CN110562955B - Reed-based carbon dots, CDs-Cu2O/CuO composite material and preparation method thereof - Google Patents
Reed-based carbon dots, CDs-Cu2O/CuO composite material and preparation method thereof Download PDFInfo
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Abstract
The invention provides reed-based carbon dots, CDs-Cu2The invention relates to an O/CuO composite material, a preparation method and application thereof. The obtained reed-based carbon dots have good reducibility, and are used as reducing agents to control and synthesize CDs-Cu by using an ecological-friendly, economic and effective ultrasonic method2O/CuO，CDs‑Cu2And (3) an O composite material. Prepared CDs-Cu2The O/CuO composite material has a remarkable enhancement effect on the electrocatalytic oxidation of hydrazine. The invention not only makes full use of agricultural wastes and provides a new way for the utilization of reed wastes, but also can replace expensive electrode materials and provide a new idea for simplifying the process.
Description
Technical Field
The invention relates to a preparation method of a carbon dot and an electric detection material, in particular to a reed-based carbon dot and CDs-Cu2An O/CuO composite material, a preparation method and an application thereof.
Background
Fluorescent carbon quantum dots, Carbon Dots (CDs) for short, are carbon nanomaterials which are emerging in recent years. CDs are widely derived from natural biomass such as roses, bamboo leaf cellulose, carnation, orange juice, grasses, soybeans, and the like. Many sustainable carbon-based materials are used for CDs synthesis because these materials are environmentally friendly, economically viable materials. Most CDs are used for fluorescent ion detection, cell imaging, etc., and are also reported as reducing agents for synthesizing new complexes. Achyut et al prepared CDs from tea leaves and used for reducing graphene oxide, and applied the composite material to high-elasticity cotton-based conductive fabric.
The reed is one of the main plants for wetland growth, and has important ecological function in the aspect of environmental protection. It is called "second forest" and has many ecological functions, such as climate regulation, sewage purification and biological diversity maintenance. However, the current utilization form is single, and the reed can not be effectively utilized, which leads to serious waste of reed resources. Ban et al prepared a unique porous layer of activated carbon (RHC) using natural reed membrane as a precursor, and prepared graphene-like RHC by hydrothermal treatment and carbonization. At present, the research of synthesizing CDs by using reed as a raw material has not been reported.
Disclosure of Invention
The invention aims to provide a preparation method of reed-based carbon dots, which is used for obtaining carbon dots with excellent reducibility and providing a new way for utilizing reeds.
The purpose of the invention is realized as follows:
a preparation method of reed-based carbon dots comprises the following steps: adding reed raw materials and deionized water into an autoclave, carrying out hydrothermal carbonization, carrying out centrifugal separation on the obtained reaction liquid to obtain a reed-based carbon dot supernatant, and carrying out vacuum drying on the supernatant to obtain reed-based carbon dot solid powder (CDs). The reed is prepared from dry reed (whole reed) picked from white lake in winter, and by pulverizing or cutting into blocks.
The mass ratio of the reed raw material to the deionized water is 1:10-1: 20; the hydrothermal carbonization temperature is 120-200 ℃ and the time is 2-5 h. Preferably, the mass ratio is 1: 12; the hydrothermal carbonization temperature is 180 ℃ and the time is 3 h; the centrifugal speed is 10000 rpm, and the centrifugal time is 5 min; the vacuum drying temperature of the supernatant is 50 ℃, and the time is 48 h.
The invention also provides CDs-Cu2Preparation of O/CuO composite materialThe method comprises the following steps: under the conditions of stirring and ultrasonic treatment, adding NaOH aqueous solution dropwise into CuSO4Adding PVP solution into the aqueous solution after dripping to obtain a mixed solution; then, under the conditions of stirring and ultrasonic treatment, dripping the reed-based carbon dot solution into the mixed solution, and carrying out aging treatment for 24 hours; washing the obtained product with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain CDs-Cu2An O/CuO composite; the reed-based carbon dot solution is prepared by mixing the obtained reed-based carbon dots with the volume of 1.2-2.5 mu g/mL-1(preferably 2. mu. gmL)-1) Is dispersed in deionized water.
