CN110433839B - Preparation method of cobalt carbon nitrogen material loaded with cerium dioxide - Google Patents
Preparation method of cobalt carbon nitrogen material loaded with cerium dioxide Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 79
- WBVDQFAPFUMTFF-UHFFFAOYSA-N [C].[N].[Co] Chemical compound [C].[N].[Co] WBVDQFAPFUMTFF-UHFFFAOYSA-N 0.000 title claims abstract description 58
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011259 mixed solution Substances 0.000 claims abstract description 32
- 239000007787 solid Substances 0.000 claims abstract description 30
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 24
- 238000001291 vacuum drying Methods 0.000 claims abstract description 23
- 238000005406 washing Methods 0.000 claims abstract description 22
- 238000001816 cooling Methods 0.000 claims abstract description 15
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims abstract description 13
- 235000011114 ammonium hydroxide Nutrition 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 12
- 239000012621 metal-organic framework Substances 0.000 claims abstract description 11
- QQZMWMKOWKGPQY-UHFFFAOYSA-N cerium(3+);trinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ce+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O QQZMWMKOWKGPQY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 42
- 239000000243 solution Substances 0.000 claims description 35
- LXBGSDVWAMZHDD-UHFFFAOYSA-N 2-methyl-1h-imidazole Chemical compound CC1=NC=CN1 LXBGSDVWAMZHDD-UHFFFAOYSA-N 0.000 claims description 27
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 16
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 16
- 238000002156 mixing Methods 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 229910017052 cobalt Inorganic materials 0.000 claims description 8
- 239000010941 cobalt Substances 0.000 claims description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 8
- 239000012153 distilled water Substances 0.000 claims description 7
- 238000000034 method Methods 0.000 claims description 7
- 229910052573 porcelain Inorganic materials 0.000 claims description 7
- 229910000420 cerium oxide Inorganic materials 0.000 claims description 3
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 claims description 3
- 239000012300 argon atmosphere Substances 0.000 claims description 2
- 229940044927 ceric oxide Drugs 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 229910052684 Cerium Inorganic materials 0.000 abstract description 6
- -1 cerium ions Chemical class 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 230000005540 biological transmission Effects 0.000 abstract description 3
- 229910001429 cobalt ion Inorganic materials 0.000 abstract description 3
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 abstract description 3
- 150000002500 ions Chemical class 0.000 abstract description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 10
- 239000001257 hydrogen Substances 0.000 description 6
- 229910052739 hydrogen Inorganic materials 0.000 description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 5
- 229910052786 argon Inorganic materials 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000005868 electrolysis reaction Methods 0.000 description 2
- 230000002349 favourable effect Effects 0.000 description 2
- 238000004502 linear sweep voltammetry Methods 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 230000004075 alteration Effects 0.000 description 1
- 150000001721 carbon Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- GWXLDORMOJMVQZ-UHFFFAOYSA-N cerium Chemical compound [Ce] GWXLDORMOJMVQZ-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000005087 graphitization Methods 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000007769 metal material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000000737 periodic effect Effects 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
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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
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
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- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses a preparation method of a cobalt carbon nitrogen material loaded with cerium dioxide, which comprises the following steps: (1) preparing a metal organic framework material ZIF-67; (2) putting ZIF-67 in a high temperature resistant container, heating up under reducing atmosphere, keeping the temperature at constant temperature, cooling to room temperature to obtain cobalt carbon nitrogen material; (3) adding the cobalt carbon nitrogen material obtained in the step (2) into ammonia water, performing ultrasonic treatment to obtain a mixed solution 2, adding cerium nitrate hexahydrate into the mixed solution 2, performing ultrasonic treatment, centrifuging, washing to obtain a solid 2, and performing vacuum drying on the solid 2 to obtain the cobalt carbon nitrogen material loaded with cerium dioxide. The hollow structure of the prepared cobalt carbon nitrogen material is beneficial to the transmission of ions, and the vacancy of N contained in the cobalt carbon nitrogen material and the interconversion of cobalt ions and cerium ions with different valence states are beneficial to improving the catalytic activity of electrochemical oxygen evolution of the cobalt carbon nitrogen material.
