CN115888787B - Ozone-reinforced graphite nitrogen-doped graphene catalytic material and preparation method thereof - Google Patents
Ozone-reinforced graphite nitrogen-doped graphene catalytic material and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 106
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 55
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 claims abstract description 35
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- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N urea group Chemical group NC(=O)N XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 239000012159 carrier gas Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
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- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical group [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 3
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 3
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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 an ozone (O 3) reinforced graphene-doped catalytic material and a preparation method thereof, wherein the preparation method of the graphene-doped catalytic material comprises the steps of preparing O 3 by utilizing an ozone generator, maintaining the ozone concentration in a graphene oxide aqueous solution to be 5-25mg/L, carrying out hydrothermal reaction for 0.5-4 h at 40-150 ℃, mixing graphene dispersion liquid etched by O 3 with 2.00-10.00 wt% of nitrogen precursor, and carrying out low-temperature thermal annealing at 40-200 ℃ for 1-8 h. According to the preparation method, the synergistic effect of O 3 etching pretreatment, hydrothermal synthesis and low-temperature annealing is utilized, the etching duration and the reaction temperature of O 3 are regulated and controlled under proper reaction conditions, the graphite nitrogen proportion with high conductivity, high catalytic activity and stability is improved, and the catalytic activity of the hybridized graphene material is improved; the invention can improve the selectivity of directional regulation of the catalytic material, is beneficial to improving the performance of the catalytic material by taking a microstructure as an entry point, and has important significance in the aspects of deepening theoretical research and marketizing 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-reinforced graphene nitrogen-doped graphene catalytic material and a preparation method thereof.
Background
Graphene has 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 for electrocatalytic oxidation, adsorption materials, super capacitor manufacturing, and the like. Since the remaining p z orbitals on each carbon of graphene overlap with the p z orbitals of the adjacent atom, one full band of pi orbitals (valence band) and one empty band of pi orbitals (conduction band) are formed. Thus, graphene can be considered as a metal with a zero fermi surface or a semiconductor with a zero band gap. Therefore, the induction of the band gap of the graphene can greatly improve the electrocatalytic performance of the graphene, so that the feasibility of application of the graphene in the electrocatalytic field is improved.
Heteroatom doping is the most common method for opening the band gap of graphene and improving the catalytic activity of graphene. Compared with carbon, nitrogen atoms have higher electronegativity, and introduction of the nitrogen atoms into graphene can generate polarization, so that the electrochemical performance of the graphene is improved. The nitrogen atom can mainly form three different bonding structures with graphene: the direct substitution of one carbon atom in the lattice forms graphitic nitrogen, which combines with two carbon atoms in the six-membered ring with vacancies to form pyridine nitrogen, and the five-membered ring forms pyrrole nitrogen. Different bonding configurations play different roles in the modification process of graphene. The pyridine nitrogen and the graphite nitrogen have little influence on the graphene structure, and can keep the stability of the graphene structure. Pyridine nitrogen and pyrrole nitrogen can utilize oxidation-reduction reaction to improve Faraday capacitance of the material, while graphite nitrogen can enhance conductivity and capability of providing electrons to adjacent carbon atoms, so that electron transmission in the electrocatalytic reaction process is facilitated. Doping of the graphite nitrogen structure is therefore believed to be effective in improving the electrochemical properties of graphene. However, in many treatment methods, nitrogen atoms often exhibit defects of complex doping morphology in the graphene structure, and basically appear in a complex morphology of "pyridine-type nitrogen-graphite-pyrrole-type nitrogen". At present, a technical method for doping single-form nitrogen with graphene still needs to be further studied.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides an ozone-reinforced graphite nitrogen-doped graphene catalytic material and a preparation method thereof, and solves the problem that the nitrogen atom hybridization structure in the prior art is difficult to regulate.
The preparation of the ozone-reinforced graphite nitrogen-doped graphene catalytic material has the advantages of strong structure regulation and control capability, simplicity in operation, low preparation energy consumption (low-temperature operation) and the like. In the O 3 etching pretreatment process, O 3 can attack graphene to generate defects, a large amount of oxygen groups are introduced to occupy edge sites of the graphene, and nitrogen is more prone to filling the defects of the graphene structure to form a center doped graphite nitrogen configuration along with the addition of a nitrogen precursor. Therefore, the structural regulation and preparation of the high-catalytic-performance material can be realized by utilizing an ozone reinforced graphite nitrogen doping method.
