CN115888787A - Ozone-enhanced graphite nitrogen-doped graphene catalytic material and preparation method thereof - Google Patents
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention discloses ozone (O) 3 ) The preparation method of the reinforced graphite nitrogen-doped graphene catalytic material comprises the step of preparing O by using an ozone generator 3 Keeping the concentration of ozone in the graphene oxide aqueous solution to be 5-25mg/L, carrying out hydrothermal reaction at 40-150 ℃ for 0.5-4 h, and carrying out O reaction 3 Mixing the etched graphene dispersion liquid with 2.00-10.00 wt% of nitrogen precursor, and thermally annealing the strip at a low temperature of 40-200 DEG CReacting for 1-8h under the condition of reaction. The invention utilizes O 3 The synergistic effect of the pre-etching treatment, the hydrothermal synthesis and the low-temperature annealing is realized by regulating and controlling O under proper reaction conditions 3 The etching time and the reaction temperature are prolonged, the graphite nitrogen proportion of high conductivity, high catalytic activity and stability is improved, and the catalytic activity of the hybridized graphene material is improved; the method can improve the selectivity of directional regulation and control of the catalytic material, is beneficial to improving the performance of the catalytic material by taking a microstructure as a cut-in point, and has important significance in the aspects of deepening theoretical research and marketing application and popularization of the hybrid graphene material.
Description
Technical Field
The invention belongs to the technical field of graphene catalysts, and particularly relates to an ozone-enhanced graphite nitrogen-doped graphene catalytic material and a preparation method thereof.
Background
Graphene combines many excellent physicochemical properties, such as a large specific surface area, excellent mechanical strength and flexibility, excellent thermal conductivity and electrical conductivity, and excellent electrochemical properties, and can be used not only for electrocatalytic oxidation, but also as an adsorption material, a supercapacitor, and the like. Due to the remaining p on each carbon of graphene z P of orbital and adjacent atom z The orbitals overlap, forming a full band of pi orbitals (valence band) and an empty band of pi orbitals (conduction band). Thus, graphene can be considered as a metal with a vanishing fermi surface, or a semiconductor with a zero band gap. Therefore, the induction of the graphene to generate the band gap can greatly improve the electrocatalysis performance of the graphene, so that the feasibility of the application of the graphene in the electrocatalysis field is improved.
Heteroatom doping is the most common method for opening the band gap of graphene and improving the catalytic activity of the graphene. Compared with carbon, nitrogen atoms have higher electronegativity, and can generate polarization when being introduced into graphene, so that the electrochemical performance of the graphene is improved. The nitrogen atoms can mainly form three different bonding structures with graphene: directly substituting one carbon atom in the crystal lattice to form graphite nitrogen, combining with two carbon atoms in a six-membered ring and forming pyridine nitrogen along with vacancies, and forming pyrrole nitrogen in the form of a five-membered ring. Different bonding configurations play different roles in the graphene modification process. Pyridine nitrogen and graphite nitrogen have little influence on the graphene structure, and the stability of the graphene structure can be maintained. Pyridine nitrogen and pyrrole nitrogen can improve the Faraday capacitance of the material by using oxidation-reduction reaction, while graphite nitrogen can enhance the conductivity and the ability of providing electrons to adjacent carbon atoms, thereby being beneficial to the electron transmission in the electrocatalytic reaction process. Therefore, doping of the nitrogen structure of the graphite is considered to be effective in improving the electrochemical performance of the graphene. However, in many processing methods, nitrogen atoms often present defects with complex doping patterns in the graphene structure, and basically appear in a complex form of "pyridine type nitrogen-graphite type nitrogen-pyrrole type nitrogen". At the present stage, a technical method for doping graphene with nitrogen in a single form still needs to be further researched.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an ozone-enhanced graphite nitrogen-doped graphene catalytic material and a preparation method thereof, and solves the problem of difficulty in regulating and controlling a nitrogen atom hybridization structure in the background technology.