Description
Technical Field
The invention belongs to the field of inorganic material chemistry, relates to the technical field of photoelectrocatalysis water decomposition, and particularly relates to a preparation method of a cobalt carbon nitrogen material loaded with cerium dioxide.
Background
With the increasing depletion of fossil fuels and the increasing severity of global environmental issues, global industrial development and ecosystems encounter unprecedented challenges. Electrolyzed water is considered one of the most promising green sustainable clean energy technologies. However, anodic Oxygen Evolution Reaction (OER), an important half-reaction in the electrolysis of water, involves a complex four-electron reaction process, requiring an efficient electrocatalyst to reduce the overpotential and thus increase the reaction rate. Although the noble metals such as ruthenium and iridium have high activity, the materials are rare in resources and expensive in price, and the wide application of the noble metals is severely restricted, so that the development of a catalyst with low cost, high activity and high stability to replace noble metal materials has very important significance. Metal-organic frameworks (MOFs) are a new type of porous material formed by periodic coordination of Metal sites and organic ligands. The material has high specific surface area and high porosity. The MOF carbon derivative material after high-temperature calcination has high graphitization degree and good conductivity.
After the ZIF-67 is calcined, a highly graphitized cobalt carbon nitrogen material can be formed, the cobalt carbon nitrogen material has good conductivity and electrocatalytic activity, larger Co nano particles in the cobalt carbon nitrogen material can be etched slightly by ammonia water treatment, the defect sites of nitrogen in the Co nano particles are exposed, a nitrogen-doped carbon catalyst containing defects is prepared, and cerium ions can be oxidized into cerium dioxide under the action of oxygen in an alkaline environment to serve as a catalyst promoter to further improve the catalytic activity of the cobalt carbon nitrogen material. Cobalt and cerium have flexible valence states, namely divalent and trivalent and quadrivalent respectively, cobalt ions and cerium ions with different valence states continuously change in valence state under the action of current, and the cerium ions can generate vacant sites of oxygen in the continuous change of the valence state, so that the oxygen is favorably electro-catalytically separated, and the hollow structure can increase the electron transfer capacity and the charge transmission efficiency of the hollow structure and improve the catalytic activity and the stability of the hollow structure.
Disclosure of Invention
In order to solve the problems in the prior art, the invention aims to provide a preparation method of a cobalt carbon nitrogen material loaded with cerium dioxide. The cobalt carbon nitrogen material loaded with cerium dioxide prepared by the method has excellent performance, uniform appearance and size and rich vacancy of active N, and can effectively coordinate the change of valence states between two metal elements, thereby improving the capacity of oxygen evolution by water electrolysis.
The object of the invention is achieved by at least one of the following solutions.
The invention provides a preparation method of a cobalt carbon nitrogen material loaded with cerium dioxide, which comprises the following steps:
(1) mixing cobalt nitrate hexahydrate and a solvent to obtain a cobalt nitrate solution; mixing the 2-methylimidazole with a solvent to obtain a 2-methylimidazole solution; mixing a cobalt nitrate solution and a 2-methylimidazole solution, and performing ultrasonic treatment to obtain a mixed solution 1; standing, centrifuging and washing the mixed solution 1 to obtain a solid 1; vacuum drying the solid 1 to obtain a metal organic framework material ZIF-67;
(2) putting the ZIF-67 obtained in the step (1) into a high-temperature resistant container, heating in a reducing atmosphere, keeping the temperature at a constant temperature, and cooling to room temperature to obtain a black cobalt carbon nitrogen material;
(3) adding the cobalt carbon nitrogen material obtained in the step (2) into ammonia water, performing ultrasonic treatment to obtain a mixed solution 2, adding cerium nitrate hexahydrate into the mixed solution 2, performing ultrasonic treatment, centrifuging, washing to obtain a solid 2, and performing vacuum drying on the solid 2 to obtain the cobalt carbon nitrogen material loaded with cerium dioxide.
