CN107824797B - Porous high-specific-surface-area bismuth nanoparticle modified nitrogen-doped carbon nanosheet material and preparation method and application thereof - Google Patents

Porous high-specific-surface-area bismuth nanoparticle modified nitrogen-doped carbon nanosheet material and preparation method and application thereof Download PDF

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CN107824797B
CN107824797B CN201710932505.5A CN201710932505A CN107824797B CN 107824797 B CN107824797 B CN 107824797B CN 201710932505 A CN201710932505 A CN 201710932505A CN 107824797 B CN107824797 B CN 107824797B
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黄奕莹
鲁志伟
叶建山
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GUANGZHOU INGSENS SENSOR TECHNOLOGY Co Ltd
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Abstract

The invention belongs to the field of nano materials, and discloses a nitrogen-doped carbon nano sheet material modified by porous bismuth nano particles with high specific surface area, and a preparation method and application thereof. The method comprises the following steps: adding a polyvinylpyrrolidone solution serving as a nitrogen source and a carbon source into a beaker; adding bismuth salt into the nitrogen source solution, stirring and adjusting the pH value by using a weak acid solution to completely dissolve the bismuth salt; placing the prepared solution in an electrothermal blowing dry box for drying to obtain a solid precursor; and grinding the solid precursor into fine powder, putting the fine powder into a porcelain boat, and heating and roasting the porcelain boat in a tubular furnace under a protective gas environment to obtain the nanosheet material. The method integrates the synthesis and doping of the carbon nano material and the modification of the bismuth nano particles into one, and the obtained nitrogen-doped carbon nano sheet material modified by the bismuth nano particles has stable structure and performance and shows better heavy metal detection performance. The preparation method provided by the invention is simple and feasible in process, low in cost and suitable for large-scale production.

Description

Porous high-specific-surface-area bismuth nanoparticle modified nitrogen-doped carbon nanosheet material and preparation method and application thereof
Technical Field
The invention belongs to the field of nano materials, relates to the technical field of nitrogen-doped carbon nano materials, and particularly relates to a porous high-specific-surface-area bismuth nanoparticle modified nitrogen-doped carbon nano sheet material, and a preparation method and application thereof.
Background
The carbon nano material is the most common material in nature, and plays a very important role in the field of energy and materials. The carbon nano material has the characteristics of high conductivity, high specific surface area, good chemical stability and convenience for large-scale production, and is widely applied to the fields of energy storage, gas separation, heavy metal adsorption and detection and the like. However, pure carbon materials have poor hydrophilic properties and low activity, and are not favorable for deposition, dispersion and interaction of heavy metals on the surface of the carbon materials, so that the application of the carbon materials is limited to a certain extent. At present, the common method is to modify and dope the carbon nano material. For example, the carbon nano material carrier has polarity due to the action of doping atoms such as N, S, P and the like, and more active sites are provided for the deposition of metal particles.
Among the numerous heteroatoms, the doping of nitrogen atoms was the first and most studied doping element. At present, nitrogen-doped carbon materials mainly have the following synthesis modes: in-situ doping and post-treatment doping methods. The in-situ doping method is to use small organic molecules (such as urea, melamine and the like) containing nitrogen elements to carry out chemical vapor deposition growth to obtain the carbon material doped with the nitrogen elements, and the method needs expensive instruments and equipment and has the defect that large-scale industrial production cannot be met. The post-treatment doping method is to perform later functionalization on the prepared carbon material in activating gas containing nitrogen elements, however, the activating process is usually completed at a higher temperature, so that production energy consumption and safety factors are two important problems restricting the development of the carbon material.
The bismuth nanoparticles have unique physical and chemical properties and are widely concerned, and are widely applied to analysis and detection of heavy metal ions and biological micromolecules, electro-catalysis and battery industries. The conventional method for preparing the nitrogen-doped carbon nanosheet material modified by the metal nanoparticles comprises the following two steps: firstly, preparing a carbon material, and then doping nitrogen element. The conventional preparation method has the disadvantages of complex operation process and complicated steps, thereby limiting the wide application of the conventional preparation method. In addition, other substances are used as nitrogen sources, so that the cost is increased, uneven mixing is easily caused, the surface area is small, and finally, nitrogen doping is not uniform. Meanwhile, the carbon nanosheet framework material with higher nitrogen doping amount and high specific surface area has no relevant report or publication in the literature and patents. Therefore, the research on the preparation method and the application of the nitrogen-doped carbon nanosheet material modified by the bismuth nanoparticles with the advantages of convenience and easiness in realization and high specific surface area has very important significance.
