CN115125547A - Preparation and application of Mo/Nb double-doped Co hollow mesoporous carbon nano box catalyst - Google Patents
Preparation and application of Mo/Nb double-doped Co hollow mesoporous carbon nano box catalyst Download PDFInfo
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Abstract
The invention discloses a preparation method of a Mo/Nb double-doped Co hollow mesoporous carbon nano-box catalyst, which comprises the following steps: (1) preparing a precursor cube ZIF-67; (2) annealing the product obtained in the step (1) in a tubular furnace in an inert gas atmosphere to obtain Co @ MCNBs; (3) mixing and stirring an ethanol solution containing ZIF-67 and an ethanol solution containing cobalt transition metal salt and niobium transition metal salt, loading niobium element through a hydrothermal reaction of a high-pressure reaction kettle, centrifugally collecting a solid, drying the solid in a vacuum oven, and annealing the dried solid in a tube furnace in an inert gas atmosphere to obtain Co (Nb) @ MCNBs; (4) adding a molybdenum transition metal salt ethanol solution into the raw material in the step (3), mixing and stirring, and obtaining Co (Mo) @ MCNBs by adopting the same preparation method as the step (3); (5) and (3) adding an ethanol solution of niobium transition metal salt into the raw material of (4), mixing and stirring, and preparing Co (Mo, Nb) @ MCNBs by the same method as the method of (3). The catalyst has the advantages of high specific surface area, more active sites and good electrochemical performance.
Description
Technical Field
The invention belongs to the technical field of water electrolysis catalysts, and particularly relates to a preparation method of a Mo/Nb double-doped Co hollow mesoporous carbon nano-box catalyst and application of the Mo/Nb double-doped Co hollow mesoporous carbon nano-box catalyst in a water electrolysis device.
Background
In the 21 st century, along with the development of industry, the exploitation and utilization of energy sources promote the civilized progress of human beings, the demand of various countries on energy sources is more and more urgent, and the current energy source structure mainly comprises: natural gas, coal, petroleum, and the like. However, excessive mining causes rapid depletion of fossil energy, energy crisis is prominent, and environmental pollution and a series of climate problems gradually emerge from the water surface, so that close attention needs to be paid to the ecological crisis. As is well known, economic development and energy density are not separable. With the gradual exhaustion of traditional energy and the environmental problems of global warming, acid rain, haze and the like caused by the traditional energy, the healthy life of human beings is seriously influenced, and the potential of the sustainable growth of national economy is also influenced. Therefore, green and sustainable energy needs to be developed, and a reasonable design of an efficient renewable energy conversion system is a key for realizing efficient and sustainable energy utilization. Among them, efficient utilization of natural resources is also a key means, but natural resources exist in the world, such as: the solar energy, the wind energy, the geothermal energy, the biomass energy and the like have instability, discontinuity and are limited by regions, and if the solar energy, the wind energy, the geothermal energy, the biomass energy and the like are applied to the whole country on a large scale, some problems of safety and facility waste may exist. The limited availability and application of petroleum energy is an unavoidable risk to environmental protection, and it is therefore highly desirable to develop an alternative, sustainable, clean energy technology to supply or replace fossil energy. The advent of electrochemical energy storage devices has provided a critical direction, as it were, to solve this problem.
In the era of rapid global economic development, human beings are increasingly apprehended about environmental pollution, and among them, fossil energy pollution is a non-trivial aspect. As a zero-emission energy source, hydrogen is considered as an alternative energy carrier for replacing fossil fuel energy, and in recent years, development plans of hydrogen energy are established in all countries. The main methods for producing hydrogen industrially include: the hydrogen is produced by pyrolyzing natural gas or water gas, but the methods not only have huge energy consumption in practice, but also cause certain pollution to the environment; the hydrogen production by electrolyzing water is safe and reliable, and the produced hydrogen is purer and has little pollution. In comparison, the water electrolysis technology is also important.