One of the technical schemes adopted for solving the technical problems is as follows: the preparation method of the ozone-reinforced graphite nitrogen-doped graphene catalytic material comprises the following steps:
Preparing O 3 by utilizing an ozone generator, introducing graphene oxide and water, wherein the graphene oxide and the graphene oxide in the water account for 75-85 wt%, performing hydrothermal reaction for 0.5-4 h at 40-150 ℃, mixing the graphene dispersion liquid etched by O 3 with a nitrogen precursor accounting for 2.00-10.00 wt%, and reacting for 1-8h under the low-temperature annealing condition at 40-200 ℃ to obtain the ozone-reinforced graphite nitrogen-doped graphene catalytic material.
In a preferred embodiment of the invention, the graphene oxide and graphene oxide in water account for 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 invention, O 3 is generated by utilizing a 10KHz-15KHz ozone generator to pretreat and etch graphene, the ozone concentration is maintained to be 5-25mg/L in graphene oxide aqueous solution, hydrothermal reaction is carried out for 1-3 h at 60-120 ℃, graphene dispersion liquid etched by O 3 is mixed with 3.50-8.00 wt% of nitrogen precursor, and the mixture is reacted for 2-6 h under the low-temperature thermal annealing condition 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 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-reinforced graphite nitrogen-doped graphene catalytic material is prepared by the method.
In a preferred embodiment of the present invention, a graphite nitrogen doped graphene material is included.
In a preferred embodiment of the present invention, the graphite nitrogen-doped structure comprises more than 95wt% of the total nitrogen-hybridized structure.
Compared with the background technology, the technical proposal has the following advantages:
(1) According to the preparation method, the ozone-reinforced graphene nitrogen-doped graphene catalytic material is prepared, O 3 is utilized to attack graphene to generate defects in the O 3 etching pretreatment process, a large number of oxygen groups are introduced to occupy edge sites of the graphene in the process, and nitrogen is induced 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 strong structure regulation and control capability, simple operation, low preparation energy consumption (low-temperature operation) and the like, the loading form of nitrogen is directionally regulated and controlled under proper reaction conditions, the doping proportion of graphite nitrogen with high catalytic activity is improved, and an important technical means is provided for the reaction mechanism research of improving the electrocatalytic performance and the micro-molecular structure of the hybrid material.
(2) The ozone-reinforced graphite nitrogen-doped graphene catalytic material has good electrocatalytic activity under normal temperature and normal pressure.
(3) The invention can improve the selectivity of directional regulation of the catalytic material, is beneficial to improving the performance of the catalytic material by taking a microstructure as an entry point, and has important significance in the aspects of deepening theoretical research and marketizing application and popularization of the hybrid graphene material.
Drawings
FIG. 1 is a transmission electron microscope image of an ozone-enhanced graphite nitrogen-doped graphene catalytic material of example 1;
FIG. 2 is an X-ray photoelectron spectroscopy analysis of the ozone enhanced graphite nitrogen doped graphene catalytic material of example 1;
FIG. 3 is a graph showing the efficiency of degradation of bisphenol A by ozone enhanced graphene nitrogen doped graphene catalytic materials and graphene catalyst materials in example 1 and comparative example;
Fig. 4 is a graph showing the degradation efficiency of antibiotic a by the ozone enhanced graphite nitrogen doped graphene catalytic material in example 1.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the present invention will be described in more detail 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-reinforced graphite nitrogen-doped graphene catalytic material specifically comprises the following steps:
(1) Weighing the following raw materials: 75-85 wt% of graphene oxide, and the balance of water;
(2) Preparing O 3 by utilizing an ozone generator, introducing graphene oxide and water, and performing hydrothermal reaction for 0.5-4 hours at the temperature of 40-150 ℃;
(3) Mixing the dispersion liquid obtained in the step (2) with 2.00-10.00 wt% of nitrogen precursor, and reacting for 1-8 hours under the low-temperature annealing condition of 40-200 ℃ to obtain the ozone-reinforced graphite nitrogen-doped graphene catalytic material, wherein the graphite nitrogen doped structure accounts for more than 95% of the total nitrogen hybridized structure.
The nitrogen precursor is urea or melamine.