Disclosure of Invention
In order to overcome the defects and shortcomings of the prior art, the invention aims to provide a preparation method of a nitrogen-doped carbon nanosheet material modified by porous bismuth nanoparticles with high specific surface area. The method is easy to implement and simple to operate, the polyvinylpyrrolidone solution is used as a nitrogen source, the bismuth salt provides metal bismuth ions, the direct roasting mode is adopted, the synthesis and doping of the carbon nano sheet material and the modification of the bismuth nano particles are combined into one, and the obtained carbon nano framework material has the advantages of being porous, high in specific surface area, stable in structure and performance and capable of being used for rapid analysis and detection of trace heavy metal ions.
The invention also aims to provide the nitrogen-doped carbon nanosheet material modified by the porous bismuth nanoparticles with high specific surface area, which is prepared by the preparation method.
The invention further aims to provide application of the nitrogen-doped carbon nanosheet material modified by the porous bismuth nanoparticles with high specific surface area.
The purpose of the invention is realized by the following technical scheme:
a preparation method of a nitrogen-doped carbon nanosheet material modified by porous bismuth nanoparticles with high specific surface area comprises the following steps:
(a) taking polyvinylpyrrolidone as a carbon source and a nitrogen source, adding a solvent, and fully dissolving to obtain a nitrogen source solution;
(b) adding bismuth salt into the nitrogen source solution obtained in the step (a), stirring, and adjusting the pH value by using a weak acid solution to completely dissolve the bismuth salt to obtain a mixed solution;
(c) putting the nitrogen source solution obtained in the step (b) into an electrothermal blowing drying oven to be dried to obtain a solid precursor;
(d) and grinding the obtained solid precursor into fine powder, putting the fine powder into a porcelain boat, and placing the porcelain boat in a tube furnace for heating and roasting in a protective gas atmosphere to obtain the porous bismuth nanoparticle modified nitrogen-doped carbon nanosheet material with high specific surface area.
The polyvinylpyrrolidone in the step (a) is one or more than two of polyvinylpyrrolidone with molecular weight range of K25-K30.
The solvent in the step (a) is one or more than two of deionized water, absolute ethyl alcohol, glycol, glycerol and polyethylene glycol; the concentration of the nitrogen source solution is 0.01g/mL-0.1 g/mL.
The bismuth salt in the step (b) is bismuth nitrate, bismuth acetate or bismuth chloride; the weak acid solution is glacial acetic acid, dilute nitric acid or dilute sulfuric acid; the pH value is adjusted to be between 4.0 and 5.5.
The mass ratio of the polyvinylpyrrolidone in the step (a) to the bismuth salt in the step (b) is 1: 0.1-5.
The drying temperature in the electrothermal blowing drying box in the step (c) is 110-.
And (d) the protective gas in the step (d) is one or two of nitrogen and argon, and the flow rate of the protective gas is 30-60 mL/min.
And (d) raising the temperature of the tubular furnace to 900 ℃ at the calcining temperature at the heating rate of 2-8 ℃/min under the protective gas atmosphere, and carbonizing for 1-3 hours.
The nitrogen-doped carbon nano-sheet material modified by the porous bismuth nano-particles with high specific surface area, which is prepared by the preparation method, is of a nano-sheet frame structure and has the specific surface area of 400-800m 2Per g, pore volume of 0.7-1.2cm 3The pore size distribution is 1.0-5nm, and the mass content of nitrogen is 4-10%.
The application of the nitrogen-doped carbon nanosheet material modified by the porous bismuth nanoparticles with high specific surface area in electrochemical analysis and detection of trace heavy metal ions.
