CN107413367B - High-dispersion cobalt ferrite nanoparticle loaded oxa-carbon nitride and preparation method thereof - Google Patents
High-dispersion cobalt ferrite nanoparticle loaded oxa-carbon nitride and preparation method thereof Download PDFInfo
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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Abstract
The invention provides a high-dispersion cobalt ferrite nanoparticle loaded oxygen-nitrogen-oxide carbon and a preparation method thereof, which comprises the following steps: 1. calcining melamine for the first time, grinding the calcined product into powder, and then calcining for the second time to obtain carbon nitride powder; weighing the carbon nitride powder, dispersing the carbon nitride powder in a sulfuric acid/nitric acid mixed solution, and stirring for reaction; after the reaction is finished, washing the solid product to be neutral, and then freeze-drying the solid product to obtain the oxa-carbon nitride; 2. dispersing the oxa-carbon nitride in distilled water to obtain a suspension A, adding cobalt nitrate hexahydrate, ferric nitrate nonahydrate and glycine into the suspension A, ultrasonically mixing uniformly to obtain a mixed solution B, transferring the mixed solution B into an alumina crucible, calcining, and cooling to room temperature to obtain the high-dispersion cobalt ferrite nano particle loaded oxa-carbon nitride. The highly dispersed cobalt ferrite nano particle loaded oxa-carbon nitride prepared by the invention provides help for overcoming the aggregation condition of nano particles in the calcining process.
Description
Technical Field
The invention belongs to the field of electrochemical functional nano material preparation, and relates to a method for simply and effectively preparing high-dispersion cobalt ferrite nano particle loaded oxa-carbon nitride.
Background
Oxygen Evolution Reactions (OERs) are of particular interest as an important half-reaction for the electrolysis of water due to their clean, efficient nature. The catalyst plays a crucial role in the electrolysis of water and is also the main barrier for the current production of high performance, low cost technologies. The catalysts used for electrolytic water at present mainly comprise noble metals such as platinum, yttrium and rubidium, but the price is high, the abundance is low, and the large-scale use is limited. Therefore, the development of efficient, low-cost electrocatalysts plays a crucial role in the research of electrolyzed water.
In recent years, spinel-type Cobalt Ferrite (CFO) has received much attention due to its low cost, abundant content, environmental friendliness and excellent catalytic performance. High-temperature calcination is a common method for preparing cobalt ferrite nanoparticles, but during the high-temperature calcination, the inevitable aggregation and sintering of the nanoparticles can reduce active sites in the reaction, thereby seriously affecting the catalytic performance of the nanoparticles. In order to overcome this drawback, it is necessary to find a suitable method for improving the dispersibility of the nanoparticles.
Many studies have shown that the immobilization of nanoparticles on the surface of two-dimensional materials (2D) can effectively lead to their aggregation, thereby improving the catalytic performance of the material as a whole. The graphite type Carbon Nitride (CN) is widely applied to the fields of electrocatalysis, degradation, photocatalysis and the like due to the unique electronic structure, low cost and good stability. However, the poor conductivity and small specific surface area of graphite-type carbon nitride will limit its further application. In recent years, chemical doping has been extensively studied to improve the surface properties of carbon nitride and to improve its catalytic performance. Because of low cost, rich content and no toxicity, oxygen atoms are introduced into the carbon nitride as doping elements in large quantity, and the oxygen oxidation process is favorable for increasing the specific surface area of the carbon nitride, improving the conductivity and water solubility of the carbon nitride and improving the chemical property of the surface of the carbon nitride, thereby improving the catalytic performance of the carbon nitride. However, the oxa-nitrogenated carbon (OCN) is rarely applied to electrocatalysis due to the lack of necessary catalytic sites, and it is important to introduce nanoparticles on the surface of the oxa-nitrogenated carbon to increase the catalytic sites in order to expand the application of the oxa-nitrogenated carbon in the field of electrocatalysis.
Therefore, based on the preparation technology of the electrocatalytic functional nano material, the invention develops a method for simply preparing the high-dispersion cobalt ferrite nano particle loaded oxygen-doped nitrone, and the method is effectively applied to the oxygen evolution reaction.