The method comprises the steps of obtaining electric energy through renewable energy sources, converting the electric energy into chemical energy by utilizing an electrolytic water technology, storing the chemical energy in hydrogen, subpackaging the hydrogen to the whole society, and converting the chemical energy into the electric energy again through a fuel cell reaction and utilizing the electric energy, so that a whole-process clean pollution-free new energy system based on hydrogen-water circulation can be established. Where hydrogen is present as an energy carrier of high energy density. The electrolysis of water to produce hydrogen is an important technical component to achieve this cycle. Although cheaper, conventional methane steam reforming hydrogen production technology still relies on the use of fossil fuels and produces and releases CO 2 . Along with the gradual expansion of the utilization scale of renewable energy sources, the water electrolysis technology also has wider application prospect
The hydrogen production by electrolysis of water, consisting of an anode (oxygen evolution OER) and a cathode (hydrogen evolution HER), is considered a promising approach due to its almost zero emissions.
Anode: 2H 2 O→O 2 +4H + +4e-
Cathode: 2H + +2e-→H 2
And (3) total reaction: 2H 2 O→O 2 +2H 2
The Oxygen Evolution Reaction (OER) mainly comprises three main steps:
(1)H 2 adsorption of O/OH-on the surface of electrocatalysts
(2) Formation of reaction intermediates
(3)O 2 Release of the molecule. In the electrolyzed water, the theoretical thermodynamic potential is 1.23V, but because the battery voltage in the electrolyzed water needs an overlarge potential, the charge transfer rate in the reaction process is slow, the process of producing hydrogen and oxygen becomes slow, the energy is additionally consumed, and the result is that the thermodynamic potential is far more than 1.23V. Noble metals, such as Ru, Pt and Ir-based materials, due to their large surface area; excellent electrocatalytic reaction and excellent conductivity is combustionIdeal selection of water splitting process of the fuel cell. However, stability, insufficient availability and cost limit commercialization. To avoid these problems, over the past decades scientists have been working to find readily synthesized and widely available alternatives to significantly reduce the excess potential of the OER process. Therefore, the water electrolysis hydrogen production technology needs to compete with the traditional hydrogen production industry, and a proper, stable and cheap OER/HER catalyst needs to be searched to reduce extra consumed energy, keep a lower overpotential, improve the reaction rate and ensure that the water electrolysis process is more environment-friendly.
Disclosure of Invention
According to the invention, a carbon cube is used as a conductive network, and oxometallate and metal oxide particles formed by doping molybdenum and niobium are loaded on the conductive carbon network, so that the Mo and Nb element double-doped Co hollow mesoporous carbon nano box with high specific surface area, multiple active sites and good electrochemical performance can be obtained, and oxygen-containing vacancies Co can grow in the Co hollow mesoporous carbon nano box 2 Mo 3 O 8 /Nb 2 O 5 Heterojunction catalyst, and is applied to water electrolysis device.
In order to realize the aim, the invention provides a preparation method of a Mo/Nb double-doped Co hollow mesoporous carbon nano-box catalyst, which specifically comprises the following steps:
step one, preparing a cobalt-based zeolite imidazolate framework material (ZIF-67): mixing cobalt transition metal salt, an aqueous solution of hexadecyl trimethyl ammonium bromide and an aqueous solution of dimethyl imidazole, stirring for reaction, centrifuging, and drying in a vacuum oven to obtain a precursor cube ZIF-67;
step two, preparation of Co hollow mesoporous carbon nano-box catalyst (Co @ MCNBs): annealing the product obtained in the step one in a tubular furnace in an inert gas atmosphere to obtain Co @ MCNBs;
step three, growing oxygen-containing vacancy Nb in the Co hollow mesoporous carbon nano box 2 O 5 Preparation of heterojunction catalyst (Co (Nb) @ MCNBs): mixing and stirring an ethanol solution containing ZIF-67 and an ethanol solution containing cobalt transition metal salt and niobium transition metal salt, loading niobium element through hydrothermal reaction in a high-pressure reaction kettle, centrifugally collecting solids, and drying the solids in a vacuum ovenThen annealing in a tube furnace in an inert gas atmosphere to obtain Co (Nb) @ MCNBs;
step four, growing oxygen-containing vacancy Co on the Co hollow mesoporous carbon nano box 2 Mo 3 O 8 Preparation of heterojunction catalyst (Co (Mo) @ MCNBs): mixing and stirring an ethanol solution containing ZIF-67 and an ethanol solution containing cobalt transition metal salt and molybdenum transition metal salt, loading molybdenum element through a hydrothermal reaction of a high-pressure reaction kettle, centrifugally collecting solids, drying the solids in a vacuum oven, and annealing in a tube furnace in an inert gas atmosphere to obtain Co (Mo) @ MCNBs;
step five, growing oxygen-containing vacancy Co in the Co hollow mesoporous carbon nano box 2 Mo 3 O 8 And Nb 2 O 5 Preparation of heterojunction catalyst (Co (Mo, Nb) @ MCNBs): mixing and stirring an ethanol solution containing ZIF-67 and an ethanol solution containing cobalt transition metal salt, molybdenum transition metal salt and niobium transition metal salt, loading molybdenum element and niobium element through hydrothermal reaction of a high-pressure reaction kettle, centrifugally collecting solids, drying the solids in a vacuum oven, and annealing in a tubular furnace in an inert gas atmosphere to obtain Co (Mo, Nb) @ MCNBs.
