CN112206802A - Preparation method of monatomic catalyst, prepared product and application - Google Patents

Preparation method of monatomic catalyst, prepared product and application Download PDF

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CN112206802A
CN112206802A CN202011037298.5A CN202011037298A CN112206802A CN 112206802 A CN112206802 A CN 112206802A CN 202011037298 A CN202011037298 A CN 202011037298A CN 112206802 A CN112206802 A CN 112206802A
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nitrogen
containing organic
organic ligand
transition metal
monatomic catalyst
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邢立文
高鸿毅
其他发明人请求不公开姓名
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Suzhou Adewangsi New Materials Co ltd
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
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    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
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    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
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Abstract

The invention relates to the technical field of catalyst preparation, in particular to a preparation method of a monatomic catalyst. The method comprises the following steps: dissolving nitrogen-containing organic ligand and transition metal salt in an organic solvent to form a solution, stirring, refluxing, centrifuging, washing and drying the solution to obtain solid powder, and performing heat treatment in inert gas to obtain the monatomic catalyst. At least five single atom sites of the invention are randomly distributed on the nitrogen-doped carbon skeleton derived from the MOF, thereby increasing the chaos degree of the system and increasing the entropy value of the system. From the thermodynamic perspective, the monatomic catalyst prepared by the method is more favorable for improving the structural stability of the whole system.

Description

Preparation method of monatomic catalyst, prepared product and application
Technical Field
The invention relates to the field of catalysts, in particular to a preparation method of a monatomic catalyst, a prepared product and application.
Background
The metal monatomic catalyst refers to a catalyst having excellent catalytic performance, in which a metal is uniformly dispersed on a carrier in an atomic scale. Because of the characteristics of high atom utilization rate, highly unsaturated coordination of metal sites, strong interaction between metal sites and a carrier and the like, the metal monatomic catalyst usually shows ultrahigh catalytic activity and selectivity, and has become one of important research hotspots in the current scientific and industrial fields.
Metal Organic Framework (MOF) materials provide a powerful synthesis platform for the preparation of Metal monatomic catalysts due to the ordered distribution of Metal nodes and the intrinsic physicochemical properties such as a clear coordination environment. The metal organic framework is a crystalline porous material with a periodic network structure formed by connecting an inorganic metal center (metal ions or metal clusters) and bridged organic ligands with each other through self-assembly. MOFs are an organic-inorganic hybrid material, also called coordination polymers, which differ from inorganic porous materials and from organic complexes in general. People can realize the preparation of various transition metal monatomic catalysts by regulating and controlling the temperature, atmosphere, heat preservation time and the like of heat treatment and taking the pre-synthesized MOF as a precursor. At present, the MOF-derived metal monatomic catalysts usually show that a single metal site is supported on a MOF-derived carbon-based support, and under certain severe reaction conditions, leaching and loss of the metal site still can occur, which indicates that the structural stability of the system needs to be further improved. From the second law of thermodynamics point of view, the MOF-derived single metal site catalyst system has less disorder of metal sites and low entropy, thus resulting in low stability of the overall structure.
In view of this, the invention is particularly proposed.
Disclosure of Invention
The invention aims to provide a preparation method of a monatomic catalyst.
The second invention of the invention aims to provide the monatomic catalyst prepared by the method.
The second invention of the present invention is to provide the use of the monatomic catalyst.
In order to realize the purpose of the invention, the technical scheme is as follows:
the invention relates to a preparation method of a monatomic catalyst, which comprises the following steps:
s1, dissolving the nitrogen-containing organic ligand and the transition metal salt in an organic solvent to form a solution;
the nitrogen-containing organic ligand is selected from heterocyclic compounds with nitrogen atoms as heteroatoms, and the transition metal salt is selected from soluble salts of at least 5 elements of chromium, manganese, iron, cobalt, nickel, copper, zinc and cadmium;
s2, stirring, refluxing, centrifuging, washing and drying the solution to obtain solid powder;
s3, carrying out heat treatment in inert gas to obtain the monatomic catalyst.
