CN117643910A - Monoatomic porous material catalyst, preparation method and application thereof in anaerobic conversion reaction of methane - Google Patents
Monoatomic porous material catalyst, preparation method and application thereof in anaerobic conversion reaction of methane Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 65
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
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Abstract
The invention belongs to the technical field of catalyst material preparation, and provides a single-atom porous material catalyst, a preparation method and application thereof in methane anaerobic conversion reaction. The method comprises the steps of introducing a reaction gas containing a gaseous metal precursor, a carbon source and a nitrogen source into a plasma reaction chamber, and performing chemical vapor deposition by utilizing plasma to obtain the monoatomic porous material catalyst. The preparation method provided by the invention can select gaseous, liquid or solid raw materials as sources of gaseous metal precursors. The invention can prepare various types of single-atom porous material catalysts, and enriches the application range of the single-atom porous material catalysts. The invention realizes the control of the particle size, morphology and distribution of the single-atom porous material catalyst by adjusting the reaction parameters, and the prepared single-atom porous material catalyst can be used for the anaerobic conversion reaction of methane. Therefore, the preparation method provided by the invention is simple to operate, has strong universality and has good industrial application prospect.
Description
Technical Field
The invention belongs to the technical field of catalyst material preparation, and particularly relates to a single-atom porous material catalyst, a preparation method and application thereof in methane anaerobic conversion reaction.
Background
The monoatomic porous material refers to a material which is formed by uniformly dispersing metal elements on a carrier in the form of single atoms and has a raisin-bread structure similar to a Thomson model. The catalyst prepared from the single-atom porous material shows excellent catalytic activity and selectivity in various catalytic reactions, such as CO, due to the low coordination metal center and uniform active sites of the single-atom porous material 2 Reduction, redox, hydrogen evolution, water gas shift, hydrogenation, dehydrogenation, electrocatalysis, photocatalysis, and the like. Therefore, the catalyst of the single-atom porous material has wide application prospect in the fields of energy sources, environment, biology and the like. However, preparing a highly efficient, stable, uniformly distributed catalyst of a single-atom porous material remains a challenge.
The preparation method of the single-atom porous material catalyst at present mainly comprises the following steps: (1) The wet precipitation method is to mix the metal salt solution with the carrier and then to obtain the monoatomic catalyst through the steps of drying, roasting and the like. (2) The solution gel method is to mix the metal salt solution and the organic precursor and then to obtain the monoatomic catalyst through the steps of high temperature hydrolysis, gelation, drying, roasting and the like. (3) The atomization method is to atomize the metal salt solution by ultrasonic wave or compressed air and then to obtain the monoatomic catalyst by pyrolysis treatment. (4) The zero-valent metal deposition process includes contacting zero-valent metal or its alloy with carrier, and acid washing or oxidation treatment to obtain monoatomic catalyst. (5) According to the surface anchoring method, an organic ligand containing a specific coordination group is combined with the surface of a carrier to capture a target metal element, and then the monoatomic catalyst is obtained after acid washing and roasting.
The preparation method has common problems that only organic metal compounds or metal salt solutions containing specific groups can be selected as reaction raw materials and prepared under high-temperature conditions, and the single-atom material catalyst prepared by the method has limited types and limited application range, namely, has poor universality due to limited sources of raw materials and severe preparation conditions.
Guo Xiaoguang (Science, 344 (6184), 5 th 2014, pages 616-619) discloses a single-site iron catalyst of silicide lattice limited domain, which is used for selective activation of methane under anaerobic condition, can be used for efficiently producing ethylene which is an important basic chemical raw material, high-value chemicals such as aromatic hydrocarbon and hydrogen, and the like in one step, and the method disclosed in the paper has innovation, but also has a certain problem, the preparation process of the catalyst used in the method is complex, the wide application of the method is limited, and the method uses SiO with extremely low specific surface area 2 The limited domain Fe center results in an extremely low content of metal active center exposed to the outside, thus limiting the activity of the catalyst to some extent.