Preferably, in the first step, the mass ratio of the cobalt transition metal salt solution, cetyl trimethyl ammonium bromide, dimethyl imidazole and water is 0.2-1: 0.2-1: 0.2-1: 20-40.
Preferably, the mass ratio of the ZIF-67 to the cobalt transition metal salt solution to the niobium transition metal salt solution to the ethanol in the third step is 0.2-1: 0.2-1: 0.2-1: 10-100.
The mass ratio of the ZIF-67 to the cobalt transition metal salt solution to the molybdenum transition metal salt solution to the ethanol in the preferable step four is 0.2-1: 0.2-1: 0.2-1: 10-100.
Preferably, the mass ratio of the ZIF-67 to the cobalt transition metal salt solution to the molybdenum transition metal salt solution to the niobium transition metal salt solution to the ethanol in the step five is 0.2-1: 0.2-1: 0.2-1: 0.2-1: 10-100.
Preferably, Co (NO) is used as the cobalt transition metal salt in the first step 3 ) 2 ·6H 2 O、CoCl 2 ·6H 2 O、Co(CH 3 COO) 2 、 CoCl 2 、CoSO 4 ·7H 2 O、CoSO 4 ·H 2 And one or more of O.
Preferably, in the second, third, fourth and fifth steps, the inert gas atmosphere is N 2 One or more of Ar and He;
preferably, the annealing process in the second, third, fourth and fifth steps is to heat the material to 600-700 ℃ at a heating rate of 1 ℃/min for 3h in an inert atmosphere.
According to the application of the Mo/Nb double-doped Co hollow mesoporous carbon nano box catalyst as an electrolytic water electrode material, the Mo/Nb double-doped Co hollow mesoporous carbon nano box catalyst and a Co hollow mesoporous carbon nano box are applied to an electrolytic water device OER and HER reaction, niobium oxide containing oxygen vacancies and molybdenum cobaltate heterojunction are effectively loaded in a metal double-doping mode, niobium element plays a synergistic promotion role, the niobium-containing heterojunction can promote the cooperation with other heterojunctions, and the effect that 1+1 is more than 2 is achieved; the occurrence of oxygen vacancies is more beneficial to the adsorption of hydroxyl radicals, thereby promoting the OER reaction; the hollow nanometer box structure can expose more active sites, improve the activity of the active sites and increase the electrocatalytic performance of the catalyst.
Compared with the prior art, the invention has the following beneficial effects:
(1) the invention uses Co source to replace noble metal to be Pt, Ir and Ru group, which reduces cost and enlarges application range.
(2) At present, most of the metals studied in electrocatalysts are Fe, Ni, V and the like, and the exploration on some elements which are not common and abundant on the earth is less. In the invention, the element Nb is explored, and the Nb can form good connection with other main phase active substances due to the activity and the complex chemical property of the Nb, and is a development synergistic promoter in the field of electrocatalysis.
(3) According to the invention, two heterojunctions are grown outside the Co hollow mesoporous carbon nanometer box, the appearance that micropores exist in the hollow part of the original nanometer box is not changed, and the grown particles are more uniform and ordered through the chemical synergistic effect among the heterojunctions, so that defects are introduced, the increase of oxygen vacancies is caused, the adsorption of hydroxyl radicals is improved, and the electrochemical OER performance is enhanced.
