CN111193042A - Nitrogen-doped graphene @ copper-iron ball composite material and preparation method and application thereof - Google Patents
Nitrogen-doped graphene @ copper-iron ball composite material and preparation method and application thereof Download PDFInfo
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Abstract
The invention provides a nitrogen-doped graphene @ copper-iron ball composite material and a preparation method and application thereof. Compared with the traditional preparation method, the method disclosed by the invention is simple, rapid and environment-friendly, the reaction condition is mild, the yield is high, the prepared composite material is uniform in appearance, high in nitrogen doping amount and uniform in doping, and the prepared composite material has excellent electro-catalytic performance on hydrogen evolution reaction.
Description
Technical Field
The invention relates to a nitrogen-doped graphene composite material, a preparation method and application thereof, and particularly relates to a nitrogen-doped graphene @ copper-iron ball composite material and a preparation method and application thereof.
Background
Hydrogen is a clean energy with high heat value and no pollution, and has a very important position in the energy field. However, in nature, hydrogen in the molecular state does not exist. At present, molecular hydrogen is generally produced by water decomposition reaction (H)2O→H2+O2) Among them, the electrochemical decomposition of water is one of important hydrogen production methods because of its advantages such as high hydrogen production efficiency and easy industrialization. The electrochemical decomposition of water is divided into two half-reactions, respectively hydrogen evolution reaction (HER, 2H)++2e→H2) And oxygen evolution reaction (OER, H)2O→2H++2e+O2). However, the electrochemical water decomposition reaction rate is slow and a high overpotential is required, and therefore, the development of a novel hydrogen evolution reaction electrocatalyst to accelerate the water decomposition reaction rate and reduce the reaction overpotential is an urgent problem to be solved.
For hydrogen evolution reactions, the most effective electrocatalyst at present is the platinum-based catalyst, since its catalytic onset overpotential is close to zero, close to the thermodynamic potential. However, platinum resources are scarce and expensive, which limits the large-scale commercial application of platinum-based electrocatalysts. Therefore, the development of a low-cost, efficient and stable hydrogen evolution reaction electrocatalyst is a bottleneck problem to be solved at present. Recently, some transition metal catalysts, such as Ni2P、FeP、CoP、Cu3P and InP, which have been prepared, have high HER catalytic activity and low cost, but the preparation process is complicated and requires severe experimental conditions. For some time, nickel-based alloy materials have been commercially used as hydrogen evolution catalysts in alkaline electrolytes. However, these catalysts do not work under the strongly acidic conditions found in proton exchange membrane technology and do not participate in proton exchange membrane based electrolysis processes.
In order to further reduce the preparation cost and improve the electrocatalytic performance of the catalyst, the nitrogen-doped carbon nanomaterial-supported non-noble metal catalyst gradually becomes a hot point of research. Liu et al have reported a method for preparing three-dimensional graphene loaded CeO2The hollow microsphere method is used for electrocatalytic research of hydrogen evolution reaction, and the gradient of the tafel is 112.8 mv/dec; displaying (Chen)Preparation of graphene-loaded nanoporous Ni and MoS by et al2As an effective catalyst for hydrogen evolution reaction, the gradient of the column fiell is 71.3 mv/dec. The composite material obtained by combining the nitrogen-doped carbon nano tube loaded FeNi alloy nano particles with the subject can be used for catalyzing hydrogen evolution reaction and presents better stability; also, a subject group prepares the nitrogen-doped graphene nanotube-metal hybrid material by calcining Co-MOF or Fe-MOF and dinitramide, and presents higher hydrogen evolution catalytic performance. However, the above materials have low nitrogen doping amount (the atomic ratio of nitrogen element is less than 2), uneven doping, and complicated preparation method, which is not convenient for popularization and application.
Disclosure of Invention
The invention aims to provide a preparation method of a nitrogen-doped graphene @ copper-iron ball composite material, and aims to solve the problems of complicated steps, low nitrogen doping amount and uneven doping of the existing preparation method.
The purpose of the invention is realized as follows:
a preparation method of a nitrogen-doped graphene @ copper-iron ball composite material comprises the following steps:
(1) preparing a graphene oxide turbid liquid, adding a nitrogen source and an initiator into the turbid liquid, stirring until the reaction is finished, and centrifugally separating, washing and drying the obtained product to obtain a graphene oxide @ nitrogen source polymer;
(2) preparing a potassium ferricyanide solution and a copper chloride solution, adding the copper chloride solution into the potassium ferricyanide solution, stirring, and performing ultrasonic treatment to obtain a mixed solution; placing the mixed solution in a dark environment for aging until precipitates are generated, and performing centrifugal separation, washing and drying on the obtained product to obtain a metal organic framework complex;
(3) dispersing the graphene oxide @ nitrogen source polymer obtained in the step (1) in water, adding the metal organic framework complex obtained in the step (2), stirring until the reaction is finished, and performing centrifugal separation, washing and drying on the obtained product to obtain precursor powder;
(4) and heating the precursor powder to 800-1000 ℃ in an inert atmosphere for carbonization, and preserving heat for 1-2h to obtain the nitrogen-doped graphene @ copper-iron ball composite material.
