CN111420691A - Metal monoatomic catalyst and preparation method thereof - Google Patents

Metal monoatomic catalyst and preparation method thereof Download PDF

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CN111420691A
CN111420691A CN202010202772.9A CN202010202772A CN111420691A CN 111420691 A CN111420691 A CN 111420691A CN 202010202772 A CN202010202772 A CN 202010202772A CN 111420691 A CN111420691 A CN 111420691A
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metal
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oxide
monoatomic
mixed solution
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CN111420691B (en
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徐保民
钟熊伟
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Southwest University of Science and Technology
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Abstract

The invention belongs to the technical field of catalysts, and particularly relates to a preparation method of a metal monatomic catalyst, which comprises the following steps: performing laser treatment on a mixed solution containing a metal material and a dispersing agent in a first protective gas atmosphere to obtain a metal monoatomic mixed solution; mixing the metal monoatomic mixed solution with a substrate material, and then carrying out hydrothermal reaction to obtain a precursor loaded with metal monoatomic; and mixing the precursor with a nitrogen-containing compound in a second protective gas atmosphere, and then sintering to obtain the nitrogen-doped metal monatomic catalyst. The preparation method of the metal monatomic catalyst can obtain the metal monatomic catalyst only through simple laser treatment, hydrothermal reaction and sintering treatment, realizes metal monatomic active site catalysis, improves the catalytic performance of the material, is simple and easy to operate, and is easy to realize industrial large-scale production and application.

Description

Metal monoatomic catalyst and preparation method thereof
Technical Field
The invention belongs to the technical field of catalysts, and particularly relates to a metal monatomic catalyst and a preparation method thereof.
Background
With the wide application of chemical products in human life, the development of industrial chemistry has increasingly important key effects on social and technological advances. The catalyst has the advantages of improving the chemical reaction rate, reducing the reaction cost, improving the yield, saving the reaction time and the like, so the catalyst is a core material of industrial chemistry. The metal monatomic catalyst is a catalyst which improves the catalytic activity by using a metal monatomic site, is high-efficiency and exerts the metal utilization rate to the maximum extent, and therefore, has the advantages of low cost, high catalytic activity and the like. The metal monoatomic catalyst does not exist in a metal valence state but exists to form an M-N-C or M-O covalent bond with a base material, so the metal monoatomic catalyst exhibits high catalytic activity and high stability in strong acid, strong basicity, strong oxidation and strong reduction.
In recent years, professor Dodelet reports that N-M-C (wherein N, M, C represent nitrogen, transition metal and carbon element, respectively) catalyst has high catalytic activity in journal of "science" in 2009. FeO in the institute of billows, university of Connection, until 2011xThe surface grows monoatomic Pt, and the catalyst Pt/FeOxHas very high CO oxidation catalytic activity, which is also the first proposed single atom concept. So far, the metal monoatomic catalyst is applied and broken through in the chemical field just like a bamboo shoot in spring after rain. For example, Li Yamama courtyard smartly anchors metal monatomic through ZIF-8 and ZIF-67 precursors, and then carries out high-temperature carbonization to obtain the metal monatomic catalyst. The method for preparing the metal monatomic catalyst at present mainly comprises the following steps: preparing metal organic framework particles or metal precursors to adsorb metal oxides or porous carbon materials, and finally preparing the metal monatomic catalyst through high-temperature carbonization or high-temperature reduction. However, these methods have a long process flow, require the use of toxic precursors and toxic solvents, have the disadvantages of single species of metal, and long time for the metal to be monatomicAfter being used, the catalyst is easy to agglomerate and lose part of activity, thereby causing that the high-efficiency metal monatomic catalyst cannot be produced on a large scale.
Disclosure of Invention
The invention aims to provide a preparation method of a metal monatomic catalyst, and aims to solve the technical problems that the preparation method of the metal monatomic catalyst is long in process, needs to use a toxic precursor and a toxic solvent, and is single in type of the prepared monatomic metal, poor in stability and the like.
It is another object of the present invention to provide a metal monoatomic catalyst.
In order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a preparation method of a metal monatomic catalyst comprises the following steps:
performing laser treatment on a mixed solution containing a metal material and a dispersing agent in a first protective gas atmosphere to obtain a metal monoatomic mixed solution;
mixing the metal monoatomic mixed solution with a substrate material, and then carrying out hydrothermal reaction to obtain a precursor loaded with metal monoatomic;
and mixing the precursor with a nitrogen-containing compound in a second protective gas atmosphere, and then sintering to obtain the nitrogen-doped metal monatomic catalyst.
Preferably, the laser processing step includes: and irradiating the metal material in the mixed solution containing the metal material for 0.01-5 hours by adopting laser with the power of 30-1000 w.
Preferably, the content of the dispersant is 0.01 to 10% by mass of the total mass of the metal material-containing mixed solution being 100%.
Preferably, the mass percentage of the metal monoatomic compound solution is 0.1-5%.
Preferably, the laser is of a type selected from: at least one of far infrared laser, mid-infrared laser, near-infrared laser, visible laser, and near-ultraviolet laser.
Preferably, the metallic material is selected from: at least one metal simple substance of iron, cobalt, nickel, copper, manganese, platinum, palladium, gold, silver, ruthenium, iridium and tungsten, or an alloy formed by at least two metals of iron, cobalt, nickel, copper, manganese, platinum, palladium, gold, silver, ruthenium, iridium and tungsten.
