CN113295746B - Preparation method and application of sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material - Google Patents
Preparation method and application of sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material Download PDFInfo
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- 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
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B21/00—Nitrogen; Compounds thereof
- C01B21/06—Binary compounds of nitrogen with metals, with silicon, or with boron, or with carbon, i.e. nitrides; Compounds of nitrogen with more than one metal, silicon or boron
- C01B21/0605—Binary compounds of nitrogen with carbon
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/182—Graphene
- C01B32/184—Preparation
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- C01B32/00—Carbon; Compounds thereof
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- C01B32/182—Graphene
- C01B32/194—After-treatment
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- 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
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Abstract
The invention relates to a preparation method and application of a sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material. The invention aims to solve the problems of lower detection sensitivity and high cost of a working electrode of the existing electrochemical sensor for detecting heavy metal ions. The detection performance of the electrochemical sensing material is enhanced by the bonding mode of various heavy metal ions. And by compounding the carbon nitride/graphene composite material with graphene, the electrochemical detection performance of the carbon nitride/graphene composite material on heavy metal ions is improved by utilizing the excellent conductivity of the graphene. The invention is applied to the field of electrochemical detection of heavy metal ions.
Description
Technical Field
The invention relates to a preparation method and application of a sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material.
Background
Heavy metal ion pollution is one of main sources of water pollution, and the pollution of the water is extremely threatening due to the fact that the heavy metal ion cannot be self-degraded. Heavy metal ions can be discharged into water bodies from various ways, such as chemical industry, papermaking, mineral processing, waste treatment and the like. In addition, the heavy metal ions can be discharged into the atmosphere and the soil along with the metal smelting, the agricultural irrigation and other modes. The heavy metal ions are absorbed by the roots of plants and crops, drunk and ingested by poultry and livestock, and enriched in fresh water and seawater fish, and then gradually deposited in human bodies through human diets, so that serious injury is caused to human health.
There are many methods for detecting heavy metal ions, such as: atomic absorption spectrometry, atomic fluorescence spectrometry, inductively coupled plasma mass spectrometry, inductively coupled plasma atomic emission spectrometry, high performance thin layer chromatography, and the like. However, these methods have certain limitations such as: the atomic absorption spectrometry is easy to cause secondary volatilization pollution of mercury, the atomic fluorescence spectrometry is used for measuring certain elements with harsh requirements on acidity, the inductive coupling plasma mass spectrometry is greatly influenced by sample media, and the inductive coupling plasma atomic emission spectrometry cannot cope with complex matrixes and the like. Moreover, the equipment has the defects of high common price and cost, large space requirement, complex pretreatment and incapability of realizing in-situ detection. The electrochemical method is adopted to measure the current change generated by the oxidation-reduction reaction on the surface of the electrode to detect heavy metal ions, so that the method becomes a main heavy metal ion testing means. Most importantly, the electrochemical detection device is small in size and convenient to carry, and can realize in-situ detection of heavy metal ions.
The sensitivity and selectivity of the working electrode are key for electrochemical detection of heavy metal ions, and the surface of the working electrode can be used for special detection of various metal ions after being modified by different materials. The traditional electrodes comprise mercury electrodes, gold electrodes, silver electrodes, bismuth membrane electrodes, antimony membrane electrodes and the like, and all have high detection sensitivity on target ions. In the early stage, a suspended mercury electrode and a mercury membrane electrode are adopted for detecting heavy metal ions, but the pollution of mercury to the environment, the storage and treatment of mercury and other problems cause great limitation, and mercury electrode materials are forbidden to be used at present; then, mercury-free electrodes such as bismuth and antimony appear, target ions are detected by codeposition of bismuth, antimony and target metal ions on the glassy carbon electrode, the detection limit can reach the level of mg/L, but bismuth film and antimony film electrodes are easily affected by the pH value of the solution, and corresponding hydroxide can be generated to cause irreversible damage of the film electrodes when the pH value is=4; gold and silver electrodes are high in price and high in sensitivity, nano particles, layered structures, porous structures, array structures and the like can be manufactured through structural design and can be used for detecting heavy metal ions, but the selectivity of the gold and silver electrodes is generally poor, the nano particles are easy to oxidize and lose efficacy, and long-time use and repeated use are difficult to meet. The glassy carbon electrode has low price and good conductivity, but has low detection sensitivity, and the sensitivity is improved by modifying the surface of the glassy carbon electrode, so that the preparation of the low-price working electrode is a main target for the development of the electrochemical sensor.
Disclosure of Invention
The invention aims to solve the problems of lower detection sensitivity and high cost of a working electrode of an existing electrochemical sensor for detecting heavy metal ions, and provides a preparation method and application of a sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material.
The preparation method of the sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material comprises the following steps:
1. preparation of graphite phase carbon nitride
Dispersing melamine and cyanuric acid in distilled water, stirring to form melamine-cyanuric acid supermolecule precursor, drying, grinding into powder, placing into a crucible, placing the crucible into a muffle furnace, heating to 550 ℃, and preserving heat for 2h, wherein the heating rate is 10 ℃/min; cooling to obtain graphite phase carbon nitride; then dispersing graphite-phase carbon nitride in distilled water to prepare graphite-phase carbon nitride aqueous solution; wherein the molar ratio of melamine to cyanuric acid is 1:2;
2. preparation of sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material
Adding graphene aqueous solution to H 2 SO 4 Stirring the solution to obtain graphene-H 2 SO 4 Dispersion, adding graphite phase carbon nitride aqueous solution into graphene-H 2 SO 4 Stirring in the dispersion liquid to obtain a sulfur doped porous tube bundle-shaped carbon nitride/graphene composite material; wherein graphene aqueous solution and H 2 SO 4 The volume ratio of the solution is 1:50, graphite phase carbon nitride aqueous solution and graphene-H 2 SO 4 The volume ratio of the dispersion liquid is 1:1。
The sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material is applied to electrochemical detection of heavy metal ions.