Preferably, the molar ratio of the cobalt nitrate hexahydrate to the 2-methylimidazole in the step (1) is 1 (0.5-1.5);
the solvent is methanol; standing the mixed solution 1 for 12-24 h; the temperature of vacuum drying is 80-100 ℃; the vacuum drying time is 10-14 h; the washing is washing with methanol; the volume ratio of the molar weight of the cobalt nitrate hexahydrate in the cobalt nitrate solution to the solvent is 1: (35-40) mmol/ml; the volume ratio of the molar weight of the 2-methylimidazole in the 2-methylimidazole solution to the solvent is (0.5-1.5): (35-40) mmol/ml.
Preferably, the high-temperature resistant container in the step (2) is a porcelain boat; the reducing atmosphere is hydrogen and argon atmosphere; heating to 600-1000 ℃ in a reducing atmosphere, and preserving heat for 1-4 h at 600-1000 ℃; the cooling rate is 10-20 ℃/min.
Preferably, the mass fraction of the ammonia water in the step (3) is 0.5-1%; the ultrasonic time is 1-2 h; the molar weight ratio of the mass of the cobalt carbon nitrogen material to the cerium nitrate hexahydrate is 0.1-1 g/mmol; the volume ratio of the mass of the cobalt carbon nitrogen material to the ammonia water is 1: (1-5) mg/ml; the washing is washing with distilled water; the temperature of vacuum drying is 80-100 ℃; the vacuum drying time is 10-14 h.
Compared with the prior art, the invention has the following beneficial effects and advantages:
(1) the invention adopts a calcination-etching method to synthesize a hollow polyhedral cobalt carbon nitrogen material loaded with cerium dioxide, the hollow structure of the material is favorable for transferring ions, and the vacancy of N contained in the material and the interconversion of cobalt ions and cerium ions with different valence states are favorable for improving the catalytic activity of electrochemical oxygen evolution of the material.
(2) The product prepared by the method has uniform shape and size, can show excellent electrochemical performance when being used as an electrocatalytic material for producing oxygen by electrolyzing water, and has the electrochemical performance of 10mA/cm-2The overpotential thereof is 305mV at the current density of (1).
Drawings
FIG. 1 is an X-ray diffraction (XRD) pattern of the ceria-supported cobalt carbonitride material prepared in example 3;
fig. 2 is a Scanning Electron Micrograph (SEM) of the ceria-supported cobalt carbonitride material prepared in example 3;
FIG. 3 is a Transmission Electron Microscope (TEM) image of the ceria-supported cobalt carbonitride material prepared in example 3;
fig. 4 is a graph of Linear Sweep Voltammetry (LSV) performance test of the ceria-supported cobalt carbon nitrogen material prepared in example 3.
Detailed Description
The invention is described in further detail below with reference to the figures and the specific embodiments.
Example 1
The embodiment provides a preparation method of a cobalt carbon nitrogen material loaded with cerium dioxide, which comprises the following steps:
(1) respectively mixing 0.002mol of cobalt nitrate hexahydrate and 0.001mol of 2-methylimidazole with 70ml of methanol to obtain a cobalt nitrate solution and a 2-methylimidazole solution; mixing a cobalt nitrate solution and a 2-methylimidazole solution, and performing ultrasonic treatment to obtain a mixed solution 1; standing the mixed solution 1 for 12 hours, centrifuging, and washing with methanol to obtain a solid 1; vacuum drying the solid 1 in a vacuum oven at the temperature of 80 ℃ for 10 hours to obtain a purple powdery metal organic framework material ZIF-67;
(2) putting the ZIF-67 obtained in the step (1) into a porcelain boat, heating to 600 ℃ under the atmosphere of hydrogen and argon, preserving the heat at 600 ℃ for 1 hour, and cooling to room temperature at a cooling rate of 10 ℃/min to obtain a black cobalt carbon nitrogen material;
(3) adding 0.015g of the cobalt carbon nitrogen material obtained in the step (2) into 55ml of ammonia water with the mass fraction of 0.5%, performing ultrasonic treatment for 1 hour to obtain a mixed solution 2, adding 0.05mmol of cerium nitrate hexahydrate into the mixed solution 2, performing ultrasonic treatment for 1 hour, centrifuging, washing with distilled water to obtain a solid 2, and performing vacuum drying on the solid 2 at the temperature of 80 ℃ for 10 hours to obtain the cobalt carbon nitrogen material loaded with cerium dioxide, namely a sample-1.