Preferably, the solvent in the mixed solution is selected from: at least one of water, methanol, ethanol, acetone, dichloromethane, isopropanol, ethylene glycol, dimethyl sulfoxide and dimethylformamide.
Preferably, the dispersant is selected from: block polymer P127, block polymer P123, polyethylene oxide, polyethylene glycol, disodium lauryl sulfosuccinate, disodium cocomonoethanolamide sulfosuccinate, monolauryl phosphate, potassium monolauryl phosphate, lauryl alcohol ether phosphate, potassium lauryl alcohol ether phosphate, ammonium fatty alcohol polyoxyethylene ether sulfate, cocomonoethanolamide, and at least one of cocoethyleneglycolamide.
Preferably, the step of hydrothermal reaction comprises: and mixing the metal monoatomic mixed solution with a substrate material, and reacting for 0.5-72 hours in a high-pressure reaction kettle at the temperature of 80-200 ℃.
Preferably, the volume ratio of the metal monoatomic mixed solution to the substrate material is (1.5-20): 1.
preferably, the substrate material is selected from: at least one of carbon material, carbide, sulfide, nitride and oxide.
Preferably, the carbon material is selected from: the carbon material comprises at least one of active carbon, a metal organic framework material ZIF-8, a metal organic framework material ZIF-67, a carbon nano tube, graphite and graphene.
Preferably, the carbide is selected from: at least one of tungsten carbide, titanium carbide, iron carbide and molybdenum carbide.
Preferably, the oxide is selected from: at least one of aluminum oxide, silicon oxide, titanium oxide, vanadium oxide, manganese oxide, cobalt oxide, nickel oxide, iron oxide, copper oxide, zinc oxide, niobium oxide, molybdenum oxide, ruthenium oxide, iridium oxide, silver oxide, cadmium oxide, lanthanum oxide, cerium oxide, and samarium oxide.
Preferably, the sulphide is selected from: at least one of iron sulfide, vanadium sulfide, nickel sulfide, cobalt sulfide, cadmium sulfide, niobium sulfide and zinc sulfide.
The nitride is selected from: at least one of titanium nitride, vanadium nitride, silicon nitride and boron nitride.
Preferably, the step of sintering treatment comprises: and mixing the precursor and the nitrogen-containing compound, and heating to 400-1200 ℃ at a heating rate of 1-50 ℃/min for reaction for 0.5-72 hours.
Preferably, the mass ratio of the precursor to the nitrogen-containing compound is 1: (0.001-0.3).
Preferably, the nitrogen-containing compound is selected from: at least one of melamine, cyanuric acid, triethylamine, ammonium borate, ammonium bicarbonate, ammonium sulfate, ammonium chloride and ammonium nitrate.
Preferably, the first protective gas is selected from: at least one of nitrogen, argon, helium.
Preferably, the second shielding gas is selected from: at least one of nitrogen, argon, helium, hydrogen, ammonia, and methane.
Preferably, the content of metal monoatomic atoms in the nitrogen-doped metal monoatomic catalyst is 0.2-7%.
Accordingly, a metal monoatomic catalyst is prepared by the preparation method of the metal monoatomic catalyst.
The invention provides a preparation method of a metal monatomic catalyst, which comprises the steps of carrying out laser treatment on a mixed solution containing a metal material and a dispersing agent, enabling the metal material to enter the solution in a monatomic form, then mixing the metal monatomic mixed solution with a substrate material, carrying out hydrothermal reaction, enabling metal monatomic to be loaded on the substrate material to obtain a precursor, mixing the precursor with a nitrogen-containing compound, and carrying out sintering treatment, wherein the nitrogen-containing compound is thermally decomposed in the high-temperature sintering process, nitrogen atoms are doped into the substrate material to form chemical bonding with the metal monatomic, so that the metal monatomic is more firmly anchored on the surface of the substrate material, the nitrogen-doped metal monatomic catalyst with stable bonding is obtained, and the metal monatomic is prevented from falling off, agglomeration and the like, and the catalytic effect and the service life. The preparation method of the metal monatomic catalyst can obtain the metal monatomic catalyst only through simple laser treatment, hydrothermal reaction and sintering treatment, realizes metal monatomic active site catalysis, improves the catalytic performance of the material, is simple and easy to operate, and is easy to realize industrial large-scale production and application.
The metal monatomic catalyst provided by the invention is prepared by the method, the bonding stability of the metal monatomic and the substrate material is good, the content of the metal monatomic in the catalyst is 0.2-7%, the metal monatomic activity is high, and the catalytic effect is good; and the catalyst is doped with nitrogen elements, so that the combination stability of metal single atoms and a substrate material can be improved, the conductivity of the catalyst can be improved, and the catalytic effect is further improved.
Drawings
FIG. 1 is a schematic view of laser treatment in a method for preparing a metal monoatomic catalyst according to an embodiment of the present invention.
FIG. 2 is a transmission electron microscope image of a metal monoatomic catalyst according to example 1 of the present invention.
FIG. 3 is a transmission electron microscope image of a metal monoatomic catalyst according to example 2 of the present invention.
FIG. 4 is a transmission electron micrograph of a metal monoatomic catalyst according to example 3 of the present invention.
FIG. 5 is a transmission electron micrograph of a metal monoatomic catalyst according to example 4 of the present invention.
Detailed Description
In order to make the purpose, technical solution and technical effect of the embodiments of the present invention clearer, the technical solution in the embodiments of the present invention is clearly and completely described, and it is obvious that the described embodiments are a part of the embodiments of the present invention, but not all embodiments. All other embodiments obtained by a person of ordinary skill in the art without any inventive step in connection with the embodiments of the present invention shall fall within the scope of protection of the present invention.