Optionally, the nitrogen-containing organic ligand is selected from at least one of substituted or unsubstituted imidazole, substituted or unsubstituted pyrazole, and substituted or unsubstituted pyrrole;
the substituted or unsubstituted imidazole is preferably at least one of 2-methylimidazole, 4-nitroimidazole, 2-methyl-5-nitroimidazole and benzimidazole.
Optionally, the mass volume ratio of the nitrogen-containing organic ligand to the organic solvent is 1-6 g: 100-500 mL.
Optionally, the organic solvent is selected from alcohols, preferably any one or more of methanol, ethanol, isopropanol, more preferably methanol.
Optionally, the soluble salt is selected from at least one of nitrate, hydrochloride, acetate and sulfate;
preferably, the transition metal salt is selected from Fe (NO)3)2、Co(NO3)2、Ni(NO3)2、Cu(NO3)2、Zn(NO3)2、Cd(NO3)2At least five kinds of the components are selected from the group,
more preferably, the transition metal salt is selected from Fe (NO)3)2·6H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O、Cu(NO3)2·3H2O、Zn(NO3)2·6H2O。
Optionally, the mass ratio of the nitrogen-containing organic ligand to the total amount of the transition metal salt is 1-6: 2.04 to 7.3;
preferably, the nitrogen-containing organic ligand, Fe (NO)3)2·6H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O、Cu(NO3)2·3H2O and Zn (NO)3)2·6H2The mass ratio of O is 1-6: 0.005-0.5: 0.005-0.1: 0.02-0.4: 0.01-0.3: 2-6;
more preferably, the nitrogen-containing organic ligand, Fe (NO)3)2·6H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O、Cu(NO3)2·3H2O and Zn (NO)3)2·6H2The mass ratio of O is 3-4: 0.05-0.15: 0.01-0.05: 0.08-0.25: 0.05-0.15: 3 to 4.
Optionally, in step S1, dissolving the nitrogen-containing organic ligand in an organic solvent which accounts for 40% to 60% of the total volume of the organic solvent, and dissolving the transition metal salt in the rest of the organic solvent.
Optionally, the temperature of the heat treatment is 200-1200 ℃, and preferably 800-1000 ℃; the time of the heat treatment is 1 to 4 hours, preferably 2 to 3 hours.
The invention also relates to the monatomic catalyst prepared by the method.
The invention also relates to the application of the monatomic catalyst prepared by the method in the electrocatalytic hydrogen evolution reaction.
The invention has at least the following beneficial effects:
the monatomic catalyst prepared by the method is a monatomic catalyst containing at least 5 transition metal monatomics. Compared with the catalyst of MOF derived single metal sites, at least five single atom sites are randomly distributed on the MOF derived nitrogen-doped carbon skeleton, so that the disorder degree of the system can be increased, the entropy value of the system can be increased, and the catalyst is a high-entropy single atom catalyst. From the thermodynamic perspective, the high-entropy monatomic catalyst is more favorable for improving the structural stability of the whole system.
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One or more embodiments are illustrated by the corresponding figures in the drawings, which are not meant to be limiting. The word "exemplary" is used exclusively herein to mean "serving as an example, embodiment, or illustration. Any embodiment described herein as "exemplary" is not necessarily to be construed as preferred or advantageous over other embodiments.
FIG. 1 is a powder X-ray diffraction pattern of a multi-component MOF precursor and a simulated ZIF-8 obtained in example 1 of the present invention;
FIG. 2 is a powder X-ray diffraction pattern of the polymodal catalyst of example 1 of the present invention;
FIG. 3 is an SEM of the multiple monatomic catalyst of example 1 of the present invention, wherein 3a is a bright-field high-resolution TEM and 3b is a spherical aberration-corrected high-angle annular dark-field scanning TEM;
FIG. 4 is an X-ray energy spectrum analysis element distribution diagram of each metal element in the monatomic catalyst in example 1 of the invention;
fig. 5 is a graph showing electrochemical hydrogen evolution stability of the monatomic catalyst according to example 1 of the present invention.