In the step (1), the nitrogen source is pyrrole, the initiator is sodium persulfate, or the nitrogen source is dopamine; the reaction time is 24-25h, the centrifugal rate is 4000r/min, the drying temperature is 45-60 ℃, and the drying time is 12-14 h.
In the step (2), the ultrasonic treatment time is 30-40min, the ultrasonic power is 350W, the temperature is room temperature, the aging time is 6-7h, the centrifugal rate is 9000r/min, the drying temperature is 45-60 ℃, and the drying time is 12-14 h.
In the step (3), the reaction time is 5-6h, the centrifugation speed is 5000r/min, the drying temperature is 45-60 ℃, and the drying time is 12-14 h.
In the step (4), the inert atmosphere is nitrogen atmosphere, and the heating rate is 5 ℃/min.
According to the invention, a complex is formed through a coordination reaction of potassium ferricyanide and copper chloride, the complex is loaded on a graphene oxide substrate through interaction of the complex and polypyrrole, and conversion of three substances is realized through one-step calcination, namely, graphene oxide is reduced to graphene, polypyrrole is converted to nitrogen, and the complex is calcined to copper-iron alloy balls, so that the high-content uniform nitrogen-doped graphene @ copper-iron ball composite material is finally obtained.
Compared with the prior art, the synthesis method disclosed by the invention is simple, rapid, environment-friendly, high in yield and mild in reaction, and especially the first three steps of operation can be completed only under a normal temperature condition. The nitrogen-doped graphene @ copper-iron ball composite material prepared by the method has the advantages of uniform appearance, high nitrogen doping amount, uniform doping, excellent electro-catalytic performance on hydrogen evolution reaction, lower initial potential, higher current density and smaller Tafel slope, and provides a new choice for research in related fields of energy storage, conversion, fuel cells and the like as a catalyst.
The invention also provides an application method of the obtained nitrogen-doped graphene @ copper-iron ball composite material, the nitrogen-doped graphene @ copper-iron ball composite material is dispersed into a dispersing agent to obtain a dispersion liquid, the dispersion liquid is dropwise coated on the surface of a glassy carbon electrode, and the glassy carbon electrode is dried to be used for hydrogen evolution reaction, wherein the dispersing agent is N' N-dimethylformamide.
Drawings
Fig. 1 is a schematic diagram of a preparation process of the nitrogen-doped graphene @ copper-iron ball composite material.
FIG. 2 is a transmission electron microscope image, wherein the images (A) and (B) are respectively the transmission electron microscope images of the non-carbonized copper-iron alloy spheres at 500nm and 200nm, the image (C) is the transmission electron microscope image of the carbonized copper-iron alloy spheres, and the images (D), (E) and (F) are respectively the transmission electron microscope images of the nitrogen-doped graphene @ copper-iron sphere composite material prepared in example 1 at 1 μm, 200nm and 10 nm.
Fig. 3 is an element scan image of the nitrogen-doped graphene @ copper iron ball composite prepared in example 1, wherein (a) is a C element scan image, (B) is an N element scan image, (C) is an O element scan image, (D) is an Fe element scan image, and (E) is a Cu element scan image.
Fig. 4 is an energy spectrum image of the nitrogen-doped graphene @ copper-iron ball composite material prepared in example 1.
Fig. 5 is an X-ray photoelectron spectrum of the nitrogen-doped graphene @ copper-iron sphere composite material prepared in example 1.
Fig. 6 is an X-ray diffraction pattern of the nitrogen-doped graphene @ copper-iron sphere composite material prepared in example 1, wherein (a) represents the nitrogen-doped graphene @ copper-iron sphere composite material prepared in example 1, (b) represents a copper-iron carbide alloy, (c) represents an non-copper-iron carbide alloy, and (d) represents Graphene Oxide (GO).
Fig. 7 is a linear sweep voltammetry polarization plot, wherein (a) represents the nitrogen-doped graphene @ copper-iron sphere composite prepared in example 1, (b) represents a copper-iron carbide alloy, (C) represents an uncarbonized copper-iron alloy, (d) represents Graphene Oxide (GO), (e) represents Pt/C.
Fig. 8 is a tafel plot corresponding to fig. 7.
Detailed Description
The present invention is further illustrated by the following examples in which the procedures and methods not described in detail are conventional and well known in the art, and the starting materials or reagents used in the examples are commercially available, unless otherwise specified, and are commercially available.