The relevant morphology and properties of sample-1 can be found in the corresponding figure of example 3.
Example 2
The embodiment provides a preparation method of a cobalt carbon nitrogen material loaded with cerium dioxide, which comprises the following steps:
(1) respectively mixing 0.002mol of cobalt nitrate hexahydrate and 0.0015mol of 2-methylimidazole with 80ml of methanol to obtain a cobalt nitrate solution and a 2-methylimidazole solution; mixing a cobalt nitrate solution and a 2-methylimidazole solution, and performing ultrasonic treatment to obtain a mixed solution 1; standing the mixed solution 1 for 15 hours, centrifuging, and washing with methanol to obtain a solid 1; vacuum drying the solid 1 in a vacuum oven at the temperature of 90 ℃ for 11 hours to obtain a purple powdery metal organic framework material ZIF-67;
(2) putting the ZIF-67 obtained in the step (1) into a porcelain boat, heating to 700 ℃ under the atmosphere of hydrogen and argon, preserving the heat at 700 ℃ for 1.5 hours, and cooling to room temperature at a cooling rate of 15 ℃/min to obtain a black cobalt carbon nitrogen material;
(3) adding 0.015g of the cobalt carbon nitrogen material obtained in the step (2) into 65ml of ammonia water with the mass fraction of 0.6%, performing ultrasonic treatment for 1.5 hours to obtain a mixed solution 2, adding 0.06mmol of cerium nitrate hexahydrate into the mixed solution 2, performing ultrasonic treatment for 1.5 hours, centrifuging, washing with distilled water to obtain a solid 2, and performing vacuum drying on the solid 2 at 90 ℃ for 11 hours to obtain the cobalt carbon nitrogen material loaded with cerium dioxide, namely the sample-2.
The relevant morphology and properties of sample-2 can be seen in the corresponding figure of example 3.
Example 3
The embodiment provides a preparation method of a cobalt carbon nitrogen material loaded with cerium dioxide, which comprises the following steps:
(1) respectively mixing 0.002mol of cobalt nitrate hexahydrate and 0.002mol of 2-methylimidazole with 75ml of methanol to obtain a cobalt nitrate solution and a 2-methylimidazole solution; mixing a cobalt nitrate solution and a 2-methylimidazole solution, and performing ultrasonic treatment to obtain a mixed solution 1; standing the mixed solution 1 for 18 hours, centrifuging, and washing with methanol to obtain a solid 1; vacuum drying the solid 1 in a vacuum oven at the temperature of 80 ℃ for 12 hours to obtain a purple powdery metal organic framework material ZIF-67;
(2) putting the ZIF-67 obtained in the step (1) into a porcelain boat, heating to 800 ℃ under the atmosphere of hydrogen and argon, preserving the heat at 800 ℃ for 2 hours, and cooling to room temperature at a cooling rate of 10 ℃/min to obtain a black cobalt carbon nitrogen material;
(3) adding 0.02g of the cobalt carbon nitrogen material obtained in the step (2) into 60ml of ammonia water with the mass fraction of 0.7%, performing ultrasonic treatment for 1 hour to obtain a mixed solution 2, adding 0.07mmol of cerium nitrate hexahydrate into the mixed solution 2, performing ultrasonic treatment for 2 hours, centrifuging, washing with distilled water to obtain a solid 2, and performing vacuum drying on the solid 2 at the temperature of 80 ℃ for 12 hours to obtain the cobalt carbon nitrogen material loaded with cerium dioxide, namely a sample-3.
The XRD pattern of sample-3 prepared in this example is shown in fig. 1, and it can be seen from fig. 1 that the diffraction angle of this sample-3 is 28.63 °, 33.11 °, 47.53 °, and 56.43 ° and the diffraction peak of the (111) (200) (220) (311) crystal plane of ceria appears, and the diffraction peak of the (111) crystal plane of cobalt appears at 44.3 ° indicating that the material contains ceria and cobalt nanoparticles.