In the description of the present invention, it is to be understood that the terms "first", "second" and the like are used for descriptive purposes only and are not to be construed as indicating or implying relative importance or implying any number of technical features indicated. Thus, a feature defined as "first" or "second" may explicitly or implicitly include one or more of that feature. In the description of the present invention, "a plurality" means two or more unless specifically defined otherwise.
The weight of the related components mentioned in the description of the embodiments of the present invention may not only refer to the specific content of each component, but also represent the proportional relationship of the weight among the components, and therefore, the content of the related components is scaled up or down within the scope disclosed in the description of the embodiments of the present invention as long as it is in accordance with the description of the embodiments of the present invention. Specifically, the weight described in the description of the embodiment of the present invention may be a unit of mass known in the chemical industry field, such as μ g, mg, g, and kg.
The embodiment of the invention provides a preparation method of a metal monatomic catalyst, which comprises the following steps:
s10, carrying out laser treatment on a mixed solution containing a metal material and a dispersing agent in a first protective gas atmosphere to obtain a metal monoatomic mixed solution;
s20, mixing the metal monoatomic mixed solution with a substrate material, and then carrying out hydrothermal reaction to obtain a precursor loaded with metal monoatomic;
and S30, mixing the precursor with a nitrogen-containing compound in a second protective gas atmosphere, and then sintering to obtain the nitrogen-doped metal monatomic catalyst.
According to the preparation method of the metal monatomic catalyst provided by the embodiment of the invention, the mixed solution containing the metal material and the dispersing agent is subjected to laser treatment, so that the metal material enters the solution in a monatomic form, then the metal monatomic mixed solution is mixed with the substrate material and then subjected to hydrothermal reaction, so that the metal monatomic is loaded on the substrate material to obtain the precursor, then the precursor is mixed with the nitrogen-containing compound and then subjected to sintering treatment, the nitrogen-containing compound is subjected to thermal decomposition in the high-temperature sintering process, the nitrogen atoms are doped into the substrate material to form chemical bonding with the metal monatomic, so that the metal monatomic is more firmly anchored on the surface of the substrate material, the nitrogen-doped metal monatomic catalyst with stable bonding is obtained, and the metal monatomic is prevented from falling, agglomeration and the like, so that. According to the preparation method of the metal monatomic catalyst, the metal monatomic catalyst can be obtained only through simple laser treatment, hydrothermal reaction and sintering treatment, the metal monatomic active site catalysis is realized, the catalytic performance of the material is improved, the operation is simple and easy, and the industrial large-scale production and application are easy to realize.
Specifically, in S10, the mixed solution containing the metal material and the dispersant is subjected to laser processing in the first protective gas atmosphere to obtain a metal monoatomic mixed solution. In the embodiment of the invention, the mixed solution of the metal material is subjected to laser treatment under the atmosphere of protective gas such as nitrogen, argon, helium and the like to prevent metal oxidation, and the metal material is irradiated by laser to enable the metal to enter the mixed solution in a form of single atom to form the metal single atom mixed solution.
In some embodiments, the step of laser processing comprises: and irradiating the metal material in the mixed solution containing the metal material for 0.01-5 hours by adopting laser with the power of 30-1000 w. According to the embodiment of the invention, the metal material in the mixed solution containing the metal material is irradiated for 0.01-5 hours by adopting the laser with the power of 30-1000 w, so that the metal material enters the mixed solution in the form of single atoms, and the forming rate of the single atoms in the metal material can be reasonably adjusted by adjusting the laser power and the laser irradiation time, thereby adjusting the content of the metal single atoms in the mixed solution. If the laser power is too high, the metal material formed by the laser enters the mixed solution in a non-monatomic form such as a block form, and the monatomic metal cannot be formed; if the laser power is too low, the metal material cannot dissociate to form metal monoatomic atoms. If the laser irradiation time is too long, the concentration of metal monoatomic atoms in the mixed solution is too high, and the metal monoatomic atoms are easy to agglomerate and exist in the mixed solution in a non-monoatomic form, so that the activity of the prepared catalyst is reduced. In some embodiments, the power of the laser may be 30w, 50w, 100w, 200w, 500w, 800w, 1000w, or the like, and the irradiation time may be 0.01 hour, 0.1 hour, 0.5 hour, 1 hour, 1.5 hours, 2 hours, 3 hours, 4 hours, or 5 hours.
In some embodiments, the type of laser is selected from: at least one of far infrared laser, mid-infrared laser, near-infrared laser, visible laser, and near-ultraviolet laser. The specific type of the laser is not particularly limited in the embodiment of the invention, and the laser can be any laser type such as far infrared laser, mid-infrared laser, near-infrared laser, visible laser, near-ultraviolet laser and the like, as long as the laser power can reach 30 w-1000 w to effectively excite the metal monoatomic atoms on the metal material.
In some embodiments, the metal monoatomic solution includes 0.1% to 5% of metal monoatomic atoms by mass. According to the embodiment of the invention, the mixed solution containing the metal material is subjected to laser treatment, so that the metal material enters the mixed solution in a monatomic form after being excited by laser to form the mixed solution with the metal monatomic content of 0.1-5%, and the mixed solution with the metal monatomic content can effectively ensure the content of the metal monatomic in the prepared metal monatomic catalyst, thereby ensuring the activity of the catalyst. If the content of the metal monoatomic solution is too high, the metal monoatomic solution is easy to agglomerate in the mixed solution, and reaction sites are reduced, so that the activity of the catalyst is reduced.
