CN110078056B - Carbon nano tube with electrochemiluminescence activity - Google Patents
Carbon nano tube with electrochemiluminescence activity Download PDFInfo
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- CN110078056B CN110078056B CN201910379645.3A CN201910379645A CN110078056B CN 110078056 B CN110078056 B CN 110078056B CN 201910379645 A CN201910379645 A CN 201910379645A CN 110078056 B CN110078056 B CN 110078056B
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Abstract
The invention provides a carbon nano tube with electrochemiluminescence activity. The method for preparing the carbon nanotube comprises the following steps: adding the dried carbon nano tube crude product into a concentrated nitric acid solution, stirring and refluxing, and carrying out mixed acid ultrasonic treatment; cooling to room temperature, adding water for dilution, carrying out vacuum filtration, and washing a filter cake with water for multiple times until the filtrate is neutral; collecting the filter cake, and drying to obtain the carbon nano tube with electrochemiluminescence activity. The invention adopts simple and low-cost nitric acid chemical oxidation, mixed acid ultrasonic treatment and subsequent simple washing and drying to obtain the carbon nano tube with electrochemiluminescence activity. The obtained carbon nano tube has rich defect states on the surface and a large number of oxygen-containing groups such as carboxyl, hydroxyl and the like. The carbon nano-tube shows good electrochemiluminescence activity.
Description
Technical Field
The invention relates to a carbon nano tube with electrochemiluminescence activity and a preparation method thereof, belonging to the technical field of analysis and detection.
Background
Electrochemiluminescence is a phenomenon in which luminescence is generated by electrolysis. The electrochemiluminescence technology is a new technology developed by crossing electrochemistry and chemiluminescence, has good controllability of electrochemistry and good sensitivity of chemiluminescence, and is widely applied to the existing analysis and test technology, environmental analysis, food safety analysis and detection, biological and life analysis and modern medical diagnosis. The development of electrochemiluminescence technology depends on the discovery and application of electrochemiluminescence materials with good performance. The traditional electroluminescent materials are electroluminescent molecules such as luminol, ruthenium bipyridine (Ru (bpy)3 2+) These molecular electrochemiluminescence probes have the advantage of high luminescence efficiency, but have the disadvantages of difficult modification, expensive reagents and the like, and limit the wide application of the electrochemiluminescence technology. After 2002, the developed semiconductor quantum dots with electrochemiluminescence activity, such as CdS, CdSe, CdTe, CdSe/ZnSe, PbS and the like, have the advantages of high electrochemiluminescence activity, easiness in preparation and modification and low cost, but have the defects of poor water solubility, poor chemical stability, strong toxicity and the like, so that the application of the semiconductor quantum dots is greatly limited. In recent years, carbon-based quantum dots, including carbon quantum dots and graphene quantum dots, have been found to be goodThe nano material is a zero-dimensional material, has over-good water solubility, is difficult to fix on the surface of an electrode, constructs a high-sensitivity sensor, and accordingly influences the application of the electrochemiluminescence technology of carbon-based quantum dots to a great extent. Therefore, the search for an electrochemiluminescence nano material which has good electrochemiluminescence activity, low biotoxicity and environmental toxicity, is easy to carry out chemical and biological modification, is easy to fix on the surface of an electrode, is low in cost and is easy to prepare is very challenging work.
Disclosure of Invention
The invention aims to provide a carbon nano tube with electrochemiluminescence activity, and the method for preparing the carbon nano tube has the advantages of simple operation and low cost, and the prepared carbon nano tube has good electrochemiluminescence activity.
The invention is realized by the following technical scheme:
a carbon nanotube having electrochemiluminescence activity, which is prepared by a method comprising:
a. adding the dried carbon nano tube crude product into a nitric acid solution, and stirring and refluxing;
b. carrying out mixed acid ultrasonic treatment;
c. cooling to room temperature, adding water for dilution, filtering, and washing the filter cake with water for multiple times until the filtrate is neutral;
d. collecting the filter cake, and drying to obtain the carbon nano tube with electrochemiluminescence activity.
Preferably, the concentration of the nitric acid solution in the step a is 1-12 mol/L, and the preferred concentration is 7.5 mol/L.
