CN115475641B - Metal atom anchored boron-nitrogen co-doped carbon material and preparation method thereof - Google Patents

Metal atom anchored boron-nitrogen co-doped carbon material and preparation method thereof Download PDF

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CN115475641B
CN115475641B CN202210890312.9A CN202210890312A CN115475641B CN 115475641 B CN115475641 B CN 115475641B CN 202210890312 A CN202210890312 A CN 202210890312A CN 115475641 B CN115475641 B CN 115475641B
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nitrogen
boron
carbon material
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CN115475641A (en
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闫理停
赵学波
赵彦超
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Qilu University of Technology
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Abstract

The invention provides a preparation method of a boron-nitrogen co-doped carbon material anchored by metal atoms, which is characterized by comprising the following steps: 1) Synthesizing Metal Organic Frameworks (MOFs) precursors doped with different metals by using a solvothermal method; 2) Calcining MOFs precursors doped with different metals under a certain inert atmosphere, washing and centrifuging (or vacuum filtering) by using ethanol, and drying to obtain the metal atom anchored boron-nitrogen co-doped carbon material with the three-dimensional flower cluster spherical super structure. The preparation method is simple, efficient, low in cost and easy for industrial production. The boron-nitrogen co-doped carbon material anchored by the three-dimensional flower-shaped metal atoms has larger specific surface area, shows excellent catalytic activity in electrocatalytic nitrogen reduction reaction and is an excellent three-dimensional carbon material by introducing different metal/nonmetal heteroatoms to modify the carbon material with the three-dimensional flower-shaped spherical super structure.

Description

Metal atom anchored boron-nitrogen co-doped carbon material and preparation method thereof
Technical Field
The invention relates to the technical field of electrochemistry and new energy materials, in particular to a boron-nitrogen co-doped carbon material anchored by metal atoms and a preparation method thereof.
Background
Ammonia (NH) 3 ) Is considered as not only an important substance in industry, agriculture and medical and health industries, but also a carbon-free hydrogen storage material. Although the atmosphere contains nitrogen, a rich raw material for synthesizing ammonia, the nitrogen is converted into NH due to the chemical inertness of the nitrogen-nitrogen triple bond 3 Quite difficult. At present, the industrial preparation of ammonia is mainly based on a Haber-Bosch method, but the method has high pollution degree and high energy consumption. The electrocatalytic nitrogen reduction synthesis of ammonia (NRR) has the characteristic of mild reaction conditions and canSo as to convert renewable electric power into chemical energy in NH3, and is an ideal alternative process for the Haber-Bosch method. Unfortunately, the adsorption performance of nitrogen is poor, the N.ident.N bond energy is large (941 KJ. Mol -1 ) And the occurrence of competing hydrogen evolution reactions in aqueous solutions greatly hamper the development of electrocatalytic nitrogen reduction technologies. The use of catalysts to increase the reaction rate and selectivity is the most cost effective method in modern chemical industry production. Monoatomic catalysts (SACs) are receiving increasing attention for their complete exposure of the active site. However, noble metal monoatomic catalysts have limited applications due to their limited reserves, high price, etc., and transition metals (e.g., fe, co, ni) are considered to be one of the materials that is most promising alternatives to noble metal monoatomic catalysts. The choice of the carrier for the single-atom catalyst is also important. Because the metal monoatomic-carrier interaction can stabilize the metal sites of atomic dispersion, a new opportunity is provided for adjusting the electronic structure of monoatomic metal and the coordination environment thereof so as to optimize the catalytic performance. The carrier of the common single-atom catalyst is mainly a carbon material, but the acting force of carbon and metal is weak, and metal-H bonds are easy to form in the electrocatalytic reaction process, so that FE is lower. Studies have shown that BN can anchor metal atoms as a substrate, but BN has poor electrical conductivity. Interestingly, BN doped in the carbon matrix can cause electron defects in the carbon matrix, promote chemisorption of nitrogen, and increase the N 2 The capture capacity of the lone pair electrons of the molecule. It is an important challenge to use B/N co-doped carbon materials as substrates to anchor metal atoms to produce active sites with high dispersion and uniform distribution.
Chinese patent CN114635152a discloses a single-atom dispersed transition metal supported carbon-based catalyst and a method for preparing the same. Synthesizing transition metal doped zinc oxide by a solution-sol-gel-high temperature firing mode, performing high temperature reaction with 2-methylimidazole, and then performing acid washing and drying to obtain the carbon-based single-atom catalyst. The method realizes the effective finite field of doped metal, constructs a micron-sized framework of ZIF-8, and finally obtains a single-atom active site and a micron-sized mass transfer channel left after the framework is removed by pickling. However, the preparation process of the method is complex, the reaction conditions are not well controlled, the consistency of the product is unstable, the production efficiency is low, and the method is not beneficial to large-scale industrial production.
Chinese patent CN114672838A discloses a method for preparing a carbon-based nitrogen coordinated metal monoatomic or cluster catalyst, which uses small organic molecules containing nitrogen and volatile organic metal salts which are easy to sublimate as raw materials, and the raw materials are mixed with activated carbon for grinding, and then the mixture is subjected to high-temperature treatment in a tube furnace after uniform grinding, and the mixture is cooled to obtain the carbon-based nitrogen coordinated metal monoatomic or cluster catalyst. However, the porous carbon material prepared by the method cannot regulate the structure and the composition of the material, and cannot integrate multifunctional composite carbon materials with different internal structures.
Therefore, it is necessary to develop a catalyst material which is simple in preparation method and well anchors metal atoms.
Disclosure of Invention
The invention aims at overcoming the defects of the prior art and providing a boron-nitrogen co-doped carbon material anchored by metal atoms and a preparation method thereof.
In the invention, the metal organic framework compound is called MOFs for short, and the metal-atom-anchored boron-nitrogen co-doped carbon material is obtained by using the metal organic framework compound as a carrier through simple heat treatment, and the material shows excellent catalytic activity in electrocatalytic nitrogen reduction reaction and is an excellent three-dimensional carbon material.