According to the invention, the sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material can be prepared, wherein carbon nitride in the sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material is in a nanotube bundle state, and holes are formed on the tubes. The graphene is in a flake form. This structure has two benefits, the first sulfur-doped porous tube bundle carbon nitride is prepared from melamine and cyanuric acid as raw materials, so that the carbon nitride has a large residual-HN content 2 -SH, N atoms, S atoms. -NH 2 the-SH can be bonded with heavy metal ions through chelation, and the N atom and the S atom can be bonded with heavy metal ions through coordination. The detection performance of the electrochemical sensing material is enhanced by the bonding mode of various heavy metal ions. However, the graphite phase carbon nitride has poor conductivity, and the graphene has excellent conductivity through the combination with the graphene, so that the conductivity of the graphite phase carbon nitride can be obviously improved, the electron transfer is accelerated, and the electrochemical detection performance of the carbon nitride/graphene composite material on heavy metal ions is improved. The pores of the porous tube bundle carbon nitride are beneficial to the permeation of heavy metal ion solution, so that heavy metal ions can be quickly combined with-HN 2 The adsorption of SH, N atoms, S atoms and the like can increase the capturing probability of heavy metal ions by active sites and enhance the electrochemical detection performance of the heavy metal ions.
The prepared sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material is specific to Cd 2+ ,Pb 2+ ,Hg 2+ Has higher sensitivity. In the pair Cd 2+ ,Pb 2+ ,Hg 2+ When three ions are detected electrochemically at the same time, in the detection range of 0.25-3 mu mol/L, the sulfur doped porous tube bundle carbon nitride/graphene composite material is used for Cd 2+ ,Pb 2+ ,Hg 2+ The detection limits of the three ions are 1.17,0.38 and 0.61nmol/L respectively. In the pair Cd 2+ ,Pb 2+ ,Hg 2+ In the electrochemical single detection of three ions, the sulfur doped porous tube bundle is in the detection range of 0.05-5 mu mol/LCd-shaped carbon nitride/graphene composite material pair 2+ The detection limit of the ions was 2.3nmol/L. In the detection range of 0.025-8.5 mu mol/L, the sulfur doped porous tube bundle carbon nitride/graphene composite material is used for preparing Pb 2+ The detection limit of the ions was 0.78nmol/L. In the detection range of 0.05-7.5 mu mol/L, the sulfur doped porous tube bundle carbon nitride/graphene composite material is used for resisting Hg 2+ The detection limit of the ions was 1.15nmol/L. And the sulfur doped porous tube bundle carbon nitride/graphene composite material has good repeatability, accuracy and anti-interference performance.
Drawings
FIG. 1 is a scanning electron microscope image of graphite phase carbon nitride prepared in example 1;
FIG. 2 is a scanning electron microscope image of graphite phase carbon nitride prepared in example 2;
FIG. 3 is a scanning electron microscope image of graphite phase carbon nitride prepared in example 3;
FIG. 4 is a scanning electron microscope image of graphite phase carbon nitride prepared in example 4;
FIG. 5 is a scanning electron microscope image of graphite phase carbon nitride prepared in example 5;
FIG. 6 is a scanning electron microscope image of graphite phase carbon nitride prepared in example 6;
FIG. 7 is a scanning electron microscope image of graphite phase carbon nitride prepared in example 7;
FIG. 8 is a scanning electron microscope image of graphite phase carbon nitride prepared in example 8;
FIG. 9 is a scanning electron microscope image of graphite phase carbon nitride prepared in example 9;
FIG. 10 is a scanning electron microscope image of graphite phase carbon nitride prepared in example 10;
FIG. 11 is a scanning electron microscope image of graphite-phase carbon nitride prepared in example 11;
FIG. 12 is a scanning electron microscope image of graphite-phase carbon nitride prepared in example 12;
FIG. 13 is a partial scanning electron microscope image of graphite phase carbon nitride prepared in example 12;
FIG. 14 is a scanning electron microscope image of graphite phase carbon nitride prepared in example 13;
FIG. 15 is a scanning electron microscope image of graphite phase carbon nitride prepared in example 14;
FIG. 16 is a scanning electron microscope image of the sulfur-doped porous tube bundle carbon nitride/graphene composite material prepared in example 9;
FIG. 17 is a transmission electron microscopy image of the sulfur doped porous tube bundle carbon nitride/graphene composite prepared in example 9;
FIG. 18 is a plot of Cd in the sulfur-doped porous tube bundle carbon nitride/graphene composite material prepared in example 9 2+ ,Pb 2+ ,Hg 2 + Electrochemical simultaneous detection result graphs of three ions;
FIG. 19 is a sulfur-doped porous tube bundle carbon nitride/graphene composite pair Cd prepared in example 9 2+ ,Pb 2+ ,Hg 2+ Electrochemical single detection result graphs of three ions.
Detailed Description
The first embodiment is as follows: the preparation method of the sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material comprises the following steps:
1. preparation of graphite phase carbon nitride
Dispersing melamine and cyanuric acid in distilled water, stirring to form melamine-cyanuric acid supermolecule precursor, drying, grinding into powder, placing into a crucible, placing the crucible into a muffle furnace, heating to 550 ℃, and preserving heat for 2h, wherein the heating rate is 10 ℃/min; cooling to obtain graphite phase carbon nitride; then dispersing graphite-phase carbon nitride in distilled water to prepare graphite-phase carbon nitride aqueous solution; wherein the molar ratio of melamine to cyanuric acid is 1:2;
2. preparation of sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material
Adding graphene aqueous solution to H 2 SO 4 Stirring the solution to obtain graphene-H 2 SO 4 Dispersion, adding graphite phase carbon nitride aqueous solution into graphene-H 2 SO 4 Stirring in the dispersion liquid to obtain a sulfur doped porous tube bundle-shaped carbon nitride/graphene composite material; wherein graphene aqueous solution and H 2 SO 4 The volume ratio of the solution is 1:50, graphite phase nitridingAqueous carbon solution and graphene-H 2 SO 4 The volume ratio of the dispersion liquid is 1:1.
in this embodiment, the molar volume ratio of melamine to distilled water is 0.01mol:100mL.
The second embodiment is as follows: the first difference between this embodiment and the specific embodiment is that: and step one, stirring is mechanical stirring for 2 hours. The other is the same as in the first embodiment.
