CN110721724A - Nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles and preparation method and application thereof - Google Patents
Nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles and preparation method and application thereof Download PDFInfo
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Abstract
A nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles and a preparation method and application thereof relate to a preparation method of a porous carbon material. The invention aims to solve the problems that the existing method for preparing the porous carbon has complicated and time-consuming operation steps, high overpotential, high requirement on equipment, harm to the environment, limitation on the preparation of the porous carbon material, unsuitability for large-scale production and incapability of meeting new application requirements in the fields of energy, catalysis, biology and the like. A nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles grows on foamed nickel in situ. The method comprises the following steps: firstly, pretreating foamed nickel; secondly, growing a cobalt-based zeolite imidazole ester framework material nanosheet array in situ on the foamed nickel; and thirdly, calcining. A nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles is used as a catalyst for hydrogen production by electrolyzing water and is applied to the field of energy. The invention can obtain the nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles.
Description
Technical Field
The invention relates to a preparation method of a porous carbon material.
Background
Carbon material is an ancient and young material, which is closely related to human life. In recent years, porous carbon materials have become a new material system which has been rapidly developed, and applications thereof in various fields have been paid attention, particularly in energy-related fields. The porous carbon material has the characteristics of low cost, light weight, no toxicity, surface chemical inertia, high temperature resistance, acid and alkali resistance, high mechanical stability, good conductivity, adsorptivity, large specific surface area, large pore volume and the like, and can be used for preparing the catalyst for the treatment of CO2The fields of adsorption, hydrogen storage, catalysis, fuel cells, electrochemical double-layer capacitors and the like show huge application potential and are concerned by various fields.
The preparation methods of the porous carbon material are various, and the following two preparation methods are commonly used:
(1) an activation method: the activation method is a conventional method for preparing a porous carbon material, and includes: (a) chemical activation, physical activation, or a combination of physical and chemical activation; (b) catalytic activation of a carbon precursor; (c) high molecular polymer which can be carbonized and pyrolyzed is mixed and carbonized; (d) carbonizing the polymer aerogel; (e) carbonizing and activating the biomass. The porous carbon material prepared by the traditional carbonization and activation methods is often disordered, and the shape and the pore diameter of the pore channel are difficult to control; and certain activating agents (such as potassium hydroxide and phosphoric acid) have strong corrosivity at high temperature, so that the material requirement of equipment is improved, and the production cost is increased.
(2) Template method: the template method is a method for effectively controlling the pore structure by using a template so as to prepare a material with an ordered structure and uniform pore diameter. The template method can be divided into the following methods according to the different templates used: (a) the soft template method is a method for directly synthesizing ordered mesoporous carbon, self-assembly is carried out through the interaction of a carbon precursor and a soft template, and then the carbon precursor is carbonized to obtain a porous carbon material; (b) the hard template method comprises the steps of utilizing a material with a special pore structure as a hard template, introducing a carbon precursor into a pore channel of the hard template, carbonizing and removing the hard template to obtain a porous carbon material with the special pore structure; (c) the double-template method utilizes a hard template to control the morphology of the carbon material or the formation of macropores, and simultaneously utilizes a soft template to control the formation of ordered mesoporous channels, thereby obtaining the porous carbon material with a hierarchical channel structure. The template method has the outstanding advantages that the structure controllability is good, but strong acid or strong base is needed for removing the template, the template cannot be recycled, and the cost is increased, so that economic and environmental waste is caused; the operation steps are complicated, time-consuming and harmful to the environment, so that the preparation of the porous carbon material is greatly limited and is not suitable for large-scale production.
On the other hand, the vigorous development of a plurality of new technologies such as sensors, fuel cells, capacitors, nano bioreactors and the like puts forward new requirements on the performance of the porous carbon material, and the porous carbon material with single component cannot meet the application requirements. Heteroatom (N, B, O, P, halogen and the like) doping and transition metal nanoparticle modification are effective ways for changing the geometric structure and surface (interface) surface electrons and properties of the porous carbon material. At present, nitrogen atoms are considered to be the most desirable heteroatoms in carbon materials. Particularly, nitrogen is doped into the carbon nano material loaded with single metal or double metals of Ni, Co, Mo and Fe, and the strong interaction between nitrogen and transition metal can greatly increase the stability, bring obvious change of electronic structure and improve the electrochemical activity.
With the development of application in the fields of energy, catalysis, biology and the like, the controlled synthesis and the performance research of porous carbon are more and more emphasized. Therefore, the design of the porous carbon material with novel synthetic components and structure has great significance for the development of technologies such as sensors, fuel cells, capacitors, nano bioreactors and the like.
Disclosure of Invention
The invention aims to solve the problems that the existing method for preparing porous carbon has complicated operation steps, consumes time, has high overpotential, has high requirements on equipment, is harmful to the environment, limits the preparation of porous carbon materials, is not suitable for large-scale production and cannot meet the new application requirements in the fields of energy, catalysis, biology and the like, and provides a cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material, and a preparation method and application thereof.
The nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles grows on foamed nickel in situ, the cobalt particles are embedded on the nitrogen-nickel co-doped porous carbon material, the content of cobalt is 5-30%, the content of nickel is 0.1-5%, and the content of nitrogen is 3-8%; the cobalt particles are ellipsoidal crystals, and the size of the cobalt particles is 5 nm-30 nm.