The preparation method provided by the invention prepares the three-dimensional metal atom anchored boron-nitrogen co-doped carbon material by a simple, efficient and low-cost method and is easy to industrialize. Carbon materials with different metal atom anchors and heteroatom doping can be prepared by utilizing the regulation and control of MOFs composition and structure. The prepared carbon material has larger specific surface area, boron and nitrogen doping can be uniformly introduced by utilizing the flexibility and diversity of organic ligands in MOFs, so that a uniform carbon network skeleton and a metal catalytic center are formed, and the synergistic effect of the carbon material is beneficial to electrochemical catalysis, hydrodesulfurization, selective hydrogenation and other hydrogenation reactions, so that the carbon material has a wide application prospect.
The technical scheme of the invention is realized as follows:
a preparation method of a boron-nitrogen co-doped carbon material anchored by metal atoms comprises the following steps:
1) Preparation of MOFs precursor:
weighing a certain amount of organic ligand, zinc nitrate hexahydrate, metal salt and boric acid, dissolving in a solvent, and fully stirring; synthesizing MOFs precursor;
2) And placing MOFs precursors doped with different metals into a corundum porcelain boat, then placing the corundum porcelain boat into a tube furnace, heating to 500-1100 ℃ under a certain inert atmosphere, calcining for 0.5-12 hours, washing and centrifuging by using ethanol, and drying to obtain the metal atom anchored boron-nitrogen co-doped carbon material with the three-dimensional flower cluster spherical super structure.
Preferably, the synthesis method for preparing the MOFs precursor in the step 1) adopts a solvothermal method.
Preferably, the organic ligand in the step 1) is selected from one or more of imidazole, 2-methylimidazole, 4 '-bipyridine, 2' -bipyridine, phenanthroline and pyrazine.
Preferably, the metal salt in the step 1) is selected from one or more of nickel, cobalt or iron metal salts; the metal salt in the step 1) is selected from one or a combination of more of sulfate hydrate, nitrate hydrate, chloride hydrate, acetate hydrate or acetylacetone metal salt.
Preferably, the molar ratio of the organic ligand to the zinc nitrate hexahydrate in the step 1) is (1:10) to (10:1).
Preferably, the solvent in the step 1) is one or more of methanol, ethanol, N-dimethylformamide or water.
Preferably, the reaction conditions of the solvothermal method used for preparing the MOFs precursor in the step 1) are as follows: transferring the mixed solution of the organic ligand, the metal salt and the boric acid dissolved in the solvent into a reaction kettle with a polytetrafluoroethylene lining, heating to 100-150 ℃ for reaction for 6-72 hours, centrifugally separating the product, and cleaning to obtain the MOFs precursor.
Preferably, the mass ratio of the zinc nitrate hexahydrate to the boric acid in the step 1) is (1:50) to (5:1).
Preferably, the mass ratio of the zinc nitrate hexahydrate to the substances of the different metal salts in the step 1) is (1000:1) to (100:1).
Preferably, the inert atmosphere in the step 2) is any one of argon, nitrogen or helium; the temperature rising rate of the inert atmosphere is 1-20 ℃/min, and the temperature rises from room temperature to 500-1100 ℃; the gas flow rate of the inert atmosphere is 1-100 mL/min.
Based on the same inventive concept, the invention also provides a boron-nitrogen co-doped carbon material anchored by metal atoms, which is prepared by adopting the preparation method.
Advantageous effects
The invention provides a boron-nitrogen co-doped carbon material anchored by metal atoms and a preparation method thereof, and the boron-nitrogen co-doped carbon material has the beneficial effects that:
1. according to the invention, metal doped MOFs with different structures and compositions are used as precursors, and uniformly doped three-dimensional flower-shaped metal atom anchored boron-nitrogen co-doped carbon materials with controllable element content can be obtained through simple heat treatment. Compared with the traditional heteroatom doped carbon material, the boron nitrogen co-doping method for preparing the metal atom anchored boron nitrogen co-doped carbon material has the advantages of being more uniform in activity distribution, obvious in advantage, larger in specific surface area, capable of carrying out various modifications and functionalization on the carbon material through MOFs structure and composition diversity, and very beneficial to popularization and development of the carbon material.
2. The boron nitrogen co-doped carbon material anchored by metal atoms can improve the mass-charge transfer efficiency in the catalytic process, and the catalytic effect of the catalyst can be greatly improved through the synergistic effect of the boron nitrogen co-doped carbon material and metal active centers derived from MOFs.
3. In addition, the preparation process has low requirements on a reaction device, has no participation of harmful gases, organic substances and other reactants, has simple process and is suitable for large-scale industrial production.
Drawings
FIG. 1 is an X-ray powder diffraction pattern (XRD) of a three-dimensional flower-like metallic iron atom anchored boron nitrogen co-doped carbon material prepared in example 1;
FIG. 2 is a Scanning Electron Microscope (SEM) image of a three-dimensional flower-like metallic iron atom anchored boron nitrogen co-doped carbon material prepared in example 1;
FIG. 3 is a scanning electron microscope high-magnification view (SEM) of a three-dimensional flower-like metallic iron atom anchored boron nitrogen co-doped carbon material prepared in example 1;
FIG. 4 is a graph showing the distribution of particle diameters of three-dimensional flower-like metallic iron atom-anchored boron-nitrogen co-doped carbon materials prepared in example 1;
FIG. 5 is a Transmission Electron Microscope (TEM) image of a three-dimensional flower-like metallic iron atom anchored boron nitrogen co-doped carbon material prepared in example 1;
FIG. 6 is a transmission electron microscope high-magnification (TEM) of a three-dimensional flower-like metallic iron atom anchored boron nitrogen co-doped carbon material prepared in example 1;
FIG. 7 is a selected area electron diffraction pattern (SAED) of a three-dimensional flower-like metallic iron atom anchored boron nitrogen co-doped carbon material prepared in example 1;
FIG. 8 is a high angle annular dark field scanning transmission electron microscopy (HAADF-STEM) of three-dimensional flower-like metallic iron atom anchored boron nitrogen co-doped carbon materials prepared in example 1;
FIG. 9 is a graph of nitrogen physisorption of three-dimensional flower-like metallic iron atom anchored boron nitrogen co-doped carbon materials prepared in example 1;
FIG. 10 is a pore size distribution diagram of a three-dimensional flower-like metallic iron atom anchored boron nitrogen co-doped carbon material prepared in example 1;
FIG. 11 is a Mapping element distribution diagram of a boron nitrogen co-doped carbon material anchored by three-dimensional flower-like metallic iron atoms prepared in example 1.