Example 1
(1) Preparation of graphene oxide @ polypyrrole compound
Dissolving 40mg of graphene oxide in 80mL of deionized water, stirring for 1min, and carrying out ultrasonic treatment for 10min (the power of an ultrasonic machine is 350W) to fully disperse the graphene oxide to obtain a black suspension;
120mg (NH)4)2S2O8And adding the mixture and 120 mu L of pyrrole into the black suspension, stirring for 24h, performing high-speed centrifugal separation (4000 r/min) on the obtained product, performing centrifugal washing with deionized water for three times, and performing vacuum drying at 45 ℃ for 12h to obtain the graphene oxide @ polypyrrole composite.
(2) Preparation of metal organic framework complexes
500 mg of K3Fe(CN)6Dissolving the mixture in 500 mL of deionized water to form a solution A, wherein the solution A is light yellow; 209.3mg of CuCl2And 1mL of concentrated hydrochloric acid (37 wt%) in 400 mL of deionized water to form solution B, which is a light green transparent liquid; then adding the solution B into the solution A, stirring for 5min, performing ultrasonic treatment at room temperature for 30min (the power of an ultrasonic machine is 350W), and changing the color of the mixed solution into light orange; aging the mixed solution in dark for 6h to generate precipitate; and (3) centrifugally separating the obtained product at a high speed (9000 r/min), centrifugally washing the product with deionized water for three times, and then drying the product in vacuum at the temperature of 45 ℃ for 12 hours to obtain the copper-iron alloy ball metal organic framework complex.
(3) Preparation of the precursor
And (2) dispersing the graphene oxide @ polypyrrole compound obtained in the step (1) in 10mL of deionized water, adding the copper-iron alloy ball obtained in the step (2), stirring for 5h (black suspension at this time), performing high-speed centrifugal separation (5000 r/min) on the obtained product, performing centrifugal washing three times with deionized water, and performing vacuum drying at 45 ℃ for 12h to obtain dry precursor powder.
(4) Preparation of nitrogen-doped graphene @ copper-iron ball composite material
And heating the precursor powder to 800 ℃ at a heating rate of 5 ℃/min in a nitrogen atmosphere for carbonization, and keeping the temperature for 1h to obtain the high-content uniform nitrogen-doped graphene @ copper-iron ball composite material.
The preparation process of the invention is schematically shown in figure 1.
The resulting material was subjected to structural characterization, the results of which are shown in FIGS. 2-6.
Fig. 2 shows transmission electron microscope images of non-carbonized copper-iron alloy spheres, and the nitrogen-doped graphene @ copper-iron sphere composite material prepared in this example. As can be seen from the figure, the copper-iron spheres after non-carbonization and carbonization are in a uniform cubic shape, while the copper-iron spheres loaded on the nitrogen-doped graphene are uniformly dispersed, uniform in shape and high in yield.
Fig. 3 and 4 are element scanning images and energy spectrum images of the nitrogen-doped graphene @ copper-iron ball composite material prepared in the embodiment. As can be seen from the figure, the nitrogen-doped graphene @ copper-iron ball composite material prepared in this example is composed of C, O, N, Cu and Fe elements, and each element exists uniformly.
Fig. 5 and 6 are an X-ray photoelectron spectrum and an X-ray diffraction spectrum of the nitrogen-doped graphene @ copper-iron sphere composite material prepared in this example, and also show the presence of C, O, N, Cu and Fe element. Moreover, the atomic ratio of the N element is 2.92 given by X-ray photoelectron spectroscopy data, which shows that the nitrogen doping amount of the material prepared by the embodiment is obviously higher than that of the prior art.
Hydrogen evolution reaction electrocatalysis performance test
The nitrogen-doped graphene @ copper-iron ball prepared in the embodiment 1 is applied to hydrogen evolution reaction electrocatalysis, and compared with non-carbonized copper-iron balls, carbonized copper-iron balls and graphene oxide materials in electrocatalysis performance, the method specifically comprises the following steps:
1) a three-electrode test system (Autolab 302N electrochemical workstation) is adopted, silver/silver chloride is used as a reference electrode, a platinum wire is used as a counter electrode, the prepared material modified glassy carbon electrode is used as a working electrode, and the solution is 0.5 mol/L sulfuric acid solution.
2) 1mg of the prepared material was dispersed in 1mL of N' N-dimethylformamide solution to a concentration of 1mg/mL, and 5 μ L of the dispersion was sucked and dropped on the surface of a glassy carbon electrode, and dried under an infrared lamp (150W).
3) And placing the three electrodes in an electrolytic cell, soaking the three electrodes in a sulfuric acid solution, selecting an electrochemical method, setting parameters, and performing hydrogen evolution reaction electrochemical test.