A preparation method of a cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material comprises the following steps:
firstly, pretreatment of foamed nickel:
carrying out ultrasonic cleaning on the foamed nickel by using dilute hydrochloric acid, deionized water and absolute ethyl alcohol as cleaning agents in sequence, and then carrying out vacuum drying to obtain pretreated foamed nickel;
secondly, growing a cobalt-based zeolite imidazole ester framework material nanosheet array in situ on the foamed nickel:
①, dissolving cobalt nitrate hexahydrate in deionized water to obtain an aqueous solution of cobalt nitrate hexahydrate;
the concentration of the cobalt nitrate hexahydrate aqueous solution in the step two ① is 0.05-0.15 mol/L;
②, dissolving dimethyl imidazole in deionized water to obtain a dimethyl imidazole aqueous solution;
the concentration of the dimethyl imidazole aqueous solution in the second step ② is 0.3-0.7 mol/L;
③, mixing the cobalt nitrate hexahydrate aqueous solution with the dimethyl imidazole aqueous solution, and stirring to obtain a mixed solution;
the volume ratio of the cobalt nitrate hexahydrate aqueous solution to the dimethyl imidazole aqueous solution in the second step ③ is (0.9-1.1): 0.9-1.1;
④, firstly immersing the pretreated foamed nickel into the mixed solution, then standing for 5-10 h at room temperature, washing the foamed nickel by using deionized water and absolute ethyl alcohol in sequence, and finally drying in an oven to obtain the foamed nickel with the surface growing with the cobalt-based zeolite imidazole ester framework material nanosheet array;
thirdly, calcining:
firstly, placing foamed nickel with a cobalt-based zeolite imidazole ester framework material nanosheet array growing on the surface in a high-temperature tubular furnace, then heating to 600-800 ℃ at a heating rate of 0.5-6 ℃/min, and finally calcining for 2-5 h at the temperature of 600-800 ℃ to obtain the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material.
A nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles is used as a catalyst for hydrogen production by electrolyzing water and is applied to the field of energy.
The principle and the advantages of the invention are as follows:
the material grows on the foamed nickel in situ, the foamed nickel is used as a conductive substrate (current collector), the material is strong in binding property with the current collector and good in stability, and the three-dimensional network structure of the foamed nickel has high conductivity and a transparent structure, so that the diffusion resistance of an electrolyte is small, and the proton transport capacity is high;
secondly, the nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles obtained by the method grows on the foamed nickel in situ, the foamed nickel is used as a nickel source, and high-loading monatomic doping with the content of about 3.5% is realized in the porous carbon material, and the content is obviously higher than the common situation (<0.5 wt%). The surface free energy, the quantum size effect, the unsaturated coordination environment and the metal-carrier interaction which are suddenly increased by the monoatomic atom can effectively regulate and control the selectivity, the activity and the stability of the monoatomic atom in the chemical process, so that the monoatomic atom has the advantages of high homogeneous catalysis selectivity, easy product separation realization of heterogeneous phase and the like, and has obvious advantages in the catalysis field;
the carbon material used in the invention is prepared by taking a foliated cobalt-based metal-organic frameworks (Co-MOFs) array as a sacrificial template, so that the microstructure of the foliated array is partially reserved in the obtained product, and the obtained product belongs to a two-dimensional porous carbon material. The porous carbon material is obviously different from a three-dimensional porous carbon material obtained by cobalt-based MOF (such as ZIF67) with a polyhedral structure;
the nickel-nitrogen Co-doped porous carbon material loaded with cobalt nanoparticles is prepared by taking a cobalt-based metal-organic framework (MOFs) as a precursor, some cobalt nanoparticles are dispersed on the surface of the material, the cobalt nanoparticles have a crystal structure, the particle size is about 10 nm-20 nm, usually, due to the fact that a transition metal has empty d-orbit and d-orbit electrons, empty orbitals can be provided to serve as electrophilic reagents in a chemical reaction, or lone-pair electrons are provided to serve as nucleophilic reagents to form an intermediate product, so that single metal or double metal nanoparticles in transition metals Ni and Co are loaded on the carbon nanostructure, the strong coupling interaction between graphitized carbon and the metal particles can reduce reaction activation energy, faster electron transfer is ensured, the chemical reaction is promoted, and the electronic structure of the carbon material is adjusted, Effective ways to improve their physicochemical properties;
fifthly, the nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles is prepared by taking MOFs as a precursor, because the MOFs is a zeolite-like material formed by self-assembling a nitrogen-containing polydentate organic ligand and metal atoms or metal atom clusters, the nitrogen content of the porous carbon material obtained by the invention is about 8%, the doping of N element is an effective way for improving the electrochemical performance of porous carbon, and the nitrogen atom and the carbon atom are adjacent in the periodic table of elements, and because the nitrogen atom and the carbon atom are adjacent in the periodic table of elementsThe N pair of sp2Carbon doping has two major advantages: (1) the N and C atom radiuses are similar, so that lattice mismatch can be reduced, and the excellent properties of the parent carbon material cannot be damaged by doping of nitrogen atoms; (2) n has one more electron than C, and after being doped into the carbon material, the nitrogen atom has a lone pair of electrons. The lone pair of electrons can increase the charge density of the carbon material, so that the carbon material forms an n-type semiconductor, thereby enhancing the electron transfer capability and chemical activity of the material;
the nickel-nitrogen co-doped porous carbon material loaded with the cobalt nanoparticles is prepared by taking MOFs as a precursor, has a natural three-dimensional hierarchical pore network structure, and the porous carbon is used as an electrode material, so that the matching of the pore diameter and the size of electrolyte ions needs to be considered to promote the transport of ions;
the nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles is prepared by taking MOFs as a precursor through high-temperature carbonization, the graphitization degree, namely the conductivity, of the porous carbon material has a great influence on the electrochemical performance of the porous carbon material, and the electrochemical performance of the porous carbon material can be effectively improved by performing high-temperature treatment on the porous carbon. Research shows that when the porous carbon is used as an electrode material, the porous carbon obtained by carbonizing MOFs shows better electrochemical performance than that of common activated carbon;
the nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles, which is obtained by the invention, can show excellent activity and good stability which are obviously superior to those of each single component in the fields of catalytic energy storage and the like, and the main reasons are as follows: (1) due to the strong interaction between nitrogen and nickel/cobalt, strong chemical bonding between the transition metal and the nitrogen-doped carbon carrier can greatly increase the stability, bring about more obvious change of the electronic structure, promote the electron transfer of the material interface and improve the electrochemical activity. (2) More importantly, the strong coupling between the transition metal and N-C at the interface can often bring about a so-called synergistic effect for the hybrid, loading the mono-or bi-metal of the metals Ni, Co on the nitrogen-doped carbon nanostructure, significantly improving the electrochemical performance compared to that without nitrogen doping.
The cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material is a porous carbon material with magnetic properties, wherein cobalt and nickel components in the material are ferromagnetic materials, and the introduction of the cobalt and nickel components provides the porous carbon material with magnetic properties, namely magnetism, which is very important for electronic materials;
the nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles and the preparation method thereof have the advantages of ingenious design, simple process, low cost and strong reproducibility, and provide a new method and thought for developing a high-load monatomic catalytic material;
eleven, the nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles prepared by the method has good hydrogen evolution performance at 10mA/cm2Under the condition, the overpotential of the nickel-nitrogen co-doped porous carbon material loaded with the cobalt nanoparticles prepared by the method is only 64 mV; at a constant current density of 30mA/cm2Under the condition, after the nickel-nitrogen co-doped porous carbon material loaded with the cobalt nanoparticles prepared by the invention is subjected to a stability test for 45 hours, the voltage retention rate can reach 94.4%.
The invention can obtain the nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles.
Drawings
FIG. 1 is a scanning electron microscope image of an array of Co-ZIF nanosheets grown vertically on nickel foam obtained in step two of the example;
FIG. 2 is an X-ray diffraction spectrum of a Co-ZIF nanosheet array grown vertically on nickel foam obtained in step two of the example;
FIG. 3 is a scanning electron microscope image of the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material obtained in step three of the example;
FIG. 4 is an X-ray diffraction spectrum of a nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles obtained in step three of the example, wherein "xxx" is a signal of carbon;
fig. 5 is a first transmission electron microscope image of the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material obtained in step three of the example;
fig. 6 is a second transmission electron microscope image of the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material obtained in step three of the example;
fig. 7 is a scanning transmission electron microscope image of the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material obtained in step three of the example, where the region 1 is a sampling region and the region 2 is a test calibration sampling region;
FIG. 8 is a distribution plot of the area of the C element in region 1 of FIG. 7;
FIG. 9 is a distribution plot of the area of the N elements in region 1 of FIG. 7;
FIG. 10 is a distribution diagram of the area of Co element in the region 1 of FIG. 7;
FIG. 11 is a surface distribution diagram of Ni element in region 1 of FIG. 7;
fig. 12 is a third transmission electron microscope image of the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material obtained in step three of the example;
fig. 13 is a linear voltammetry characteristic graph, in which 1 is a linear voltammetry characteristic curve of a Pt/C electrode, 2 is a linear voltammetry characteristic curve of a cobalt nanoparticle-supported nickel-nitrogen-co-doped porous carbon material prepared in example one, 3 is a linear voltammetry characteristic curve of a cobalt nanoparticle-supported nickel-nitrogen-co-doped porous carbon material prepared in example two, 4 is a linear voltammetry characteristic curve of a cobalt nanoparticle-supported nickel-nitrogen-co-doped porous carbon material prepared in example three, 5 is a linear voltammetry characteristic curve of a cobalt nanoparticle-supported nickel-nitrogen-co-doped porous carbon material prepared in example four, and 6 is a linear voltammetry characteristic curve of a cobalt nanoparticle-supported nickel-nitrogen-co-doped porous carbon material prepared in example five;
fig. 14 is a stability characteristic graph of the nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles prepared in example one.
Detailed Description
The first embodiment is as follows: in the embodiment, a nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles grows on foamed nickel in situ, cobalt particles are embedded in a nitrogen-nickel co-doped porous carbon material, the content of cobalt is 5-30%, the content of nickel is 0.1-5%, and the content of nitrogen is 3-8%; the cobalt particles are ellipsoidal crystals, and the size of the cobalt particles is 5 nm-30 nm.