FIG. 12 is a Linear Sweep Voltammetry (LSV) plot of catalytic electrochemical nitrogen reduction (NRR) in 0.1M KOH for a three-dimensional flower-like metallic iron atom anchored boron nitrogen co-doped carbon material prepared in example 1;
FIG. 13 is a linear sweep voltammetry plot b (LSV) of a three-dimensional flower-like metallic iron atom anchored boron nitrogen co-doped carbon material prepared in example 1 in 0.1M HCl catalyzing electrochemical nitrogen reduction (NRR);
FIG. 14 is a stability test of three-dimensional flower-like metallic iron atom anchored boron nitrogen co-doped carbon materials prepared in example 1;
FIG. 15 is a schematic representation of the yield and Faraday efficiency of nitrogen reduction synthesis of ammonia catalyzed by the three-dimensional flower-like metallic iron atom anchored boron nitrogen co-doped carbon material prepared in example 1;
FIG. 16 is an X-ray powder diffraction pattern (XRD) of a three-dimensional flower-like metallic cobalt atom-anchored boron-nitrogen co-doped carbon material prepared in example 2;
FIG. 17 is a Scanning Electron Microscope (SEM) image of a three-dimensional flower-like metallic cobalt atom anchored boron nitrogen co-doped carbon material prepared in example 2;
FIG. 18 is a scanning electron microscope high-magnification (SEM) of a three-dimensional flower-like metallic cobalt atom anchored boron nitrogen co-doped carbon material prepared in example 2;
FIG. 19 is a graph showing the particle diameter distribution of a three-dimensional flower-like metallic cobalt atom-anchored boron-nitrogen co-doped carbon material prepared in example 2;
FIG. 20 is a graph of nitrogen physisorption of three-dimensional flower-like metallic cobalt atom anchored boron-nitrogen co-doped carbon materials prepared in example 2;
FIG. 21 is a pore size distribution plot of a three-dimensional flower-like metallic cobalt atom anchored boron nitrogen co-doped carbon material prepared in example 2;
FIG. 22 is an X-ray powder diffraction pattern (XRD) of a three-dimensional flower-like metallic nickel atom-anchored boron-nitrogen co-doped carbon material prepared in example 3;
FIG. 23 is a Scanning Electron Microscope (SEM) image of a three-dimensional flower-like metallic nickel atom anchored boron nitrogen co-doped carbon material prepared in example 3;
FIG. 24 is a scanning electron microscope high-magnification (SEM) image of a three-dimensional flower-like metallic nickel atom anchored boron nitrogen co-doped carbon material prepared in example 3;
FIG. 25 is a graph of particle diameter distribution of a three-dimensional flower-like metallic nickel atom anchored boron nitrogen co-doped carbon material prepared in example 3;
FIG. 26 is a graph of nitrogen physisorption of three-dimensional flower-like metallic nickel atom anchored boron nitrogen co-doped carbon materials prepared in example 3;
FIG. 27 is a pore size distribution plot of a three-dimensional flower-like metallic nickel atom anchored boron nitrogen co-doped carbon material prepared in example 3.
Detailed Description
The following description of the embodiments of the present invention will clearly and fully describe the technical solutions of the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. The terminology used in the description of the invention herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the invention. The term "and/or" as used in this specification includes any and all combinations of one or more of the associated listed items.
The experimental methods used in the following examples are conventional methods unless otherwise specified.
Materials, reagents and the like used in the examples described below are commercially available unless otherwise specified.
A preparation method of a boron-nitrogen co-doped carbon material anchored by metal atoms comprises the following steps:
1) Preparation of MOFs precursor:
weighing a certain amount of organic ligand, zinc nitrate hexahydrate, different metal salts and boric acid, dissolving in a solvent, and fully stirring; then synthesizing MOFs precursor by using a solvothermal method;
2) And placing MOFs precursors doped with different metals into a corundum porcelain boat, then placing the corundum porcelain boat into a tube furnace, heating to 500-1100 ℃ under a certain inert atmosphere, calcining for 0.5-12 hours, washing and centrifuging by using ethanol, and drying to obtain the metal atom anchored boron-nitrogen co-doped carbon material with the three-dimensional flower cluster spherical super structure.
According to the invention, MOFs materials doped with different metals are synthesized by a conventional solvothermal method, and the MOFs materials are subjected to simple heat treatment to obtain the uniformly doped boron-nitrogen co-doped carbon material with the metal atoms anchored by the three-dimensional flower-cluster spherical super structure, wherein the element content of the boron-nitrogen co-doped carbon material is controllable. In the invention, MOFs can be used as a carrier loaded by metal atoms and can prevent the metal atoms from gathering, so that the catalytic efficiency of the metal atoms is greatly improved. More importantly, the rich metal active centers in MOFs and the boron nitrogen and other heteroatoms are uniformly distributed on the molecular level, so that the flower cluster-shaped spherical super-structure carbon material can have uniform metal active centers and nitrogen doping, which are beneficial to enhancing the catalytic activity and the functionality of the carbon material. According to the invention, the metal atom anchored boron-nitrogen co-doped carbon material of the three-dimensional flower cluster-shaped spherical super structure is prepared by utilizing the pyrolysis mode of MOFs precursors doped with different metals, and the preparation method is simple in process and beneficial to large-scale production.
In the present invention, the organic ligand, the metal salt and boric acid are not particularly limited, and are commercially available products.
The method of vacuum filtration in step 2) of the present invention is not particularly limited, and the method of vacuum filtration known to those skilled in the art may be used.
Preferably, the synthesis method for preparing the MOFs precursor in the step 1) adopts a solvothermal method.
Preferably, the organic ligand in the step 1) is selected from any one of imidazole, 2-methylimidazole, 4 '-bipyridine, 2' -bipyridine, phenanthroline and pyrazine. Wherein imidazole, 2-methylimidazole, 4 '-bipyridine, 2' -bipyridine, phenanthroline and pyrazine are nitrogen-containing organic ligands; more preferably, the nitrogen-containing organic ligand is selected from imidazole or 2-methylimidazole; most preferably, the use of a nitrogen-containing organic ligand selected from the group consisting of 2-methylimidazole results in a better structure of the MOFs precursor prepared in step 1).