In the design reaction process, O 3 etching pretreatment is utilized to form graphene structural defects and a large amount of oxygen group graphene edge site doping, and then nitrogen precursor addition is utilized to induce nitrogen to fill the graphene structural defects to form a central doped graphite nitrogen configuration.
Example 1
The preparation method of the ozone-reinforced graphite nitrogen-doped graphene catalytic material comprises the following steps of:
(1) Weighing the following raw materials: 80wt% of graphene oxide, and the balance of water to form a graphene oxide aqueous solution;
(2) Generating O 3 by using a 10KHz ozone generator, maintaining the ozone concentration to be 10mg/L in the graphene oxide aqueous solution in the step (1), performing hydrothermal reaction at 120 ℃ for 2 hours, and performing pretreatment to etch graphene to obtain graphene dispersion after O 3 etching;
(3) Mixing the dispersion liquid obtained in the step (2) with 5.00 weight percent of urea precursor, and reacting for 2 hours under the low-temperature annealing condition of 60 ℃ to obtain the ozone-reinforced graphite nitrogen-doped graphene catalytic material, wherein the graphite nitrogen doped structure accounts for more than 95 percent of the total nitrogen hybridized structure.
The microscopic morphology of the ozone-enhanced graphite nitrogen-doped graphene catalytic material is shown in fig. 1, and the analysis of the morphology of the doped nitrogen in the ozone-enhanced graphite nitrogen-doped graphene catalytic material is shown in fig. 2. As shown in fig. 1, the hybrid material has typical graphene characteristics-transparent sheets overlap each other and create significant wrinkles. The O 3 pretreatment and the introduction of nitrogen atoms are not used for changing the original basic morphology structure of the graphene. FIG. 2 is an N1s spectrum, with nitrogen doped configurations comprising graphite 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
The preparation method of the ozone-reinforced graphite nitrogen-doped graphene catalytic material comprises the following steps of:
(1) Weighing the following raw materials: 85wt% of graphene oxide, and the balance of water to form a graphene oxide aqueous solution;
(2) Generating O 3 by using a 5KHz ozone generator, maintaining the ozone concentration to be 15mg/L in the graphene oxide aqueous solution in the step (1), performing hydrothermal reaction at 100 ℃ for 3 hours, and performing pretreatment to etch graphene to obtain graphene dispersion after O 3 etching; (3) Mixing the dispersion liquid obtained in the step (2) with 8.00 weight percent of nitrogen precursor, and reacting for 2 hours under the low-temperature annealing condition of 120 ℃ to obtain the ozone-reinforced graphite nitrogen-doped graphene catalytic material, wherein the graphite nitrogen doped structure accounts for more than 95 percent of the total nitrogen hybridized structure.
Example 3
The preparation method of the ozone-reinforced graphite nitrogen-doped graphene catalytic material comprises the following steps of:
(1) Weighing the following raw materials: 75wt% of graphene oxide, and the balance of water to form a graphene oxide aqueous solution;
(2) Generating O 3 by using a 10KHz ozone generator, maintaining the ozone concentration to be 8mg/L in the graphene oxide aqueous solution in the step (1), performing hydrothermal reaction at 120 ℃ for 1h, and performing pretreatment to etch graphene to obtain graphene dispersion after O 3 etching;
(3) Mixing the dispersion liquid obtained in the step (2) with 5.50wt% of nitrogen precursor, and reacting for 3 hours under the low-temperature annealing condition at 120 ℃ to obtain the ozone-reinforced graphite nitrogen-doped graphene catalytic material, wherein the graphite nitrogen doped structure accounts for more than 95% of the total nitrogen hybridized structure.
Comparative example
The comparative example differs from the example in that: undoped graphene is employed.
The electrocatalytic activity test was performed on the ozone-enhanced graphite nitrogen doped graphene catalytic material prepared in this example 1:
electrocatalytically degraded bisphenol a (BPA) was tested using a potentiostat.
BPA is used as a target pollutant, and the material performance is judged according to the electrocatalytic oxidative degradation effect. Coating 4mg of aza-graphene on 2cm multiplied by 2cm carbon cloth by using conductive adhesive, and drying to obtain an anode; taking a copper sheet with the length of 8cm multiplied by 2cm as a cathode; the distance between the two is controlled to be 1cm, a constant potential current meter (Shanghai's day) of DJS-292B is used for adjusting the external current, 1g/L nitrogen aCl is used as electrolyte, 200mL of 10mg/L BPA solution is degraded in a 250mL beaker, and a magnetic stirrer is used for keeping the solution uniformly stirred in the whole process. The potentiostat switch was turned on and 1mL of water sample was taken over the set time period and added to a 2mL centrifuge tube that had been filled with 1mL of methanol quencher. The well mixed liquid was filtered for impurities using a 0.22 μm filter head, and the BPA content of the filtered liquid was measured using an high performance liquid chromatograph (wattsu, usa) of actty ARC.