The concentration of NaOH aqueous solution is 1M, CuSO4The concentration of the aqueous solution is 0.1M, and the concentration of the PVP aqueous solution is 50 g/L; aqueous NaOH solution and CuSO4The volume ratio of the aqueous solution is 1 to (0.5-1), and the dropping speed of the NaOH aqueous solution is 0.1-3 mL min-1(ii) a The amount of PVP added and CuSO4The volume ratio of (1) to (7.5-30); adding amount of reed-based carbon dot solution and CuSO4The volume ratio of (1) to (4-7.5) and the dropping speed of 0.1-3 mL min-1. The vacuum drying temperature is 60 ℃, and the drying time is 3 h.
The invention takes the reed as a carbon source and adopts a one-step hydrothermal method to synthesize the reed-based carbon dots, thereby fully utilizing agricultural wastes and providing a new way for utilizing the reed wastes. Meanwhile, the obtained reed-based carbon dots have good reducibility, and are used as reducing agents to control and synthesize CDs-Cu by using an ecological-friendly, economic and effective ultrasonic method2O/CuO composite material. Prepared CDs-Cu2The O/CuO composite material has a remarkable enhancement effect on the electrocatalytic oxidation of hydrazine due to the synergistic effect of CDs and copper oxide. Mixing CDs-Cu2The electrochemical sensor prepared from the O/CuO composite material has good analysis and detection effects, low detection limit (0.024 mu M), and high sensitivity (4.45 mu A mM)-1) And the linear range is wide (0.99-5903 mu M).
The preparation method is simple, rapid, nontoxic, green and environment-friendly, wide in raw material source and low in cost, can fully utilize agricultural wastes, can replace expensive electrode materials, and provides a new idea for complex processes.
Drawings
FIG. 1 is a CV curve of hydrazine, in which A represents that the electrochemical sensor used is GCE (bare glassy carbon electrode), B represents that the electrochemical sensor used is CDs-GCE, and C represents that the electrochemical sensor used is CDs-Cu2O-GCE, D represents the electrochemical sensor used is CDs-Cu2O/CuO-GCE。
FIG. 2 shows CDs-Cu with different hydrazine concentrations2Current-time curves for O/CuO-GCE.
FIG. 3 shows hydrazine and CDs-Cu in different concentrations2The linear relationship between the current responses of O/CuO-GCE.
FIG. 4 shows the results of electrochemical detection of hydrazine by the material obtained in example 5.
FIG. 5 shows the results of electrochemical detection of hydrazine by the material obtained in example 6.
Detailed Description
The present invention is further illustrated by the following examples in which the procedures and methods not described in detail are conventional and well known in the art, and the starting materials or reagents used in the examples are commercially available, unless otherwise specified, and are commercially available.
In the following examples, the reed material used was dry reed (whole reed) picked from white lake in winter, ground into powder by a pulverizer, or cut into pieces.
Example 1: synthesis of reed-based carbon dots
Adding 10g of reed powder and 120mL of deionized water into an autoclave, heating the autoclave in an oven to 180 ℃ and keeping the temperature for 3h, centrifuging the obtained reaction solution at 10000 rpm for 5min to remove precipitates, and obtaining a reed-based carbon dot supernatant; and finally, drying the supernatant in vacuum at 50 ℃ for 48 hours to obtain reed-based carbon dot solid powder.
The obtained reed-based carbon dot solid powder is added in an amount of 2 mu gmL-1Is dispersed in deionized water to obtain a CDs solution for further use.
Example 2: synthesis of reed-based carbon dots
Adding 10g of blocky reeds and 100mL of deionized water into an autoclave, heating the autoclave in an oven to 120 ℃, keeping the temperature for 5 hours, centrifuging the obtained reaction solution at 10000 rpm for 5min, and removing precipitates to obtain a reed-based carbon dot supernatant; and finally, drying the supernatant in vacuum at 50 ℃ for 48 hours to obtain reed-based carbon dot solid powder.