SEM image and TEM image of sample-3 are shown in FIG. 2 and FIG. 3, respectively, and it can be seen from FIG. 2 that the structure of sample-3 is polyhedral; it can be seen from FIG. 3 that sample-3 is a hollow structure.
The test chart of the Linear Sweep Voltammetry (LSV) performance of the cobalt carbon nitrogen material without supported cerium oxide obtained in the step (2) and the sample-3 obtained in the step (3) is shown in FIG. 4, and it can be seen from FIG. 4 that the current density of the sample-3 is 10mA/cm-2When the overpotential is 305mV (the reference electrode is Ag/AgCl, the potential is 1.23V), the cobalt carbon nitrogen material without supported cerium oxide has a current density of 10mA/cm-2And the overpotential is 372mV, so that the electrocatalytic oxygen evolution activity of the cobalt carbon nitrogen material loaded with the cerium dioxide is improved.
Example 4
The embodiment provides a preparation method of a cobalt carbon nitrogen material loaded with cerium dioxide, which comprises the following steps:
(1) respectively mixing 0.002mol of cobalt nitrate hexahydrate and 0.003mol of 2-methylimidazole with 75ml of methanol to obtain a cobalt nitrate solution and a 2-methylimidazole solution; mixing a cobalt nitrate solution and a 2-methylimidazole solution, and performing ultrasonic treatment to obtain a mixed solution 1; standing the mixed solution 1 for 15 hours, centrifuging, and washing with methanol to obtain a solid 1; vacuum drying the solid 1 in a vacuum oven at the temperature of 90 ℃ for 11 hours to obtain a purple powdery metal organic framework material ZIF-67;
(2) putting the ZIF-67 obtained in the step (1) into a porcelain boat, heating to 900 ℃ under the atmosphere of hydrogen and argon, preserving the heat at 900 ℃ for 3 hours, and cooling to room temperature at a cooling rate of 15 ℃/min to obtain a black cobalt carbon nitrogen material;
(3) adding 0.03g of the cobalt carbon nitrogen material obtained in the step (2) into 65ml of ammonia water with the mass fraction of 0.8%, performing ultrasonic treatment for 2 hours to obtain a mixed solution 2, adding 0.08mmol of cerium nitrate hexahydrate into the mixed solution 2, performing ultrasonic treatment for 1.5 hours, centrifuging, washing with distilled water to obtain a solid 2, and performing vacuum drying on the solid 2 at 90 ℃ for 11 hours to obtain the cobalt carbon nitrogen material loaded with cerium dioxide, namely a sample-4.
The relevant morphology and properties of sample-4 can be seen in the corresponding figure of example 3.
Example 5
The embodiment provides a preparation method of a cobalt carbon nitrogen material loaded with cerium dioxide, which comprises the following steps:
(1) respectively mixing 0.002mol of cobalt nitrate hexahydrate and 0.002mol of 2-methylimidazole with 70ml of methanol to obtain a cobalt nitrate solution and a 2-methylimidazole solution; mixing a cobalt nitrate solution and a 2-methylimidazole solution, and performing ultrasonic treatment to obtain a mixed solution 1; standing the mixed solution 1 for 24 hours, centrifuging, and washing with methanol to obtain a solid 1; vacuum-drying the solid 1 in a vacuum oven at the temperature of 100 ℃ for 14 hours to obtain a purple powdery metal organic framework material ZIF-67;
(2) putting the ZIF-67 obtained in the step (1) into a porcelain boat, heating to 1000 ℃ under the atmosphere of hydrogen and argon, preserving the heat at 1000 ℃ for 4 hours, and cooling to room temperature at a cooling rate of 20 ℃/min to obtain a black cobalt carbon nitrogen material;
(3) adding 0.05g of the cobalt carbon nitrogen material obtained in the step (2) into 60ml of ammonia water with the mass fraction of 1%, performing ultrasonic treatment for 1.5 hours to obtain a mixed solution 2, adding 0.1mmol of cerium nitrate hexahydrate into the mixed solution 2, performing ultrasonic treatment for 2 hours, centrifuging, washing with distilled water to obtain a solid 2, and performing vacuum drying on the solid 2 at 100 ℃ for 14 hours to obtain the cobalt carbon nitrogen material loaded with cerium dioxide, namely a sample-5.