Detailed Description
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention. Furthermore, in the following detailed description, numerous specific details are set forth in order to provide a better understanding of the present invention. It will be understood by those skilled in the art that the present invention may be practiced without some of these specific details. In some embodiments, materials, elements, methods, means, and the like that are well known to those skilled in the art are not described in detail in order to not unnecessarily obscure the present invention.
Throughout the specification and claims, unless explicitly stated otherwise, the word "comprise", or variations such as "comprises" or "comprising", will be understood to imply the inclusion of a stated element or component but not the exclusion of any other element or component.
The embodiment of the invention provides a monatomic catalyst, which is a nitrogen-doped carbon skeleton loaded with metal atoms, wherein the metal atoms comprise at least 5 of chromium atoms, manganese atoms, iron atoms, cobalt atoms, nickel atoms, copper atoms, zinc atoms and cadmium atoms; the nitrogen-doped carbon skeleton consists of carbon atoms and nitrogen atoms.
From the second law of thermodynamics, the MOF-derived single metal site catalyst system has a low degree of disorder of metal sites and a low entropy value, thus resulting in a low stability of the overall structure. The monatomic catalyst provided by the embodiment of the invention increases the chaos of the metal sites and increases the entropy of the metal sites, so that the structural stability of the MOF derived monatomic catalyst is improved.
Wherein the pore volume of the nitrogen-doped carbon skeleton is 0.2-1.2 cm3A specific surface area of 600 to 1500m, a mean pore diameter of 1 to 5nm2/g。
Further optionally, the metal atom accounts for 0.5-1.5% of the mass of the monatomic catalyst, more preferably 0.8-1.15%, and most preferably 0.98-1%. If the mass percentage of the metal atoms is too large, the agglomeration in the high-temperature treatment stage may be serious, the reaction is not easy to control, and the catalyst in a single atom state cannot be obtained; if the mass percentage of the metal atom is too small, the activity of the catalyst tends to decrease. Further optionally, the metal atoms are iron atoms (II), cobalt atoms, nickel atoms, copper atoms, and zinc atoms; by selecting the metal atom in 5 above, the stability of the monatomic catalyst will be improved.
Specifically, the content of each metal atom in the monatomic catalyst prepared by the embodiment of the invention is close, so that the entropy value of the catalyst can be further improved, and the high-entropy monatomic catalyst is obtained.
The mass percentage of iron atoms in the monatomic catalyst is 0.1-0.3%, preferably 0.16-0.23%, more preferably 0.17-0.18%, and most preferably 0.174%;
the mass percentage of zinc atoms in the single atom catalyst is 0.1-0.3%, preferably 0.16-0.23%, more preferably 0.22-0.23%, most preferably 0.224%;
the mass percentage of copper atoms in the monatomic catalyst is 0.1 to 0.3%, preferably 0.16 to 0.23%, more preferably 0.18 to 0.19%, and most preferably 0.19%;
the mass percentage of nickel atoms in the single-atom catalyst is 0.1-0.3%, preferably 0.16-0.23%, more preferably 0.18-0.19%, and most preferably 0.182%;
the content of cobalt atoms in the monoatomic catalyst is 0.1 to 0.3% by mass, preferably 0.16 to 0.23% by mass, more preferably 0.21 to 0.22% by mass, and most preferably 0.21% by mass.
The monatomic catalyst provided by the embodiment of the invention is a crystalline porous material with a periodic network structure formed by connecting transition metal salt and a nitrogen-containing organic ligand through self-assembly, and the preparation method comprises the following steps:
s1, dissolving the nitrogen-containing organic ligand and the transition metal salt in an organic solvent to form a solution;
wherein, the nitrogen-containing organic ligand is selected from heterocyclic compounds with nitrogen atoms as heteroatoms, and the transition metal salt is selected from soluble salts of at least 5 elements of chromium, manganese, iron (II), cobalt, nickel, copper, zinc and cadmium;
s2, stirring, refluxing, centrifuging, washing and drying the solution to obtain solid powder, namely a multi-element MOF precursor; preferably, the particle size of the multi-component MOF precursor is 100-500 nm, preferably 200-300 nm.