The test results are shown in fig. 7-8, which show that the nitrogen-doped graphene @ cupro spheres have higher electrocatalytic performance for hydrogen evolution reaction, and show lower initial potential, higher current density and smaller tafel slope (67.0 mv/dec) compared to non-carbonized cupro alloy spheres, and graphene oxide.
Comparative example 1
The nitrogen-doped graphene @ iron-manganese sphere composite material prepared by the method in example 1 is not precipitated after aging in step (2) for 6 hours, which indicates that iron-manganese alloy is not formed, so that the experiment cannot be continued, and the target product cannot be obtained.
Comparative example 2
The nitrogen-doped graphene @ iron-chromium sphere composite material prepared by the method in example 1 is precipitated after aging in the step (2) for 6 hours, but the obtained material has poor electrocatalytic performance when used for hydrogen evolution reaction electrocatalysts due to irregular appearance and nonuniform size.
Comparative example 3
The nitrogen-doped graphene @ iron-cobalt sphere composite material prepared by the method in example 1 is precipitated after aging in the step (2) for 6 hours, but the obtained material has poor electrocatalytic performance when used for a hydrogen evolution reaction electrocatalyst due to irregular morphology and non-uniform size.
Comparative example 4
The nitrogen-doped graphene @ iron-nickel ball composite material prepared by the method in example 1 is precipitated after aging in the step (2) for 6 hours, but the obtained material has poor electrocatalytic performance when used for hydrogen evolution reaction electrocatalysts due to irregular appearance and nonuniform size.
Claims (9)
1. A preparation method of a nitrogen-doped graphene @ copper-iron ball composite material is characterized by comprising the following steps:
(1) preparing a graphene oxide turbid liquid, adding a nitrogen source and an initiator into the turbid liquid, stirring until the reaction is finished, and centrifugally separating, washing and drying the obtained product to obtain a graphene oxide @ nitrogen source polymer;
(2) preparing a potassium ferricyanide solution and a copper chloride solution, adding the copper chloride solution into the potassium ferricyanide solution, stirring, and performing ultrasonic treatment to obtain a mixed solution; placing the mixed solution in a dark environment for aging until precipitates are generated, and performing centrifugal separation, washing and drying on the obtained product to obtain a metal organic framework complex;
(3) dispersing the graphene oxide @ nitrogen source polymer obtained in the step (1) in water, adding the metal organic framework complex obtained in the step (2), stirring until the reaction is finished, and performing centrifugal separation, washing and drying on the obtained product to obtain precursor powder;
(4) and heating the precursor powder to 800-1000 ℃ in an inert atmosphere for carbonization, and preserving heat for 1-2h to obtain the nitrogen-doped graphene @ copper-iron ball composite material.
2. The preparation method of the nitrogen-doped graphene @ copper-iron sphere composite material according to claim 1, wherein in the step (1), the nitrogen source is pyrrole, the initiator is sodium persulfate, or the nitrogen source is dopamine; the reaction time is 24-25h, the drying temperature is 45-60 ℃, and the drying time is 12-14 h.
3. The preparation method of the nitrogen-doped graphene @ copper-iron sphere composite material as claimed in claim 1, wherein in the step (2), the ultrasonic treatment time is 30-40min, the aging time is 6-7h, the drying temperature is 45-60 ℃, and the drying time is 12-14 h.
4. The preparation method of the nitrogen-doped graphene @ copper-iron sphere composite material as claimed in claim 1, wherein in the step (3), the reaction time is 5-6 hours, the drying temperature is 45-60 ℃, and the drying time is 12-14 hours.
5. The preparation method of the nitrogen-doped graphene @ copper-iron ball composite material according to claim 1, wherein in the step (4), the inert atmosphere is a nitrogen atmosphere, and the heating rate is 5 ℃/min.
6. The nitrogen-doped graphene @ copper-iron sphere composite material prepared according to any one of claims 1 to 5.
7. The application of the nitrogen-doped graphene @ copper-iron ball composite material prepared according to any one of claims 1 to 5 as a catalyst in a hydrogen evolution reaction.
8. Use according to claim 7, characterized in that it comprises the following steps: and dispersing the nitrogen-doped graphene @ copper-iron ball composite material into a dispersing agent to obtain a dispersion liquid, dripping the dispersion liquid on the surface of a glassy carbon electrode, and drying.
9. Use according to claim 8, characterized in that the dispersant is N' N-dimethylformamide.
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Cited By (2)
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| CN111710877A (en) * | 2020-07-13 | 2020-09-25 | 广西师范大学 | N-F co-doped graphene Cu single-atom Pt-loaded catalyst and preparation method and application thereof |
| CN113422070A (en) * | 2021-06-18 | 2021-09-21 | 福州大学 | Preparation method of iron-based dopamine supramolecular modification-based copper hydroxide two-dimensional nanocomposite |
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