Disclosure of Invention
In view of the above, the present invention aims to provide a catalyst of a single-atom porous material, a preparation method and an application thereof in a methane anaerobic conversion reaction. The preparation method provided by the invention has the advantages of simplicity in operation and strong universality, and the catalyst of the single-atom porous material has high catalytic activity.
In order to achieve the above object, the present invention provides the following technical solutions:
a preparation method of a catalyst of a single-atom porous material comprises the following steps:
placing a carrier material in a plasma reaction chamber of a plasma apparatus;
introducing raw material gas into a plasma reaction chamber, and performing chemical vapor deposition by using plasma to obtain the monoatomic porous material catalyst;
the raw material gas includes a reaction gas;
the reactant gas includes a gaseous metal precursor, a carbon source, and a nitrogen source.
Preferably, the support material comprises carbon nanotubes, living organismsOne or more of activated carbon, graphene, porous silica, molecular sieve, and porous boron nitride; the specific surface area of the carrier material is more than or equal to 200m 2 /g。
Preferably, the active ingredient of the gaseous metal precursor has the general formula MR x Wherein M is a metal element including one or more of Fe, co, ni, cu, zn, pd, ag, pt, au, ru, rh, ir, ti, al and Mo; r is a ligand, comprising one or more of carbonyl-C=O, halogen, carboxyl R ' -CO-O and acyl R ' -CO-, wherein R ' is H atom or straight-chain alkane or alkene group with 1-4 carbon atoms, x represents coordination number, and the position is connected with metal element.
Preferably, the carbon source is one or more of alkane, alkene and alkyne with 1-4 carbon atoms;
the nitrogen source comprises NH 3 、N 2 、N 2 O, NO and NO 2 One or more of the following;
the feed gas also includes a diluent gas that is one or more of an inert gas and/or hydrogen.
Preferably, in the raw material gas, the volume ratio of the gaseous metal precursor, the carbon source, the nitrogen source and the diluent gas is 0.001-1:0.01-3:0.01-3:0-3.
Preferably, the total pressure of the raw material gas introduced into the plasma reaction chamber is 0.01-3 bar, and the flow rate of the raw material gas introduced into the plasma reaction chamber is 1-100 mL/min.
Preferably, the plasma generating method is dielectric barrier discharge, and parameters of the dielectric barrier discharge include: the voltage is 5-50 kV, the current is 10-100 mA, and the reaction time is 0.1-6 h.
The invention also provides the monoatomic porous material catalyst prepared by the preparation method according to the technical scheme, wherein the monoatomic porous material catalyst is a metal-nitrogen-carbon M-N-C monoatomic material, M is a metal atom, N is a nitrogen atom, C is a carbon atom, and the metal atom comprises one or more of Fe, co, ni, cu, zn, pd, ag, pt, au, ru, rh, ir, ti, al and Mo.
The invention also provides application of the monoatomic porous material catalyst in the anaerobic conversion reaction of methane, which comprises the following steps:
under the action of a catalyst of a monoatomic porous material, the raw material gas carries out methane anaerobic conversion reaction;
the temperature of the anaerobic conversion reaction of methane is 750-1150 ℃;
the airspeed of the anaerobic methane conversion reaction is 1000-50000 mL/gcat/h.
The feed gas comprises methane;
the methane accounts for 1-100% of the volume fraction of the raw material gas.
Preferably, the feed gas further comprises an assist gas;
the auxiliary gas comprises a chemically inert gas and/or a chemically non-inert gas;
the chemical inert gas is one or more of nitrogen, helium and argon; the chemical inert gas accounts for less than or equal to 99 percent of the volume of the raw material gas;
the chemical non-inert gas is one or more of carbon monoxide, hydrogen, carbon dioxide, water, C2-4 monohydric alcohol, C2-4 alkane and C2-4 alkene; the chemical non-inert gas accounts for less than or equal to 10 percent of the volume fraction of the raw material gas.