Example 3: synthesis of reed-based carbon dots
Adding 10g of reed powder and 200 mL of deionized water into an autoclave, heating the autoclave in an oven to 200 ℃ and keeping for 2h, centrifuging the obtained reaction solution at 10000 rpm for 5min to remove precipitates, and obtaining a reed-based carbon dot supernatant; and finally, drying the supernatant in vacuum at 50 ℃ for 48 hours to obtain reed-based carbon dot solid powder.
Example 4: CDs-Cu2Synthesis of O/CuO composite material
Under the condition of magnetic stirring, the dropping speed is 0.1-3 mL min -130 mL of NaOH (1M) aqueous solution was slowly dropped into 30 mL of CuSO4(0.1M) aqueous solution, 3 mL of PVP aqueous solution (50 g/L) was then added thereto, sonicated (150W, 40 KHz) for 60 min, magnetic stirring was continued and 40 mL of the CDs solution obtained in example 1 was slowly dropped into the above-obtained mixture solution at a rate of 0.1-3 mL min-1After dropping, the mixed solution was aged for 24 hours (without stirring and sonication, only during aging). Washing the obtained product with deionized water and anhydrous ethanol, and vacuum drying at 60 deg.C for 3 hr to obtain CDs-Cu2And the relative content of the copper oxide in the O/CuO composite material can be calculated through the peak height of an XRD (X-ray diffraction) pattern.
Example 5: CDs-Cu2Synthesis of O/CuO composite material
In the same manner as in example 4, the dropwise addition rate was 0.1-3 mL min under magnetic stirring-130 mL of NaOH (1M) aqueous solution was slowly dropped into 30 mL of CuSO4(0.1M) aqueous solution, then 1 mL of PVP aqueous solution (50 g/L) was added thereto, sonicated for 60 min, magnetic stirring was continued and 40 mL of the CDs solution obtained in example 1 was slowly dropped into the resulting mixture solution at a rate of 0.1-3 mL min-1Aging the mixed solution 24 after droppingh (without stirring and sonication, only aging process). Washing the obtained product with deionized water and anhydrous ethanol, and vacuum drying at 60 deg.C for 3 hr to obtain CDs-Cu2O/CuO composite material.
Example 6: CDs-Cu2Synthesis of O/CuO composite material
In the same manner as in example 4, the dropwise addition rate was 0.1-3 mL min under magnetic stirring-130 mL of NaOH (1M) aqueous solution was slowly dropped into 30 mL of CuSO4(0.1M) aqueous solution, 4 mL of PVP aqueous solution (50 g/L) was then added thereto, sonicated for 60 min, magnetic stirring was continued and 40 mL of the CDs solution obtained in example 1 was slowly dropped into the resulting mixture solution at a rate of 0.1-3 mL min-1After dropping, the mixed solution was aged for 24 hours. Washing the obtained product with deionized water and anhydrous ethanol, and vacuum drying at 60 deg.C for 3 hr to obtain CDs-Cu2O/CuO composite material.
Example 7: CDs-Cu2Synthesis of O composite
In the same manner as in example 4, the dropwise addition rate was 0.1-3 mL min under magnetic stirring-130 mL of NaOH (1M) aqueous solution was slowly dropped into 30 mL of CuSO4(0.1M) in water, then sonicated for 60 min, magnetic stirring was continued and 40 mL of the CDs solution from example 1 was slowly added dropwise to the resulting mixture solution at a rate of 0.1-3 mL min-1After dropping, the mixed solution was aged for 24 hours. Washing the obtained product with deionized water and anhydrous ethanol, and vacuum drying at 60 deg.C for 3 hr to obtain CDs-Cu2And (3) an O composite material.
Example 8
The products obtained in examples 1, 4 and 7 were respectively combined with GCE (bare glassy carbon electrode) to prepare electrochemical sensors (the preparation method is conventional), which are CDs-GCE and CDs-Cu, respectively2O/CuO-GCE and CDs-Cu2O-GCE. Mixing GCE, CDs-GCE, CDs-Cu2O-GCE and CDs-Cu2And performing electrochemical detection on hydrazine by using O/CuO-GCE.