In some embodiments, the mixed solution includes a metal material, a solvent, and a dispersant. According to the embodiment of the invention, the metal material is placed in the mixed solution of the solvent and the dispersing agent, wherein the dispersing agent can adsorb metal single atoms released by the metal material excited by laser, and the metal single atoms are prevented from being agglomerated in the mixed solution to lose activity. In some embodiments, after the metal material is placed in the mixed solution of the solvent and the dispersing agent, excess inert gas is introduced to exhaust the active gas in the solution, so as to avoid the damage of the active gas to the metal material and the subsequent excited metal monoatomic atoms.
In some embodiments, the content of the dispersant is 0.01-10% based on 100% of the total mass of the mixed solution containing the metal material, the content of the dispersant is effective to ensure that metal single atoms exist stably in the mixed solution, prevent the metal single atoms from agglomerating and deactivating, and influence subsequent mixed hydrothermal reaction of the metal single atom mixed solution and the substrate material if the content of the dispersant is too high.
In some embodiments, the metallic material is selected from: at least one metal simple substance of iron, cobalt, nickel, copper, manganese, platinum, palladium, gold, silver, ruthenium, iridium and tungsten, or an alloy formed by at least two metals of iron, cobalt, nickel, copper, manganese, platinum, palladium, gold, silver, ruthenium, iridium and tungsten. The metal monoatomic catalysts released by the metal materials after laser excitation adopted by the embodiment of the invention have better catalytic activity, and the prepared metal monoatomic catalysts have high activity and good stability.
In some embodiments, the solvent in the mixed solution is selected from: at least one of water, methanol, ethanol, acetone, dichloromethane, isopropanol, ethylene glycol, dimethyl sulfoxide and dimethylformamide. In some embodiments, the dispersant is selected from: block polymer P127, block polymer P123, polyethylene oxide, polyethylene glycol, disodium lauryl sulfosuccinate, disodium cocomonoethanolamide sulfosuccinate, monolauryl phosphate, potassium monolauryl phosphate, lauryl alcohol ether phosphate, potassium lauryl alcohol ether phosphate, ammonium fatty alcohol polyoxyethylene ether sulfate, cocomonoethanolamide, and at least one of cocoethyleneglycolamide. The solvents and the dispersing agents adopted in the embodiment of the invention have better dispersing effect on the metal monoatomic atoms and the substrate material, can effectively prevent the metal monoatomic atoms from agglomerating and deactivating in the solution, and is beneficial to the subsequent hydrothermal reaction of the metal monoatomic mixed solution and the substrate material; in addition, the solvents and the dispersing agents adopted in the embodiment of the invention are colorless and transparent, have small scattering on laser beams, and cannot influence the excitation treatment of the laser on metal materials in the mixed solution.
In some embodiments, as shown in fig. 1, a metal is placed in a mixed solution of a solvent and a dispersion liquid, an inert gas is introduced into the mixed solution through a gas inlet, the gas in the solution is removed and then removed from a gas outlet, and then the metal is subjected to laser treatment by using a laser so that a metal material enters the mixed solution in a monatomic form.
Specifically, in step S20, the metal monoatomic solution is mixed with a base material and then subjected to a hydrothermal reaction, thereby obtaining a precursor loaded with a metal monoatomic group. According to the embodiment of the invention, the metal monoatomic mixed solution and the substrate material are mixed and then subjected to hydrothermal reaction, so that the metal monoatomic in the mixed solution is adsorbed onto the substrate material, and in the hydrothermal reaction process at a certain temperature, the metal monoatomic and the substrate material form chemical combination, the interaction between the metal monoatomic and the substrate material is enhanced, and the stability of the catalyst is improved. The substrate with the base material as the catalyst is used for anchoring metal monoatomic atoms, prevents the metal monoatomic atoms from agglomerating, improves the monoatomic stability and can enhance electron transmission.
In some embodiments, the step of hydrothermal reacting comprises: and mixing the metal monoatomic mixed solution with a substrate material, and reacting for 0.5-72 hours in a high-pressure reaction kettle at the temperature of 80-200 ℃. According to the embodiment of the invention, the metal monoatomic mixed solution and the substrate material mixture are subjected to hydrothermal reaction for 0.5-72 hours in a high-pressure reaction kettle at the temperature of 80-200 ℃, so that the metal monoatomic and the substrate material are fully combined to form the precursor. If the temperature is too low or the reaction time is too short, the metal monoatomic atoms in the mixed solution are insufficiently combined with the substrate material, the content of the metal monoatomic atoms adsorbed on the substrate material is too low, and the catalytic effect of the subsequently prepared metal monoatomic catalyst is reduced.
In some embodiments, the volume ratio of the metal monoatomic mixed solution to the base material is (1.5-20): 1, the volume ratio is favorable for the hydrothermal reaction after the metal monoatomic mixed solution is mixed with the substrate material, so that the metal monoatomic mixed solution is fully combined with the substrate material. If the ratio of the metal monoatomic solution is too low or too high, the adsorption and combination between the metal monoatomic solution and the substrate material are not favorable.