Drawings
FIG. 1 shows the Co-containing vacancy growing process of Mo and Nb element double-doped Co hollow mesoporous carbon nano-box prepared in example 1 2 Mo 3 O 8 /Nb 2 O 5 The microstructure of the heterojunction catalyst under a Scanning Electron Microscope (SEM);
FIG. 2 shows comparative example 1 and examples 1, 2, 3 samples and commercial RuO 2 Linear sweep voltammetric profile (LSV) of Oxygen Evolution Reaction (OER) of the catalyst;
fig. 3 is a Linear Sweep Voltammetry (LSV) plot of the Hydrogen Evolution Reaction (HER) for the comparative example 1 and examples 1, 2, 3 sample catalysts.
Detailed Description
In order to make the purpose, technical scheme and beneficial technical effects of the present invention clearer, the following describes in detail the preparation method of the Mo/Nb double-doped Co hollow mesoporous carbon nano-box catalyst and the beneficial effects thereof in the application in the electrolysis of water with reference to the accompanying drawings and the specific embodiments. It should be understood that the embodiments described in this specification are only for the purpose of illustrating the invention and are not to be construed as limiting the invention, and the parameters, proportions and the like of the embodiments may be suitably selected without materially affecting the results.
Comparative example 1: the preparation method of the Co particle-loaded hollow mesoporous carbon nano box catalyst specifically comprises the following steps:
(1) synthesis of ZIF-67:
with 0.292g of Co (NO) 3 ) 2 .6H 2 O is a Co source dissolved in 10mL of deionized water (DI) containing 4mg of cetyltrimethylammonium bromide (CTAB). The solution was then quickly injected into 70mL of an aqueous solution containing 4.54g of 2-methylimidazole (2-MIM) and stirred at room temperature for 30 minutes. The product was collected by centrifugation at 12000rpm for 3 minutes and washed several times with ethanol.
(2) Synthesizing a hollow mesoporous carbon nano-box catalyst loaded with Co particles:
subjecting the obtained powder to argon flow at 1 deg.C for min -1 Further annealing at 650 ℃ for 3 hours, and then naturally cooling to room temperature.
Example 1: the preparation method of the Mo/Nb double-doped Co hollow mesoporous carbon nano-box catalyst specifically comprises the following steps:
(1) synthesis of ZIF-67:
with 0.292g of Co (NO) 3 ) 2 .6H 2 O is a Co source dissolved in 10mL of deionized water (DI) containing 4mg of cetyltrimethylammonium bromide (CTAB). The solution was then quickly injected into 70mL of an aqueous solution containing 4.54g of 2-methylimidazole (2-MIM) and stirred at room temperature for 30 minutes. The product was collected by centrifugation at 12000rpm for 3 minutes and washed several times with ethanol.
(2) Co hollow mesoporous carbon nano box doped with Mo and Nb elements and growing oxygen-containing vacancy Co 2 Mo 3 O 8 /Nb 2 O 5 Synthesis of heterojunction catalyst:
first, 0.06g of ZIF-67 and 5mL of a solution containing 0.05M (NH) 4 ) 2 MoS 4 Dissolved in 20ml of ethanol and stirred at a constant speed for 1 h. Then 10ml of Co (NO) -containing 3 ) 2 .6H 2 O (6mM) and NbCl 5 An ethanol solution (3mM) was slowly added dropwise to the above solution, and stirred at a constant speed for 3 hours. The above solution was then transferred to a Teflon-lined stainless steel autoclave (50mL) and maintained at 200 ℃ for 6 hours. After cooling to room temperature, the product was collected by centrifugation, washed several times with ethanol and then dried in an oven at 70 ℃. Subjecting the obtained powder to argon flow at 1 deg.C for min -1 Annealing at 650 ℃ for 3h, and naturally cooling to room temperature to obtain the Co-containing vacancy grown by the Co-doped hollow mesoporous carbon nano box with Mo and Nb elements 2 Mo 3 O 8 /Nb 2 O 5 Heterojunction catalyst Co (Mo, Nb) @ MCNBs. In the experiment, the tube furnace was kept at constant pressure throughout.
The morphology of the Co (Mo, Nb) @ MCNBs material obtained in example 1 was analyzed by a Scanning Electron Microscope (SEM), and as a result, the cubic structure was maintained and the heterojunction structure was supported on the surface as shown in fig. 1.