The second embodiment is as follows: the embodiment is a preparation method of a cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material, which is completed according to the following steps:
firstly, pretreatment of foamed nickel:
carrying out ultrasonic cleaning on the foamed nickel by using dilute hydrochloric acid, deionized water and absolute ethyl alcohol as cleaning agents in sequence, and then carrying out vacuum drying to obtain pretreated foamed nickel;
secondly, growing a cobalt-based zeolite imidazole ester framework material nanosheet array in situ on the foamed nickel:
①, dissolving cobalt nitrate hexahydrate in deionized water to obtain an aqueous solution of cobalt nitrate hexahydrate;
the concentration of the cobalt nitrate hexahydrate aqueous solution in the step two ① is 0.05-0.15 mol/L;
②, dissolving dimethyl imidazole in deionized water to obtain a dimethyl imidazole aqueous solution;
the concentration of the dimethyl imidazole aqueous solution in the second step ② is 0.3-0.7 mol/L;
③, mixing the cobalt nitrate hexahydrate aqueous solution with the dimethyl imidazole aqueous solution, and stirring to obtain a mixed solution;
the volume ratio of the cobalt nitrate hexahydrate aqueous solution to the dimethyl imidazole aqueous solution in the second step ③ is (0.9-1.1): 0.9-1.1;
④, firstly immersing the pretreated foamed nickel into the mixed solution, then standing for 5-10 h at room temperature, washing the foamed nickel by using deionized water and absolute ethyl alcohol in sequence, and finally drying in an oven to obtain the foamed nickel with the surface growing with the cobalt-based zeolite imidazole ester framework material nanosheet array;
thirdly, calcining:
firstly, placing foamed nickel with a cobalt-based zeolite imidazole ester framework material nanosheet array growing on the surface in a high-temperature tubular furnace, then heating to 600-800 ℃ at a heating rate of 0.5-6 ℃/min, and finally calcining for 2-5 h at the temperature of 600-800 ℃ to obtain the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material.
The principle and advantages of the embodiment are as follows:
the material grows on the foamed nickel in situ, the foamed nickel is used as a conductive substrate (current collector), the material is strong in binding property with the current collector and good in stability, a three-dimensional net structure of the foamed nickel has high conductivity and a transparent structure, the diffusion resistance of electrolyte is small, and the electrolyte has strong proton transport capacity;
secondly, the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material obtained in the embodiment grows on the nickel foam in situ, the nickel foam is used as a nickel source, and high-loading monatomic doping with a content of about 3.5% is realized in the porous carbon material, and the content is obviously higher than the general case (<0.5 wt%). The surface free energy, the quantum size effect, the unsaturated coordination environment and the metal-carrier interaction which are suddenly increased by the monoatomic atom can effectively regulate and control the selectivity, the activity and the stability of the monoatomic atom in the chemical process, so that the monoatomic atom has the advantages of high homogeneous catalysis selectivity, easy product separation realization of heterogeneous phase and the like, and has obvious advantages in the catalysis field;
the carbon material used in the invention is prepared by taking a foliated cobalt-based metal-organic frameworks (Co-MOFs) array as a sacrificial template, so that the microstructure of the foliated array is partially reserved in the obtained product, and the obtained product belongs to a two-dimensional porous carbon material. The porous carbon material is obviously different from a three-dimensional porous carbon material obtained by cobalt-based MOF (such as ZIF67) with a polyhedral structure;
the nickel-nitrogen Co-doped porous carbon material loaded with cobalt nanoparticles obtained in this embodiment is prepared by using a cobalt-based Metal Organic Framework (MOFs) as a precursor, and some cobalt nanoparticles are dispersed on the surface of the material, and the cobalt nanoparticles have a crystal structure, and the particle size of the cobalt nanoparticles is about 10nm to 20nm, and in general, due to the fact that a transition metal has an empty d-orbit and an empty d-orbit electron, the empty orbit can be provided to serve as an electrophilic reagent in a chemical reaction, or a lone-pair electron can be provided to serve as a nucleophilic reagent to form an intermediate product, so that single metal or double metal nanoparticles in transition metals Ni and Co are loaded on the carbon nanostructure, and the strong coupling interaction between graphitized carbon and the metal particles can reduce the reaction activation energy, ensure faster electron transfer, promote the chemical reaction, and adjust the electronic structure of the carbon material, Effective ways to improve their physicochemical properties;
fifthly, the nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles is prepared by taking MOFs as a precursor, and because the MOFs is a zeolite-like material formed by self-assembling a nitrogen-containing polydentate organic ligand and metal atoms or metal atom clusters, the nitrogen content of the porous carbon material obtained by the embodiment is about 8%, the doping of N element is an effective way for improving the electrochemical performance of the porous carbon, and the nitrogen atom and the carbon atom are adjacent in the periodic table of elements, so that N is to sp2Carbon doping has two major advantages: (1) the N and C atom radiuses are similar, so that lattice mismatch can be reduced, and the excellent properties of the parent carbon material cannot be damaged by doping of nitrogen atoms; (2) n has one more electron than C, and after being doped into the carbon material, the nitrogen atom has a lone pair of electrons. The lone pair of electrons can increase the charge density of the carbon material, so that the carbon material forms an n-type semiconductor, thereby enhancing the electron transfer capability and chemical activity of the material;
the nickel-nitrogen co-doped porous carbon material loaded with the cobalt nanoparticles is prepared by taking MOFs as a precursor, has a natural three-dimensional hierarchical pore network structure, and when the porous carbon is used as an electrode material, the matching of the pore diameter and the size of electrolyte ions needs to be considered so as to promote the transport of ions;
seventhly, the nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles, which is obtained by the embodiment, is prepared by taking MOFs as a precursor through high-temperature carbonization, the graphitization degree, namely the conductivity of the porous carbon material has a great influence on the electrochemical performance of the porous carbon material, and the electrochemical performance of the porous carbon material can be effectively improved by performing high-temperature treatment on the porous carbon. Research shows that when the porous carbon is used as an electrode material, the porous carbon obtained by carbonizing MOFs shows better electrochemical performance than that of common activated carbon;
eighthly, the nickel-nitrogen co-doped porous carbon material loaded with the cobalt nanoparticles obtained by the embodiment can show excellent activity and good stability which are obviously superior to those of each single component in the fields of catalytic energy storage and the like, and the main reasons are as follows: (1) due to the strong interaction between nitrogen and nickel/cobalt, strong chemical bonding between the transition metal and the nitrogen-doped carbon carrier can greatly increase the stability, bring about more obvious change of the electronic structure, promote the electron transfer of the material interface and improve the electrochemical activity. (2) More importantly, the strong coupling between the transition metal and N-C at the interface can often bring about a so-called synergistic effect for the hybrid, loading the mono-or bi-metal of the metals Ni, Co on the nitrogen-doped carbon nanostructure, significantly improving the electrochemical performance compared to that without nitrogen doping.