In some embodiments, the substrate material is selected from: at least one of carbon material, carbide, sulfide, nitride and oxide. In some embodiments, the carbon material is selected from the group consisting of: the material comprises at least one of active carbon, a metal organic framework material ZIF-8, a metal organic framework material ZIF-67, a carbon nano tube, graphite and graphene. In some embodiments, the carbide is selected from: at least one of tungsten carbide, titanium carbide, iron carbide and molybdenum carbide. In some embodiments, the oxide is selected from: at least one of aluminum oxide, silicon oxide, titanium oxide, vanadium oxide, manganese oxide, cobalt oxide, nickel oxide, iron oxide, copper oxide, zinc oxide, niobium oxide, molybdenum oxide, ruthenium oxide, iridium oxide, silver oxide, cadmium oxide, lanthanum oxide, cerium oxide, and samarium oxide. In some embodiments, the sulfide is selected from: at least one of iron sulfide, vanadium sulfide, nickel sulfide, cobalt sulfide, cadmium sulfide, niobium sulfide and zinc sulfide. In some embodiments, the nitride is selected from: at least one of titanium nitride, vanadium nitride, silicon nitride and boron nitride. The carbon material, carbide, sulfide, nitride, oxide, and other substrate materials used in the above embodiments of the present invention have non-metallic carbon, nitrogen, and oxygen as outer layers, and these carbon, nitrogen, and oxygen atoms and metal monoatomic atoms can form chemical bond, so that the metal monoatomic atoms are anchored on the surface of the substrate material to form chemical bonds of metal monoatomic atoms-O, metal monoatomic atoms-C, and metal monoatomic atoms-N, thereby improving the bonding stability of the metal monoatomic atoms and the substrate material, effectively preventing monoatomic agglomeration, and ensuring the catalytic performance of the metal monoatomic catalyst.
Specifically, in step S30, the precursor is mixed with a nitrogen-containing compound in a second protective gas atmosphere and then sintered to obtain the nitrogen-doped metal monatomic catalyst. According to the embodiment of the invention, the precursor and the nitrogen-containing compound are mixed and then sintered, wherein the nitrogen-containing compound is thermally decomposed in the sintering process, and nitrogen atoms can be doped into the substrate material to form chemical bonds with metal single atoms in the sintering process, so that the bonding stability of the metal single atoms and the substrate material can be improved, the conductivity and the ionic conductivity of the catalyst can be improved, and the catalytic performance of the catalyst can be effectively improved. The second protective gas can ensure that the metal elements keep activity in the sintering process and avoid being damaged by oxidation.
In some embodiments, the step of sintering comprises: and mixing the precursor and the nitrogen-containing compound, and heating to 400-1200 ℃ at a heating rate of 1-50 ℃/min for reaction for 0.5-72 hours. In the embodiment of the invention, after the precursor and the nitrogen-containing compound are mixed, the mixture is heated to 400-1200 ℃ at a heating rate of 1-50 ℃/min and reacts for 0.5-72 hours, if the heating rate is too high, the reaction speed is too high, and the nitrogen-containing compound cannot react with the precursor; if the sintering temperature is too low, enough energy is not available to enable the nitride to react with the precursor after being heated and decomposed, and nitrogen atoms cannot be doped into the substrate material to form combination with metal single atoms; if the temperature is too high, the nitrogen is decomposed and volatilized too fast, and does not flow into the precursor after being doped with nitrogen atoms; if the reaction time is too short or too long, the doping amount of nitrogen in the precursor is not favorable, so that the catalytic effect and the stability of the prepared metal monatomic catalyst are influenced.
In some embodiments, the mass ratio of the precursor to the nitrogen-containing compound is 1: (0.001-0.3). According to the embodiment of the invention, the mass ratio of the precursor to the nitrogen-containing compound is 1: (0.001-0.3), and sintering, wherein the doping proportion of nitrogen elements in the precursor is fully ensured by the material components in the proportion, so that the metal monatomic catalyst prepared by sintering has excellent catalytic effect and stability. If the mass ratio of the content of the nitrogen-containing compound is too low, the content of nitrogen element doped in the catalyst is too low, which is not beneficial to improving the combination stability of metal single atoms in the catalyst and the catalytic effect of the catalyst.
In some embodiments, the nitrogen-containing compound is selected from: at least one of melamine, cyanuric acid, triethylamine, ammonium borate, ammonium bicarbonate, ammonium sulfate, ammonium chloride and ammonium nitrate, wherein the nitrogen-containing compounds can be heated and decomposed to generate ammonia gas and carbon nitrogen compounds in the high-temperature sintering process, so that nitrogen atoms are doped into the substrate material to form chemical combination with metal single atoms, and the conductivity and the stability of the catalyst are improved.
In some embodiments, the second shielding gas is selected from: the catalyst comprises at least one of nitrogen, argon, helium, hydrogen, ammonia and methane, wherein inert gases such as nitrogen, argon and helium can prevent metal monatomic from being oxidized, and reducing gases such as hydrogen, ammonia and methane can reduce partial metal oxides, nitrides and carbides, so that the content of metal monatomic, nitrogen and carbon elements in the catalyst is ensured.
In some embodiments, the nitrogen-doped metal monatomic catalyst has a metal monatomic content of 0.2% to 7%. The content of metal single atoms in the nitrogen-doped metal single atom catalyst prepared by the embodiment of the invention is 0.2-7%, and the catalytic activity of the catalyst is effectively ensured.
Correspondingly, the embodiment of the invention also provides a metal monatomic catalyst prepared by the preparation method of the metal monatomic catalyst.
The metal monatomic catalyst provided by the embodiment of the invention is prepared by the method of the embodiment, the metal monatomic is well combined with the substrate material, the content of the metal monatomic in the catalyst is 0.2% -7%, the metal monatomic activity is high, and the catalytic effect is good; and the catalyst is doped with nitrogen elements, so that the combination stability of metal single atoms and a substrate material can be improved, the conductivity of the catalyst can be improved, and the catalytic effect is further improved.