Preferably, the metal salt in the step 1) is selected from any one of zinc, nickel, cobalt or iron metal salt; the metal salt in the step 1) is selected from any one of sulfate hydrate, nitrate hydrate, chloride hydrate or acetate hydrate metal salt; more preferably, the metal salt is selected from iron or cobalt metal salts, and the metal salt is selected from acetylacetonate; most preferably, the metal salt is selected from ferric acetylacetonate, a variety of MOFs can be obtained, and the effect of autocatalysis of MOFs to form the carbon material is optimal.
Preferably, the mass ratio of the zinc nitrate hexahydrate to the substances of the different metal salts in the step 1) is (1000:1) - (100:1), and at the molar ratio, the concentration of the different metal salts in the step 1) is 0.01-0.1 g/L; most preferably, the molar ratio of zinc nitrate hexahydrate to different metal salts in step 1) is 225:1, at which molar ratio the concentration of the organic ligand is 0.5mol/L, the concentration of the metal salt is 0.13mol/L, and the concentration of zinc nitrate hexahydrate is 0.17g/L, at which molar ratio and the concentrations of the organic ligand and the metal salt a metal atom doped MOF precursor can be obtained.
Preferably, the molar ratio of the organic ligand to the zinc nitrate in the step 1) is (1:10) - (10:1), and at the molar ratio, the concentration of the organic ligand in the step 1) is 0.01-0.5 mol/L, and the concentration of the zinc nitrate hexahydrate is 0.1-5 mol/L; more preferably, the molar ratio of the organic ligand to the zinc nitrate hexahydrate in the step 1) is (1:2) - (5:1), and at the molar ratio, the concentration of the organic ligand in the step 1) is 0.05-0.5 mol/L, and the concentration of the zinc nitrate hexahydrate is 0.1mol/L; most preferably, the molar ratio of the organic ligand to the zinc nitrate hexahydrate in the step 1) is 4:1, and when the concentration of the organic ligand is 0.5mol/L, the concentration of the zinc nitrate hexahydrate is 0.13mol/L, and when the molar ratio and the concentration of the organic ligand and the zinc nitrate hexahydrate are the molar ratio, the MOFs structure with better structure can be obtained.
Preferably, the solvent in the step 1) is any one of methanol, ethanol and N, N-dimethylformamide. In the invention, MOFs precursor is synthesized by a solvothermal method, and the solvent is methanol, ethanol or N, N-dimethylformamide. Most preferably, the solvent in the step 1) is methanol, which is cheap and easy to obtain, has good compatibility and can be suitable for various MOFs precursor structures.
Preferably, the reaction conditions of the solvothermal method used for preparing the MOFs precursor in the step 1) are as follows: transferring a mixed solution of an organic ligand, metal salt and boric acid dissolved in a solvent into a reaction kettle with a polytetrafluoroethylene lining, heating to 100-150 ℃ for reaction for 6-72 hours, centrifugally separating and cleaning a product to obtain MOFs precursors; more preferably, the temperature is raised to 120-150 ℃ for reaction for 24 hours; most preferably, the reaction is carried out at a temperature of 150℃for 24 hours.
Preferably, the inert atmosphere in the step 2) is any one of argon, nitrogen or helium, and most preferably, the inert atmosphere is argon; the temperature rising rate of the inert atmosphere is 1-20 ℃/min, the temperature rises from room temperature to 500-1100 ℃, more preferably, the temperature rising rate is 5-10 ℃/min, most preferably, the temperature rising rate is 5 ℃/min; the gas flow rate of the inert atmosphere is 1-100 mL/min, more preferably, the gas flow rate of the inert atmosphere is 20-100 mL/min, the excessive purge gas flow rate (more than 100 mL/min) can generate disturbance at high temperature, the excessively low gas flow rate (less than 10 mL/min) can influence the reaction of the surface of the bulk material in the thermal reaction process, and most preferably, the gas flow rate of the inert atmosphere is 40mL/min.
Preferably, the heat treatment temperature in the step 2) is 500-1100 ℃, and the heat treatment time is 0.5-12 hours; more preferably, the heat treatment temperature is 700-1000 ℃, zinc in MOFs can not be removed at too low temperature (lower than 700 ℃), the graphitization degree and the aggregation degree of metal centers can be increased, the number of active sites is reduced, and the catalytic activity is further affected, and the heat treatment time is 4-8 hours when the heat treatment temperature is 700-1000 ℃; most preferably, the heat treatment temperature is 900 ℃ and the heat treatment time is 6 hours.
Based on the same inventive concept, the invention also provides a boron-nitrogen co-doped carbon material anchored by three-dimensional flower-shaped metal atoms, which is modified by introducing different metal/nonmetal heteroatoms and has larger specific surface area, and nitrogen heteroatoms and the like can be uniformly introduced into the carbon material to modify the composite film, so as to form a carbon network skeleton with uniform boron-nitrogen doping and a metal catalytic center.
The phase of the boron nitrogen co-doped carbon material anchored by the three-dimensional flower-shaped metal atoms is determined by an X-ray powder diffraction pattern, and a Bruker D8X-ray diffractometer is adopted.
The morphology of the boron nitrogen co-doped carbon material anchored by the three-dimensional flower-shaped metal atoms is obtained through a field emission Scanning Electron Microscope (SEM) photo, and a German zeiss Gemini 500 field emission scanning electron microscope is adopted.
The internal morphology and element distribution of the boron nitrogen co-doped carbon material anchored by the three-dimensional flower-shaped metal atoms prepared by the invention pass through a Transmission Electron Microscope (TEM) photo and an EDS element distribution diagram, and a Japanese JEOL JEM2100F transmission electron microscope is adopted.
The specific surface area of the boron nitrogen co-doped carbon material anchored by the three-dimensional flower-shaped metal atoms is shown by a low-temperature nitrogen adsorption and desorption curve, and an Autosorb-iQ2 full-automatic specific surface area and aperture distribution analyzer of the company Kang Da in the United states is adopted.