Example 2: the preparation method of the Nb-doped Co hollow mesoporous carbon nano-box catalyst comprises the following steps:
(1) synthesis of ZIF-67:
with 0.292g of Co (NO) 3 ) 2 .6H 2 O is a Co source dissolved in 10mL of deionized water (DI) containing 4mg of cetyltrimethylammonium bromide (CTAB). The solution was then quickly injected into 70mL of an aqueous solution containing 4.54g of 2-methylimidazole (2-MIM) and stirred at room temperature for 30 minutes. The product was collected by centrifugation at 12000rpm for 3 minutes and washed several times with ethanol.
(2) Growing oxygen-containing vacancy Nb by Nb element doped Co hollow mesoporous carbon nano box 2 O 5 Synthesis of heterojunction catalyst:
0.06g of ZIF-67 was first dissolved in 20ml of ethanol and stirred at a constant speed for 1 hour. Then 10ml of Co (NO) -containing 3 ) 2 .6H 2 O (6mM) and NbCl 5 An ethanol solution (3mM) was slowly added dropwise to the above solution, and stirred at a constant speed for 3 hours. The above solution was then transferred to a Teflon-lined stainless steel autoclave (50mL) and maintained at 200 ℃ for 6 hours. After cooling to room temperature, the product was collected by centrifugation, washed several times with ethanol and then dried in an oven at 70 ℃. Subjecting the obtained powder to argon flow at 1 deg.C for min -1 Annealing at 650 ℃ for 3h, and then naturally cooling to room temperature to obtain Nb element doped Co hollow mesoporous carbon nano box grown oxygen-containing vacancy Nb 2 O 5 Heterojunction catalyst Co (Nb) @ MCNBs. In the experiment, the tube furnace was kept at constant pressure throughout.
Example 3: the preparation method of the Mo-doped Co hollow mesoporous carbon nano-box catalyst specifically comprises the following steps:
(1) synthesis of ZIF-67:
with 0.292g of Co (NO) 3 ) 2 .6H 2 O is a Co source dissolved in 10mL of deionized water (DI) containing 4mg of cetyltrimethylammonium bromide (CTAB). The solution was then quickly injected into 70mL of an aqueous solution containing 4.54g of 2-methylimidazole (2-MIM) and stirred at room temperature for 30 minutes. The product was collected by centrifugation at 12000rpm for 3 minutes and washed several times with ethanol.
(2) Co-doped Mo element hollow mesoporous carbon nano box growing oxygen-containing vacancy Co 2 Mo 3 O 8 Synthesis of heterojunction catalyst:
first, 0.06g of ZIF-67 and 5mL of a solution containing 0.05M (NH) 4 ) 2 MoS 4 Dissolved in 20ml of ethanol and stirred at a constant speed for 1 h. Then 10ml of Co (NO) -containing 3 ) 2 .6H 2 An ethanol solution of O (6mM) was slowly added dropwise to the above solution, and the mixture was stirred at a constant speed for 3 hours. The above solution was then transferred to a Teflon-lined stainless steel autoclave (50mL) and maintained at 200 ℃ for 6 hours. After cooling to room temperature, the product was collected by centrifugation, washed several times with ethanol and then dried in an oven at 70 ℃. Subjecting the obtained powder to argon flow at 1 deg.C for min -1 Annealing at 650 ℃ for 3h, and naturally cooling to room temperature to obtain the Co-doped Mo hollow mesoporous carbon nano box with grown oxygen-containing vacancies 2 Mo 3 O 8 Heterojunction catalyst Co (Mo) @ MCNBs. In the experiment, the tube furnace was kept at constant pressure throughout.
Evaluation of bifunctional catalytic Performance:
all electrochemical tests were performed using an electrochemical workstation model CHI 760E test system, and were performed at room temperature.