In order to make the details and operation of the above-mentioned embodiments of the present invention clearly understood by those skilled in the art and to make the performance of the metal monatomic catalyst and the method for preparing the same according to the embodiments of the present invention remarkably improved, the above-mentioned technical solutions are exemplified by a plurality of examples below.
Example 1
A metal monatomic catalyst comprising the following preparation steps:
1) the cobalt metal block was placed in a 30ml ethanol solution containing 0.1 wt% of block polymer P123.
2) Excess argon was passed through the solution.
3) And irradiating the surface of the metal cobalt by a visible laser with the laser power of 30w to enable the cobalt atoms to enter the solution in a form, wherein the irradiation time is 0.2 h.
4) And ultrasonically mixing the metal monoatomic dispersion solution with ZIF-8, and reacting for 5 hours in a high-pressure reaction kettle at the temperature of 80 ℃. Carrying out centrifugal separation to obtain a cobalt monoatomic ZIF-8 precursor;
5) the precursor material is mixed with 20 wt% of ammonium chloride, and then is calcined for 2 hours at 400 ℃ in an argon atmosphere, so that the metal monatomic catalyst Co-N-C can be finally obtained, the mass percentage of cobalt atoms is shown in table 1, and the obtained catalyst is applied to 0.1 mol/L HClO4Solution, oxygen reduction performance is tested.
Example 2
A metal monatomic catalyst comprising the following preparation steps:
1) cobalt metal powder was placed in 50ml of an ethanol solution containing 5 wt% P127.
2) The solution was purged with excess nitrogen.
3) Irradiating the surface of the metal cobalt by a visible laser with the laser power of 100w to enable the cobalt atoms to enter the solution in a form, wherein the irradiation time is 0.5 h.
4) The metal monoatomic dispersion solution and the active carbon are stirred and mixed, and then the mixture reacts for 6 hours in a high-pressure reaction kettle at the temperature of 120 ℃. Centrifugally separating to obtain an active carbon precursor loaded with a cobalt monoatomic atom;
5) the precursor material is mixed with 0.1 wt% of ammonium nitrate, and then calcined for 5 hours at 1200 ℃ in an argon atmosphere, so that the metal monatomic catalyst Co-N-C can be finally obtained, the mass percentage of cobalt atoms is shown in table 1, and the obtained catalyst is applied to a 0.1 mol/L KOH solution to test the oxygen reduction performance.
Example 3
A metal monatomic catalyst comprising the following preparation steps:
1) the iron metal block was placed in a solution of 100ml of 10 wt% coco glycol amide in methylene chloride.
2) Excess argon was passed through the solution.
3) Irradiating the surface of the metal cobalt by a visible laser with the laser power of 500w to enable the iron atoms to enter the solution in a form, wherein the irradiation time is 0.2 h.
4) And stirring and mixing the metal monoatomic dispersion solution and the graphene oxide, and reacting for 72 hours in a high-pressure reaction kettle at 200 ℃. Carrying out centrifugal separation to obtain an active graphene oxide precursor loaded with a cobalt monoatomic atom;
5) the precursor material is mixed with 30 wt% of melamine, and then calcined for 15h at 900 ℃ in the mixed atmosphere of argon and hydrogen, finally the metal monatomic catalyst Fe-N-C can be obtained, the mass percentage of iron atoms is shown in table 1, and the obtained catalyst is applied to 0.1 mol/L KHCO3And (5) testing the reduction performance of carbon dioxide.
Example 4
A metal monatomic catalyst comprising the following preparation steps:
1) the platinum metal sheet was placed in 120ml of an aqueous solution containing 0.2 wt% of laureth phosphate.
2) Excess argon was passed through the solution.
3) Irradiating the surface of the metal platinum by a visible laser with the laser power of 1000w to enable platinum atoms to enter the solution in a form, wherein the irradiation time is 5 h.
4) The solution with the metal monoatomic dispersion is mixed with graphite and reacts for 5 hours in a high-pressure reaction kettle at 200 ℃. Centrifugally separating to obtain a carbon nano tube precursor loaded with cobalt monoatomic atoms;
5) calcining the precursor material and 20.6 wt% of triethylamine at 1000 ℃ for 72H in argon atmosphere to finally obtain the metal monatomic catalyst Pt-N-C, wherein the mass percentage of platinum atoms is shown in Table 1, and the obtained catalyst is applied to 0.5 mol/L H2SO4Solution, test hydrogen evolution catalytic performance.
Example 5
A metal monatomic catalyst comprising the following preparation steps:
1) the gold powder was placed in 80ml of an ethylene glycol solution containing 10 wt% potassium monododecyl phosphate.
2) Excess argon was passed through the solution.
3) Irradiating the surface of the metal platinum by a visible laser with the laser power of 800w to enable platinum atoms to enter the solution in a form, wherein the passing irradiation time is 3 h.
4) The solution with the metal monoatomic dispersion is mixed with alumina powder and reacts for 10 hours in a high-pressure reaction kettle at 120 ℃. Centrifugally separating to obtain a carbon nano tube precursor loaded with cobalt monoatomic atoms;
5) the precursor material and 12.7 wt% of ammonium chloride are calcined for 52 hours at 600 ℃ in an ammonia atmosphere, and finally the metal monatomic catalytic Au-N-C can be obtained, wherein the mass percentage of gold atoms is shown in table 1, and the obtained catalyst is applied to catalytic hydrogenation reaction of acetylene at 120 ℃.