The ozone-enhanced graphite nitrogen-doped graphene catalytic material developed by the invention has the advantages of strong structure regulation and control capability, simplicity in operation, low preparation energy consumption (low-temperature operation) and the like. O is 3 During the etching pretreatment, O 3 The graphene can be attacked to generate defects, a large number of oxygen groups are introduced to occupy the edge sites of the graphene, and nitrogen is more prone to fill the defects of the graphene structure to form a center-doped graphene nitrogen configuration with the addition of a nitrogen precursor. Therefore, the structure regulation and preparation of the high-catalytic-performance material can be realized by using the ozone-enhanced graphite nitrogen doping method.
One of the technical schemes adopted by the invention for solving the technical problems is as follows: the preparation method of the ozone-enhanced graphite nitrogen-doped graphene catalytic material comprises the following steps:
preparation of O by ozone generator 3 Introducing graphene oxide and water, wherein the graphene oxide accounts for 75-85 wt% of the total weight of the graphene oxide and the water, carrying out hydrothermal reaction at 40-150 ℃ for 0.5-4 h, and carrying out O reaction 3 Mixing the etched graphene dispersion liquid with a nitrogen precursor accounting for 2.00-10.00 wt%, and reacting for 1-8h under the condition of low-temperature thermal annealing at 40-200 ℃ to obtain the ozone-enhanced graphene nitrogen-doped catalytic material.
In a preferred embodiment of the present invention, the ratio of graphene oxide to graphene oxide in water is 77-82 wt%.
In a preferred embodiment of the present invention, the concentration of ozone in the graphene oxide aqueous solution is maintained at 5-25mg/L.
In a preferred embodiment of the present invention, O is generated using a 10KHz-15KHz ozone generator 3 Pre-treating and etching graphene, keeping the concentration of ozone in the graphene oxide aqueous solution to be 5-25mg/L, carrying out hydrothermal reaction at 60-120 ℃ for 1-3 h, and carrying out O 3 Mixing the etched graphene dispersion liquid with 3.50-8.00 wt% of nitrogen precursor, and reacting for 2-6 h under the condition of low-temperature thermal annealing at 50-120 ℃.
In a preferred embodiment of the present invention, the carrier gas is carbon monoxide or methane.
In a preferred embodiment of the present invention, the nitrogen precursor is urea or melamine.
The second technical scheme adopted by the invention for solving the technical problems is as follows: the ozone-enhanced graphite nitrogen-doped graphene catalytic material is prepared by the method.
In a preferred embodiment of the present invention, the graphene material includes a graphite nitrogen-doped graphene material.
In a preferred embodiment of the present invention, the graphite nitrogen-doped structure accounts for more than 95wt% of the total nitrogen-doped structure.
Compared with the background technology, the technical scheme has the following advantages:
(1) The method is characterized in that the preparation of the ozone-enhanced graphite nitrogen-doped graphene catalytic material is carried out by utilizing O 3 During the etching pretreatment, O 3 The method comprises the steps of attacking graphene to generate defects, introducing a large number of oxygen groups to occupy edge sites of the graphene in the process, and inducing nitrogen to fill the defects of the graphene structure along with the addition of a nitrogen precursor to form a center-doped graphene nitrogen configuration. The preparation method has the advantages of novel material preparation route, strong structure regulation and control capability, simple operation, low preparation energy consumption (low-temperature operation) and the like, directionally regulates and controls the nitrogen loading form under proper reaction conditions, improves the graphite nitrogen doping proportion with high catalytic activity, and provides an important technical means for improving the electrocatalytic performance of the hybrid material and researching the reaction mechanism of the micro molecular structure.
(2) The ozone-enhanced graphite nitrogen-doped graphene catalytic material disclosed by the invention has good electrocatalytic activity under the conditions of normal temperature and normal pressure.
(3) The method can improve the selectivity of directional regulation and control of the catalytic material, is beneficial to improving the performance of the catalytic material from the point of taking a microstructure as a cut-in point, and has important significance in the aspects of deepening theoretical research and marketing application and popularization of the hybrid graphene material.