The electrocatalytic performance of the three-dimensional flower-cluster metal atom anchored boron-nitrogen co-doped carbon material prepared by the invention is measured by an electrochemical workstation of Shanghai Chen Hua CHI 660E.
For further understanding of the present application, the metal atom-anchored boron-nitrogen co-doped carbon material and the preparation method thereof provided by the present invention are specifically described below with reference to examples.
Example 1
A preparation method of a boron-nitrogen co-doped carbon material anchored by metal atoms comprises the following steps:
1) Preparation of Fe-MBON-1MOFs precursor: 2.232 g of nickel nitrate hexahydrate, 2.464 g of 2-methylimidazole, 10 mg of ferric acetylacetonate and 5.5668 g of boric acid are weighed and dissolved in 60mL of methanol, the mixture is fully stirred and then transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining, the reaction is carried out for 12 hours at 150 ℃, the product is centrifugally separated to obtain supernatant and precipitate, and the precipitate is taken and washed with methanol for three times to obtain a metal-doped Fe-MBON-1 precursor;
2) Weighing 0.7g of the Fe-MBON-1 precursor in the step 1), placing the precursor in a corundum porcelain boat, placing the porcelain boat in a tubular furnace, evacuating air in the tubular furnace, and introducing 40mL/min of nitrogen as a protective atmosphere; heating to 900 deg.C at a heating rate of 5 deg.C/min, and maintaining at this temperature for 6 hours (during which 40mL/min argon purging is continuously used), washing with ethanol to remove impurities after calcination, and vacuum filtering (with a filter membrane diameter of 5 cm). And after the suction filtration is finished, drying the material in an oven at 80 ℃ to obtain the boron-nitrogen co-doped carbon material anchored by the three-dimensional flower-shaped iron atoms.
Fig. 1 is an X-ray powder diffraction pattern (XRD) of a boron nitrogen co-doped carbon material anchored by three-dimensional flower-shaped iron atoms prepared in this example, and as can be seen from fig. 1, the composite phase of the boron nitrogen co-doped carbon material prepared in this example. It can be seen from FIG. 1 that the peaks of carbon are mainly corresponding to the (002) and (100) crystal planes of graphitic carbon, which also indicates that the introduction of metal atoms does not cause a change in the diffraction peaks of B/N-C.
FIGS. 2 to 4 are Scanning Electron Microscope (SEM) images of three-dimensional flower-shaped metal iron atom anchored boron nitrogen co-doped carbon materials prepared in example 1, and FIGS. 2 and 3 are SEM images of Fe-B/N-C; FIG. 4 is a graph showing the particle diameter distribution of Fe-B/N-C. As can be seen from FIGS. 2 to 4, the Fe-B/N-C has a flower cluster-shaped super-structure morphology, and the diameter ranges from 6 μm to 8 μm.
FIGS. 5 to 7 are Transmission Electron Microscopy (TEM) and selective electron diffraction (SAED) views of three-dimensional flower-like metallic iron atom-anchored boron-nitrogen co-doped carbon materials prepared in example 1, and in FIG. 5, (a and B) are TEM views of Fe-B/N-C; FIG. 6 is a high-power TEM image of Fe-B/N-C; FIG. 7 is a SAED pattern of Fe-B/N-C. It can be seen from fig. 5-7 that lattice fringe spacing of about 0.344nm corresponds to the (002) plane of the BCN nanoplatelets, and that fig. 7 reveals the presence of BCN corresponding to the (002) and (110) crystal planes, respectively.
FIG. 8 is a high angle annular dark field scanning transmission electron micrograph (HAADF-STEM) of a three-dimensional flower-like metallic iron atom anchored boron nitrogen co-doped carbon material prepared in example 1, where (a and B) are HAADF-STEM views of Fe-B/N-C. It can be seen from fig. 8 that the Fe atoms are highly dispersed and no significant element aggregation is found.
FIGS. 9 to 10 are graphs showing the nitrogen physisorption curves of the three-dimensional flower-like metallic iron atom-anchored boron-nitrogen co-doped carbon material prepared in example 1, FIG. 9 isNitrogen adsorption and desorption drawing of Fe-B/N-C; FIG. 10 is a pore size distribution diagram of Fe-B/N-C. As can be seen from the physical adsorption curve and pore size distribution diagram of nitrogen in FIGS. 9-10, the obtained material has relatively high specific surface area of 237m 2 Such large specific surface area and pore volume contribute to the exertion of the catalytic activity of the iron atom anchored boron nitrogen co-doped carbon material.
FIG. 11 is a Mapping element distribution diagram of a boron nitrogen co-doped carbon material anchored by three-dimensional flower-like metallic iron atoms prepared in example 1. It can be seen from FIG. 11 that the elements in Fe-B/N-C are uniformly distributed.
FIGS. 12-13 are linear sweep voltammetry graphs (LSVs) of three-dimensional flower-like metallic iron atom anchored boron-nitrogen co-doped carbon material catalyzed electrochemical nitrogen reduction (NRR) prepared in example 1, FIG. 12 is a graph of the atomic ratio of boron to nitrogen in N 2 Or an LSV curve of Fe-B/N-C in Ar saturated 0.1 MKOH; FIG. 13 is a graph at N 2 Or an LSV curve of Fe-B/N-C in Ar saturated 0.1M HCl. As can be seen from FIGS. 12-13, fe-B/N-C was used to treat N in 0.1M HCl electrolyte 2 The difference in current density from Ar was much greater than that in the 0.1M KOH electrolyte, so 0.1M HCl was used as the electrolyte in example 1.
Fig. 14 is a stability test of three-dimensional flower-like metallic iron atom-anchored boron-nitrogen co-doped carbon material prepared in example 1. As can be seen from FIG. 14, in the 30-hour chronoamperometric test, the occasional small fluctuation of Fe-B/N-C was caused by the progress of the hydrogen evolution reaction, which caused bubbles to adhere to the carbon paper, which caused the catalyst on the carbon paper to fall off. The inset in the figure shows the ammonia production of Fe-B/N-C after 30h chronoamperometric testing.