Disclosure of Invention
The invention aims to provide a method which integrates the advantages of simple preparation process, simple operation and the like to synthesize the ultra-dispersed cobalt ferrite nanoparticle-loaded oxa-carbon nitride for the research of oxygen evolution reaction.
The invention is realized by the following technical scheme:
the high-dispersion cobalt ferrite nanoparticle-supported oxa-carbon nitride is formed by compounding a cobalt ferrite nanoparticle and an oxa-carbon nitride, wherein the cobalt ferrite nanoparticle is supported on the oxa-carbon nitride, and the average particle size of the cobalt ferrite nanoparticle is 2.5 nm.
A preparation method of high-dispersion cobalt ferrite nano-particle loaded oxa-carbon nitride comprises the following steps:
step 1, preparation of oxa-carbon nitride (OCN):
calcining melamine for the first time, grinding the calcined product into powder, and then calcining for the second time to obtain carbon nitride powder; weighing the carbon nitride powder, dispersing the carbon nitride powder in a sulfuric acid/nitric acid mixed solution, and stirring for reaction; after the reaction is finished, washing the solid product to be neutral, and then carrying out freeze drying on the solid product to obtain the oxa-carbon nitride which is marked as OCN;
step 2, preparing the high-dispersion cobalt ferrite nano particle loaded with oxygen-nitrogen oxide (CFO/OCN):
dispersing the oxa-carbon nitride obtained in the step 1 in distilled water to obtain a suspension A, adding cobalt nitrate hexahydrate, ferric nitrate nonahydrate and glycine into the suspension A, ultrasonically mixing uniformly to obtain a mixed solution B, transferring the mixed solution B into an alumina crucible, calcining, and cooling to room temperature to obtain the highly dispersed cobalt ferrite nano particle loaded oxa-carbon nitride, which is marked as CFO/OCN.
In the step 1, the temperature of the first calcination and the second calcination is both 500-600 ℃, and the calcination time is 4 h; the stirring reaction time is 4-6h, and the volume ratio of sulfuric acid to nitric acid in the sulfuric acid/nitric acid mixed solution is 1: 1.
In the step 2, the dosage ratio of the oxa-carbon nitride, the distilled water, the cobalt nitrate hexahydrate, the ferric nitrate nonahydrate and the glycine is 5-60 mg: 4-5 mL: 20-30 mg: 40-60 mg: 80-100 mg.
Preferably, in the step 2, the mass ratio of the cobalt nitrate hexahydrate to the ferric nitrate nonahydrate is 1: 2.
In the step 2, the calcining temperature is 500-600 ℃, the calcining time is 2-4h, the calcining environment is an argon environment, and the heating rate is 2-5 ℃/min.
The invention has the beneficial effects that:
(1) the invention adopts a high-temperature calcination method to prepare the high-dispersion cobalt ferrite nano particle loaded oxa-carbon nitride, and provides help for overcoming the aggregation condition of nano particles in the calcination process;
(2) the composite material prepared by the method is a non-noble metal material, so that the cost is effectively reduced, and meanwhile, the specific surface area and the conductivity of the nano particles are improved due to the good dispersibility and particle size of the nano particles, so that the performance of the nano particles in an oxygen evolution reaction is better improved.
Drawings
FIG. 1A is a transmission electron microscope image of CFO nanoparticles, B and C are transmission electron microscope images of CFO/OCN composite materials, and D is a high-power transmission electron microscope image of CFO/OCN composite materials;
FIG. 2 is an X-ray diffraction pattern of the CFO/OCN composite material and the CFO nanoparticles;
FIG. 3 is an X-ray photoelectron spectrum of a CFO/OCN composite;
FIG. 4A is a linear sweep voltammogram of CFO/OCN with different OCN contents, B is a comparison graph of linear sweep voltammograms of different materials, C is a comparison graph of Tafel curves of different materials, and D is a comparison graph of impedances of different materials;
fig. 5A is a linear sweep voltammogram obtained before cyclic voltammetry and after 1000 cycles of cyclic voltammetry for different materials, and B is a linear sweep voltammogram obtained before cyclic voltammetry and after 1000 cycles of cyclic voltammetry for CFO/OCN composite and 20% Pt/C.