And a third specific embodiment: this embodiment differs from the first or second embodiment in that: drying in step one refers to drying in an oven at 80 ℃ for 24 hours. The other embodiments are the same as those of the first or second embodiment.
The specific embodiment IV is as follows: this embodiment differs from one of the first to third embodiments in that: the concentration of the graphite-phase carbon nitride aqueous solution in the first step is 1g/L. The other is the same as in one of the first to third embodiments.
Fifth embodiment: this embodiment differs from one to four embodiments in that: and in the second step, the concentration of the graphene aqueous solution is 5g/L. The others are the same as in one to one fourth embodiments.
Specific embodiment six: this embodiment differs from one of the first to fifth embodiments in that: step two H 2 SO 4 The concentration of (C) was 0.02mol/L. The other is the same as in one of the first to fifth embodiments.
Seventh embodiment: this embodiment differs from one of the first to sixth embodiments in that: stirring for 2H in the second step to obtain graphene-H 2 SO 4 And (3) a dispersion. The others are the same as in one of the first to sixth embodiments.
Eighth embodiment: this embodiment differs from one of the first to seventh embodiments in that: and in the second step, stirring for 1h to obtain the sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material. The other is the same as in one of the first to seventh embodiments.
Detailed description nine: the sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material is applied to electrochemical detection of heavy metal ions.
Detailed description ten: this embodiment differs from the ninth embodiment in that: the sulfur doped porous tube bundle carbon nitride/graphene composite material is used as an electrode or electrode modification material of the heavy metal ion electrochemical detection sensor. The other steps are the same as those in the embodiment nine.
The following experiments were performed to verify the beneficial effects of the present invention:
example 1, a method for preparing a carbon nitride/graphene composite material:
1.26g of melamine and 1.77g of cyanuric acid are dispersed in 100mL of distilled water, and mechanically stirred for 2 hours to form a hydrogel-like melamine-cyanuric acid supermolecule precursor. And (3) drying the melamine-cyanuric acid supermolecule precursor in an oven at 80 ℃ for 24 hours, grinding the precursor into powder, placing the powder into a crucible, placing the crucible into a muffle furnace, heating to 500 ℃, and preserving heat for 2 hours, wherein the heating rate is 10 ℃/min. After cooling, graphite-phase carbon nitride is obtained.
Dispersing 0.5g graphene in 100mL distilled water to obtain 5g/L graphene aqueous solution, taking 2mL graphene aqueous solution, adding into 100mL H with concentration of 0.02mol/L 2 SO 4 Stirring for 2H in the solution to obtain graphene-H 2 SO 4 And (3) a dispersion. 100mL of graphite phase carbon nitride aqueous solution was added to 100mL of graphene-H 2 SO 4 And (3) stirring for 1h in the dispersion liquid to obtain the carbon nitride/graphene composite material.
The scanning electron microscope of the graphite phase carbon nitride prepared in the embodiment is shown in fig. 1.
Example 2, a method for preparing a carbon nitride/graphene composite material:
1.26g of melamine and 3.54g of cyanuric acid are dispersed in 100mL of distilled water, and mechanically stirred for 2 hours to form a hydrogel-like melamine-cyanuric acid supermolecule precursor. And (3) drying the melamine-cyanuric acid supermolecule precursor in an oven at 80 ℃ for 24 hours, grinding the precursor into powder, placing the powder into a crucible, placing the crucible into a muffle furnace, heating to 500 ℃, and preserving heat for 2 hours, wherein the heating rate is 10 ℃/min. After cooling, graphite-phase carbon nitride is obtained. 0.1g of graphite-phase carbon nitride is dispersed in 100mL of distilled water to prepare 1g/L of graphite-phase carbon nitride aqueous solution for later use.
Dispersing 0.5g graphene in 100mL distilled water to obtain 5g/L graphene aqueous solution, taking 2mL graphene aqueous solution, adding into 100mL H with concentration of 0.02mol/L 2 SO 4 Stirring for 2H in the solution to obtain graphene-H 2 SO 4 And (3) a dispersion. 100mL of graphite phase carbon nitride aqueous solution was added to 100mL of graphene-H 2 SO 4 And (3) stirring for 1h in the dispersion liquid to obtain the carbon nitride/graphene composite material.
The scanning electron microscope of the graphite phase carbon nitride prepared in the embodiment is shown in fig. 2.
Example 3, a method for preparing a carbon nitride/graphene composite material:
1.26g of melamine and 5.31g of cyanuric acid are dispersed in 100mL of distilled water, and mechanically stirred for 2 hours to form a hydrogel-like melamine-cyanuric acid supermolecule precursor. And (3) drying the melamine-cyanuric acid supermolecule precursor in an oven at 80 ℃ for 24 hours, grinding the precursor into powder, placing the powder into a crucible, placing the crucible into a muffle furnace, heating to 500 ℃, and preserving heat for 2 hours, wherein the heating rate is 10 ℃/min. After cooling, graphite-phase carbon nitride is obtained. 0.1g of graphite-phase carbon nitride is dispersed in 100mL of distilled water to prepare 1g/L of graphite-phase carbon nitride aqueous solution for later use.
Dispersing 0.5g graphene in 100mL distilled water to obtain 5g/L graphene aqueous solution, taking 2mL graphene aqueous solution, adding into 100mL H with concentration of 0.02mol/L 2 SO 4 Stirring for 2H in the solution to obtain graphene-H 2 SO 4 And (3) a dispersion. 100mL of graphite phase carbon nitride aqueous solution was added to 100mL of graphene-H 2 SO 4 And (3) stirring for 1h in the dispersion liquid to obtain the carbon nitride/graphene composite material.
The scanning electron microscope of the graphite phase carbon nitride prepared in the embodiment is shown in fig. 3.
Example 4, a method for preparing a carbon nitride/graphene composite material:
1.26g of melamine and 1.77g of cyanuric acid are dispersed in 100mL of distilled water, and mechanically stirred for 2 hours to form a hydrogel-like melamine-cyanuric acid supermolecule precursor. And (3) drying the melamine-cyanuric acid supermolecule precursor in an oven at 80 ℃ for 24 hours, grinding the precursor into powder, placing the powder into a crucible, placing the crucible into a muffle furnace, heating to 550 ℃, and preserving heat for 2 hours, wherein the heating rate is 10 ℃/min. After cooling, graphite-phase carbon nitride is obtained.
