD) (Cu K radiation) from Germany and BET was measured using a Micromeritics Tristar3000 analyzer from USA. Performance testing DPV tests were performed at different concentrations of malachite green using the shanghai chen CHI630E electrochemical workstation.
Example 1
preparation of the material: firstly, calcining the collected crab shells in air at 350 ℃, removing organic protein and chitin, and then grinding the crab shells into powder in a mortar. The calcined crab shell powder is added into the ethanol solution of the thermosol and the triblock copolymer P123 for soaking by adopting a method of combining a hard template with the self-assembly of a surfactant. The impregnated composite was evaporated at 25 ℃ for 6 h and subsequently thermally cured at 100 ℃ for a further 24 h to obtain a calcium carbonate/resol/P123 composite. The obtained compound is heated at 350 deg.C and 1 deg.C for min in nitrogen atmosphere-1And pyrolyzing for 2 h to remove the P123 template. Then the composite material is heated for 5 min at 900 ℃ in the nitrogen atmosphere-1And pyrolyzing for 2 h for further carbonization. And finally, treating the calcium carbonate template of the obtained calcium carbonate/carbon composite material by adopting (6M) hydrochloric acid solution. Washing with ultrapure water and ethanol, and drying in air at 80 ℃ for 24 h to obtain the mesoporous carbon nanofiber array material.
Structural characterization: the carbon material is characterized by a Scanning Electron Microscope (SEM) and a Transmission Electron Microscope (TEM) (see figure 1), and the material is a porous fiber array. The material was further characterized by X-ray diffraction (XRD) with a characteristic peak of carbon in the XRD pattern and by a specific surface area of 1200 m in the BET pattern (see FIG. 2)2 g-1The pore diameter is larger than 50 nm.
Electrochemical sensing of malachite green: the prepared mesoporous carbon nanofiber array material is used for electrochemical detection of malachite green. The specific experimental steps are as follows:
accurately weighing 2 mg of prepared carbon material by using an analytical balance, adding 1 mL of aqueous ethanol Nafion solution, ultrasonically vibrating for 2 h to uniformly disperse the material, then using a 2.5 mL liquid transfer gun to take 10 mu L of the material to be smeared on the surface of the polished glassy carbon electrode, and baking the material by using an infrared lamp for later use. The malachite green detection adopts Differential Pulse Voltammetry (DPV), and a three-electrode system is composed of a working electrode (a glassy carbon electrode modified by materials), a counter electrode (a platinum wire) and a reference electrode (saturated calomel). 20 mL of 0.05M H was taken2SO4adding malachite green with different concentrations into the solution, and placing into an electrolytic cell with a stirrer. Setting electrochemical DPV detection parameters: amplitude of 50 mV, pulse period of 0.5 s, standing time of 2 s, accumulation time of 500 s, initial potential of 0V, and final potential of + 1.0V. And sequentially measuring current response values of 0.1 mu M, 0.2 mu M, 0.45 mu M, 0.70 mu M, 1.2 mu M, 1.70 mu M, 2.20 mu M, 4.68 mu M, 7.16 mu M, 12.13 mu M and 17.10 mu M, and obtaining a working curve (see a working curve in fig. 3 from bottom to top).
Selectivity of electrochemical sensor for malachite green: the material has specificity and strong selectivity for detecting malachite green. The specific operation steps are as follows:
And selecting 5 mu M malachite green in the DPV detection step to perform an interference experiment. Determining DPV current intensity of 5 mu M malachite green when no interferents are added, and sequentially adding 2500 mu M Na into 5 mu M malachite green solution+, Mg2+, Cu2+, Ca2+, SO4 2-, 5000 μM Cl- and NO3 -DPV current intensity was measured at 250. mu.M violet (CV), as shown in FIG. 4, and the sensor had good specificity in the presence of ions and other dyes commonly found in these waters.
Claims (7)
1. A preparation method of an ordered mesoporous carbon nanofiber array material is characterized by comprising the following specific steps:
(1) Calcining the crab shell in the air at a low temperature to remove organic protein and chitin in the crab shell;
(2) grinding the product obtained in the step (1) into powder in a mortar to obtain crab shell powder;
(3) And (3) demolding the crab shell powder obtained in the step (2) by adopting a method of self-assembling a hard template and a surfactant, and then calcining at high temperature under the protection of nitrogen to obtain the ordered mesoporous carbon nanofiber array material.
2. The production method according to claim 1, characterized in that the low-temperature calcination temperature in step (1) is 300 ℃ to 400 ℃.