Preparation of a working electrode: accurately weighing 5mg Mo and Nb elements double-doped Co hollow mesoporous carbon nano box to grow oxygen-containing vacancy Co 2 Mo 3 O 8 /Nb 2 O 5 Heterojunction catalyst, 0.5mg acetylene black and 0.5mg polyvinylidene fluoride (PVDF), then mixing and dissolving in 750mL n-methyl-pyrrolidone (NMP), carrying out ultrasonic treatment on the mixture for 30min, finally dripping the prepared ink on the surface of carbon paper with the area of 0.5cm multiplied by 0.5cm, drying by an infrared lamp, then continuously dripping, repeating, and finally weighing to obtain the load of about 0.4 mg. As a control experiment, commercial RuO 2 The catalyst was also prepared and tested using the same preparation method.
And (3) electrochemical performance testing: a standard three-electrode electrochemical test system was used in the test procedure, where the counter electrode was Pt mesh and the reference electrode was Saturated Calomel Electrode (SCE) and the working electrode prepared above.
The OER-LSV curves of the comparative example 1 and examples 1, 2, 3 samples in a 1.0M KOH solution were tested using an electrochemical workstation as shown in FIG. 2, and the comparative example 1 and examples 1, 2, 3 samples at a current density of 10mA cm -2 The overpotentials of OERs were 364mV, 284mV, 351mV and 317mV, respectively. Specific commercial RuO under the same test conditions 2 The overpotential and the blank carbon paper of the catalyst are low, which indicates that the Mo and Nb elements are double-doped Co hollow mesoporous carbon nano-box grows oxygen-containing vacancy Co 2 Mo 3 O 8 /Nb 2 O 5 The heterojunction catalyst sample has excellent OER electrocatalytic activity and can be applied to the anode of a water electrolysis device.
The HER-LSV curves of comparative example 1 and examples 1, 2, 3 samples in a 1.0M KOH solution were tested using an electrochemical workstation as shown in FIG. 2, and comparative example 1 and examples 1, 2, 3 samples at a current density of 10mA cm -2 And the HER overpotentials are 206mV, 229mV, 314mV and 245mV respectively, which shows that the hollow mesoporous carbon nano-box catalyst sample loaded with the Co particles also has certain HER electrocatalytic activity and can be applied to the negative electrode of the water electrolysis device.
Finally, it should also be mentioned that: the above embodiments are only used to illustrate the technical solution of the present invention, and not to limit the same; while the invention has been described in detail and with reference to the foregoing embodiments, it will be understood by those skilled in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some or all of the technical features may be equivalently replaced; and the modifications or the substitutions do not make the essence of the corresponding technical solutions depart from the scope of the technical solutions of the embodiments of the present invention.
Claims (9)
1. A preparation method of a Mo/Nb double-doped Co hollow mesoporous carbon nano-box catalyst specifically comprises the following steps:
step one, preparing a cobalt-based zeolite imidazolate framework material (ZIF-67): mixing cobalt transition metal salt, an aqueous solution of hexadecyl trimethyl ammonium bromide and an aqueous solution of dimethyl imidazole, stirring for reaction, centrifuging, and drying in a vacuum oven to obtain a precursor cube ZIF-67;
step two, preparation of Co hollow mesoporous carbon nano-box catalyst (Co @ MCNBs): annealing the product obtained in the step one in a tubular furnace in an inert gas atmosphere to obtain Co @ MCNBs;
step three, growing oxygen-containing vacancy Nb in the Co hollow mesoporous carbon nano box 2 O 5 Preparation of heterojunction catalyst (Co (Nb) @ MCNBs): mixing and stirring an ethanol solution containing ZIF-67 and an ethanol solution containing cobalt transition metal salt and niobium transition metal salt, loading niobium element through a hydrothermal reaction of a high-pressure reaction kettle, centrifugally collecting a solid, drying the solid in a vacuum oven, and annealing the dried solid in a tube furnace in an inert gas atmosphere to obtain Co (Nb) @ MCNBs;
step four, growing oxygen-containing vacancy Co on the Co hollow mesoporous carbon nano box 2 Mo 3 O 8 Preparation of heterojunction catalyst (Co (Mo) @ MCNBs): mixing and stirring an ethanol solution containing ZIF-67 and an ethanol solution containing cobalt transition metal salt and molybdenum transition metal salt, loading molybdenum element through a hydrothermal reaction of a high-pressure reaction kettle, centrifugally collecting solids, drying the solids in a vacuum oven, and annealing in a tube furnace in an inert gas atmosphere to obtain Co (Mo) @ MCNBs;
step five, growing oxygen-containing vacancy Co in the Co hollow mesoporous carbon nano box 2 Mo 3 O 8 And Nb 2 O 5 Preparation of heterojunction catalyst (Co (Mo, Nb) @ MCNBs): mixing and stirring an ethanol solution containing ZIF-67 and an ethanol solution containing cobalt transition metal salt, molybdenum transition metal salt and niobium transition metal salt, loading molybdenum element and niobium element through hydrothermal reaction of a high-pressure reaction kettle, centrifugally collecting solids, drying the solids in a vacuum oven, and annealing in a tube furnace in an inert gas atmosphere to obtain Co (Mo, Nb) @ MCNBs.