Dispersing 0.5g graphene in 100mL distilled water to obtain 5g/L graphene aqueous solution, taking 2mL graphene aqueous solution, adding into 100mL H with concentration of 0.02mol/L 2 SO 4 Stirring for 2H in the solution to obtain graphene-H 2 SO 4 And (3) a dispersion. 100mL of graphite phase carbon nitride aqueous solution was added to 100mL of graphene-H 2 SO 4 And (3) stirring for 1h in the dispersion liquid to obtain the carbon nitride/graphene composite material.
The scanning electron microscope of the graphite phase carbon nitride prepared in the embodiment is shown in fig. 4.
Example 5, a method for preparing a carbon nitride/graphene composite material:
1.26g of melamine and 5.31g of cyanuric acid are dispersed in 100mL of distilled water, and mechanically stirred for 2 hours to form a hydrogel-like melamine-cyanuric acid supermolecule precursor. And (3) drying the melamine-cyanuric acid supermolecule precursor in an oven at 80 ℃ for 24 hours, grinding the precursor into powder, placing the powder into a crucible, placing the crucible into a muffle furnace, heating to 550 ℃, and preserving heat for 2 hours, wherein the heating rate is 10 ℃/min. After cooling, graphite-phase carbon nitride is obtained. 0.1g of graphite-phase carbon nitride is dispersed in 100mL of distilled water to prepare 1g/L of graphite-phase carbon nitride aqueous solution for later use.
Dispersing 0.5g graphene in 100mL distilled water to obtain 5g/L graphene aqueous solution, taking 2mL graphene aqueous solution, adding into 100mL H with concentration of 0.02mol/L 2 SO 4 Stirring for 2H in the solution to obtain graphene-H 2 SO 4 And (3) a dispersion. 100mL of graphite phase carbon nitride aqueous solution was added to 100mL of graphene-H 2 SO 4 And (3) stirring for 1h in the dispersion liquid to obtain the carbon nitride/graphene composite material.
The scanning electron microscope of the graphite phase carbon nitride prepared in the embodiment is shown in fig. 5.
Example 6, a method for preparing a carbon nitride/graphene composite material:
1.26g of melamine and 1.77g of cyanuric acid are dispersed in 100mL of distilled water, and mechanically stirred for 2 hours to form a hydrogel-like melamine-cyanuric acid supermolecule precursor. And (3) drying the melamine-cyanuric acid supermolecule precursor in an oven at 80 ℃ for 24 hours, grinding the precursor into powder, placing the powder into a crucible, placing the crucible into a muffle furnace, heating to 600 ℃, and preserving heat for 2 hours, wherein the heating rate is 10 ℃/min. After cooling, graphite-phase carbon nitride is obtained.
Dispersing 0.5g graphene in 100mL distilled water to obtain 5g/L graphene aqueous solution, taking 2mL graphene aqueous solution, adding into 100mL H with concentration of 0.02mol/L 2 SO 4 Stirring for 2H in the solution to obtain graphene-H 2 SO 4 And (3) a dispersion. 100mL of graphite phase carbon nitride aqueous solution was added to 100mL of graphene-H 2 SO 4 And (3) stirring for 1h in the dispersion liquid to obtain the carbon nitride/graphene composite material.
The scanning electron microscope of the graphite phase carbon nitride prepared in the embodiment is shown in fig. 6.
Example 7, a method for preparing a carbon nitride/graphene composite material:
1.26g of melamine and 3.54g of cyanuric acid are dispersed in 100mL of distilled water, and mechanically stirred for 2 hours to form a hydrogel-like melamine-cyanuric acid supermolecule precursor. And (3) drying the melamine-cyanuric acid supermolecule precursor in an oven at 80 ℃ for 24 hours, grinding the precursor into powder, placing the powder into a crucible, placing the crucible into a muffle furnace, heating to 600 ℃, and preserving heat for 2 hours, wherein the heating rate is 10 ℃/min. After cooling, graphite-phase carbon nitride is obtained. 0.1g of graphite-phase carbon nitride is dispersed in 100mL of distilled water to prepare 1g/L of graphite-phase carbon nitride aqueous solution for later use.
Dispersing 0.5g graphene in 100mL distilled water to obtain 5g/L graphene aqueous solution, taking 2mL graphene aqueous solution, adding into 100mL H with concentration of 0.02mol/L 2 SO 4 Stirring for 2H in the solution to obtain graphene-H 2 SO 4 And (3) a dispersion. 100mL of graphite phase carbon nitride aqueous solution was added to 100mL of graphene-H 2 SO 4 And (3) stirring for 1h in the dispersion liquid to obtain the carbon nitride/graphene composite material.
The scanning electron microscope of the graphite phase carbon nitride prepared in the embodiment is shown in fig. 7.
Example 8, a method for preparing a carbon nitride/graphene composite material:
1.26g of melamine and 5.31g of cyanuric acid are dispersed in 100mL of distilled water, and mechanically stirred for 2 hours to form a hydrogel-like melamine-cyanuric acid supermolecule precursor. And (3) drying the melamine-cyanuric acid supermolecule precursor in an oven at 80 ℃ for 24 hours, grinding the precursor into powder, placing the powder into a crucible, placing the crucible into a muffle furnace, heating to 600 ℃, and preserving heat for 2 hours, wherein the heating rate is 10 ℃/min. After cooling, graphite-phase carbon nitride is obtained. 0.1g of graphite-phase carbon nitride is dispersed in 100mL of distilled water to prepare 1g/L of graphite-phase carbon nitride aqueous solution for later use.
Dispersing 0.5g graphene in 100mL distilled water to obtain 5g/L graphene aqueous solution, taking 2mL graphene aqueous solution, adding into 100mL H with concentration of 0.02mol/L 2 SO 4 Stirring for 2H in the solution to obtain graphene-H 2 SO 4 And (3) a dispersion. 100mL of graphite phase carbon nitride aqueous solution was added to 100mL of graphene-H 2 SO 4 And (3) stirring for 1h in the dispersion liquid to obtain the carbon nitride/graphene composite material.