Drawings
FIG. 1 is a transmission electron microscope of the ozone enhanced nitrogen-doped graphene catalytic material of example 1;
FIG. 2 is an X-ray photoelectron spectroscopy analysis chart of the ozone-enhanced nitrogen-doped graphene catalytic material in example 1;
fig. 3 is a graph of the efficiency of degradation of bisphenol a by ozone enhanced graphene nitrogen doped catalytic material and graphene catalytic material in example 1 and comparative example;
fig. 4 is a graph of the efficiency of degrading antibiotic a with the ozone-enhanced graphite nitrogen-doped graphene catalytic material in example 1.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in more detail below with reference to the accompanying drawings and specific embodiments, but the scope of the present invention is not limited to these embodiments.
The preparation method of the ozone-enhanced graphite nitrogen-doped graphene catalytic material specifically comprises the following steps:
(1) Weighing the following raw materials in parts by weight: 75-85 wt% of graphene oxide, and the balance of water;
(2) Preparation of O by ozone generator 3 Introducing graphene oxide and water, and carrying out hydrothermal reaction at 40-150 ℃ for 0.5-4 h;
(3) And (3) mixing the dispersion liquid obtained in the step (2) with 2.00-10.00 wt% of nitrogen precursor, and reacting for 1-8h under the condition of low-temperature thermal annealing at 40-200 ℃ to obtain the ozone-enhanced graphite nitrogen-doped graphene catalytic material, wherein the graphite nitrogen-doped structure accounts for more than 95% of the total nitrogen hybrid structure.
The nitrogen precursor is urea or melamine.
Wherein O is used 3 The synergistic effect of pre-etching treatment, hydrothermal synthesis and low-temperature annealing, and in the designed reaction process of the invention, O is 3 Etching pretreatment is carried out to form graphene structure defects and a large amount of oxygen group graphene edge site doping, then nitrogen precursor is added, and nitrogen is induced to fill the graphene structure defects to form a center doped graphite nitrogen configuration.
Example 1
An ozone-enhanced graphite nitrogen-doped graphene catalytic material is specifically prepared by the following steps:
(1) Weighing the following raw materials according to raw material components: 80wt% of graphene oxide, and the balance of water to form a graphene oxide aqueous solution;
(2) O generation with 10KHz ozone generator 3 Keeping the concentration of ozone in the graphene oxide aqueous solution in the step (1) to be 10mg/L, carrying out hydrothermal reaction at 120 ℃ for 2h, pretreating and etching the graphene to obtain O-containing solution 3 Etching the graphene dispersion liquid;
(3) And (3) mixing the dispersion liquid obtained in the step (2) with 5.00wt% of urea precursor, and reacting for 2h under the condition of low-temperature thermal annealing at 60 ℃ to obtain the ozone-enhanced graphite nitrogen-doped graphene catalytic material, wherein the graphite nitrogen-doped structure accounts for more than 95% of the total nitrogen hybrid structure.
The microscopic morphology of the ozone-enhanced nitrogen-doped graphene catalytic material is shown in fig. 1, and the analysis of the morphology of the nitrogen-doped graphene catalytic material doped with ozone-enhanced nitrogen is shown in fig. 2. As shown in fig. 1, the hybrid material has typical graphene characteristics-transparent flakes overlap each other and create significant wrinkles. Description of O 3 The pretreatment and the introduction of nitrogen atoms do not change the original basic morphological structure of graphene. FIG. 2 is a N1s spectrum with a nitrogen-doped configuration comprising graphitic nitrogen (401.7 eV), pyrrole nitrogen (399.9 eV). The hybrid material prepared by the invention takes graphite nitrogen as a dominant form (98.90%).