Compared with the prior art, the invention has the following advantages and effects:
(1) the method directly adopts a roasting mode to prepare the bismuth nanoparticle modified nitrogen-doped carbon nanosheet material, simplifies the three-step preparation routes of synthesis and doping of the carbon nanosheet material and modification of the bismuth nanoparticles into one step, and is simple to operate and easy to implement.
(2) The nitrogen-doped carbon nanomaterial is prepared by adopting a direct roasting mode after preparing a precursor from a carbon source and a nitrogen source, the porous carbon nanosheet frame material with high specific surface area can be obtained, the cost is low, the structure and the performance are stable, and the method is suitable for large-scale production.
(3) The nitrogen-doped carbon nanosheet material modified by the bismuth nanoparticles can be used for rapid trace analysis and detection of heavy metal ions, such as detection of zinc, lead, cadmium, copper, mercury and the like.
Drawings
Fig. 1 is an XRD pattern of a bismuth nanoparticle modified nitrogen-doped carbon nanosheet material used in example 1 of the present invention.
Fig. 2 is an SEM image of a bismuth nanoparticle-modified nitrogen-doped carbon nanosheet material used in example 1 of the present invention.
Fig. 3 is a TEM image of a bismuth nanoparticle modified nitrogen doped carbon nanosheet material used in example 1 of the present invention.
Fig. 4 is an XPS chart in which a is an overall XPS chart of a bismuth nanoparticle-modified nitrogen-doped carbon nanosheet material used in example 1 of the present invention; b is a characteristic XPS plot of carbon in example 1 of the invention; c is a characteristic XPS plot of oxygen in example 1 of the present invention; d is a characteristic XPS plot of nitrogen in example 1 of the invention; e is the characteristic XPS diagram of bismuth in example 1 of the present invention.
Fig. 5 is a nitrogen adsorption-desorption graph of the nitrogen-doped carbon nanosheet material modified with bismuth nanoparticles used in example 1 of the present invention.
FIG. 6 is a graph showing the peak profile obtained by square wave anodic stripping voltammetry in example 2 of the present invention.
Detailed Description
The present invention is further illustrated by the following examples in conjunction with the accompanying drawings, but should not be construed as limiting the scope of the present invention, and it is intended that the present invention shall not be limited to the following examples, and that the skilled person can make various insubstantial changes and modifications in accordance with the above disclosure.
Example 1
A preparation method of a nitrogen-doped carbon nanosheet material modified by bismuth nanoparticles with porous surfaces and high specific surface area specifically comprises the following steps:
(1) taking 0.5g of polyvinylpyrrolidone K28 as a carbon source and a nitrogen source, adding 50mL of ethylene glycol (carbon source) for full dissolution to obtain 0.01g/L of nitrogen source solution;
(2) adding 0.05g of bismuth nitrate into the nitrogen source solution obtained in the step (1), stirring, and adjusting the pH value to 5.5 with acetic acid, wherein the bismuth nitrate is completely dissolved to obtain a mixed solution;
(3) placing the mixed solution obtained in the step (2) in an electrothermal blowing drying oven at 110 ℃ for 14h until a light yellow solid precursor is obtained;
(4) grinding the obtained faint yellow solid precursor into fine powder, putting the fine powder into a porcelain boat, placing the porcelain boat into a tubular furnace for heating and roasting under the protection of nitrogen with the flow rate of 40mL/min, heating the mixture from room temperature to 600 ℃ at the heating rate of 5 ℃/min in the roasting process, then preserving the heat for 2 hours at the high temperature of 600 ℃, finally cooling the mixture to the room temperature, and taking out a sample to obtain the porous high-specific-surface-area bismuth nanoparticle modified nitrogen-doped carbon nanosheet material.