The scanning electron microscope of the graphite phase carbon nitride prepared in the embodiment is shown in fig. 8.
Example 9: a preparation method of a sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material comprises the following steps:
1.26g of melamine and 3.54g of cyanuric acid are dispersed in 100mL of distilled water, and mechanically stirred for 2 hours to form a hydrogel-like melamine-cyanuric acid supermolecule precursor. And (3) drying the melamine-cyanuric acid supermolecule precursor in an oven at 80 ℃ for 24 hours, grinding the precursor into powder, placing the powder into a crucible, placing the crucible into a muffle furnace, heating to 550 ℃, and preserving heat for 2 hours, wherein the heating rate is 10 ℃/min. After cooling, graphite-phase carbon nitride is obtained. 0.1g of graphite-phase carbon nitride is dispersed in 100mL of distilled water to prepare 1g/L of graphite-phase carbon nitride aqueous solution for later use.
Dispersing 0.5g graphene in 100mL distilled water to obtain 5g/L graphene aqueous solution, taking 2mL graphene aqueous solution, adding into 100mL H with concentration of 0.02mol/L 2 SO 4 In solutionStirring for 2H to obtain graphene-H 2 SO 4 And (3) a dispersion. 100mL of graphite phase carbon nitride aqueous solution was added to 100mL of graphene-H 2 SO 4 And stirring for 1h in the dispersion liquid to obtain the sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material.
The scanning electron microscope of the graphite phase carbon nitride prepared in the embodiment is shown in fig. 9.
As can be seen from a comparison of FIGS. 1 to 9, at a reaction temperature of 500 ℃, the obtained carbon nitride had a rod shape without pores. At a reaction temperature of 600 ℃, the obtained carbon nitride takes on a flake shape or a flocculent shape. The porous tube bundle shape forming mechanism mainly utilizes melamine and cyanuric acid to release small molecule gas and molecule rearrangement to form a carbon nitride network during thermal shrinkage. At 500 ℃, the reaction temperature is lower, and the decomposition of melamine and cyanuric acid is milder. The melamine and the cyanuric acid form a bar-shaped precursor through hydrogen bonding, and the bar-shaped precursor is heated to obtain the bar-shaped morphology. When the reaction temperature reaches 550 ℃, melamine and cyanuric acid are decomposed more severely to generate gases such as ammonia, hydrogen sulfide and the like, and holes are formed on the surface, so that the porous tube bundle shape is obtained. When the reaction temperature reaches 600 ℃, the melamine and the cyanuric acid are extremely severely decomposed, a large amount of ammonia gas and hydrogen sulfide overflow, so that the tube bundle shape cannot be maintained, and the tube bundle is broken to form a sheet shape or a flocculent shape. And between ammonia and hydrogen sulfide, hydrogen sulfide is easier to decompose and overflow, so that holes are easier to form in melamine and cyanuric acid with higher proportion, and the tube bundle shape is easier to be damaged with higher proportion of cyanuric acid. When the reaction temperature is 550 ℃, only the mole ratio of melamine to cyanuric acid is 1:2, so that the better tube bundle shape can be maintained, and the shape detection effect is best.
The test of the test effect was performed on the carbon nitride/graphene composite materials prepared in examples 1 to 8 and the sulfur-doped porous tube bundle carbon nitride/graphene composite material prepared in example 9, under the following test conditions: dispersing 0.005g porous tube bundle carbon nitride/graphene composite material in 1mL deionized water, adding 50 μL of 5%Carbon/graphene composite dispersion. And (3) taking 5 mu L of porous tube bundle carbon nitride/graphene composite material dispersion liquid, dripping the dispersion liquid on the surface of the glassy carbon electrode, and drying to obtain the porous tube bundle carbon nitride/graphene composite material modified glassy carbon electrode. A porous tube bundle carbon nitride/graphene composite material modified glassy carbon electrode is used as a working electrode, a platinum sheet is used as a counter electrode, and Ag/AgCl is used as a reference electrode to construct a three-electrode system. 40mL of acetic acid-sodium acetate with pH=5.0 is taken as a buffer solution, 20mL of potassium chloride is taken as an electrolyte, 40mL of deionized water is added, and Cd is adopted 2+ ,Pb 2+ ,Hg 2+ Cd concentrations of 1. Mu. Mol/L each 2+ ,Pb 2+ ,Hg 2+ The mixed solution is the liquid to be measured. Testing Cd by SWASV mode of CHI-660e electrochemical workstation 2+ ,Pb 2+ ,Hg 2+ The dissolution current of the mixed solution, the deposition potential of-1.2V, the deposition time of 300s, the test range of-1.0-0.6V, the voltage increment of 0.004V, the voltage amplitude of 0.025V and the current frequency of 15Hz. The test results are shown in Table 1.
TABLE 1
Cd 2+ Detecting current (mu A) | Pb 2+ Detecting current (mu A) | Hg 2+ Detecting current (mu A) | |
500℃1:1 | 6.04 | 32.96 | 22.28 |
500℃1:2 | 7.98 | 40.46 | 26.10 |
500℃1:3 | 6.13 | 30.10 | 21.70 |
550℃1:1 | 10.65 | 38.47 | 26.89 |
550℃1:2 | 23.02 | 46.72 | 32.11 |
550℃1:3 | 15.86 | 40.77 | 27.06 |
600℃1:1 | 13.50 | 39.19 | 24.38 |
600℃1:2 | 12.59 | 37.46 | 22.58 |
600℃1:3 | 9.84 | 30.65 | 17.77 |
Example 10, a method for preparing a carbon nitride/graphene composite material:
1.26g of melamine and 3.54g of cyanuric acid are dispersed in 100mL of distilled water, and mechanically stirred for 2 hours to form a hydrogel-like melamine-cyanuric acid supermolecule precursor. And (3) drying the melamine-cyanuric acid supermolecule precursor in an oven at 80 ℃ for 24 hours, grinding the precursor into powder, placing the powder into a crucible, placing the crucible into a muffle furnace, heating to 550 ℃, and preserving heat for 1 hour, wherein the heating rate is 5 ℃/min. After cooling, graphite-phase carbon nitride is obtained. 0.1g of graphite-phase carbon nitride is dispersed in 100mL of distilled water to prepare 1g/L of graphite-phase carbon nitride aqueous solution for later use.