Example 2
An ozone-enhanced graphite nitrogen-doped graphene catalytic material is specifically prepared by the following steps:
(1) Weighing the following raw materials in parts by weight: 85wt% of graphene oxide, and the balance of water to form a graphene oxide aqueous solution;
(2) O generation with 5KHz ozone generator 3 Keeping the concentration of ozone in the graphene oxide aqueous solution in the step (1) to be 15mg/L, carrying out hydrothermal reaction for 3h at 100 ℃, carrying out pretreatment and etching on graphene to obtain O-containing graphene 3 Etching the graphene dispersion liquid; (3) And (3) mixing the dispersion liquid obtained in the step (2) with 8.00wt% of nitrogen precursor, and reacting for 2 hours at the low temperature of 120 ℃ under the thermal annealing condition to obtain the ozone-enhanced graphite nitrogen-doped graphene catalytic material, wherein the graphite nitrogen-doped structure accounts for more than 95% of the total nitrogen hybrid structure.
Example 3
An ozone-enhanced graphite nitrogen-doped graphene catalytic material is specifically prepared by the following steps:
(1) Weighing the following raw materials according to raw material components: forming a graphene oxide aqueous solution by using 75wt% of graphene oxide and the balance of water;
(2) O generation with 10KHz ozone generator 3 Keeping the concentration of ozone in the graphene oxide aqueous solution in the step (1) to be 8mg/L, carrying out hydrothermal reaction at 120 ℃ for 1h, pretreating and etching the graphene to obtain O-containing solution 3 Etching the graphene dispersion liquid;
(3) And (3) mixing the dispersion liquid obtained in the step (2) with 5.50wt% of nitrogen precursor, and reacting for 3 hours at the low temperature of 120 ℃ under the thermal annealing condition to obtain the ozone-enhanced graphite nitrogen-doped graphene catalytic material, wherein the graphite nitrogen-doped structure accounts for more than 95% of the total nitrogen hybrid structure.
Comparative example
The comparative examples differ from the examples in that: undoped graphene is used.
The ozone-enhanced graphite nitrogen-doped graphene catalytic material prepared in the embodiment 1 was subjected to an electrocatalytic activity test:
the electrocatalytic degradation of bisphenol A (BPA) was tested using a potentiostatic amperemeter.
And evaluating the material performance by taking the BPA as a target pollutant according to the electrocatalytic oxidation degradation effect. Coating 4mg of azagraphene on 2cm multiplied by 2cm carbon cloth by using a conductive adhesive, and drying the conductive adhesive to be used as an anode; a copper sheet with the thickness of 8cm multiplied by 2cm is taken as a cathode; the distance between the two was controlled to 1cm, the impressed current was adjusted with a constant potential current meter (Shanghai Xinrui) of DJS-292B, 1g/L of nitrogen aCl was used as electrolyte, 200mL of 10mg/L BPA solution was degraded in a 250mL beaker, and the solution was kept stirring uniformly with a magnetic stirrer throughout the process. The switch of the potentiostatic amperemeter is turned on, and 1mL of water sample is added into a 2mL centrifuge tube filled with 1mL of methanol quencher within a set time. The liquid after the uniform mixing was filtered of impurities with a 0.22 μm filter head, and the BPA content of the filtered liquid was measured with an Acquity ARC high performance liquid chromatograph (wawter, usa).
An electrocatalytic activity test is performed on the ozone-enhanced graphite nitrogen-doped graphene catalytic material of example 1, and a BPA degradation efficiency graph of the ozone-enhanced graphite nitrogen-doped graphene catalytic material shown in fig. 3 and an antibiotic degradation efficiency graph of the ozone-enhanced graphite nitrogen-doped graphene catalytic material shown in fig. 4 are respectively obtained. As can be seen from fig. 3, when the ozone-enhanced graphite nitrogen-doped graphene catalytic material is used, the degradation effect of BPA is significantly better than that of graphene. FIG. 4 shows that the degradation efficiency of the antibiotics paracetamol and tetracycline hydrochloride can reach 85-95%. The ozone-enhanced graphite nitrogen-doped graphene catalytic material can be used for remarkably improving the removal rate of BPA and antibiotics, and the important function of graphite type nitrogen-doping is demonstrated.
The above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and these modifications or substitutions do not depart from the spirit of the corresponding technical solutions of the embodiments of the present invention.