Electrocatalytic activity tests were performed on the ozone-enhanced graphene-nitrogen-doped catalytic material of example 1, respectively obtaining an efficiency map of degradation of BPA by the ozone-enhanced graphene-nitrogen-doped catalytic material of fig. 3, and an efficiency map of degradation of antibiotics by the ozone-enhanced graphene-nitrogen-doped catalytic material of fig. 4. As can be seen from fig. 3, when the ozone-reinforced graphite nitrogen-doped graphene catalytic material is adopted, the degradation effect of BPA is obviously better than that of graphene. The degradation efficiency of the antibiotics paracetamol and tetracycline hydrochloride in FIG. 4 can reach 85-95%. Ozone reinforced graphite nitrogen doped graphene catalytic material remarkably improves the removal rate of BPA and antibiotics, and illustrates the important effect of graphite type nitrogen hybridization.
The above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some or all of the technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit of the invention.
Claims (9)
1. A preparation method of an ozone-reinforced graphite nitrogen-doped graphene catalytic material is characterized by comprising the following steps of: the method comprises the following steps:
1) After O 3 is generated, graphene oxide and water are introduced, wherein the graphene oxide accounts for 75-85 wt%, and the graphene oxide is subjected to hydrothermal reaction at 40-150 ℃ for 0.5-4 hours to obtain graphene dispersion liquid after O 3 etching;
2) Mixing the graphene dispersion liquid subjected to O 3 etching with a nitrogen precursor, wherein the nitrogen precursor accounts for 2.00-10.00 wt%, and reacting for 1-8 h under the low-temperature annealing condition of 40-200 ℃ under the protection of carrier gas to obtain an ozone-reinforced graphite nitrogen-doped graphene catalytic material; wherein the carrier gas is carbon monoxide or methane and the nitrogen precursor is urea or melamine.
2. The method for preparing the ozone-enhanced graphite nitrogen-doped graphene catalytic material according to claim 1, which is characterized in that: in the step 1), the graphene oxide accounts for 77-82 wt%.
3. The method for preparing the ozone-enhanced graphite nitrogen-doped graphene catalytic material according to claim 1, which is characterized in that: in the step 2), the nitrogen precursor accounts for 3.50-8.00 wt%.
4. The method for preparing the ozone-enhanced graphite nitrogen-doped graphene catalytic material according to claim 1, which is characterized in that: o 3 pretreatment etched graphene is generated by using a 5KHz-20KHz ozone generator.
5. The method for preparing the ozone-enhanced graphite nitrogen-doped graphene catalytic material according to claim 1, which is characterized in that: in the step 2), the concentration of ozone in the graphene oxide aqueous solution is maintained to be 5-25 mg/L.
6. The method for preparing the ozone-enhanced graphite nitrogen-doped graphene catalytic material according to claim 1, which is characterized in that: in the step 1), the hydrothermal reaction is carried out for 1-3 hours at the temperature of 60-120 ℃.
7. The method for preparing the ozone-enhanced graphite nitrogen-doped graphene catalytic material according to claim 1, which is characterized in that: in the step 2), the reaction is carried out for 2 to 6 hours under the low temperature thermal annealing condition of 50 to 120 ℃.
8. An ozone-reinforced graphite nitrogen-doped graphene catalytic material is characterized in that: the method of any one of claims 1-7.
9. The ozone enhanced graphite nitrogen doped graphene catalytic material according to claim 8, wherein: the graphite nitrogen doped structure accounts for more than 95% of the total nitrogen hybridized structure.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP3047905A1 (en) * | 2015-01-21 | 2016-07-27 | 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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| EP3247494B1 (en) * | 2015-01-21 | 2020-04-29 | Université de Strasbourg | Method for preparing highly nitrogen-doped mesoporous carbon composites |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP3047905A1 (en) * | 2015-01-21 | 2016-07-27 | 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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