Ninthly, the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material obtained in the embodiment is a porous carbon material with magnetic properties, wherein cobalt and nickel components in the material are ferromagnetic materials, and the introduction of the cobalt and nickel components provides the porous carbon material with magnetic properties, namely magnetism, which is very important for electronic materials;
the nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles and the preparation method thereof have the advantages of ingenious design, simple process, low cost and strong reproducibility, and provide a new method and thought for developing a high-load monatomic catalytic material;
eleventh, this embodimentThe nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles prepared in the formula has good hydrogen evolution performance at 10mA/cm2Under the condition, the overpotential of the nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles prepared by the embodiment is only 64 mV; at a constant current density of 30mA/cm2Under the condition, after the nickel-nitrogen co-doped porous carbon material loaded with the cobalt nanoparticles prepared by the embodiment is subjected to a stability test for 45 hours, the voltage retention rate can reach 94.4%.
The nickel-nitrogen co-doped porous carbon material loaded with the cobalt nanoparticles can be obtained by the embodiment.
The third concrete implementation mode: the present embodiment differs from the first or second embodiment in that: the mass fraction of the dilute hydrochloric acid in the step one is 1-20%, the ultrasonic cleaning power is 100-180W, and the ultrasonic cleaning time is 10-30 min; the vacuum drying temperature in the step one is 50-90 ℃, and the vacuum drying time is 4-10 h. The other steps are the same as in the first or second embodiment.
Fourth embodiment the present embodiment is different from the first to third embodiments in that the concentration of the cobalt nitrate hexahydrate aqueous solution in the second step ① is 0.1mol/L, and the other steps are the same as the first to third embodiments.
Fifth embodiment five the difference between this embodiment and one of the first to fourth embodiments is that the concentration of the aqueous solution of dimethylimidazole in step two ② is 0.5 mol/l.
Sixth embodiment a point of difference between this embodiment and one of the first to fifth embodiments is that the volume ratio of the cobalt nitrate hexahydrate aqueous solution to the dimethylimidazole aqueous solution described in the second step ③ is 1:1, and the other steps are the same as those of the first to fifth embodiments.
Seventh embodiment mode, the difference between this embodiment mode and one of the first to sixth embodiment modes is that the stirring speed in the second step ③ is 500r/min to 1000r/min, and the stirring time is 5min to 30 min.
Eighth specific embodiment the difference between this embodiment and one of the first to seventh specific embodiments is that in the second step ④, the nickel foam is washed with deionized water for 1 to 3 times, then washed with absolute ethyl alcohol for 1 to 3 times, and finally dried in an oven at 40 to 60 ℃ for 2 to 4 hours.
The specific implementation method nine: the difference between this embodiment and the first to eighth embodiments is: in the third step, firstly, the foamed nickel with the surface growing with the cobalt-based zeolite imidazole ester framework material nanosheet array is placed in a high-temperature tubular furnace, then the temperature is raised to 600-700 ℃ at the heating rate of 4-5 ℃/min, and finally the foamed nickel is calcined for 3-4 h at the temperature of 600-700 ℃ to obtain the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material. The other steps are the same as those in the first to eighth embodiments.
The detailed implementation mode is ten: the embodiment is that a nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles is used as a catalyst for hydrogen production by water electrolysis in the field of energy.