Preferably, the amount ratio of the carbon nanotube crude product in the step a to the nitric acid solution is 0.01-10 g of carbon nanotube crude product per 100mL of nitric acid, and preferably 0.1g of carbon nanotube crude product per 100mL of nitric acid.
Preferably, the reflux temperature in the step a is 20-200 ℃, and the reflux time is 1-30 h. The reflux time is preferably 12 h.
Preferably, in the above technical solution, the mixed acid treatment in step b is to mix one or more acids to form an acid solution mixture; the acid is a lewis acid. Preferably, the volume ratio of the nitric acid to the sulfuric acid is 1: 3 to form mixed acid.
Preferably, the ultrasonic treatment time in the step b is 0-72 h. Preferably the sonication time is 0.5 h.
Preferably, the filtration method in step c is vacuum filtration or centrifugal ultrafiltration. Preferably, the filtration is carried out with a 0.2 um filter membrane.
The invention takes the industrial prepared carbon nano tube crude product as the raw material, adopts simple and cheap acid oxidation treatment and mixed acid ultrasonic treatment methods, and leads the surface of the carbon nano tube to generate rich defects, surface states and proper oxidation degree on the basis of keeping the tubular structure of the carbon nano tube by researching and controlling the acid oxidation condition, the ultrasonic treatment condition, the reaction temperature, the reaction time and the concentration and the composition of acid of the carbon nano tube, thereby preparing the carbon nano tube with electrochemiluminescence activity.
In conclusion, the beneficial effects of the invention are as follows:
the preparation method has the characteristics of easily obtained raw materials, low preparation cost, simple and convenient experimental requirements, high yield and the like. The electrochemiluminescence carbon nano tube prepared by the method has the advantages of relatively uniform size, good hydrophilicity, good luminescence property, easiness in fixing and modifying and the like.
Drawings
FIG. 1 is a photograph showing the dispersion of the crude product of carbon nanotubes (a) and the electrochemiluminescence functionalized carbon nanotubes (b, c, d, e) of examples 1, 2, 3, 4 in pure water.
FIG. 2 is a transmission electron microscope image of the electrochemiluminescence functionalized carbon nanotube in example 1.
FIG. 3 is a photoelectron spectrum of the electrochemiluminescence functionalized carbon nanotube in example 1.
Fig. 4 is an electrochemiluminescence response curve of the electrochemiluminescence functionalized carbon nanotube in example 1, wherein:
(a) the electrochemiluminescence response of the carbon nano tube in the absence of a coreactant; (b) electrochemiluminescence response of persulfate coreactants per se; (c) the electrochemiluminescence response of carbon nanotubes in the presence of persulfate co-reactants.
Detailed Description
The present invention will be further described with reference to the accompanying drawings.
This detailed description is to be construed as illustrative only and is not limiting, since modifications will occur to those skilled in the art upon reading the preceding specification, and it is intended to be protected by the following claims.
Example 1
Adding 0.03g of dry crude multiwalled carbon nanotube powder into 30mL of 7.5M nitric acid, refluxing for 12h under the condition of 140 ℃ oil bath, naturally cooling to room temperature, diluting a suspension to 100mL with water, performing suction filtration by using a 0.2-mum filter membrane, dispersing a filter cake into 10mL of nitric acid-sulfuric acid mixed acid (volume ratio is 1: 3), performing ultrasonic treatment for 0.5h at room temperature, diluting the suspension to 100mL with water, performing suction filtration by using the 0.2-mum filter membrane, washing the filter cake with distilled water, and performing suction filtration until the filtrate is neutral. Collecting the purified black filter cake, and drying at the temperature lower than 100 ℃ to obtain the multi-wall carbon nano tube with the electrochemiluminescence property.
The electrochemiluminescence carbon nanotube (figure 1 b) and the carbon nanotube raw material (figure 1 a) have good hydrophilicity and water dispersibility.
Transmission electron microscopy (fig. 2) shows that the electrochemiluminescence functionalized carbon nanotubes still maintain a good tubular structure.