Dispersing 0.5g graphene in 100mL distilled water to obtain 5g/L graphene aqueous solution, taking 2mL graphene aqueous solution, adding into 100mL H with concentration of 0.02mol/L 2 SO 4 Stirring for 2H in the solution to obtain graphene-H 2 SO 4 And (3) a dispersion. 100mL of graphite phase carbon nitride aqueous solution was added to 100mL of graphene-H 2 SO 4 And (3) stirring for 1h in the dispersion liquid to obtain the carbon nitride/graphene composite material.
The scanning electron microscope of the graphite phase carbon nitride prepared in the embodiment is shown in fig. 10.
Example 11, a method for preparing a carbon nitride/graphene composite material:
1.26g of melamine and 3.54g of cyanuric acid are dispersed in 100mL of distilled water, and mechanically stirred for 2 hours to form a hydrogel-like melamine-cyanuric acid supermolecule precursor. And (3) drying the melamine-cyanuric acid supermolecule precursor in an oven at 80 ℃ for 24 hours, grinding the precursor into powder, placing the powder into a crucible, placing the crucible into a muffle furnace, heating to 550 ℃, and preserving heat for 2 hours, wherein the heating rate is 5 ℃/min. After cooling, graphite-phase carbon nitride is obtained. 0.1g of graphite-phase carbon nitride is dispersed in 100mL of distilled water to prepare 1g/L of graphite-phase carbon nitride aqueous solution for later use.
Dispersing 0.5g graphene in 100mL distilled water to obtain 5g/L graphene aqueous solution, taking 2mL graphene aqueous solution, adding into 100mL H with concentration of 0.02mol/L 2 SO 4 Stirring for 2H in the solution to obtain graphene-H 2 SO 4 And (3) a dispersion. 100mL of graphite phase carbon nitride aqueous solution was added to 100mL of graphene-H 2 SO 4 And (3) stirring for 1h in the dispersion liquid to obtain the carbon nitride/graphene composite material.
The scanning electron microscope of the graphite phase carbon nitride prepared in the embodiment is shown in fig. 11.
Example 12 a method for preparing a carbon nitride/graphene composite material:
1.26g of melamine and 3.54g of cyanuric acid are dispersed in 100mL of distilled water, and mechanically stirred for 2 hours to form a hydrogel-like melamine-cyanuric acid supermolecule precursor. And (3) drying the melamine-cyanuric acid supermolecule precursor in an oven at 80 ℃ for 24 hours, grinding the precursor into powder, placing the powder into a crucible, placing the crucible into a muffle furnace, heating to 550 ℃, and preserving heat for 1 hour, wherein the heating rate is 10 ℃/min. After cooling, graphite-phase carbon nitride is obtained. 0.1g of graphite-phase carbon nitride is dispersed in 100mL of distilled water to prepare 1g/L of graphite-phase carbon nitride aqueous solution for later use.
Dispersing 0.5g graphene in 100mL distilled water to obtain 5g/L graphene aqueous solution, taking 2mL graphene aqueous solution, adding into 100mL H with concentration of 0.02mol/L 2 SO 4 Stirring for 2H in the solution to obtain graphene-H 2 SO 4 And (3) a dispersion. 100mL of graphite phase carbon nitride aqueous solution was added to 100mL of graphene-H 2 SO 4 And (3) stirring for 1h in the dispersion liquid to obtain the carbon nitride/graphene composite material.
The sem image of the graphite phase carbon nitride prepared in this example is shown in fig. 12, and the sem image with partial enlargement is shown in fig. 13.
Example 13, a method for preparing a carbon nitride/graphene composite material:
1.26g of melamine and 3.54g of cyanuric acid are dispersed in 100mL of distilled water, and mechanically stirred for 2 hours to form a hydrogel-like melamine-cyanuric acid supermolecule precursor. And (3) drying the melamine-cyanuric acid supermolecule precursor in an oven at 80 ℃ for 24 hours, grinding the precursor into powder, placing the powder into a crucible, placing the crucible into a muffle furnace, heating to 550 ℃, and preserving heat for 3 hours, wherein the heating rate is 10 ℃/min. After cooling, graphite-phase carbon nitride is obtained. 0.1g of graphite-phase carbon nitride is dispersed in 100mL of distilled water to prepare 1g/L of graphite-phase carbon nitride aqueous solution for later use.
Dispersing 0.5g graphene in 100mL distilled water to obtain 5g/L graphene aqueous solution, taking 2mL graphene aqueous solution, adding into 100mL H with concentration of 0.02mol/L 2 SO 4 Stirring for 2H in the solution to obtain graphene-H 2 SO 4 And (3) a dispersion. 100mL of graphite phase carbon nitride aqueous solution was added to 100mL of graphene-H 2 SO 4 And (3) stirring for 1h in the dispersion liquid to obtain the carbon nitride/graphene composite material.
The scanning electron microscope of the graphite phase carbon nitride prepared in the embodiment is shown in fig. 14.
Example 14, a method for preparing a carbon nitride/graphene composite material:
1.26g of melamine and 3.54g of cyanuric acid are dispersed in 100mL of distilled water, and mechanically stirred for 2 hours to form a hydrogel-like melamine-cyanuric acid supermolecule precursor. And (3) drying the melamine-cyanuric acid supermolecule precursor in an oven at 80 ℃ for 24 hours, grinding the precursor into powder, placing the powder into a crucible, placing the crucible into a muffle furnace, heating to 550 ℃, and preserving heat for 4 hours, wherein the heating rate is 10 ℃/min. After cooling, graphite-phase carbon nitride is obtained. 0.1g of graphite-phase carbon nitride is dispersed in 100mL of distilled water to prepare 1g/L of graphite-phase carbon nitride aqueous solution for later use.