Detailed Description
The present invention will be further described with reference to the following examples.
Example 1:
preparation of Oxazindon (OCN)
(1) Weighing 2g of melamine, adding the melamine into a crucible, calcining for 4h at the temperature of 500-600 ℃, taking out, grinding the product into powder, and continuously calcining for 4h at the temperature to obtain carbon nitride powder. Then, 0.1g of carbon nitride powder is weighed, the adding amount of sulfuric acid and nitric acid is added into the system according to the volume ratio of 1:1, stirring is carried out for 4-6h, then the obtained suspension is subjected to centrifugal treatment, and the suspension is washed with distilled water for multiple times until the suspension is neutral. And finally, carrying out freeze drying treatment to obtain the final product of the oxa-carbon nitride.
Example 2:
preparing the ultra-dispersed cobalt ferrite nanoparticle-loaded oxa-carbon nitride (CFO/OCN) by a high-temperature calcination method:
(2) dispersing oxa-carbon nitride in a certain amount of distilled water, carrying out ultrasonic treatment to obtain a suspension A, then adding 20-30mg of cobalt nitrate hexahydrate and 40-60mg of ferric nitrate nonahydrate into the suspension A according to the mass ratio of 1:2, then adding 80-100mg of glycine, carrying out ultrasonic treatment to obtain a suspension B, finally adding the suspension B into an alumina crucible, carrying out high-temperature calcination, and cooling to room temperature to obtain the CFO/OCN composite material.
Example 3:
optimization of content of oxa-carbon nitride in CFO/OCN composite material
(3) Adding different masses of oxa-carbon nitride (5mg, 10mg, 20mg, 40mg, 60mg) into a certain amount of distilled water, and performing the operation according to the step (2) to obtain CFO/OCN composite materials with different contents of the oxa-carbon nitride.
Example 4:
modification of glassy carbon electrodes
(4) Pretreating the surface of a glassy carbon electrode: before use, glassy carbon electrodes (GCE, phi 3.0mm) were first sanded with metallographic abrasive paper and then coated with 1.0 μm, 0.3 μm Al, respectively2O3Polishing the polishing powder on polishing cloth, washing with secondary water, ultrasonically cleaning in 0.1mol/L HCl, 0.1mol/L NaOH and absolute ethyl alcohol for one minute, ultrasonically cleaning with secondary water for one minute, and air drying at room temperature for later use.
(5) Modification of glassy carbon electrode: weighing 2mg of catalyst, adding 1mL of mixed solution of distilled water and absolute ethyl alcohol, wherein the volume ratio of distilled water to absolute ethyl alcohol is 1:1, then adding 30 mu L of naphthol, carrying out ultrasonic treatment for at least one hour to obtain uniform suspension, finally transferring 5 mu L of suspension by using a liquid transfer gun, dripping on the surface of the glassy carbon electrode in the step (4), and airing at room temperature.
Example 5:
electrocatalytic performance test
The electrolyte used in the test was a 1mol/L KOH solution which had to be aerated with high purity oxygen before the test, wherein the aeration time was half an hour, and furthermore, the tests were all carried out with aeration of oxygen afterwards. Then, specific electrocatalytic performance tests are as follows:
(6) testing of Linear Sweep Voltammograms (LSVs): and (3) inserting the glassy carbon electrode prepared in the step (5) into a 1mol/L KOH solution to serve as a working electrode, and respectively using a saturated calomel electrode and a platinum wire electrode as a reference electrode and a counter electrode to form a three-electrode system. Before testing, cyclic voltammetry curve testing is required, and after a signal is stable, linear sweep voltammetry curve is carried out. Wherein, the voltage range of scanning is 0-0.8V, and the scanning speed is 5 mV/s.
(7) Testing of electrochemical impedance: and (3) inserting the glassy carbon electrode prepared in the step (5) into a 1mol/L KOH solution to serve as a working electrode, and respectively using a saturated calomel electrode and a platinum wire electrode as a reference electrode and a counter electrode to form a three-electrode system. Before the test, a cyclic voltammetry curve test is required, and after a signal is stable, the electrochemical impedance of the catalyst in a solution is tested. Wherein the set voltage is 0.66V, the frequency range is 0.01Hz to 10kHz, and the alternating voltage is 10 mV.