And S3, carrying out heat treatment in inert gas to obtain the nitrogen-doped carbon material loaded with at least five monoatomic sites.
The preparation method adopted by the embodiment of the invention comprises the following steps: the selected specific raw materials are cheap and easy to obtain; the reaction process is simple, the flow is short, and the method is suitable for large-scale high-throughput preparation; is suitable for various transition metal salts and has wide application range.
Specifically, the nitrogen-containing organic ligand in the embodiment of the present invention is selected from an organic heterocyclic compound in which the heteroatom is a nitrogen atom, preferably an aromatic heterocyclic compound in which the heteroatom is a nitrogen atom that is soluble in an organic solvent, more preferably an aromatic heterocyclic compound in which the heteroatom is a nitrogen atom that is soluble in an alcohol, and specifically may be selected from at least one of substituted or unsubstituted imidazole, substituted or unsubstituted pyrazole, and substituted or unsubstituted pyrrole.
More preferably, the nitrogen-containing organic ligand is selected from substituted or unsubstituted imidazole, specifically at least one selected from 2-methylimidazole, 4-nitroimidazole, 2-methyl-5-nitroimidazole and benzimidazole. The embodiment of the invention selects the nitrogen-containing organic ligand which can be dissolved in the selected organic solvent, and can avoid adding water into the solvent. If water is added to the solvent, the water will hydrolyze the transition metal salt to produce hydroxide, which affects the coordination of the metal to the organic ligand.
The organic solvent of the embodiment of the present invention is selected from alcohols, preferably any one or more of methanol, ethanol, and isopropanol, and more preferably methanol. The alcohol solvent in the embodiment of the invention is an anhydrous alcohol solvent.
Specifically, the mass-volume ratio of the nitrogen-containing organic ligand to the organic solvent in the embodiment of the invention is 1-6 g: 100-500 mL, preferably 1-6 g: 200-400 mL. The volume of organic solvent can affect the particle size of the first step formation of the multi-component MOF precursor (ZIF). If the organic solvent is added excessively, the ZIF particles formed will be larger. If too little is added, the particles of ZIF formed will be smaller.
Specifically, the soluble salt in the embodiment of the present invention is selected from at least one of nitrate, hydrochloride, acetate and sulfate; nitrate is more preferred for solubility requirements.
Preferably, the transition metal salt of the embodiments of the present invention is selected from Fe (NO)3)2、Co(NO3)2、Ni(NO3)2、Cu(NO3)2、Zn(NO3)2、Cd(NO3)2At least five of them.
More preferably, the transition metal salts of the embodiments of the present invention are selected from Fe (NO)3)2·6H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O、Cu(NO3)2·3H2O、Zn(NO3)2·6H2O。
Specifically, the mass ratio of the nitrogen-containing organic ligand to the transition metal salt in the embodiment of the invention is 1-6: 2.04 to 7.3. If the amount of the nitrogen-containing organic ligand added is too large, the resulting ZIF particles will be too large. If too little is added, the resulting particles of ZIF will be smaller and less preferred, the nitrogen-containing organic ligand, Fe (NO)3)2·6H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O、Cu(NO3)2·3H2O and Zn (NO)3)2·6H2The mass ratio of O is 1-6: 0.005-0.5: 0.005-0.1: 0.02-0.4: 0.01-0.3: 2 to 6. In the preparation of the multi-element MOF precursor, zinc is added in an excessive manner, one part of zinc is volatilized in the heating process due to low boiling point of zinc, and the excessive addition can inhibit sintering and agglomeration of other metals in the subsequent heating process, so that the distribution of metal atoms in the prepared single-atom catalyst is more uniform. The inventor finds that different divalent metal ions have different degrees of difficulty in coordination and combination with imidazole, that is, it is not easy to successfully dope multiple metal ions simultaneously, and the amount of the metal ions needs to be adjusted to prepare the monatomic catalyst with the metal atom content close to that of the monatomic catalyst. Preferably, nitrogen-containing organic ligand, Fe (NO)3)2·6H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O、Cu(NO3)2·3H2O and Zn (NO)3)2·6H2The mass ratio of O is 3-4: 0.05-0.15: 0.01-0.05: 0.08-0.25: 0.05-0.15: 3 to 4.