And (3) testing the structural performance: the nitrogen-doped carbon nanosheet material modified with the metal bismuth nanoparticles obtained above was characterized by XRD (solid powder X-ray diffraction analysis) technique (see fig. 1), and a characteristic peak of C (002) graphitization diffraction and a characteristic peak of Bi, i.e., characteristic peaks of Bi (012) at 2 θ of 28.2 °, Bi (104) at 2 θ of 38.1 ° and Bi (110) at 2 θ of 39.7 °, respectively, appeared in the material. The material is characterized by adopting a Scanning Electron Microscope (SEM) technology (as shown in figure 2), and the material is shown as a carbon nano sheet framework structure framework and has a porous structure. The material is characterized by a Transmission Electron Microscope (TEM) technology (as shown in FIG. 3), and the result shows that Bi nanoparticles have the size of 5-20nm and are uniformly distributed in a carbon nanosheet framework. Analyzing the material by X-ray photoelectron spectroscopy (XPS) technique (as shown in FIG. 4), wherein 284.8eV shows C1 s peak, 400.1eV shows N1 s peak, and 530.5eV shows O1 s peak; 157.2eV (Bi 4 f) 7/2) And 162.7eV (Bi 4 f) 5/2) Two Bi peaks appear, which indicates that the prepared material contains four elements of C, N, O and Bi, and the element content of N in the carbon material is 5.71 according to element analysis tests, and is between 4 and 10 percent according to the difference of initial raw materials (nitrogen sources). The specific surface area of the material was measured using a BET specific surface area tester (see FIG. 5), and the specific surface areaThe volume is 400-600m 2Per g, pore volume of 0.7-1.2cm 3(ii) a pore size distribution of 1.0 to 5nm (depending on the starting material);
testing heavy metal detection performance: and analyzing and detecting heavy metals of lead and cadmium in tap water by using the obtained nitrogen-doped carbon nanosheet material modified by the porous bismuth nanoparticles with high specific surface area. The specific experimental steps are as follows:
accurately weighing 2mg of carbon material by using an analytical balance, adding 2mL of 0.125% Nafion ethanol solution, ultrasonically vibrating to uniformly disperse the material, then taking 10 mu L of solution by a liquid transfer machine, smearing the solution on the surface of the polished glassy carbon electrode, and baking the solution by using an infrared lamp for later use. Heavy metal detection adopts Square Wave Anodic Stripping Voltammetry (SWASV), a three-electrode system is formed by a glassy carbon electrode, a counter electrode (platinum electrode) and an Ag-AgCl electrode, 10mL of acetic acid-sodium acetate buffer solution (pH4.5) is added into an electrolytic cell with a stirrer, three electrodes are immersed in the buffer solution, and square wave anodic stripping voltammetry detection parameters of an electrochemical analyzer are set: amplitude: 25 mV; potential increment: 4 mV; frequency: 15 mV; the enrichment potential is-1.2V; the enrichment time is 360s, and the stirring speed is 500 r/min; standing for 15 s; the initial potential for dissolution was-1.0V, and the final potential was 0V. The current response values of 0.1, 0.3, 0.5, 0.7, 1.0, 2, 4, 6, 8 and 10 mug/L are measured sequentially to obtain the working curve (as shown in FIG. 6). And then modifying the electrode again, taking 5mL of tap water, mixing with 5mL of acetic acid-sodium acetate buffer solution with pH of 4.5, determining in the same determination process as the working curve, and sequentially adding three standard samples to obtain the lead and cadmium contents of the tap water of 0.2 mu g/L and 0.35 mu g/L respectively. Meets the national drinking water standard.
Example 2
A preparation method of a nitrogen-doped carbon nanosheet material modified by bismuth nanoparticles with porous surfaces and high specific surface area specifically comprises the following steps:
1.0g of polyvinylpyrrolidone K30 was used as a carbon source and a nitrogen source, 10mL of water was added to the polyvinylpyrrolidone K30 to sufficiently dissolve the polyvinylpyrrolidone K30 in a beaker, 5g of bismuth acetate was added to the beaker, and the mixture was stirred and adjusted to pH4.5 with alkene nitric acid, at which time bismuth nitrate was completely dissolved. And (3) placing the prepared solution in an electrothermal blowing drying oven at the temperature of 130 ℃ for 12 hours until a light yellow solid precursor is obtained, grinding the light yellow solid precursor into fine powder, placing the fine powder into a porcelain boat, and placing the porcelain boat in a tubular furnace for heating and roasting under the protection of a mixed gas of nitrogen and argon at the flow rate of 30 mL/min. And heating the bismuth nanoparticle modified nitrogen-doped carbon nanosheet material to 900 ℃ from room temperature at the heating rate of 8 ℃/min in the roasting process, then preserving the heat at the high temperature of 900 ℃ for 3h, finally cooling to room temperature, and taking out a sample to obtain the porous bismuth nanoparticle modified nitrogen-doped carbon nanosheet material with the high specific surface area.