(8) Electrochemical stability test: and (3) inserting the glassy carbon electrode prepared in the step (5) into a 1mol/L KOH solution to serve as a working electrode, and respectively using a saturated calomel electrode and a platinum wire electrode as a reference electrode and a counter electrode to form a three-electrode system. And then carrying out linear sweep voltammetry to obtain a corresponding linear sweep voltammetry atlas, then carrying out cyclic voltammetry testing on the electrode, wherein the number of sweep cycles is 1000, and then carrying out linear sweep voltammetry testing, and comparing the testing results of the front group and the rear group to obtain the stability condition in the corresponding electrocatalysis process. Wherein the voltage range of the cyclic voltammetry curve test is 0-0.8V, and the sweep rate is 100 mV/s.
FIG. 1A is a transmission electron microscope image of CFO nanoparticles, B and C are transmission electron microscope images of CFO/OCN composite materials, and D is a high-power transmission electron microscope image of CFO/OCN composite materials. As can be seen from the figure, the pure CFO nanoparticles are obviously agglomerated together in the high-temperature calcination process, and have a larger average particle size of 4.78nm, and after the CFO nanoparticles are doped into the OCN, the CFO nanoparticles are uniformly dispersed on the surface of the OCN and have a smaller average particle size of 2.5nm, so that the agglomeration of the CFO nanoparticles in the high-temperature calcination process can be well prevented by the doping of the OCN. Graph D illustrates that the (220) crystal plane of the CFO plays a major role in the catalytic process.
FIG. 2 is an X-ray diffraction pattern of the CFO/OCN composite material and the CFO nanoparticles. It can be seen from the figure that the CFO/OCN composite material has a good crystal form, and no other impurities are generated.
FIG. 3 is an X-ray photoelectron spectrum of the CFO/OCN composite material. The CFO/OCN composite material contains five elements of C, N, O, Fe and Co, and the successful preparation of the composite is proved.
FIG. 4A is a linear sweep voltammogram of CFO/OCN with different OCN contents, B is a comparison graph of linear sweep voltammograms of different materials, C is a comparison graph of Tafel curves of different materials, and D is a comparison graph of impedances of different materials. It can be seen from FIG. A that the electrocatalytic performance of the CFO/OCN composite material is the best when the added OCN mass is 40 mg; as can be seen from the graph B, the pure OCN has almost no electrocatalytic performance, while the pure CFO nano-particle has poor electrocatalytic performance, when the CN is doped, the electrocatalytic performance of the obtained CFO/CN composite material is improved, and further, when the OCN is doped, the current density of the obtained CFO/OCN composite material reaches 10mA/cm2Compared with the potential of the CFO/CN composite material, the potential is reduced by 61mV, which shows that the synergistic effect of the CFO nano particles and the CN is well improved by the doping of oxygen atoms; it can be seen in fig. C that the CFO/OCN composite material has the smallest Tafel slope, indicating that the material has the fastest catalytic rate during electrocatalysis; in the graph D, it can be seen that the CFO/OCN composite material has the smallest impedance, which indicates that the material has better electrical conductivity, the fastest catalytic rate in the catalytic process, and the best catalytic performance.
Fig. 5A is a linear sweep voltammogram obtained before cyclic voltammetry and after 1000 cycles of cyclic voltammetry for different materials, and B is a linear sweep voltammogram obtained before cyclic voltammetry and after 1000 cycles of cyclic voltammetry for CFO/OCN composite and 20% Pt/C. As can be seen from the figure, compared with other materials, the performance of the CFO/OCN composite material is not greatly attenuated after 1000 cycles of cyclic voltammetry curve scanning, which indicates that the material has better long-term stability.