Specifically, in step S1, the nitrogen-containing organic ligand is dissolved in an organic solvent that accounts for 40% to 60% of the total volume of the organic solvent, and the transition metal salt is dissolved in the remaining organic solvent. The respective dissolution is not only convenient for operation, but also more sufficient.
Specifically, in step S2, the mixture may be stirred uniformly by a conventional experimental method. The refluxing means that the organic solvent in which the nitrogen-containing organic ligand and the transition metal salt are dissolved is heated to a refluxing temperature (boiling point of the solvent) and preferably maintained for 12 to 24 hours. Centrifugation can be carried out by conventional laboratory methods, and preferably at 1w rpm for 2 minutes. The washing is carried out by using the organic solvent, preferably 1 to 3 times for 1 to 5 minutes each time. The drying is preferably hot air drying, and drying is carried out for 6-12 hours at the temperature of 60 ℃.
Specifically, in step S3, the inert gas is nitrogen (N)2) Argon (Ar), hydrogen argon mixture (H)2Ar), and the like. The temperature of the heat treatment is 200-1200 ℃, preferably 600-1100 ℃, and more preferably 800-1000 ℃. If the temperature is too high, the metal will sinter and agglomerate to form metal particles, rather than single atoms. The treatment time is 1 to 4 hours, preferably 2 to 3 hours. If the time is too short, the amount of Zn is left relatively more than other metals, and if the time is too long, the amount of Zn left is too little, and the aim of approaching the content of metal atoms cannot be achieved.
In one possible implementation manner, the monatomic catalyst of the embodiment of the present invention is prepared by the following method:
dissolving 3-4 g of zinc nitrate hexahydrate, 50-150 mg of copper nitrate trihydrate, 80-250 mg of nickel nitrate hexahydrate, 10-50 mg of cobalt nitrate hexahydrate and 50-150 mg of ferrous nitrate hexahydrate in 100-200 mL of methanol, and uniformly stirring and mixing; then, dissolving 3-4 g of dimethyl imidazole in 100-200 mL of methanol, and stirring and mixing uniformly; uniformly mixing the two parts of methanol solution, and heating to reflux to fully react; centrifuging, washing and drying the solution to obtain solid powder; the solid powder is heat-treated in an inert gas atmosphere.
The embodiment of the invention also provides the application of the transition metal monatomic catalyst prepared by the preparation method in the electrocatalytic hydrogen evolution reaction.
Example 1
A single-atom catalyst is a nitrogen-doped carbon skeleton loaded with Zn, Cu, Ni, Co and Fe.
The preparation method comprises the following steps:
1. 3.4g of Zn (NO) at room temperature3)2·6H2O、120mg Cu(NO3)2·3H2O、145mg Ni(NO3)2·6H2O、30mg Co(NO3)2·6H2O and 144mg Fe (NO)3)2·6H2Dissolving O in 150mL of methanol, and uniformly stirring and mixing;
2. dissolving 3.94g of dimethylimidazole in another 150mL of methanol, and uniformly stirring and mixing;
3. uniformly mixing the two parts of methanol solution, and heating to reflux to fully react; centrifuging, washing and drying the mixed solution to obtain solid powder, namely a multi-element MOF precursor (named as ZnCuNiCoFe-ZIF);
4. the solid powder is subjected to heat treatment in an inert gas atmosphere to prepare a nitrogen-doped carbon material loaded with five single atomic sites such as ZnCuNiCoFe (denoted as (Zn)1Cu1Ni1Co1Fe1)/NC)。
Will prepare Zn1Cu1Ni1Co1Fe1) The content of various metal elements is measured by adopting inductively coupled plasma emission spectroscopy, and the experimental result is shown in table 1.