Testing heavy metal detection performance: the obtained nitrogen-doped carbon nanosheet material modified by the porous bismuth nanoparticles with high specific surface area is used for analyzing and detecting heavy metals of lead and cadmium in lake water. The specific experimental steps are as follows:
accurately weighing 2mg of carbon material by using an analytical balance, adding 2mL of 0.125% Nafion ethanol solution, ultrasonically vibrating to uniformly disperse the material, then taking 10 mu L of solution by a liquid transfer machine, smearing the solution on the surface of the polished glassy carbon electrode, and baking the solution by using an infrared lamp for later use. Heavy metal detection adopts a Square Wave Anodic Stripping Voltammetry (SWASV), a glassy carbon electrode, a counter electrode (platinum electrode) and Ag-AgCl to form a three-electrode system, 10mL of acetic acid-sodium acetate buffer solution (pH4.5) is added into an electrolytic cell with a stirrer, three electrodes are immersed in the buffer solution, and square wave anodic stripping voltammetry detection parameters of an electrochemical analyzer are set as follows: amplitude: 25 mV; potential increment: 4 mV; frequency: 15 mV; the enrichment potential is-1.2V; the enrichment time is 360s, and the stirring speed is 500 r/min; standing for 15 s; the initial potential for dissolution was-1.0V, and the final potential was 0V. The current response values of 0.1, 0.3, 0.5, 0.7, 1.0, 2 and 3 mug/L are measured in sequence to obtain a working curve. And then modifying the electrode again, taking 8mL of lake water, mixing with 2mL of acetic acid-sodium acetate buffer solution with pH of 4.5, determining in the same way as the working curve, and sequentially adding three standard samples to obtain the lake water with lead and cadmium contents of 2.1 mu g/L and 1.6 mu g/L respectively.
The other implementation steps are the same as in example 1.
Example 3
A preparation method of a nitrogen-doped carbon nanosheet material modified by bismuth nanoparticles with porous surfaces and high specific surface area specifically comprises the following steps:
5.0g of polyvinylpyrrolidone K25 was used as a carbon source and a nitrogen source, 100mL of water was added to the mixture and the mixture was sufficiently dissolved in a beaker, 10g of bismuth acetate was added to the beaker, and the mixture was stirred and adjusted to pH 5.0 with alkene nitric acid, at which time bismuth nitrate was completely dissolved. And (3) placing the prepared solution in an electrothermal blowing drying oven at the temperature of 120 ℃ for 13 hours until a light yellow solid precursor is obtained, grinding the light yellow solid precursor into fine powder, placing the fine powder into a porcelain boat, and placing the porcelain boat in a tubular furnace for heating and roasting under the protection of a mixed gas of nitrogen and argon at the flow rate of 60 mL/min. And heating the bismuth nanoparticle modified nitrogen-doped carbon nanosheet material to 800 ℃ from room temperature at a heating rate of 5 ℃/min in the roasting process, then preserving the heat at the high temperature of 800 ℃ for 1h, finally cooling to room temperature, and taking out a sample to obtain the porous bismuth nanoparticle modified nitrogen-doped carbon nanosheet material with high specific surface area.