3. The method according to claim 1, wherein the hard template in the step (3) is a resol and the surfactant is a triblock copolymer P123.
4. The production method according to claim 1, wherein the high-temperature calcination temperature in the step (3) is 800 ℃ to 1500 ℃.
5. The application of the ordered mesoporous carbon nanofiber array material prepared by the preparation method of claim 1 in the aspect of electrochemical sensing analysis of malachite green.
6. The application according to claim 5, characterized by the specific steps of: grinding ordered mesoporous carbon nanofiber array materials into fine powder, uniformly dispersing the fine powder in a mixed solution consisting of water, ethanol and Nafion to obtain a suspension, modifying the surface of a glassy carbon electrode with the suspension, baking the suspension by using an infrared lamp, and then adopting a Differential Pulse Voltammetry (DPV) method to use the glassy carbon electrode modified by the mesoporous carbon nanofiber array materials as a working electrode, a platinum wire as a counter electrode and a saturated calomel electrode as a reference electrode, and performing MH at 0.05 MH2SO4Malachite green was detected in solution.
7. The use according to claim 6, wherein the mixed solution of water, ethanol and Nafion comprises 800. mu.L of water, 180. mu.L of ethanol and 20. mu.L of Nafion.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910830068.5A CN110562956A (en) | 2019-09-04 | 2019-09-04 | Preparation method and application of ordered mesoporous carbon nanofiber array material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910830068.5A CN110562956A (en) | 2019-09-04 | 2019-09-04 | Preparation method and application of ordered mesoporous carbon nanofiber array material |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN110562956A true CN110562956A (en) | 2019-12-13 |
Family
ID=68777543
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910830068.5A Pending CN110562956A (en) | 2019-09-04 | 2019-09-04 | Preparation method and application of ordered mesoporous carbon nanofiber array material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110562956A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110954582A (en) * | 2019-12-30 | 2020-04-03 | 佛山职业技术学院 | Malachite green electrochemical sensor |
| CN113104833A (en) * | 2021-04-14 | 2021-07-13 | 中国科学技术大学 | Biochar-based hard foam carbon, preparation method thereof and application thereof in electrocatalysis |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103713026A (en) * | 2014-01-08 | 2014-04-09 | 济南大学 | Preparation method and applications of aptamer electrochemical sensor for detecting malachite green (MG) |
| CN103996545A (en) * | 2014-05-19 | 2014-08-20 | 上海大学 | Preparation method for nitrogen-doped ordered mesoporous carbon/carbon fiber composite material |
| CN104201001A (en) * | 2014-07-14 | 2014-12-10 | 上海应用技术学院 | Rod-shaped nitrogen and phosphorus co-doping mesoporous carbon material and preparation method and application thereof |
| JP2017024964A (en) * | 2015-07-28 | 2017-02-02 | デンカ株式会社 | Carbon nanofiber dispersion liquid, and transparent conductive film and transparent conductive film prepared therewith |
| JP2017119736A (en) * | 2015-12-28 | 2017-07-06 | 国立大学法人愛媛大学 | Nanofiber-containing material, manufacturing method of nanofiber-containing material and nanofiber recovery method |
| CN107064105A (en) * | 2017-04-10 | 2017-08-18 | 上海应用技术大学 | It is a kind of at the same detect aquatic products in sunset yellow and malachite green method |
| CN107849706A (en) * | 2015-02-26 | 2018-03-27 | 乔治华盛顿大学 | Prepare the method and system of carbon nano-fiber |
| CN107946606A (en) * | 2017-12-27 | 2018-04-20 | 东北师范大学 | Nitrogen co-doped mesoporous carbon fiber of iron and preparation method thereof and apply in a fuel cell |
-
2019
- 2019-09-04 CN CN201910830068.5A patent/CN110562956A/en active Pending
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103713026A (en) * | 2014-01-08 | 2014-04-09 | 济南大学 | Preparation method and applications of aptamer electrochemical sensor for detecting malachite green (MG) |
| CN103996545A (en) * | 2014-05-19 | 2014-08-20 | 上海大学 | Preparation method for nitrogen-doped ordered mesoporous carbon/carbon fiber composite material |
| CN104201001A (en) * | 2014-07-14 | 2014-12-10 | 上海应用技术学院 | Rod-shaped nitrogen and phosphorus co-doping mesoporous carbon material and preparation method and application thereof |
| CN107849706A (en) * | 2015-02-26 | 2018-03-27 | 乔治华盛顿大学 | Prepare the method and system of carbon nano-fiber |
| JP2017024964A (en) * | 2015-07-28 | 2017-02-02 | デンカ株式会社 | Carbon nanofiber dispersion liquid, and transparent conductive film and transparent conductive film prepared therewith |