The following examples were used to demonstrate the beneficial effects of the present invention:
the first embodiment is as follows: a preparation method of a cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material comprises the following steps:
firstly, pretreatment of foamed nickel:
firstly, ultrasonically cleaning foamed nickel for 15min by using hydrochloric acid with the mass fraction of 10% as a cleaning agent under the ultrasonic power of 150W, then ultrasonically cleaning the foamed nickel for 15min by using deionized water as the cleaning agent under the ultrasonic power of 150W, then ultrasonically cleaning the foamed nickel for 15min by using absolute ethyl alcohol as the cleaning agent under the ultrasonic power of 150W, and finally, drying the foamed nickel in vacuum at 60 ℃ for 5h to obtain pretreated foamed nickel;
secondly, growing a cobalt-based zeolite imidazole ester framework material nanosheet array in situ on the foamed nickel:
①, dissolving 0.582g of cobalt nitrate hexahydrate in 40mL of deionized water to obtain an aqueous solution of cobalt nitrate hexahydrate;
②, dissolving 1.313g of dimethyl imidazole in 40mL of deionized water to obtain a dimethyl imidazole aqueous solution;
③, mixing the cobalt nitrate hexahydrate aqueous solution with the dimethyl imidazole aqueous solution, and stirring for 5min at the stirring speed of 1000r/min to obtain a mixed solution;
the volume ratio of the cobalt nitrate hexahydrate aqueous solution to the dimethyl imidazole aqueous solution in the step two ③ is 1: 1;
④, firstly immersing the pretreated nickel foam into the mixed solution, then standing for 5h at room temperature, firstly washing the nickel foam for 2 times by using deionized water, then washing the nickel foam for 2 times by using absolute ethyl alcohol, and finally drying in an oven at the temperature of 50 ℃ for 2h to obtain the nickel foam with a cobalt-based zeolite imidazole ester framework material (Co-ZIF) nanosheet array growing on the surface;
thirdly, calcining:
firstly, placing foamed nickel with a cobalt-based zeolite imidazole ester framework material nanosheet array growing on the surface in a high-temperature tubular furnace, then heating to 650 ℃ at a heating rate of 5 ℃/min, and finally calcining for 3h at 600 ℃ to obtain the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material.
Example two: the present embodiment is different from the first embodiment in that: in the third step, firstly, the foamed nickel with the surface growing with the cobalt-based zeolite imidazole ester framework material nanosheet array is placed in a high-temperature tubular furnace, then the temperature is raised to 600 ℃ at the heating rate of 5 ℃/min, and finally, the foamed nickel is calcined for 3 hours at the temperature of 600 ℃ to obtain the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material. Other steps and parameters are the same as those in the first embodiment.
Example three: the present embodiment is different from the first embodiment in that: in the third step, firstly, the foamed nickel with the surface growing with the cobalt-based zeolite imidazole ester framework material nanosheet array is placed in a high-temperature tubular furnace, then the temperature is raised to 700 ℃ at the heating rate of 5 ℃/min, and finally, the foamed nickel is calcined for 3 hours at the temperature of 700 ℃ to obtain the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material. Other steps and parameters are the same as those in the first embodiment.
Example four: the present embodiment is different from the first embodiment in that: in the third step, firstly, the foamed nickel with the surface growing with the cobalt-based zeolite imidazole ester framework material nanosheet array is placed in a high-temperature tubular furnace, then the temperature is raised to 750 ℃ at the heating rate of 5 ℃/min, and finally, the foamed nickel is calcined for 3 hours at the temperature of 750 ℃ to obtain the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material. Other steps and parameters are the same as those in the first embodiment.
Example five: the present embodiment is different from the first embodiment in that: in the third step, firstly, the foamed nickel with the surface growing with the cobalt-based zeolite imidazole ester framework material nanosheet array is placed in a high-temperature tubular furnace, then the temperature is raised to 800 ℃ at the heating rate of 5 ℃/min, and finally, the foamed nickel is calcined for 3 hours at the temperature of 800 ℃ to obtain the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material. Other steps and parameters are the same as those in the first embodiment.
FIG. 1 is a scanning electron microscope image of an array of Co-ZIF nanosheets grown vertically on nickel foam obtained in step two of the example;
as can be seen from FIG. 1, the synthesized product has a leaf-like appearance and grows vertically on the surface of the foamed nickel to form an array. The blade has smooth surface, uniform size, width of about 3-5 microns and thickness of about 250 nm.
FIG. 2 is an X-ray diffraction spectrum of a Co-ZIF nanosheet array grown vertically on nickel foam obtained in step two of the example;
three strong diffraction peaks in the spectral line of FIG. 2 are from foamed nickel, other diffraction peaks belong to cobalt-based zeolite imidazole ester framework material Co-ZIF, and the crystallinity of the nanosheet is good.
FIG. 3 is a scanning electron microscope image of the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material obtained in step three of the example;
as can be seen from FIG. 3, the synthesized product does not completely maintain the original foliated morphology, a plurality of fine-grained pores appear in the material structure, and the surface is not smooth any more.
FIG. 4 is an X-ray diffraction spectrum of a nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles obtained in step three of the example, wherein "xxx" in FIG. 4 is a signal of carbon;
the three strong diffraction peaks in the spectral line of FIG. 4 are from foamed nickel, the diffraction peaks belonging to the Co-ZIF of the zeolitic imidazolate framework material disappear completely, and the diffraction peaks of the carbon material (JCPDS:75-2078) appear in hopes, which indicates that the Co-ZIF of the zeolitic imidazolate framework material has been successfully carbonized.
Fig. 5 is a first transmission electron microscope image of the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material obtained in step three of the example;
fig. 6 is a second transmission electron microscope image of the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material obtained in step three of the example;
as can be seen from fig. 5 and fig. 6, the synthesized product is a two-dimensional porous structure loaded with nanoparticles, the size of the nanoparticles is about several nanometers to twenty nanometers, the porous material has a multi-layer porous structure from micropores, mesopores to macropores and a higher specific surface area, and the pore sizes are randomly distributed.