Claims (4)
1. A method for preparing high-dispersion cobalt ferrite nanoparticle-supported oxa-nitrogenated carbon for oxygen evolution reaction, which is characterized in that the high-dispersion cobalt ferrite nanoparticle-supported oxa-nitrogenated carbon is formed by compounding cobalt ferrite nanoparticles and oxa-nitrogenated carbon, the cobalt ferrite nanoparticles are supported on the oxa-nitrogenated carbon, the average particle size of the cobalt ferrite nanoparticles is 2.5nm, and the method for preparing the cobalt ferrite nanoparticle-supported oxa-nitrogenated carbon comprises the following steps:
step 1, preparation of oxa-carbon nitride:
calcining melamine for the first time, grinding the calcined product into powder, and then calcining for the second time to obtain carbon nitride powder; weighing the carbon nitride powder, dispersing the carbon nitride powder in a sulfuric acid/nitric acid mixed solution, and stirring for reaction; after the reaction is finished, washing the solid product to be neutral, and then freeze-drying the solid product to obtain the oxa-carbon nitride;
step 2, preparing the high-dispersion cobalt ferrite nano particle loaded with the oxygen-nitrogen oxide carbon:
dispersing the oxa-carbon nitride obtained in the step 1 in distilled water to obtain a suspension A, adding cobalt nitrate hexahydrate, ferric nitrate nonahydrate and glycine into the suspension A, ultrasonically mixing uniformly to obtain a mixed solution B, transferring the mixed solution B into an alumina crucible, calcining, and cooling to room temperature to obtain high-dispersion cobalt ferrite nano particle loaded oxa-carbon nitride; the dosage ratio of the oxa-carbon nitride, the distilled water, the cobalt nitrate hexahydrate, the ferric nitrate nonahydrate and the glycine is 5-60 mg: 4-5 mL: 20-30 mg: 40-60 mg: 80-100mg, wherein the mass ratio of the cobalt nitrate hexahydrate to the ferric nitrate nonahydrate is 1: 2.
2. A preparation method of high-dispersion cobalt ferrite nano particle loaded oxygen-nitrogen nitride for oxygen evolution reaction is characterized by comprising the following steps:
step 1, preparation of oxa-carbon nitride:
calcining melamine for the first time, grinding the calcined product into powder, and then calcining for the second time to obtain carbon nitride powder; weighing the carbon nitride powder, dispersing the carbon nitride powder in a sulfuric acid/nitric acid mixed solution, and stirring for reaction; after the reaction is finished, washing the solid product to be neutral, and then freeze-drying the solid product to obtain the oxa-carbon nitride;
step 2, preparing the high-dispersion cobalt ferrite nano particle loaded with the oxygen-nitrogen oxide carbon:
dispersing the oxa-carbon nitride obtained in the step 1 in distilled water to obtain a suspension A, adding cobalt nitrate hexahydrate, ferric nitrate nonahydrate and glycine into the suspension A, ultrasonically mixing uniformly to obtain a mixed solution B, transferring the mixed solution B into an alumina crucible, calcining, and cooling to room temperature to obtain high-dispersion cobalt ferrite nano particle loaded oxa-carbon nitride; the dosage ratio of the oxa-carbon nitride, the distilled water, the cobalt nitrate hexahydrate, the ferric nitrate nonahydrate and the glycine is 5-60 mg: 4-5 mL: 20-30 mg: 40-60 mg: 80-100mg, wherein the mass ratio of the cobalt nitrate hexahydrate to the ferric nitrate nonahydrate is 1: 2.
3. The method for preparing high-dispersion cobalt ferrite nanoparticle-supported oxa-carbonitride for use in oxygen evolution reaction as claimed in claim 2, wherein in step 1, the temperature of the first calcination and the second calcination are both 500-600 ℃, and the calcination time is 4 h; the stirring reaction time is 4-6h, and the volume ratio of sulfuric acid to nitric acid in the sulfuric acid/nitric acid mixed solution is 1: 1.
4. The method for preparing high-dispersion cobalt ferrite nanoparticle-supported oxa-carbonitride for use in oxygen evolution reaction as claimed in claim 2, wherein in step 2, the calcination temperature is 500-600 ℃, the calcination time is 2-4h, the calcination environment is argon environment, and the temperature rise rate is 2-5 ℃/min.
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