Example 6
A metal monatomic catalyst comprising the following preparation steps:
1) the cobalt powder was placed in a solution of 80ml of ethylene glycol containing 10 wt% potassium monododecyl phosphate.
2) Excess argon was passed through the solution.
3) And irradiating the surface of the metal platinum by a visible laser with the laser power of 120w to enable platinum atoms to enter the solution in a form, wherein the irradiation time is 0.8 h.
4) The metal monoatomic dispersion solution is mixed with cobaltosic oxide powder and reacts for 6 hours in a high-pressure reaction kettle at the temperature of 150 ℃. Carrying out centrifugal separation to obtain a cobaltosic oxide precursor loaded with cobalt monoatomic atoms;
5) calcining the precursor material and 7.9 wt% of cyanuric acid for 0.5h at 400 ℃ in a methane atmosphere to finally obtain the metal monatomic catalytic Co-Co3O4The mass percentage of cobalt atoms is shown in Table 1, and the obtained catalyst is applied to 0.1 mol/L KOH solution to test the catalytic performance of the total hydrolysis.
Example 7
A metal monatomic catalyst comprising the following preparation steps:
1) manganese metal was placed in 60ml of isopropanol solution containing 3.8 wt% disodium cocomonoethanolamide sulfosuccinate.
2) Excess argon was passed through the solution.
3) The visible laser with the laser power of 80w irradiates the surface of the metal platinum, so that platinum atoms enter the solution in a form, and the irradiation time is 1.9 h.
4) The solution with the metal monoatomic dispersion is mixed with silicon nitride and reacts for 18 hours in a high-pressure reaction kettle at the temperature of 130 ℃. Centrifugally separating to obtain a silicon nitride precursor loaded with manganese monoatomic atoms;
5) precursor material and 8.0 wt% ammonium sulfateCalcining for 36h at 900 ℃ in hydrogen atmosphere to finally obtain the metal monatomic catalytic Mn-Si3N4The mass percentage of manganese atoms is shown in Table 1, and the obtained catalyst is applied to 0.1 mol/L Na2SO4、0.1mol NaSO3And 0.01mol of Na2And S solution, and testing the photoelectric catalytic performance.
Example 8
A metal monatomic catalyst comprising the following preparation steps:
1) the metal was placed in 60ml of a dimethyl sulfoxide solution containing 6.9% by weight of polyethylene oxide.
2) The solution was purged with excess nitrogen.
3) The visible laser with the laser power of 890w irradiates the surface of the metal platinum, so that platinum atoms enter the solution in a form, and the passing irradiation time is 3.6 h.
4) The metal monoatomic dispersion solution is mixed with titanium carbide and reacts for 10 hours in a high-pressure reaction kettle at 180 ℃. Carrying out centrifugal separation to obtain an iridium-loaded monoatomic titanium carbide precursor;
5) calcining the precursor material and 25.6 wt% of ammonium bicarbonate for 54h at 800 ℃ under the argon atmosphere to finally obtain the metal monatomic catalytic Ir-Ti3C2The mass percentage of iridium atoms is shown in Table 1, and the obtained catalyst is applied to 0.1 mol/L KOH solution to test the oxygen precipitation catalytic performance.
Example 9
A metal monatomic catalyst comprising the following preparation steps:
1) the metal ruthenium was placed in 120ml of dimethylformamide containing 18% by weight of ammonium fatty alcohol polyoxyethylene ether sulfate.
2) The solution was purged with excess nitrogen.
3) And irradiating the surface of the metal platinum by a visible laser with the laser power of 750w to enable platinum atoms to enter the solution in a form, wherein the passing irradiation time is 2.5 h.
4) The solution with the metal monoatomic dispersion is mixed with cadmium sulfide and reacts for 1 hour in a high-pressure reaction kettle at the temperature of 80 ℃. Centrifugally separating to obtain a ruthenium monoatomic loaded cadmium sulfide precursor;
5) precursor material and 13.9 wt% melamineCalcining for 17H at 550 ℃ under the argon atmosphere to finally obtain the metal monatomic catalytic Ru-CdS, wherein the mass percentage of the ruthenium atoms is shown in Table 1, and the obtained catalyst is applied to 0.5 mol/L H2SO4And (4) testing the oxygen evolution catalytic performance of the solution.
Further, in order to verify the advancement of the metal monatomic catalyst prepared in the examples of the present invention, the examples of the present invention were subjected to a performance test.
Test example 1
The content of the metal monoatomic atom in the metal monoatomic catalyst prepared in the embodiment 1-9 is measured, and the test results are shown in the following table 1:
TABLE 1
Figure BDA0002419940780000161
Test example 2
The metal monatomic catalyst prepared in the embodiments 1 to 4 is observed by adopting a high-angle annular dark field scanning transmission electron microscope, transmission electron microscope pictures are respectively shown as attached figures 2 to 5, and metal monatomic in the metal monatomic catalyst prepared in each embodiment is uniformly distributed in the catalyst.
Test example 3
Further, the performances of the metal monatomic catalysts prepared in examples 1 to 9 are respectively tested, and the specific test results are respectively shown in table 1 above, so that the metal monatomic catalyst prepared in the examples of the invention has better stability and catalytic performance.
The above description is only for the purpose of illustrating the preferred embodiments of the present invention and is not to be construed as limiting the invention, and any modifications, equivalents and improvements made within the spirit and principle of the present invention are intended to be included within the scope of the present invention.