Binding energy peak (sp) of 284.7 eV in photoelectron spectrum (see FIG. 3)2C-C) indicates that the prepared electrochemiluminescence functionalized carbon nanotube has the graphene structure of the carbon nanotube, and additionally 285.3 (C-OH), 287.2 (C = O), and 288.9 (O = C-OH) binding energy peaks indicate that the prepared electrochemiluminescence functionThe surface of the functionalized carbon nano tube contains rich oxygen-containing groups. FIG. 4 is a measurement of the electrochemical activity of the prepared carbon nanotubes, in coreactant K2S2O8In the presence of the carbon nano tube, the prepared carbon nano tube shows good cathode electrochemiluminescence activity.
Example 2
Adding 0.1g of dry crude multiwalled carbon nanotube powder into 100mL of 15M nitric acid, refluxing for 7h under the condition of oil bath at 140 ℃, naturally cooling to room temperature, diluting a suspension to 300mL with water, performing suction filtration by using a 0.2-mum filter membrane, dispersing the obtained filter cake into 30mL of nitric acid-sulfuric acid mixed acid (volume ratio is 1: 2), performing ultrasonic treatment for 2h at room temperature, diluting the suspension to 300mL with water, performing suction filtration by using the 0.2-mum filter membrane, washing the filter cake with distilled water, and performing suction filtration until the filtrate is neutral. Collecting the purified black filter cake, and drying at the temperature lower than 100 ℃ to obtain the multi-wall carbon nano tube with the electrochemiluminescence property.
Example 3
Adding 0.05 g of dried crude powder of the single-walled carbon nanotube into 50 mL of 6M nitric acid, refluxing for 24 h under the condition of 140 ℃ oil bath, naturally cooling to room temperature, diluting the suspension to 200 mL by using water, carrying out centrifugal ultrafiltration by using a 10kDa ultrafiltration tube, removing the nitric acid, dispersing black solid obtained by ultrafiltration into 20 mL of nitric acid-sulfuric acid mixed acid (volume ratio is 1: 3), carrying out ultrasonic treatment for 1 h at room temperature, diluting the suspension to 200 mL by using water, carrying out centrifugal ultrafiltration by using the 10kDa ultrafiltration tube, removing the mixed acid, and washing by using water until the suspension is neutral. Collecting the purified black solid, and drying the black solid under pressure at the temperature of 80 ℃ to obtain the single-walled carbon nanotube with the electrochemiluminescence property.
Example 4
Adding 0.03g of dry crude single-walled carbon nanotube powder into 30mL of 5M nitric acid, refluxing for 15h under the condition of oil bath at 140 ℃, naturally cooling to room temperature, diluting the suspension to 100mL by using water, carrying out centrifugal ultrafiltration by using a 10kDa ultrafiltration tube, removing the nitric acid, dispersing black solid obtained by ultrafiltration into 10mL of nitric acid-sulfuric acid mixed acid (volume ratio is 1: 1), carrying out ultrasonic treatment for 0.5h at room temperature, diluting the suspension to 100mL by using water, carrying out centrifugal ultrafiltration by using the 10kDa ultrafiltration tube, removing the mixed acid, and washing by using water until the mixed acid is neutral. Collecting the purified black solid, and drying at 70 ℃ under reduced pressure to obtain the single-walled carbon nanotube with electrochemiluminescence property.
Claims (1)
1. A carbon nanotube with electrochemiluminescence activity, which is prepared by the following method: adding 0.03g of dry crude multiwalled carbon nanotube powder into 30mL of 7.5M nitric acid, refluxing for 12h under the condition of 140 ℃ oil bath, naturally cooling to room temperature, diluting a suspension to 100mL by using water, performing suction filtration by using a 0.2-micron filter membrane, and dispersing a filter cake in 10mL of solution with the volume ratio of 1: 3, performing ultrasonic treatment for 0.5h at room temperature in nitric acid-sulfuric acid mixed acid, diluting the suspension to 100mL by using water, performing suction filtration by using a 0.2-micron filter membrane, washing a filter cake by using distilled water, and performing suction filtration until the filtrate is neutral; collecting the purified black filter cake, and drying at the temperature lower than 100 ℃ to obtain the carbon nano tube with electrochemiluminescence activity; the carbon nano tube with electrochemiluminescence activity has a graphene structure, contains rich oxygen-containing groups on the surface, and is subjected to reaction in a coreactant K2S2O8In the presence of the organic electroluminescent material, the organic electroluminescent material shows good cathode electrochemiluminescence activity.
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