| JP2017119736A (en) * | 2015-12-28 | 2017-07-06 | 国立大学法人愛媛大学 | Nanofiber-containing material, manufacturing method of nanofiber-containing material and nanofiber recovery method |
| CN107064105A (en) * | 2017-04-10 | 2017-08-18 | 上海应用技术大学 | It is a kind of at the same detect aquatic products in sunset yellow and malachite green method |
| CN107946606A (en) * | 2017-12-27 | 2018-04-20 | 东北师范大学 | Nitrogen co-doped mesoporous carbon fiber of iron and preparation method thereof and apply in a fuel cell |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110954582A (en) * | 2019-12-30 | 2020-04-03 | 佛山职业技术学院 | Malachite green electrochemical sensor |
| CN110954582B (en) * | 2019-12-30 | 2024-03-22 | 佛山职业技术学院 | Malachite green electrochemical sensor |
| CN113104833A (en) * | 2021-04-14 | 2021-07-13 | 中国科学技术大学 | Biochar-based hard foam carbon, preparation method thereof and application thereof in electrocatalysis |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Wang et al. | Highly dispersed conductive polypyrrole hydrogels as sensitive sensor for simultaneous determination of ascorbic acid, dopamine and uric acid | |
| Wei et al. | Comparison of NiS 2 and α-NiS hollow spheres for supercapacitors, non-enzymatic glucose sensors and water treatment | |
| Jiang et al. | Three-dimensional nitrogen-doped graphene-based metal-free electrochemical sensors for simultaneous determination of ascorbic acid, dopamine, uric acid, and acetaminophen | |
| CN112285174B (en) | Enzyme-free glucose sensor and preparation method and application thereof | |
| CN108007998A (en) | Nickel oxide non-enzymatic glucose electrochemical sensor | |
| CN110243890B (en) | Preparation method of Mn-ZIF67 material and detection method of mercury ions | |
| US11733199B2 (en) | Fabrication method of enzyme-free glucose sensor and use of enzyme-free glucose sensor fabricated by the same | |
| CN110562956A (en) | Preparation method and application of ordered mesoporous carbon nanofiber array material | |
| CN106841344B (en) | The preparation and application of a kind of poroid single-walled carbon nanotube and its modified electrode | |
| CN110031520A (en) | The sensor of the preparation method of graphene oxide modified glassy carbon electrode and recognizable phosphite | |
| CN113030210B (en) | Preparation of carbon dot/bismuth film modified glassy carbon electrode and method for detecting cadmium and lead ions | |
| CN107824797B (en) | Porous high-specific-surface-area bismuth nanoparticle modified nitrogen-doped carbon nanosheet material and preparation method and application thereof | |
| CN106964362A (en) | Metal molybdate/carbon composite nano-fiber and preparation method thereof and composite and its application | |
| CN112362712B (en) | Electrochemical sensor electrode capable of simultaneously detecting heavy metal lead and cadmium ions in grains | |
| Wang et al. | Self-supported Co 3 O 4 nanoneedle arrays decorated with PPy via chemical vapor phase polymerization for high-performance detection of trace Pb 2+ | |
| CN109916976A (en) | The preparation method and applications of the functionalization graphene composite material of zinc germanate nanometer rods modification | |
| Bu et al. | A novel three-dimensional molecularly imprinted polypyrrole electrochemical sensor based on MOF derived porous carbon and nitrogen doped graphene for ultrasensitive determination of dopamine | |
| CN111983001A (en) | Electrochemical sensor and method for detecting Cd2+Application of (1) and detection of Cd2+Method (2) | |
| CN109867282A (en) | Prepare the method and its application of nitrogen-doped porous carbon material | |
| CN109487370A (en) | MOF-235-500 DEG C of material of spinning and its preparation method and application | |
| CN108614018A (en) | Nitrogen-doped zinc oxide/carbon hollow polyhedron optical electro-chemistry sensing material and preparation method thereof | |
| CN108414590A (en) | A kind of carbon material prepared by Direct Laser etching method and its preparation method with applied in trace heavy metal detection | |
| CN111141802A (en) | Nano material and preparation method and application thereof | |
| CN115201293B (en) | Photoelectric sensing electrode and preparation method and application thereof | |
| CN112147197A (en) | Preparation method of electrochemical sensor based on three-dimensional porous covalent organic framework |
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 | ||
| WD01 | Invention patent application deemed withdrawn after publication | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20191213 |