The relevant morphology and properties of sample-5 can be seen in the corresponding figure of example 3.
The above description is only a preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any equivalent alterations, modifications or improvements made by those skilled in the art to the above-described embodiments using the technical solutions of the present invention are still within the scope of the technical solutions of the present invention.
Claims (8)
1. A preparation method of a cobalt carbon nitrogen material loaded with cerium dioxide is characterized by comprising the following steps:
(1) mixing cobalt nitrate hexahydrate and a solvent to obtain a cobalt nitrate solution; mixing the 2-methylimidazole with a solvent to obtain a 2-methylimidazole solution; mixing a cobalt nitrate solution and a 2-methylimidazole solution, and performing ultrasonic treatment to obtain a mixed solution 1; standing, centrifuging and washing the mixed solution 1 to obtain a solid 1; vacuum drying the solid 1 to obtain a metal organic framework material ZIF-67;
(2) putting the ZIF-67 obtained in the step (1) into a high-temperature resistant container, heating in a reducing atmosphere, keeping the temperature at a constant temperature, and cooling to room temperature to obtain a black cobalt carbon nitrogen material;
(3) adding the cobalt carbon nitrogen material obtained in the step (2) into ammonia water, performing ultrasonic treatment to obtain a mixed solution 2, adding cerium nitrate hexahydrate into the mixed solution 2, performing ultrasonic treatment, centrifuging, washing to obtain a solid 2, and performing vacuum drying on the solid 2 to obtain a cobalt carbon nitrogen material loaded with cerium dioxide;
in the step (2), heating to 600-1000 ℃ in a reducing atmosphere, and preserving heat for 1-4 h at 600-1000 ℃;
the mass fraction of the ammonia water in the step (3) is 0.5-1%; the time of ultrasonic treatment is 1-2 h.
2. The preparation method of the ceria-loaded cobalt carbon nitrogen material according to claim 1, wherein the molar ratio of cobalt nitrate hexahydrate to 2-methylimidazole in the step (1) is 1 (0.5-1.5).
3. The method for preparing a ceria-supported cobalt carbonitride material according to claim 1, characterized in that the ratio of the molar amount of cobalt nitrate hexahydrate in the cobalt nitrate solution to the volume of the solvent in step (1) is 1: (35-40) mmol/ml; the volume ratio of the molar weight of the 2-methylimidazole in the 2-methylimidazole solution to the solvent is (0.5-1.5): (35-40) mmol/ml.
4. The method for preparing the ceria-loaded cobalt carbon nitrogen material according to claim 1, wherein the solvent in the step (1) is methanol; standing the mixed solution 1 for 12-24 h; the temperature of vacuum drying is 80-100 ℃; the vacuum drying time is 10-14 h; the washing was with methanol.
5. The method for preparing the cerium oxide supported cobalt carbon nitrogen material according to claim 1, wherein the high temperature resistant container in the step (2) is a porcelain boat; the reducing atmosphere is a hydrogen-argon atmosphere.
6. The preparation method of the ceria-loaded cobalt carbon nitrogen material as claimed in claim 1, wherein the cooling rate in the step (2) is 10-20 ℃/min.
7. The preparation method of the ceric oxide-loaded cobalt carbon nitrogen material according to claim 1, wherein the ratio of the mass of the cobalt carbon nitrogen material to the molar weight of the cerium nitrate hexahydrate in the step (3) is 0.1-1 g/mmol;
the volume ratio of the mass of the cobalt carbon nitrogen material to the ammonia water is 1: (1-5) mg/ml.
8. The method for preparing a ceria-supported cobalt carbonitride material according to claim 1, characterized in that the washing in step (3) is washing with distilled water; the temperature of vacuum drying is 80-100 ℃; the vacuum drying time is 10-14 h.
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