Fig. 15 is a schematic diagram showing the yield and faraday efficiency of nitrogen reduction synthesis of ammonia catalyzed by the three-dimensional flower-like metallic iron atom anchored boron nitrogen co-doped carbon material prepared in example 1. The ammonia yield and Faraday efficiency of Fe-B/N-C at different voltages can be seen from FIG. 15. Fe-B/N-C at-0.4V (vs. RHE), ammonia yield and Faraday Efficiency (FE) are maximized. After the potential exceeds-0.4V (vs. RHE), the Faraday efficiency of Fe-B/N-C is lower and lower, which is that when the potential is too large, the NRR reaction can be promoted, but the competitive hydrogen evolution reaction is promoted, the total reaction electrons on the electrode participate in the catalyst are limited, and when the number of electrons utilized by HER is increased, the number of electrons available by NRR is correspondingly reduced, so that the yield and Faraday efficiency of NRR are inhibited.
Example 2
1) Preparation of Co-MBON-1MOFs precursor: 2.232 g of zinc nitrate hexahydrate, 2.464 g of 2-methylimidazole, 10 mg of cobalt acetylacetonate and 5.5668 g of boric acid are weighed and dissolved in 60mL of methanol, the mixture is fully stirred and then transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining, the reaction is carried out for 12 hours at 150 ℃, the product is centrifugally separated to obtain supernatant and precipitate, and the precipitate is taken and washed with methanol for three times to obtain a metal doped Co-MBON-1 precursor;
2) Weighing 0.7g of the Co-MBON-1 precursor in the step 1), placing the precursor in a corundum porcelain boat, placing the porcelain boat in a tubular furnace, evacuating air in the tubular furnace, and introducing 40mL/min of nitrogen as a protective atmosphere; heating to 900 deg.C at a heating rate of 5 deg.C/min, and maintaining at this temperature for 6 hours (during which 40mL/min argon purging is continuously used), washing with ethanol to remove impurities after calcination, and vacuum filtering (with a filter membrane diameter of 5 cm). And after the suction filtration is finished, drying the material in an oven at 80 ℃ to obtain the three-dimensional flower-shaped cobalt-atom anchored boron-nitrogen co-doped carbon material.
Fig. 16 is an X-ray powder diffraction pattern (XRD) of the boron-nitrogen co-doped carbon material anchored by three-dimensional flower-shaped cobalt atoms prepared in this example, and as can be seen from fig. 16, the composite phase of the boron-nitrogen co-doped carbon material prepared in this example. It can be seen from FIG. 16 that Co-B/N-C corresponds to the (002) and (100) crystal planes of graphitic carbon, which also shows that the introduction of metallic Co atoms does not cause a change in the diffraction peaks of B/N-C.
FIGS. 17-19 are Scanning Electron Microscope (SEM) photographs of three-dimensional flower-like cobalt-atom-anchored boron-nitrogen Co-doped carbon materials prepared in this example, and FIGS. 17 and 18 are SEM photographs of Co-B/N-C; FIG. 19 is a graph showing the particle diameter distribution of Co-B/N-C. The Co-B/N-C has a flower cluster-shaped super-structure morphology, and the diameter range is 6-8 mu m.
FIGS. 20-21 illustrate three-dimensional flower-like cobalt atom anchored boron-nitrogen co-doping of the present exampleFIG. 20 is a graph showing nitrogen desorption of Co-B/N-C; FIG. 21 is a graph showing the pore size distribution of Co-B/N-C. As can be seen from the physical adsorption curve and pore size distribution diagram of nitrogen in FIGS. 20-21, the obtained material has a relatively high specific surface area of 68m 2 /g。
Example 3
1) Preparation of Ni-MBON-1MOFs precursor: 2.232 g of nickel nitrate hexahydrate, 2.464 g of 2-methylimidazole, 10 mg of cobalt acetylacetonate and 5.5668 g of boric acid are weighed and dissolved in 60mL of methanol, the mixture is fully stirred and then transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining, the reaction is carried out for 12 hours at 150 ℃, the product is centrifugally separated to obtain supernatant and precipitate, and the precipitate is taken and washed with methanol for three times to obtain a metal doped Co-MBON-1 precursor;
2) Weighing 0.7g of the Co-MBON-1 precursor in the step 1), placing the precursor in a corundum porcelain boat, placing the porcelain boat in a tubular furnace, evacuating air in the tubular furnace, and introducing 40mL/min of nitrogen as a protective atmosphere; heating to 900 deg.C at a heating rate of 5 deg.C/min, and maintaining at this temperature for 6 hours (during which 40mL/min argon purging is continuously used), washing with ethanol to remove impurities after calcination, and vacuum filtering (with a filter membrane diameter of 5 cm). And after the suction filtration is finished, drying the material in an oven at 80 ℃ to obtain the three-dimensional flower-shaped cobalt-atom anchored boron-nitrogen co-doped carbon material.
Fig. 22 is an X-ray powder diffraction pattern (XRD) of the boron-nitrogen co-doped carbon material anchored by three-dimensional flower-shaped cobalt atoms prepared in this example, and as can be seen from fig. 22, the composite phase of the boron-nitrogen co-doped carbon material prepared in this example. It can be seen from FIG. 22 that Ni-B/N-C corresponds to the (002) and (100) crystal planes of graphitic carbon, which also shows that the introduction of metallic Ni atoms does not cause a change in the diffraction peak of B/N-C.
FIGS. 23-25 are Scanning Electron Microscope (SEM) photographs of three-dimensional flower-like cobalt-atom anchored boron-nitrogen co-doped carbon materials prepared in this example, and FIGS. 23, 24 are SEM photographs of Ni-B/N-C; FIG. 25 is a graph showing the particle diameter distribution of Ni-B/N-C. The Ni-B/N-C has a flower cluster-shaped super-structure morphology, and the diameter range is 6-8 mu m.