Dispersing 0.5g graphene in 100mL distilled water to obtain 5g/L graphene aqueous solution, taking 2mL graphene aqueous solution, adding into 100mL H with concentration of 0.02mol/L 2 SO 4 Stirring for 2H in the solution to obtain graphene-H 2 SO 4 And (3) a dispersion. 100mL of graphite phase carbon nitride aqueous solution was added to 100mL of graphene-H 2 SO 4 And (3) stirring for 1h in the dispersion liquid to obtain the carbon nitride/graphene composite material.
The scanning electron microscope of the graphite phase carbon nitride prepared in the embodiment is shown in fig. 15.
As can be seen from fig. 10 to 15, when the molar ratio of melamine to cyanuric acid was determined to be 1:2 and the reaction temperature was 550 ℃. It can be seen that when the temperature rising rate is 5 ℃/min, the prepared carbon nitride presents a short rod shape, and the lower temperature rising rate is unfavorable for the formation of the carbon nitride into a tube. When the heating rate is 10 ℃/min, the reaction time is 1h, holes are not completely formed in the material, but when the reaction time is prolonged to 3h or 4h, the tube bundle morphology is broken into sheets or floccules, so that the tube bundle morphology is difficult to maintain due to the overlong reaction time.
Therefore, the conditions of the porous tube bundle morphology are limited to the molar ratio of melamine to cyanuric acid of 1:2, the reaction time of 2 hours at 550 ℃, and the heating rate of 10 ℃/min. FIG. 16 is a scanning electron microscope image of a sulfur-doped porous tube bundle-like carbon nitride/graphene composite material obtained in example 9. As can be seen from FIG. 16, carbon nitride in the sulfur-doped porous tube bundle-like carbon nitride/graphene composite material is in a nanotube bundle state, and holes are formed in the tube. The graphene is in a flake form. This structure has two benefits, the first sulfur-doped porous tube bundle carbon nitride is prepared from melamine and cyanuric acid as raw materials, so that the carbon nitride has a large residual-HN content 2 -SH, N atoms, S atoms. -NH 2 the-SH can be bonded with heavy metal ions through chelation, and the N atom and the S atom can be bonded with heavy metal ions through coordination. The detection performance of the electrochemical sensing material is enhanced by the bonding mode of various heavy metal ions. However, the graphite phase carbon nitride has poor conductivity, and the graphene has excellent conductivity through the combination with the graphene, so that the conductivity of the graphite phase carbon nitride can be obviously improved, the electron transfer is accelerated, and the electrochemical detection performance of the carbon nitride/graphene composite material on heavy metal ions is improved. Fig. 17 a transmission electron micrograph of the sulfur doped porous tube bundle carbon nitride/graphene composite obtained in example 9, the pores of the tube bundle carbon nitride being evident in fig. 17. The pores are favorable for the penetration of heavy metal ion solution, so that heavy metal ions can be quickly combined with-HN 2 The adsorption of SH, N atoms, S atoms and the like can increase the capturing probability of heavy metal ions by active sites and enhance the electrochemical detection performance of the heavy metal ions.
Thus, the sulfur-doped porous tube bundle-like carbon nitride/graphene composite material prepared in example 9 was tested for its performance in electrochemical detection of heavy metal ions. The testing method comprises the following steps: 0.005g of porous tube bundle carbon nitride/graphene composite material is dispersed in 1mL of deionized water, and 50 mu L of 5 permillage chitosan-acetic acid solution is added to obtain porous tube bundle carbon nitride/graphene composite material dispersion liquid. And (3) taking 5 mu L of porous tube bundle carbon nitride/graphene composite material dispersion liquid, dripping the dispersion liquid on the surface of the glassy carbon electrode, and drying to obtain the porous tube bundle carbon nitride/graphene composite material modified glassy carbon electrode. A porous tube bundle carbon nitride/graphene composite material modified glassy carbon electrode is used as a working electrode, a platinum sheet is used as a counter electrode, and Ag/AgCl is used as a reference electrode to construct a three-electrode system. 40mL of pH=5.0 acetic acid-sodium acetate was used as a buffer solution, 20mL of potassium chloride was used as an electrolyte, and 40mL of deionized water was added by adding Cd of different masses 2+ ,Pb 2+ ,Hg 2+ Configuring Cd with different concentrations 2+ ,Pb 2+ ,Hg 2+ The single or mixed solution is the liquid to be measured. Testing Cd by SWASV mode of CHI-660e electrochemical workstation 2+ ,Pb 2+ ,Hg 2+ The single or mixed solution has a dissolution current, a deposition potential of-1.2V, a deposition time of 300s, a test range of-1.0 to 0.6V, a voltage increment of 0.004V, a voltage amplitude of 0.025V and a current frequency of 15Hz.