2. The preparation method according to claim 1, wherein the mass ratio of the cobalt transition metal salt solution, the cetyl trimethyl ammonium bromide, the dimethyl imidazole and the water in the first step is 0.2-1: 0.2-1: 0.2-1: 20-40.
3. The preparation method according to claim 2, wherein in the third step, the mass ratio of the ZIF-67, the cobalt transition metal salt solution, the niobium transition metal salt solution and the ethanol is 0.2-1: 0.2-1: 0.2-1: 10-100.
4. The preparation method according to claim 3, wherein in the fourth step, the mass ratio of the ZIF-67, the cobalt transition metal salt solution, the molybdenum transition metal salt solution and the ethanol is 0.2-1: 0.2-1: 0.2-1: 10-100.
5. The method according to claim 4, wherein in the fifth step, the mass ratio of the ZIF-67, the cobalt transition metal salt solution, the molybdenum transition metal salt solution, the niobium transition metal salt solution and the ethanol is 0.2-1: 0.2-1: 0.2-1: 0.2-1: 10-100.
6. The method of claim 1, wherein the cobalt transition metal salt in the first step is Co (NO) 3 ) 2 ·6H 2 O、CoCl 2 ·6H 2 O、Co(CH 3 COO) 2 、CoCl 2 、CoSO 4 ·7H 2 O、CoSO 4 ·H 2 And one or more of O.
7. The method according to claim 6, wherein in the second, third, fourth and fifth steps, the inert gas atmosphere is N 2 One or more of Ar and He.
8. The preparation method of claim 7, wherein the annealing process in the second, third, fourth and fifth steps is a heat preservation for 3 hours from 600 ℃ to 700 ℃ at a heating rate of 1 ℃/min in an inert atmosphere.
9. The application of the Mo/Nb double-doped Co hollow mesoporous carbon nano-box catalyst as an electrolytic water electrode material as claimed in any one of claims 1 to 8, wherein Co (Mo, Nb) @ MCNBs is applied to anode Oxygen Evolution (OER) of an electrolytic water device, the Co-loaded hollow mesoporous carbon nano-box is applied to cathode Hydrogen Evolution (HER) of the electrolytic water device, the metal double-doping mode effectively loads niobium oxide and molybdenum cobaltate heterojunction containing oxygen vacancies, and the niobium-containing heterojunction cooperates with other heterojunctions to exert the effect of 1+1 & gt 2 in catalytic performance under the synergistic promotion of niobium elements.
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| CN112553643A (en) * | 2020-12-07 | 2021-03-26 | 上海电力大学 | Nitrogen-doped carbon-coated non-noble bimetallic cobalt-molybdenum oxide oxygen evolution reaction catalyst, preparation method and application |
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| CN112553643A (en) * | 2020-12-07 | 2021-03-26 | 上海电力大学 | Nitrogen-doped carbon-coated non-noble bimetallic cobalt-molybdenum oxide oxygen evolution reaction catalyst, preparation method and application |
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| XIAOHUI CHEN ET. AL.: "Regulation of the electronic structure of Co4N with novel Nb to form hierarchical porous nanosheets for electrocatalytic overall water splitting", 《MATERIALS TODAY PHYSICS》, vol. 15, pages 100268 * |
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| CN115555025A (en) * | 2022-10-31 | 2023-01-03 | 河北建材职业技术学院 | Preparation method of high-dispersion cobalt-molybdenum bimetallic catalyst |
| CN115555025B (en) * | 2022-10-31 | 2024-01-26 | 河北建材职业技术学院 | Preparation method of high-dispersion cobalt-molybdenum bimetallic catalyst |
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