FIG. 26. 27 is a nitrogen physical adsorption curve of the three-dimensional flower-shaped cobalt atom anchored boron-nitrogen co-doped carbon material prepared in the embodiment, and fig. 26 is a nitrogen desorption drawing of Ni-B/N-C; FIG. 27 is a pore size distribution diagram of Ni-B/N-C. As can be seen from the physical adsorption curve and the pore size distribution diagram of nitrogen, the obtained material has higher specific surface area which is 105m respectively 2 /g。
Example 4
1) Preparation of Ni-MBON-1MOFs precursor: 2.232 g of nickel nitrate hexahydrate, 2.464 g of 2-methylimidazole, 20 mg of nickel acetylacetonate and 5.5668 g of boric acid are weighed and dissolved in 60mL of methanol, the mixture is fully stirred and then transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining, the reaction is carried out for 12 hours at 150 ℃, the product is centrifugally separated to obtain supernatant and precipitate, and the precipitate is taken and washed with methanol for three times to obtain a metal-doped Ni-MBON-1 precursor;
2) Weighing 0.7g of the Ni-MBON-1 precursor in the step 1), placing the precursor in a corundum porcelain boat, placing the porcelain boat in a tubular furnace, evacuating air in the tubular furnace, and introducing 40mL/min of nitrogen as a protective atmosphere; heating to 900 deg.C at a heating rate of 5 deg.C/min, and maintaining at this temperature for 6 hours (during which 40mL/min argon purging is continuously used), washing with ethanol to remove impurities after calcination, and vacuum filtering (with a filter membrane diameter of 5 cm). And after the suction filtration is finished, drying the material in an oven at 80 ℃ to obtain the three-dimensional flower-shaped nickel atom anchored boron-nitrogen co-doped carbon material.
Example 5
1) Preparation of Ni-MBON-1MOFs precursor: 2.232 g of nickel nitrate hexahydrate, 2.464 g of 2-methylimidazole, 30 mg of nickel acetylacetonate and 5.5668 g of boric acid are weighed and dissolved in 60mL of methanol, the mixture is fully stirred and then transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining, the reaction is carried out for 12 hours at 150 ℃, the product is centrifugally separated to obtain supernatant and precipitate, and the precipitate is taken and washed with methanol for three times to obtain a metal-doped Ni-MBON-1 precursor;
2) Weighing 0.7g of the Ni-MBON-1 precursor in the step 1), placing the precursor in a corundum porcelain boat, placing the porcelain boat in a tubular furnace, evacuating air in the tubular furnace, and introducing 40mL/min of nitrogen as a protective atmosphere; heating to 900 deg.C at a heating rate of 5 deg.C/min, and maintaining at this temperature for 6 hours (during which 40mL/min argon purging is continuously used), washing with ethanol to remove impurities after calcination, and vacuum filtering (with a filter membrane diameter of 5 cm). And after the suction filtration is finished, drying the material in an oven at 80 ℃ to obtain the three-dimensional flower-shaped nickel atom anchored boron-nitrogen co-doped carbon material.
Example 6
1) Preparation of Ni-MBON-1MOFs precursor: 2.232 g of nickel nitrate hexahydrate, 2.464 g of 2-methylimidazole, 40 mg of nickel acetylacetonate and 5.5668 g of boric acid are weighed and dissolved in 60mL of methanol, the mixture is fully stirred and then transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining, the reaction is carried out for 12 hours at 150 ℃, the product is centrifugally separated to obtain supernatant and precipitate, and the precipitate is taken and washed with methanol for three times to obtain a metal-doped Ni-MBON-1 precursor;
2) Weighing 0.7g of the Ni-MBON-1 precursor in the step 1), placing the precursor in a corundum porcelain boat, placing the porcelain boat in a tubular furnace, evacuating air in the tubular furnace, and introducing 40mL/min of nitrogen as a protective atmosphere; heating to 900 deg.C at a heating rate of 5 deg.C/min, and maintaining at this temperature for 6 hours (during which 40mL/min argon purging is continuously used), washing with ethanol to remove impurities after calcination, and vacuum filtering (with a filter membrane diameter of 5 cm). And after the suction filtration is finished, drying the material in an oven at 80 ℃ to obtain the three-dimensional flower-shaped nickel atom anchored boron-nitrogen co-doped carbon material.
Example 7
1) Preparation of Fe-MBON-1MOFs precursor: 2.232 g of nickel nitrate hexahydrate, 2.464 g of 2-methylimidazole, 50 mg of ferric acetylacetonate and 5.5668 g of boric acid are weighed and dissolved in 60mL of methanol, the mixture is fully stirred and then transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining, the reaction is carried out for 12 hours at 150 ℃, the product is centrifugally separated to obtain supernatant and precipitate, and the precipitate is taken and washed with methanol for three times to obtain a metal-doped Fe-MBON-1 precursor;
2) Weighing 0.7g of the Fe-MBON-1 precursor in the step 1), placing the precursor in a corundum porcelain boat, placing the porcelain boat in a tubular furnace, evacuating air in the tubular furnace, and introducing 40mL/min of nitrogen as a protective atmosphere; heating to 900 deg.C at a heating rate of 5 deg.C/min, and maintaining at this temperature for 6 hours (during which 40mL/min argon purging is continuously used), washing with ethanol to remove impurities after calcination, and vacuum filtering (with a filter membrane diameter of 5 cm). And after the suction filtration is finished, drying the material in an oven at 80 ℃ to obtain the boron-nitrogen co-doped carbon material anchored by the three-dimensional flower-shaped iron atoms.
Example 8
1) Preparation of Fe-MBON-1MOFs precursor: 2.232 g of nickel nitrate hexahydrate, 2.464 g of 2-methylimidazole, 50 mg of ferric acetylacetonate and 5.5668 g of boric acid are weighed and dissolved in 60mL of methanol, the mixture is fully stirred and then transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining, the reaction is carried out for 12 hours at 150 ℃, the product is centrifugally separated to obtain supernatant and precipitate, and the precipitate is taken and washed with methanol for three times to obtain a metal-doped Fe-MBON-1 precursor;
2) Weighing 0.8g of the Fe-MBON-1 precursor in the step 1), placing the precursor in a corundum porcelain boat, placing the porcelain boat in a tubular furnace, evacuating air in the tubular furnace, and introducing 40mL/min of nitrogen as a protective atmosphere; heating to 900 deg.C at a heating rate of 5 deg.C/min, and maintaining at this temperature for 6 hours (during which 40mL/min argon purging is continuously used), washing with ethanol to remove impurities after calcination, and vacuum filtering (with a filter membrane diameter of 5 cm). And after the suction filtration is finished, drying the material in an oven at 80 ℃ to obtain the boron-nitrogen co-doped carbon material anchored by the three-dimensional flower-shaped iron atoms.