GCE，CDs-GCE，CDs-Cu2O-GCE and CDs-Cu2CV Curve score for hydrazine on O/CuO-GCEAs shown in fig. 1. It can be seen from figure 1 that the electrochemical response of CDs-GCE to hydrazine is higher than that of GCE, indicating that the addition of CDs can improve the electrochemical response of hydrazine oxidation. CDs-Cu2O-GCE and CDs-Cu2CDs-Cu compared to O/CuO-GCE2O/CuO-GCE has a higher electrochemical response current to hydrazine in the figure. This indicates that CDs-Cu2The O/CuO-GCE has excellent electrochemical response of hydrazine oxidation. Thus, CDs-Cu2O/CuO-GCE is an excellent sensor for electrochemical detection of hydrazine.
Continuously increasing the concentration of hydrazine hydrate to obtain CDs-Cu with different concentrations of hydrazine2Current-time curves for O/CuO-GCE, as shown in FIG. 2, different concentrations of hydrazine and CDs-Cu2The linear relationship between the current responses of O/CuO-GCE is shown in FIG. 3.
Evidence of CDs-Cu from changes in current response2O/CuO-GCE is an excellent hydrazine detection sensor. As can be seen from FIGS. 2 and 3, upon addition of hydrazine at various concentrations to the NaOH solution, the current response of hydrazine changed immediately, showing a good linear relationship, ranging from 0.99 to 5903. mu.M, with a sensitivity of 4.45. mu.A mM-1. The detection limit was 0.024. mu.M. The current response at lower concentrations of hydrazine is inset a in FIG. 2, indicating that CDs-Cu2O/CuO-GCE has high current response to hydrazine in NaOH solution, and the sensor with excellent comprehensive performance is obtained.
The composite materials obtained in examples 5 and 6 were combined with GCE (bare glassy carbon electrode) to prepare electrochemical sensors, and electrochemical detection of hydrazine was performed, and the results are shown in fig. 4 and 5, respectively.
Claims (6)
1. CDs-Cu2The preparation method of the O/CuO composite material is characterized by comprising the following steps: under the conditions of stirring and ultrasonic treatment, adding NaOH aqueous solution dropwise into CuSO4Adding PVP solution into the aqueous solution after dripping to obtain a mixed solution; then, under the conditions of stirring and ultrasonic treatment, dripping the reed-based carbon dot solution into the mixed solution, and after dripping, carrying out aging treatment; washing the obtained product with deionized water and absolute ethyl alcohol, and drying in vacuum to obtain CDs-Cu2An O/CuO composite; the reed-based carbon dot solution is prepared by dispersing reed-based carbon dot solid powder in deionized water, wherein the reed-based carbon dot solid powder is prepared according to the following steps: adding reed raw materials and deionized water into a high-pressure kettle, carrying out hydrothermal carbonization, carrying out centrifugal separation on the obtained reaction liquid to obtain a reed-based carbon dot supernatant, and carrying out vacuum drying on the supernatant to obtain reed-based carbon dot solid powder.
2. The CDs-Cu of claim 12The preparation method of the O/CuO composite material is characterized in that PVP and CuSO are used4The mass ratio of (5-20) to (48); the reed-based carbon dots and CuSO4The mass ratio of the reed-based carbon dot solution is (0.015-0.008) to 160, and the dropping speed of the reed-based carbon dot solution is 0.1-3 mL/min-1The concentration of the reed-based carbon dot solution is 1.2-2.5 mu gmL-1。
3. The CDs-Cu of claim 12The preparation method of the O/CuO composite material is characterized in that NaOH and CuSO4The mass ratio of (2.5-5) to 1, and the dropping speed of the NaOH aqueous solution is 0.1-3 mL min-1。
4. The CDs-Cu of claim 12The preparation method of the O/CuO composite material is characterized in that the vacuum drying temperature is 60 ℃, and the drying time is 3 hours.
5. CDs-Cu obtained by the production method according to any one of claims 1 to 42O/CuO composite material.
6. CDs-Cu obtained by the production method according to any one of claims 1 to 42The application of the O/CuO composite material in the electrochemical detection of hydrazine.
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