The invention provides a preparation method of a catalyst of a single-atom porous material, which comprises the following steps: placing a carrier material in a plasma reaction chamber of a plasma apparatus; introducing raw material gas into a plasma reaction chamber, and performing chemical vapor deposition by using plasma to obtain the monoatomic porous material catalyst; the raw material gas includes a reaction gas; the reactant gas includes a gaseous metal precursor, a carbon source, and a nitrogen source.
The beneficial effects are that:
on one hand, the preparation method provided by the invention is flexible in selecting the raw materials of the gaseous metal precursor, can select gaseous active ingredients to be directly used as the raw materials of the gaseous metal precursor, can also select liquid or solid active ingredients to be prepared into solution, and can become the gaseous metal precursor after being gasified by an atomizer, so that the raw material source of the gaseous metal precursor is enlarged. On the other hand, the preparation method provided by the invention can prepare a plurality of types of single-atom porous material catalysts by changing the metal element types of the gaseous metal precursor, so that the application range of the single-atom porous material catalyst is widened, and the preparation method provided by the invention has strong universality. Secondly, the preparation method provided by the invention is carried out in a plasma reaction chamber and can be carried out in a room temperature environment, so that the defect that the traditional preparation method of the monoatomic material needs to additionally provide high-temperature conditions is avoided. In addition, the preparation method provided by the invention utilizes plasma excitation to generate a large number of free electrons to surround fragments of the gaseous metal precursor, the carbon source and the nitrogen source, so that metal atoms are prevented from agglomerating, and the fragments of the gaseous metal precursor, the carbon source and the nitrogen source are directly deposited on the surface of the carrier material to form the monoatomic material. In addition, the plasmas and the high-energy electrons bombard the surface of the carrier material, so that a micro-mesoporous structure is formed on the surface of the carrier material, the catalytic area can be increased, and the catalytic efficiency is improved. Therefore, the preparation method provided by the invention is simple to operate, has strong universality and has good industrial application prospect.
Further, the preparation method provided by the invention controls the total air pressure of the raw material gas which is introduced into the plasma reaction chamber to be 0.01-3 bar; in the raw material gas, the volume ratio of the gaseous metal precursor, the carbon source, the nitrogen source and the diluent gas is 0.001-1:0.01-3:0.01-3:0-3; the plasma generation method is dielectric barrier discharge, and parameters of the dielectric barrier discharge comprise: the voltage is 5-50 kV, the current is 10-100 mA, and the reaction time is 0.1-6 h; by controlling the parameters, the particle size, morphology and distribution of the catalyst of the single-atom porous material can be accurately controlled, and the activity and stability of the catalyst of the single-atom porous material are improved; meanwhile, the deposition amount and the dispersion degree of the monoatoms on the surface of the carrier material can be controlled, so that the catalytic efficiency and the catalytic activity of the monoatomic porous material catalyst are improved.
The invention also provides application of the monoatomic porous material catalyst in the anaerobic conversion reaction of methane. The single-atom porous material catalyst provided by the invention is used for the anaerobic conversion reaction of methane, and has the advantages that the single-atom porous material catalyst greatly improves the specific surface area, can expose more active sites, improves the catalytic activity, and improves the conversion rate of methane; meanwhile, the high dispersity is caused by the larger specific surface area, so that the mutual coupling of adjacent metal elements is avoided, and the selectivity of methane anaerobic conversion is improved.
Drawings
FIG. 1 is a schematic diagram of an apparatus and flow of a plasma device;
FIG. 2 is an EXAFS fitted spectrum of an Fe-N-C single-atom porous material of example 2;
FIG. 3 is a specific surface view of Fe-N-C single-atom porous material of example 2;
FIG. 4 is a HAADF-STEM diagram of a Pt-N-C single-atom porous material of example 6.
Detailed Description
The invention provides a preparation method of a catalyst of a single-atom porous material, which comprises the following steps:
placing a carrier material in a plasma reaction chamber of a plasma apparatus;
introducing raw material gas into a plasma reaction chamber, and performing chemical vapor deposition by using plasma to obtain the monoatomic porous material catalyst;
the raw material gas includes a reaction gas;
the reactant gas includes a gaseous metal precursor, a carbon source, and a nitrogen source.