Example 9
1) Preparation of Fe-MBON-1MOFs precursor: 2.232 g of nickel nitrate hexahydrate, 2.464 g of 2-methylimidazole, 50 mg of ferric acetylacetonate and 5.5668 g of boric acid are weighed and dissolved in 60mL of methanol, the mixture is fully stirred and then transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining, the reaction is carried out for 12 hours at 150 ℃, the product is centrifugally separated to obtain supernatant and precipitate, and the precipitate is taken and washed with methanol for three times to obtain a metal-doped Fe-MBON-1 precursor;
2) Weighing 1g of the Fe-MBON-1 precursor in the step 1), placing the precursor in a corundum porcelain boat, placing the porcelain boat in a tubular furnace, evacuating air in the tubular furnace, and introducing 40mL/min of nitrogen as a protective atmosphere; heating to 900 deg.C at a heating rate of 5 deg.C/min, and maintaining at this temperature for 6 hours (during which 40mL/min argon purging is continuously used), washing with ethanol to remove impurities after calcination, and vacuum filtering (with a filter membrane diameter of 5 cm). And after the suction filtration is finished, drying the material in an oven at 80 ℃ to obtain the boron-nitrogen co-doped carbon material anchored by the three-dimensional flower-shaped iron atoms.
Example 10
A preparation method of a boron-nitrogen co-doped carbon material anchored by metal atoms comprises the following steps:
1) Preparation of Fe-MBON-1MOFs precursor: 2.232 g of nickel nitrate hexahydrate, 2.464 g of 2-methylimidazole, 15 mg of ferric acetylacetonate and 5.5668 g of boric acid are weighed and dissolved in 60mL of methanol, the mixture is fully stirred and then transferred into a high-pressure reaction kettle with a polytetrafluoroethylene lining, the reaction is carried out for 12 hours at 150 ℃, the product is centrifugally separated to obtain supernatant and precipitate, and the precipitate is taken and washed with methanol for three times to obtain a metal-doped Fe-MBON-1 precursor;
2) Weighing 0.8g of the Fe-MBON-1 precursor in the step 1), placing the precursor in a corundum porcelain boat, placing the porcelain boat in a tubular furnace, evacuating air in the tubular furnace, and introducing 40mL/min of nitrogen as a protective atmosphere; heating to 900 deg.C at a heating rate of 5 deg.C/min, and maintaining at this temperature for 6 hours (during which 40mL/min argon purging is continuously used), washing with ethanol to remove impurities after calcination, and vacuum filtering (with a filter membrane diameter of 5 cm). And after the suction filtration is finished, drying the material in an oven at 80 ℃ to obtain the boron-nitrogen co-doped carbon material anchored by the three-dimensional flower-shaped iron atoms.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (6)

1. The metal atom anchored boron-nitrogen co-doped carbon material for synthesizing ammonia by electrocatalytic nitrogen reduction reaction is characterized in that the metal atom anchored boron-nitrogen co-doped carbon material modifies the carbon material with a three-dimensional flower-cluster-shaped spherical super structure by introducing different metal/nonmetal hetero atoms to form a carbon network skeleton with uniform boron-nitrogen doping and a metal catalytic center; the boron-nitrogen co-doped carbon material anchored by the metal atoms has a three-dimensional flower-cluster-shaped spherical super structure;
the preparation method of the boron-nitrogen co-doped carbon material anchored by the metal atoms comprises the following steps:
(1) Preparation of MOFs precursor:
weighing a certain amount of organic ligand, zinc nitrate hexahydrate, metal salt and boric acid, dissolving in a solvent, and fully stirring; then synthesizing MOFs precursors doped with different metals;
the synthesis method of the MOFs precursor adopts a solvothermal method, and the reaction conditions of the solvothermal method are as follows: transferring a mixed solution of an organic ligand, zinc nitrate hexahydrate, metal salt and boric acid dissolved in a solvent into a reaction kettle with a polytetrafluoroethylene lining, heating to 100-150 ℃ for reaction for 6-72 hours, centrifugally separating and cleaning a product to obtain MOFs precursors;
the organic ligand is selected from one or a combination of more of imidazole, 2-methylimidazole, 4 '-bipyridine, 2' -bipyridine, phenanthroline and pyrazine; the metal salt is selected from any one or a combination of a plurality of nickel, cobalt or iron metal salts; the metal salt is selected from one or a combination of more of sulfate hydrate, nitrate hydrate, chloride hydrate, acetate hydrate or acetylacetone metal salt; the solvent is one or a combination of more of methanol, ethanol and N, N-dimethylformamide;
(2) And (3) heating the MOFs precursor doped with different metals obtained in the step (1) to 500-1100 ℃ under a certain inert atmosphere, calcining for 0.5-12 hours, wherein the heating rate is 1-20 ℃/min, the gas flow rate of the inert atmosphere is 1-100 mL/min, and then washing, centrifuging or vacuum filtering by using ethanol, and drying to obtain the boron-nitrogen co-doped carbon material anchored by metal atoms and provided with a three-dimensional flower cluster spherical super structure.
2. The metal atom-anchored boron-nitrogen co-doped carbon material according to claim 1, wherein in step (1) of the production method, the molar ratio of the organic ligand to zinc nitrate hexahydrate is (1:10) to (10:1).
3. The metal atom-anchored boron-nitrogen co-doped carbon material according to claim 2, wherein in step (1) of the production method, the mass ratio of the zinc nitrate hexahydrate to the metal salt is (1000:1) to (100:1).
4. The metal atom-anchored boron-nitrogen co-doped carbon material according to claim 3, wherein in the step (1) of the production method, the mass ratio of the zinc nitrate hexahydrate to boric acid is (1:50) to (5:1).
5. The metal atom anchored boron nitrogen co-doped carbon material according to claim 1, wherein in step (2) of the preparation method, different metal doped MOFs precursors are placed in corundum porcelain boats and then put into a tube furnace for calcination.
6. The metal atom anchored boron nitrogen co-doped carbon material of claim 5, wherein in step (2) of said production method, said inert atmosphere is any one of argon, nitrogen or helium; the temperature is raised to 500-1100 ℃ from the room temperature.
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