Fig. 7 is a scanning transmission electron microscope image of the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material obtained in step three of the example, where the region 1 is a sampling region and the region 2 is a test calibration sampling region;
FIG. 8 is a distribution plot of the area of the C element in region 1 of FIG. 7;
FIG. 9 is a distribution plot of the area of the N elements in region 1 of FIG. 7;
FIG. 10 is a distribution diagram of the area of Co element in the region 1 of FIG. 7;
FIG. 11 is a surface distribution diagram of Ni element in region 1 of FIG. 7;
as can be seen from fig. 7 to 11, the synthesized product in the first embodiment is a nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles, nitrogen and nickel elements are uniformly doped in the porous carbon material, the cobalt nanoparticles are embedded in the nitrogen-nickel co-doped porous carbon material, and the contents of cobalt, nickel, and nitrogen are respectively: 26.2%, 3.5% and 7.6%.
Fig. 12 is a third transmission electron microscope image of the cobalt nanoparticle-supported nickel-nitrogen co-doped porous carbon material obtained in step three of the example.
As can be seen in fig. 12, the cobalt particles are elliptical crystals with a short diameter of about 10nm and a long diameter of about 15 nm; the nickel element is doped into the material in a single atom form.
Water electrolysis hydrogen production experiment:
in a standard three-electrode electrolytic cell, the nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles prepared in the five examples is subjected to electrochemical catalytic performance test in a 1M KOH electrolyte. The nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles is used as a working electrode, the reference electrode is an Ag/AgCl electrode, and the counter electrode is a carbon rod. The linear voltammetry curve was tested and the potential obtained with the Ag/AgCl electrode as reference electrode was converted to the standard hydrogen electrode potential, see fig. 13.
Fig. 13 is a linear voltammetry characteristic graph, in which 1 is a linear voltammetry characteristic curve of a Pt/C electrode, 2 is a linear voltammetry characteristic curve of a cobalt nanoparticle-supported nickel-nitrogen-co-doped porous carbon material prepared in example one, 3 is a linear voltammetry characteristic curve of a cobalt nanoparticle-supported nickel-nitrogen-co-doped porous carbon material prepared in example two, 4 is a linear voltammetry characteristic curve of a cobalt nanoparticle-supported nickel-nitrogen-co-doped porous carbon material prepared in example three, 5 is a linear voltammetry characteristic curve of a cobalt nanoparticle-supported nickel-nitrogen-co-doped porous carbon material prepared in example four, and 6 is a linear voltammetry characteristic curve of a cobalt nanoparticle-supported nickel-nitrogen-co-doped porous carbon material prepared in example five;
as can be seen by comparison in fig. 13, the nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles has good hydrogen evolution performance, and the catalytic activity of the sample calcined at 650 ℃ in five examples is the best. At 10mA/cm2Has an overpotential (64mV) closest to that of platinum carbon.
Fig. 14 is a stability characteristic graph of the nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles prepared in example one.
In FIG. 14, the current density was constant at 30mA/cm2Under the condition, after the sample is subjected to a stability test for 45 hours, the voltage retention rate can reach 94.4%, which indicates that the material has good stability.
The foregoing is a more detailed description of the invention in connection with specific preferred embodiments and it is not intended that the invention be limited to these specific details. For those skilled in the art to which the invention pertains, several simple deductions or substitutions can be made without departing from the spirit of the invention, and all shall be considered as belonging to the protection scope of the invention.
Claims (10)
1. The nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles is characterized in that a nickel-nitrogen co-doped porous carbon material loaded with cobalt nanoparticles grows on foamed nickel in situ, cobalt particles are embedded on the nitrogen-nickel co-doped porous carbon material, the content of cobalt is 5-30%, the content of nickel is 0.1-5%, and the content of nitrogen is 3-8%; the cobalt particles are ellipsoidal crystals, and the size of the cobalt particles is 5 nm-30 nm.
2. The method for preparing the cobalt nanoparticle-supported nickel-nitrogen co-doped porous carbon material as claimed in claim 1, wherein the method for preparing the cobalt nanoparticle-supported nickel-nitrogen co-doped porous carbon material is completed according to the following steps:
firstly, pretreatment of foamed nickel:
carrying out ultrasonic cleaning on the foamed nickel by using dilute hydrochloric acid, deionized water and absolute ethyl alcohol as cleaning agents in sequence, and then carrying out vacuum drying to obtain pretreated foamed nickel;
secondly, growing a cobalt-based zeolite imidazole ester framework material nanosheet array in situ on the foamed nickel:
①, dissolving cobalt nitrate hexahydrate in deionized water to obtain an aqueous solution of cobalt nitrate hexahydrate;
the concentration of the cobalt nitrate hexahydrate aqueous solution in the step two ① is 0.05-0.15 mol/L;
②, dissolving dimethyl imidazole in deionized water to obtain a dimethyl imidazole aqueous solution;
the concentration of the dimethyl imidazole aqueous solution in the second step ② is 0.3-0.7 mol/L;
③, mixing the cobalt nitrate hexahydrate aqueous solution with the dimethyl imidazole aqueous solution, and stirring to obtain a mixed solution;
the volume ratio of the cobalt nitrate hexahydrate aqueous solution to the dimethyl imidazole aqueous solution in the second step ③ is (0.9-1.1): 0.9-1.1;
④, firstly immersing the pretreated foamed nickel into the mixed solution, then standing for 5-10 h at room temperature, washing the foamed nickel by using deionized water and absolute ethyl alcohol in sequence, and finally drying in an oven to obtain the foamed nickel with the surface growing with the cobalt-based zeolite imidazole ester framework material nanosheet array;
thirdly, calcining:
firstly, placing foamed nickel with a cobalt-based zeolite imidazole ester framework material nanosheet array growing on the surface in a high-temperature tubular furnace, then heating to 600-800 ℃ at a heating rate of 0.5-6 ℃/min, and finally calcining for 2-5 h at the temperature of 600-800 ℃ to obtain the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material.