In the present invention, the raw materials used in the present invention are preferably commercially available products unless otherwise specified.
In the invention, a carrier material is placed in a plasma reaction chamber of a plasma device, wherein the carrier material comprises one or more of carbon nano tubes, activated carbon, graphene, porous silica, molecular sieve and porous boron nitride; the specific surface area of the carrier material is preferably more than or equal to 200m 2 Preferably ≡g/g, more preferably ≡400m 2 /g。
In the invention, after a carrier material is placed in a plasma reaction chamber of plasma equipment, raw material gas is introduced into the plasma reaction chamber, and chemical vapor deposition is carried out by utilizing plasma, so that the single-atom porous material catalyst is obtained.
In the present invention, the raw material gas includes a reaction gas including a gaseous metal precursor, a carbon source, and a nitrogen source. In the present invention, the general formula of the active ingredient of the gaseous metal precursor is preferably MR x Where M is a metallic element, preferably comprising one or more of Fe, co, ni, cu, zn, pd, ag, pt, au, ru, rh, ir, ti, al and Mo, more preferably one or more of Fe, co, ni, pt, au. In the present invention, the MR x Preferably, R is a ligand, and includes one or more of carbonyl-c=o, halogen, carboxyl R ' -CO-O-, and acyl R ' -CO-, and more preferably carbonyl-c=o and halogen, wherein R ' is an H atom or a linear alkane or alkene group having 1 to 4 carbon atoms, and x represents a coordination number, where x is a metal element. In a specific embodiment of the present invention, the active component of the gaseous metal precursor is particularly preferably Fe (CO) 5 、Co 2 (CO) 8 、Ni(CO) 4 、PtCl 4 、RuCl 3 。
In the present invention, the carbon source is preferably one or more of alkane, alkene and alkyne having 1 to 4 carbon atoms, more preferably one or more of methane, ethane and ethylene.
In the present invention, the nitrogen source preferably includes NH 3 、N 2 、N 2 O, NO and NO 2 One or more of them, more preferably NH 3 、N 2 And N 2 One or more of O.
In the present invention, the raw material gas preferably further includes a diluent gas, and the diluent gas is preferably one or more of an inert gas and/or hydrogen gas, more preferably an inert gas, and still more preferably argon gas.
In the invention, the active component of the gaseous metal precursor is preferably gaseous and can be directly introduced into the plasma reaction chamber; when the active component of the gaseous metal precursor is in a liquid state or a solid state, the active component is preferably gasified or prepared into a solution, and the solution is gasified by an atomizer to form the gaseous metal precursor, and then the gaseous metal precursor is introduced into the plasma reaction chamber.
In the present invention, the volume ratio of the gaseous metal precursor, the carbon source, the nitrogen source and the diluent gas in the raw material gas is preferably 0.001 to 1:0.01 to 3:0.01 to 3:0 to 3.
In the present invention, the total pressure of the raw material gas introduced into the plasma reaction chamber is preferably 0.01 to 3bar, more preferably 0.1 to 2bar; the flow rate of the raw material gas introduced into the plasma reaction chamber is preferably 1 to 100mL/min, more preferably 5 to 50mL/min.
In the present invention, the method for generating plasma is preferably dielectric barrier discharge, and parameters of the dielectric barrier discharge include: the voltage is preferably 5 to 50kV, more preferably 10 to 30kV, the current is preferably 10 to 100mA, more preferably 20 to 60mA, the reaction time is preferably 0.1 to 6 hours, more preferably 1 to 4 hours.
In the invention, if the carrier material does not need to be removed, the monoatomic porous material obtained after chemical vapor deposition by utilizing plasma can be directly used as a catalyst; if the removal of the carrier material is required according to the actual requirements, the carrier material is removed preferably by acid washing.