TABLE 1
Symbol of element Mass fraction (%)
Zn 0.224
Cu 0.190
Ni 0.182
Co 0.210
Fe 0.174
The pore volume of the carbon skeleton is determined to be 0.8cm by adopting a nitrogen adsorption and desorption method3Per g, average pore diameter of 2.8nm and specific surface area of 1250m2/g。
Powder X-ray diffraction analysis is carried out on the prepared ZnCuNiCoFe-ZIF precursor and simulated ZIF-8 (2-methylimidazolium zinc salt MOF material, CCDC code is 602542), and the obtained spectrum is shown in figure 1. By comparison, the prepared MOFs and the simulated crystal structures were identical. Indicating that the crystal structure of the metal ions is not changed by introducing various metal ions. Preparation of the resulting (Zn)1Cu1Ni1Co1Fe1) The powder X-ray diffraction pattern of/NC is shown in FIG. 2.
FIG. 3 shows (Zn)1Cu1Ni1Co1Fe1) a/NC electron microscope photo, wherein 3a is a bright-field high-resolution transmission electron microscope photo, and 3b is a spherical aberration corrected high-angle annular dark-field scanning transmission electron microscope photo; the positions of the bright spots in FIG. 3b are the metal sites dispersed at atomic level;
FIG. 4 shows (Zn)1Cu1Ni1Co1Fe1) The X-ray energy spectrum of each metal element of/NC analyzes the element distribution diagram.
FIG. 5 shows (Zn)1Cu1Ni1Co1Fe1) /NC and (Zn)1Co1) Electrochemical analysis of/NC under acidic conditionsHydrogen reaction stability comparison chart.
Example 2
A single-atom catalyst is a nitrogen-doped carbon skeleton loaded with Zn, Cu, Ni, Co and Mn.
The preparation method comprises the following steps:
1. 3.4g of Zn (NO) at room temperature3)2·6H2O、120mg Cu(NO3)2·3H2O、145mg Ni(NO3)2·6H2O、30mg Co(NO3)2·6H2O and 125mg Mn (NO)3)2·4H2Dissolving O in 150mL of methanol, and uniformly stirring and mixing;
2. dissolving 3.94g of dimethylimidazole in another 150mL of methanol, and uniformly stirring and mixing;
3. uniformly mixing the two parts of methanol solution, and heating to reflux to fully react; centrifuging, washing and drying the mixed solution to obtain solid powder, namely a multi-element MOF precursor (named as ZnCuNiCoMn-ZIF);
4. the solid powder is subjected to heat treatment in an inert gas atmosphere to prepare a nitrogen-doped carbon material (denoted as (Zn) loaded with five single atomic sites such as ZnCuNiCoMn1Cu1Ni1Co1Mn1)/NC)。
Example 3
A single-atom catalyst is a nitrogen-doped carbon skeleton loaded with Zn, Cu, Ni, Co, Fe and Mn.
The preparation method comprises the following steps:
1. 3.4Zn (NO) at normal temperature3)2·6H2O、120mg Cu(NO3)2·3H2O、145mg Ni(NO3)2·6H2O、30mg Co(NO3)2·6H2O、144mg Fe(NO3)2·6H2O and 125mg Mn (NO)3)2·4H2Dissolving O in 150mL of methanol, and uniformly stirring and mixing;
2. dissolving 3.94g of dimethylimidazole in another 150mL of methanol, and uniformly stirring and mixing; uniformly mixing the two parts of methanol solution, and heating to reflux to fully react;
3. centrifuging, washing and drying the mixed solution to obtain solid powder, namely a multi-element MOF precursor (named as ZnCuNiCoFeMn-ZIF);
4. the solid powder is subjected to heat treatment in an inert gas atmosphere to prepare a nitrogen-doped carbon material (denoted as (Zn) loaded with six single atomic sites such as ZnCuNiCoFeMn1Cu1Ni1Co1Fe1Mn1)/NC)。
Examples of the experiments
(Zn) prepared in example 11Cu1Ni1Co1Fe1) The electrochemical hydrogen evolution stability test of the/NC is carried out under the acidic condition (0.5M sulfuric acid), and (Zn) is adopted1Co1) The results of the experiment with/NC as a control are shown in FIG. 5.