Testing heavy metal detection performance: the obtained nitrogen-doped carbon nanosheet material modified by the porous bismuth nanoparticles with high specific surface area is used for analyzing and detecting heavy metals of lead and cadmium in sewage discharge of a paper mill. The specific experimental steps are as follows:
accurately weighing 4mg of carbon material by using an analytical balance, adding 4mL of 0.125% Nafion ethanol solution, ultrasonically vibrating to uniformly disperse the material, then taking 10 mu L of solution by a liquid transfer machine, smearing the solution on the surface of the polished glassy carbon electrode, and baking the solution by using an infrared lamp for later use. Heavy metal detection adopts a Square Wave Anodic Stripping Voltammetry (SWASV), a glassy carbon electrode, a counter electrode (platinum electrode) and Ag-AgCl to form a three-electrode system, 10mL of acetic acid-sodium acetate buffer solution (pH4.5) is added into an electrolytic cell with a stirrer, three electrodes are immersed in the buffer solution, and square wave anodic stripping voltammetry detection parameters of an electrochemical analyzer are set as follows: amplitude: 25 mV; potential increment: 4 mV; frequency: 15 mV; the enrichment potential is-1.2V; the enrichment time is 360s, and the stirring speed is 500 r/min; standing for 15 s; the initial potential for dissolution was-1.0V, and the final potential was 0V. The current response values of 0.1, 0.3, 0.5, 0.7, 1.0, 2 and 3 mug/L are measured in sequence to obtain a working curve. And then modifying the electrode again, taking 5mL of sewage, mixing with 5mL of acetic acid-sodium acetate buffer solution with pH of 4.5, determining in the same working curve making process, and then sequentially adding three standard samples to obtain the lead and cadmium contents of 3.8 mu g/L and 4.5 mu g/L in the sewage respectively.
The other implementation steps are the same as in example 1.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (8)

1. A preparation method of a nitrogen-doped carbon nanosheet material modified by porous bismuth nanoparticles with high specific surface area is characterized by comprising the following steps:
(a) taking polyvinylpyrrolidone as a carbon source and a nitrogen source, adding a solvent, and fully dissolving to obtain a nitrogen source solution;
(b) adding bismuth salt into the nitrogen source solution obtained in the step (a), stirring, and adjusting the pH value by using a weak acid solution to completely dissolve the bismuth salt to obtain a mixed solution;
(c) putting the nitrogen source solution obtained in the step (b) into an electrothermal blowing drying oven to be dried to obtain a solid precursor;
(d) grinding the obtained solid precursor into fine powder, putting the fine powder into a porcelain boat, and placing the porcelain boat in a tube furnace for heating and roasting in a protective gas atmosphere to obtain a porous bismuth nanoparticle modified nitrogen-doped carbon nanosheet material with a high specific surface area;
the mass ratio of the polyvinylpyrrolidone in the step (a) to the bismuth salt in the step (b) is 1: 0.1 to 5;
and (d) raising the temperature of the tubular furnace to 900 ℃ at the calcining temperature at the heating rate of 2-8 ℃/min under the protective gas atmosphere, and carbonizing for 1-3 hours.
2. The method of claim 1, wherein: the polyvinylpyrrolidone in the step (a) is one or more than two of polyvinylpyrrolidone with molecular weight range of K25-K30.
3. The method of claim 1, wherein: the solvent in the step (a) is one or more than two of deionized water, absolute ethyl alcohol, glycol, glycerol and polyethylene glycol; the concentration of the nitrogen source solution is 0.01g/mL-0.1 g/mL.
4. The method of claim 1, wherein: the bismuth salt in the step (b) is bismuth nitrate, bismuth acetate or bismuth chloride; the weak acid solution is glacial acetic acid, dilute nitric acid or dilute sulfuric acid; the pH value is adjusted to be between 4.0 and 5.5.
5. The method of claim 1, wherein: the drying temperature in the electrothermal blowing drying box in the step (c) is 110-.
6. The method of claim 1, wherein: and (d) the protective gas in the step (d) is one or two of nitrogen and argon, and the flow rate of the protective gas is 30-60 mL/min.
7. The nitrogen-doped carbon nanosheet material modified by the porous high-specific-surface-area bismuth nanoparticles prepared by the preparation method of any one of claims 1 to 6, wherein the preparation method comprises the following steps: the carbon nano material is of a nano-sheet framework structure, and the specific surface area is 400-800m 2Per g, pore volume of 0.7-1.2cm 3The pore size distribution is 1.0-5nm, and the mass content of nitrogen is 4-10%.
8. The application of the porous high-specific-surface-area bismuth nanoparticle modified nitrogen-doped carbon nanosheet material according to claim 7 in electrochemical analysis and detection of trace heavy metal ions.
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