In the present invention, the acid-washing reagent is preferably an inorganic acid, and the concentration of the inorganic acid is preferably 0.01 to 20mol/L, more preferably 0.1 to 10mol/L; the inorganic acid preferably comprises one or more of hydrofluoric acid, hydrochloric acid, hydrobromic acid, nitric acid, sulfuric acid, acetic acid, hypochlorous acid and phosphoric acid. When the support material is porous silica and molecular sieve, it is preferred that hydrofluoric acid is used for acid washing. After the acid washing, the invention further comprises the following steps: washing and drying the monoatomic porous material from which the carrier material is removed after acid washing; the wash is preferably a centrifugal wash, the reagent of which is preferably water, and the water is preferably deionized water.
In the present invention, the apparatus and the flow chart of the plasma device are shown in fig. 1, and the following describes the preparation method of the catalyst of the monatomic porous material provided by the present invention with reference to fig. 1: and placing the carrier material in a heating and plasma excitation area of plasma equipment, controlling the inlet amount of raw material gas by using a gas flowmeter, decomposing the raw material gas into free radical fragments and free electrons by plasma after the raw material gas is introduced into a plasma reaction chamber, combining the free radical fragments of a carbon source and a nitrogen source with the free radical fragments of a metal precursor in situ to directly form a metal-nitrogen-carbon M-N-C monoatomic material, and depositing the metal-nitrogen-carbon M-N-C monoatomic material on the surface of the carrier material to obtain the monoatomic porous material catalyst.
The invention also provides the monoatomic porous material catalyst prepared by the preparation method. In the invention, the single-atom porous material catalyst is a metal-nitrogen-carbon M-N-C single-atom material, M is a metal atom, N is a nitrogen atom, C is a carbon atom, and the metal atom comprises one or more of Fe, co, ni, cu, zn, pd, ag, pt, au, ru, rh, ir, ti, al and Mo.
The invention also provides application of the monoatomic porous material catalyst in the anaerobic conversion reaction of methane.
In the present invention, when the single-atom porous material catalyst is applied to the methane anaerobic conversion reaction, it preferably comprises the steps of:
the raw material gas is subjected to methane anaerobic conversion reaction under the action of a catalyst of a monoatomic porous material.
In the invention, the temperature of the anaerobic conversion reaction of methane is 750-1150 ℃, preferably 800-1100 ℃; the airspeed of the anaerobic methane conversion reaction is 1000-50000 mL/gcat/h, preferably 2500-20000 mL/gcat/h. In the present invention, the feed gas comprises methane. In the invention, the methane accounts for 1-100% of the volume fraction of the raw material gas. In the present invention, the raw material gas preferably further includes an assist gas. In the present invention, the assist gas preferably includes a chemically inert gas and/or a chemically non-inert gas; the chemically inert gas is preferably one or more of nitrogen, helium and argon; the chemical inert gas accounts for preferably less than or equal to 99 percent of the volume of the raw material gas; the chemical non-inert gas is preferably one or more of carbon monoxide, hydrogen, carbon dioxide, water, C2-4 monohydric alcohol, C2-4 alkane and C2-4 alkene; the chemical non-inert gas accounts for preferably less than or equal to 10 percent of the volume of the raw material gas.
In the present invention, the product obtained after the methane anaerobic conversion reaction preferably includes: ethylene + acetylene, propylene, benzene, toluene and naphthalene.
In order to further illustrate the present invention, the catalyst and the preparation method of the monoatomic porous material and the application thereof in the anaerobic conversion reaction of methane are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
Commercial porous silica (specific surface area. Gtoreq.200m) 2 /g) is placed as a carrier material in a plasma reaction chamber.
The gaseous metal precursor Fe (CO) 5 Carbon source methane and nitrogen source NH 3 The raw material gases were mixed in a volume ratio of 0.06:1:1, and introduced into the plasma reaction chamber at a flow rate of 10mL/min, and the total gas pressure of the raw material gases was 0.1bar.
And (3) opening plasma equipment at room temperature, regulating the voltage to 20kV, regulating the current to 30mA, starting to generate plasma, exciting the gaseous metal precursor, the carbon source and the nitrogen source to react, directly depositing on the surface of the porous silicon dioxide, closing the equipment after the reaction time is 4 hours, and ending the reaction to obtain the Fe-N-C single-atom porous material.