Claims (10)

1. A preparation method of a metal monatomic catalyst is characterized by comprising the following steps:
performing laser treatment on a mixed solution containing a metal material and a dispersing agent in a first protective gas atmosphere to obtain a metal monoatomic mixed solution;
mixing the metal monoatomic mixed solution with a substrate material, and then carrying out hydrothermal reaction to obtain a precursor loaded with metal monoatomic;
and mixing the precursor with a nitrogen-containing compound in a second protective gas atmosphere, and then sintering to obtain the nitrogen-doped metal monatomic catalyst.
2. The method of preparing a metal monatomic catalyst according to claim 1, wherein the laser treatment step comprises: and irradiating the metal material in the mixed solution containing the metal material for 0.01-5 hours by adopting laser with the power of 30-1000 w.
3. The method for preparing a metal monatomic catalyst according to claim 2, wherein the content of the dispersant is 0.01 to 10% based on 100% by mass of the total of the mixed solution containing the metal material; and/or the presence of a gas in the gas,
the mass percentage of the metal monoatomic compound in the metal monoatomic mixed solution is 0.1-5%; and/or the presence of a gas in the gas,
the laser is selected from the following types: at least one of far infrared laser, mid-infrared laser, near-infrared laser, visible laser, and near-ultraviolet laser.
4. The method of preparing a metal monatomic catalyst according to claim 3, wherein the metal material is selected from the group consisting of: at least one metal simple substance of iron, cobalt, nickel, copper, manganese, platinum, palladium, gold, silver, ruthenium, iridium and tungsten, or an alloy formed by at least two metals of iron, cobalt, nickel, copper, manganese, platinum, palladium, gold, silver, ruthenium, iridium and tungsten; and/or the presence of a gas in the gas,
the solvent in the mixed solution is selected from: at least one of water, methanol, ethanol, acetone, dichloromethane, isopropanol, ethylene glycol, dimethyl sulfoxide and dimethylformamide; and/or the presence of a gas in the gas,
the dispersant is selected from: block polymer P127, block polymer P123, polyethylene oxide, polyethylene glycol, disodium lauryl sulfosuccinate, disodium cocomonoethanolamide sulfosuccinate, monolauryl phosphate, potassium monolauryl phosphate, lauryl alcohol ether phosphate, potassium lauryl alcohol ether phosphate, ammonium fatty alcohol polyoxyethylene ether sulfate, cocomonoethanolamide, and at least one of cocoethyleneglycolamide.
5. The method for preparing a metal monatomic catalyst according to any one of claims 1 to 4, wherein the hydrothermal reaction step comprises: mixing the metal monoatomic mixed solution with a substrate material, and reacting for 0.5-72 hours in a high-pressure reaction kettle at the temperature of 80-200 ℃; and/or the presence of a gas in the gas,
the volume ratio of the metal monoatomic mixed solution to the substrate material is (1.5-20): 1; and/or the presence of a gas in the gas,
the substrate material is selected from: at least one of carbon material, carbide, sulfide, nitride and oxide.
6. The method of preparing a metal monatomic catalyst according to claim 5, wherein the carbon material is selected from the group consisting of: at least one of activated carbon, a metal organic framework material ZIF-8, a metal organic framework material ZIF-67, a carbon nano tube, graphite and graphene; and/or the presence of a gas in the gas,
the carbide is selected from: at least one of tungsten carbide, titanium carbide, iron carbide and molybdenum carbide; and/or the presence of a gas in the gas,
the oxide is selected from: at least one of aluminum oxide, silicon oxide, titanium oxide, vanadium oxide, manganese oxide, cobalt oxide, nickel oxide, iron oxide, copper oxide, zinc oxide, niobium oxide, molybdenum oxide, ruthenium oxide, iridium oxide, silver oxide, cadmium oxide, lanthanum oxide, cerium oxide, and samarium oxide; and/or the presence of a gas in the gas,
the sulfide is selected from: at least one of iron sulfide, vanadium sulfide, nickel sulfide, cobalt sulfide, cadmium sulfide, niobium sulfide and zinc sulfide; and/or the presence of a gas in the gas,
the nitride is selected from: at least one of titanium nitride, vanadium nitride, silicon nitride and boron nitride.
7. The method for preparing a metal monatomic catalyst according to claim 1 to 4 or 6, wherein the sintering treatment comprises: mixing the precursor with a nitrogen-containing compound, heating to 400-1200 ℃ at a heating rate of 1-50 ℃/min, and reacting for 0.5-72 hours; and/or the presence of a gas in the gas,
the mass ratio of the precursor to the nitrogen-containing compound is 1: (0.001 to 0.3); and/or the presence of a gas in the gas,
the nitrogen-containing compound is selected from: at least one of melamine, cyanuric acid, triethylamine, ammonium borate, ammonium bicarbonate, ammonium sulfate, ammonium chloride and ammonium nitrate.
8. The method of preparing a metal monatomic catalyst according to claim 7, wherein the first protective gas is selected from the group consisting of: at least one of nitrogen, argon, helium; and/or the presence of a gas in the gas,
the second shielding gas is selected from: at least one of nitrogen, argon, helium, hydrogen, ammonia, and methane.
9. The method of preparing a metal monatomic catalyst according to any one of claims 1 to 4, 6 or 8, wherein the content of metal monatomic in the nitrogen-doped metal monatomic catalyst is 0.2% to 7%.
10. A metal monatomic catalyst, characterized in that it is produced by the method for producing a metal monatomic catalyst according to any one of claims 1 to 9.
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