As can be seen from FIG. 5, the electrolysis was continued for 10 hours with (Zn)1Co1) (Zn) in comparison with (NC)1Cu1Ni1Co1Fe1) The current density attenuation of/NC is small, which proves that the stability is good.
Finally, it should be noted that: the above examples are only intended to illustrate the technical solution of the present invention, but not to limit it; although the present invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical solutions described in the foregoing embodiments may still be modified, or some technical features may be equivalently replaced; and such modifications or substitutions do not depart from the spirit and scope of the corresponding technical solutions of the embodiments of the present invention.

Claims (10)

1. A preparation method of a monatomic catalyst is characterized by comprising the following steps:
s1, dissolving the nitrogen-containing organic ligand and the transition metal salt in an organic solvent to form a solution;
the nitrogen-containing organic ligand is selected from heterocyclic compounds with nitrogen atoms as heteroatoms, and the transition metal salt is selected from soluble salts of at least 5 elements of chromium, manganese, iron, cobalt, nickel, copper, zinc and cadmium;
s2, stirring, refluxing, centrifuging, washing and drying the solution to obtain solid powder;
s3, carrying out heat treatment in inert gas to obtain the monatomic catalyst.
2. The production method according to claim 1, wherein the nitrogen-containing organic ligand is selected from at least one of substituted or unsubstituted imidazole, substituted or unsubstituted pyrazole, and substituted or unsubstituted pyrrole;
the substituted or unsubstituted imidazole is preferably at least one of 2-methylimidazole, 4-nitroimidazole, 2-methyl-5-nitroimidazole and benzimidazole.
3. The preparation method according to claim 1, wherein the mass volume ratio of the nitrogen-containing organic ligand to the organic solvent is 1-6 g: 100-500 mL.
4. The method according to claim 1, wherein the organic solvent is selected from alcohols, preferably any one or more of methanol, ethanol, and isopropanol, and more preferably methanol.
5. The method according to claim 1, wherein the soluble salt is at least one selected from the group consisting of nitrate, hydrochloride, acetate and sulfate;
preferably, the transition metal salt is selected from Fe (NO)3)2、Co(NO3)2、Ni(NO3)2、Cu(NO3)2、Zn(NO3)2、Cd(NO3)2At least five kinds of the components are selected from the group,
more preferably, the transition metal salt is selected from Fe (NO)3)2·6H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O、Cu(NO3)2·3H2O、Zn(NO3)2·6H2O。
6. The preparation method according to claim 1, wherein the mass ratio of the nitrogen-containing organic ligand to the total amount of the transition metal salt is 1-6: 2.04 to 7.3;
preferably, the nitrogen-containing organic ligand, Fe (NO)3)2·6H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O、Cu(NO3)2·3H2O and Zn (NO)3)2·6H2The mass ratio of O is 1-6: 0.005-0.5: 0.005-0.1: 0.02-0.4: 0.01-0.3: 2-6;
more preferably, the nitrogen-containing organic ligand, Fe (NO)3)2·6H2O、Co(NO3)2·6H2O、Ni(NO3)2·6H2O、Cu(NO3)2·3H2O and Zn (NO)3)2·6H2The mass ratio of O is 3-4: 0.05-0.15: 0.01-0.05: 0.08-0.25: 0.05-0.15: 3 to 4.
7. The method according to claim 1, wherein in step S1, the nitrogen-containing organic ligand is dissolved in an organic solvent in an amount of 40 to 60% by volume based on the total volume of the organic solvent, and the transition metal salt is dissolved in the remaining organic solvent.
8. The method of claim 1, wherein the heat treatment is performed at a temperature of 200 to 1200 ℃, preferably 800 to 1000 ℃; the time of the heat treatment is 1 to 4 hours, preferably 2 to 3 hours.
9. A monatomic catalyst produced by the production method according to any one of claims 1 to 8.
10. Application of the monatomic catalyst prepared by the preparation method of any one of claims 1 to 8 in electrocatalytic hydrogen evolution reaction.
CN202011037298.5A 2020-09-28 2020-09-28 Preparation method of monatomic catalyst, prepared product and application Pending CN112206802A (en)

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