The sulfur-doped porous tube bundle carbon nitride/graphene composite material prepared in example 9 was for Cd 2+ ,Pb 2+ ,Hg 2+ All have better detection effect. FIG. 18 is a sulfur doped porous tube bundle carbon nitride/graphene composite vs Cd 2+ ,Pb 2+ ,Hg 2+ Electrochemical simultaneous detection of three ions. Wherein the curves in FIG. a represent current curves at concentrations of 3.00. Mu.M, 2.50. Mu.M, 2.00. Mu.M, 1.50. Mu.M, 1.00. Mu.M, 0.05. Mu.M and 0.25. Mu.M, respectively, from top to bottom. b is Cd 2+ Linear equation y=19.871x+6.7789, r 2 =0.9941; c is Pb 2+ Linear equation y=44.772x+10.143, r 2 = 0.9947; d is Hg 2+ Is used to determine the current of the current sensor,linear equation y=29.512 x+8.5058, r 2 = 0.9947. In the detection range of 0.25-3 mu mol/L, cd 2+ ,Pb 2+ ,Hg 2+ Three have obvious dissolution peaks at-0.748, -0.484 and 0.192V potentials, and the dissolution current shows good linear change along with the increase of concentration, which shows that the sulfur doped porous tube bundle-shaped carbon nitride/graphene composite material has a function of Cd 2+ ,Pb 2+ ,Hg 2+ Three ions can realize simultaneous quantitative detection, and Cd is subjected to calculation by the sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material pair 2+ ,Pb 2+ ,Hg 2+ The detection limits of the three ions are 1.17,0.38 and 0.61nmol/L respectively. FIG. 19 is a sulfur doped porous tube bundle carbon nitride/graphene composite vs Cd 2+ ,Pb 2+ ,Hg 2+ Electrochemical single detection of three ions. Wherein a is Cd 2+ Current curve under 0.05-5 mu mol/L concentration, b is Cd 2+ Is defined by the linear equation y= 10.132x-0.0784, r 2 = 0.9983; c is Pb 2 Current curve at 0.025-8.5 mu mol/L concentration, d is Pb 2+ Is defined by the linear equation y= 21.684x-0.2796, r 2 =0.9994; e is Hg 2+ Current curve at 0.05-7.5 mu mol/L concentration, f is Hg 2+ Linear equation y=15.71x+0.3437, r 2 =0.9997. In the detection range of 0.05-5 mu mol/L, cd 2+ There was a distinct elution peak at a potential of-0.748V, and the elution current showed good linear changes with increasing concentration. Calculated Cd of sulfur doped porous tube bundle carbon nitride/graphene composite material pair 2+ The detection limit of the ions was 2.3nmol/L. Pb in the detection range of 0.025-8.5 mu mol/L 2+ There is a distinct dissolution peak at a potential of-0.484V, and the dissolution current shows a good linear change with increasing concentration. Calculated sulfur doped porous tube bundle carbon nitride/graphene composite material pair Pb 2+ The detection limit of the ions was 0.78nmol/L. Hg in the detection range of 0.05-7.5 mu mol/L 2 + Has obvious dissolution peak at 0.192V potential, and with the increase of concentration, the electricity is dissolvedThe flow exhibits good linear variation. Calculated sulfur doped porous tube bundle carbon nitride/graphene composite material pair Hg 2+ The detection limit of the ions was 1.15nmol/L.
Table 2 is the sulfur doped porous tube bundle carbon nitride/graphene composite for Cd 2+ ,Pb 2+ ,Hg 2+ The rate of change of current was measured electrochemically 11 times. As can be seen from Table 1, the sulfur doped porous tube bundle carbon nitride/graphene composite material was specific to Cd 2 + ,Pb 2+ ,Hg 2+ The current change rate of the electrochemical detection is not more than 5%, which indicates that the sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material has good repeatability and accuracy.
TABLE 2 detection times vs Cd 2+ ,Pb 2+ ,Hg 2+ Detecting the influence of current
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TABLE 3 common ion pair Cd 2+ ,Pb 2+ ,Hg 2+ Detected interference
Table 3 shows the common ions and Cd 2+ ,Pb 2+ ,Hg 2+ For Cd when coexisting 2+ ,Pb 2+ ,Hg 2+ Interference of the dissolution current. From Table 2 we can see that most of the ions are for Cd 2+ ,Pb 2+ ,Hg 2+ The current interference of the electrochemical detection of (2) is less than 5%, so the sulfur doped porous tube bundle carbon nitride/graphene composite material has the following characteristics of Cd 2+ ,Pb 2+ ,Hg 2+ The detection of the method has good anti-interference performance.
Claims (10)
1. The preparation method of the sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material is characterized by comprising the following steps of:
1. preparation of graphite phase carbon nitride
Dispersing melamine and cyanuric acid in distilled water, stirring to form melamine-cyanuric acid supermolecule precursor, drying, grinding into powder, placing into a crucible, placing the crucible into a muffle furnace, heating to 550 ℃, and preserving heat for 2h, wherein the heating rate is 10 ℃/min; cooling to obtain graphite phase carbon nitride; then dispersing graphite-phase carbon nitride in distilled water to prepare graphite-phase carbon nitride aqueous solution; wherein the molar ratio of melamine to cyanuric acid is 1:2;
2. preparation of sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material
Adding graphene aqueous solution to H 2 SO 4 Stirring the solution to obtain graphene-H 2 SO 4 Dispersion, adding graphite phase carbon nitride aqueous solution into graphene-H 2 SO 4 Stirring in the dispersion liquid to obtain a sulfur doped porous tube bundle-shaped carbon nitride/graphene composite material; wherein graphene aqueous solution and H 2 SO 4 The volume ratio of the solution is 1:50, graphite phase carbon nitride aqueous solution and graphene-H 2 SO 4 The volume ratio of the dispersion liquid is 1:1.
2. the method for preparing a sulfur-doped porous tube bundle carbon nitride/graphene composite material according to claim 1, wherein the stirring in the first step is mechanical stirring for 2 hours.
3. The method for preparing a sulfur-doped porous tube bundle carbon nitride/graphene composite material according to claim 1, wherein the drying in the first step is drying in an oven at 80 ℃ for 24 hours.
4. The method for producing a sulfur-doped porous tube bundle carbon nitride/graphene composite material according to claim 1, wherein the concentration of the graphite-phase carbon nitride aqueous solution in the step one is 1g/L.
5. The method for preparing a sulfur-doped porous tube bundle carbon nitride/graphene composite material according to claim 1, wherein the concentration of the graphene aqueous solution in the second step is 5g/L.
6. The method for preparing a sulfur-doped porous tube bundle-like carbon nitride/graphene composite material according to claim 1, wherein H in the second step 2 SO 4 The concentration of (C) was 0.02mol/L.
7. The method for preparing the sulfur-doped porous tube bundle-shaped carbon nitride/graphene composite material according to claim 1, wherein the method is characterized in that graphene-H is obtained by stirring for 2H in the second step 2 SO 4 And (3) a dispersion.
8. The method for preparing the sulfur-doped porous tube bundle carbon nitride/graphene composite material according to claim 1, wherein the sulfur-doped porous tube bundle carbon nitride/graphene composite material is obtained by stirring for 1h in the second step.
9. The application of the sulfur-doped porous tube bundle carbon nitride/graphene composite material prepared by the preparation method of the sulfur-doped porous tube bundle carbon nitride/graphene composite material in electrochemical detection of heavy metal ions.
10. Use according to claim 9, characterized in that the sulfur doped porous tube bundle carbon nitride/graphene composite material is used as electrode or electrode modification material of heavy metal ion electrochemical detection sensor.
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