Claims (10)
1. A preparation method of an ozone-enhanced graphite nitrogen-doped graphene catalytic material is characterized by comprising the following steps: the method comprises the following steps:
1) Generation of O 3 Then, introducing graphene oxide and water, wherein the graphene oxide accounts for 75-85 wt%, and carrying out hydrothermal reaction at 40-150 ℃ for 0.5-4 h to obtain O 3 Etching the graphene dispersion liquid;
2) Mixing O with 3 Mixing the etched graphene dispersion liquid with a nitrogen precursor, wherein the nitrogen precursor accounts for 2.00-10.00 wt%, and reacting for 1-8h under the low-temperature thermal annealing condition of 40-200 ℃ under the protection of carrier gas to obtain the ozone-enhanced graphene nitrogen-doped catalytic material.
2. The preparation method of the ozone-enhanced graphite nitrogen-doped graphene catalytic material according to claim 1, characterized by comprising the following steps: in the step 1), the graphene oxide accounts for 77-82 wt%.
3. The preparation method of the ozone-enhanced nitrogen-doped graphene catalytic material as claimed in claim 1, wherein the preparation method comprises the following steps: in the step 2), the nitrogen precursor accounts for 3.50-8.00 wt%.
4. The preparation method of the ozone-enhanced nitrogen-doped graphene catalytic material as claimed in claim 1, wherein the preparation method comprises the following steps: generating O by using 5KHz-20KHz ozone generator 3 And (4) preprocessing and etching the graphene.
5. The preparation method of the ozone-enhanced graphite nitrogen-doped graphene catalytic material according to claim 1, characterized by comprising the following steps: in the step 2), the concentration of ozone in the graphene oxide aqueous solution is maintained to be 5-25mg/L.
6. The preparation method of the ozone-enhanced nitrogen-doped graphene catalytic material as claimed in claim 1, wherein the preparation method comprises the following steps: in the step 1), carrying out hydrothermal reaction for 1-3 h at 60-120 ℃.
7. The preparation method of the ozone-enhanced nitrogen-doped graphene catalytic material as claimed in claim 1, wherein the preparation method comprises the following steps: in the step 2), the reaction is carried out for 2 to 6 hours under the condition of low-temperature thermal annealing at the temperature of between 50 and 120 ℃.
8. The preparation method of the ozone-enhanced nitrogen-doped graphene catalytic material as claimed in claim 1, wherein the preparation method comprises the following steps: the carrier gas is carbon monoxide or methane, and the nitrogen precursor is urea or melamine.
9. The ozone-enhanced graphite nitrogen-doped graphene catalytic material is characterized in that: prepared by the method of any one of claims 1 to 8.
10. The ozone enhanced graphite nitrogen-doped graphene catalytic material as claimed in claim 9, wherein: the graphite nitrogen-doped structure accounts for more than 95% of the total nitrogen hybrid structure.
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| CN114700098A (en) * | 2022-03-11 | 2022-07-05 | 华侨大学 | Free radical induced graphite type nitrogen-doped graphene catalytic material and preparation method thereof |
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| EP3047905A1 (en) * | 2015-01-21 | 2016-07-27 | Université de Strasbourg | Method for preparing highly nitrogen-doped mesoporous carbon composites |
| US20180008968A1 (en) * | 2015-01-21 | 2018-01-11 | Université De Strasbourg | Method for preparing highly nitrogen-doped mesoporous carbon composites |
| WO2021139023A1 (en) * | 2020-01-06 | 2021-07-15 | 东南大学 | Graphite-like carbon nitride doped modified microsphere catalyst, and preparation method therefor and application thereof |
| CN113617350A (en) * | 2021-08-11 | 2021-11-09 | 北京林业大学 | Defective carbon material and preparation method and application thereof |
| CN114700098A (en) * | 2022-03-11 | 2022-07-05 | 华侨大学 | Free radical induced graphite type nitrogen-doped graphene catalytic material and preparation method thereof |
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