3. The preparation method of the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material as claimed in claim 2, wherein the mass fraction of the dilute hydrochloric acid in the step one is 1-20%, the power of ultrasonic cleaning is 100-180W, and the time of ultrasonic cleaning is 10-30 min; the vacuum drying temperature in the step one is 50-90 ℃, and the vacuum drying time is 4-10 h.
4. The method for preparing the cobalt nanoparticle-supported nickel-nitrogen co-doped porous carbon material as claimed in claim 2, wherein the concentration of the cobalt nitrate hexahydrate in the step two ① is 0.1 mol/L.
5. The method for preparing the cobalt nanoparticle-supported nickel-nitrogen co-doped porous carbon material as claimed in claim 2, wherein the concentration of the aqueous solution of dimethylimidazole in step two ② is 0.5 mol/L.
6. The method for preparing the cobalt nanoparticle-supported nickel-nitrogen co-doped porous carbon material as claimed in claim 2, wherein the volume ratio of the cobalt nitrate hexahydrate aqueous solution to the dimethylimidazole aqueous solution in the step two ③ is 1: 1.
7. The preparation method of the cobalt nanoparticle-supported nickel-nitrogen co-doped porous carbon material as claimed in claim 2, wherein the stirring speed in step two ③ is 500 r/min-1000 r/min, and the stirring time is 5 min-30 min.
8. The preparation method of the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material as claimed in claim 2, wherein in step two ④, the foam nickel is washed with deionized water for 1 to 3 times, then washed with absolute ethanol for 1 to 3 times, and finally dried in an oven at 40 to 60 ℃ for 2 to 4 hours.
9. The preparation method of the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material according to claim 2, characterized in that in the third step, firstly, the foamed nickel with the cobalt-based zeolite imidazole ester framework material nanosheet array growing on the surface is placed in a high-temperature tubular furnace, then the temperature is raised to 600-700 ℃ at the temperature rise rate of 4-5 ℃/min, and finally the temperature is calcined at 600-700 ℃ for 3-4 h, so as to obtain the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material.
10. The application of the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material as claimed in claim 2, wherein the cobalt nanoparticle-loaded nickel-nitrogen co-doped porous carbon material is used as a catalyst for hydrogen production by water electrolysis in the field of energy.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111530486A (en) * | 2020-04-23 | 2020-08-14 | 华南理工大学 | Novel nitrogen-doped carbon-loaded copper-doped cobalt phosphide double-layer hollow nanoparticle composite array material and preparation method thereof |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105140531A (en) * | 2015-09-23 | 2015-12-09 | 太原理工大学 | Three-dimensional anode material for hydrogen production by water electrolysis and preparation method of three-dimensional anode material |
| CN105598443A (en) * | 2014-11-18 | 2016-05-25 | 中国科学院大连化学物理研究所 | A heteroatom-doped carbon-packaged metal nanoparticle preparing method |
| CN107999075A (en) * | 2017-12-29 | 2018-05-08 | 济南大学 | A kind of aza material preparation method of NiO nanoparticle doped carbon and application |
| CN108923051A (en) * | 2018-07-06 | 2018-11-30 | 郑州大学 | A kind of nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle and its application |
| CN110120524A (en) * | 2019-05-21 | 2019-08-13 | 西南大学 | A kind of load cobalt protoxide/nitrogen-doped carbon nickel foam composite material and preparation method and application |
-
2019
- 2019-10-30 CN CN201911049859.0A patent/CN110721724B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105598443A (en) * | 2014-11-18 | 2016-05-25 | 中国科学院大连化学物理研究所 | A heteroatom-doped carbon-packaged metal nanoparticle preparing method |
| CN105140531A (en) * | 2015-09-23 | 2015-12-09 | 太原理工大学 | Three-dimensional anode material for hydrogen production by water electrolysis and preparation method of three-dimensional anode material |
| CN107999075A (en) * | 2017-12-29 | 2018-05-08 | 济南大学 | A kind of aza material preparation method of NiO nanoparticle doped carbon and application |
| CN108923051A (en) * | 2018-07-06 | 2018-11-30 | 郑州大学 | A kind of nitrogen-doped carbon nanometer pipe composite catalyst of package metals cobalt nano-particle and its application |
| CN110120524A (en) * | 2019-05-21 | 2019-08-13 | 西南大学 | A kind of load cobalt protoxide/nitrogen-doped carbon nickel foam composite material and preparation method and application |
Non-Patent Citations (3)
| Title |
|---|
| JINLIN YANG 等: ""Cobalt-carbon derived from zeolitic imidazolate framework on Ni foam as high-performance supercapacitor electrode material"", 《MATERIALS & DESIGN》 * |
| ZEHUI LI等: ""Atomic Co/Ni dual sites and Co/Ni alloy nanoparticles in N-doped porous Janus-like carbon frameworks for bifunctional oxygen electrocatalysis"", 《APPLIED CATALYSIS B: ENVIRONMENTAL》 * |
| 宋丹丹、崔丽莉: ""N和Co修饰的多孔碳催化剂的制备及电催化析氢性能研究"", 《长春理工大学学报（自然科学版）》 * |
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