Example 2
Commercial porous silica was placed as a support material in a plasma reaction chamber.
The gaseous metal precursor Fe (CO) 5 Carbon source ethane and nitrogen source N 2 O is mixed according to the volume ratio of 0.02:1:1 to form raw material gas, and the raw material gas is introduced into a plasma reaction chamber at the flow rate of 10mL/min, wherein the total pressure of the raw material gas is 0.1bar.
And (3) opening the plasma equipment at room temperature, adjusting the voltage to be 10kV, adjusting the current to be 50mA, starting to generate plasma, exciting the metal precursor, the carbon source and the nitrogen source to react, directly depositing on the surface of the porous silicon dioxide, closing the equipment after the reaction time is 4 hours, and ending the reaction.
After the reaction is finished, 2mol/L hydrofluoric acid is used for treating the material subjected to chemical vapor deposition, and after centrifugal washing and drying, the Fe-N-C single-atom porous material with carrier material removed is obtained.
Example 3
Commercial activated carbon was placed as a support material in a plasma reaction chamber.
Co as a gaseous metal precursor 2 (CO) 8 Carbon source ethane and nitrogen source NH 3 The raw material gases were mixed in a volume ratio of 0.09:2:1, and introduced into the plasma reaction chamber at a flow rate of 10mL/min, and the total gas pressure of the raw material gases was 1.2bar.
And (3) opening plasma equipment at room temperature, regulating the voltage to be 20kV, regulating the current to be 30mA, starting to generate plasma, exciting the metal precursor, the carbon source and the nitrogen source to react, directly depositing on the surface of the activated carbon, closing the equipment after the reaction time is 4 hours, and ending the reaction to obtain the cobalt-nitrogen-carbon Co-N-C single-atom porous material.
Example 4
Commercial ZSM-5 molecular sieves (air pre-fired at 600 ℃ C. To remove the participating templating agent) were placed as support materials in a plasma reaction chamber.
Ni (CO) as a gaseous metal precursor 4 Carbon source ethylene, nitrogen source NH 3 And a diluent gas argon, wherein the diluent gas argon is mixed according to the volume ratio of 0.12:2:1:1, and the mixture is introduced into the plasma reaction chamber at the flow rate of 20mL/min, and the total pressure of the raw material gas is 0.5bar.
And (3) opening the plasma equipment at room temperature, adjusting the voltage to 20kV, adjusting the current to 30mA, starting to generate plasma, exciting the metal precursor, the carbon source and the nitrogen source to react, directly depositing on the surface of the ZSM-5 molecular sieve, closing the equipment after the reaction time is 4 hours, and ending the reaction.
After the reaction is finished, 1mol/L hydrofluoric acid is used for treating the material subjected to chemical vapor deposition, and the nickel-nitrogen-carbon Ni-N-C monoatomic porous material from which the carrier material is removed is obtained after centrifugal washing and drying.
Example 5
Commercial ZSM-5 molecular sieves (air pre-fired at 600 ℃ C. To remove the participating templating agent) were placed as support materials in a plasma reaction chamber.
Ni (CO) as a gaseous metal precursor 4 、Fe(CO) 5 Carbon source ethylene, nitrogen source NH 3 And a diluent gas argon, wherein the diluent gas argon is mixed according to the volume ratio of 0.02:0.02:2:1:1, and the diluent gas argon is introduced into the plasma reaction chamber at the flow rate of 20mL/min, and the total pressure of the raw material gas is 0.5bar.
And (3) opening the plasma equipment at room temperature, adjusting the voltage to 20kV, adjusting the current to 30mA, starting to generate plasma, exciting the metal precursor, the carbon source and the nitrogen source to react, directly depositing on the surface of the ZSM-5 molecular sieve, closing the equipment after the reaction time is 4 hours, and ending the reaction.
After the reaction is finished, 1mol/L hydrofluoric acid is used for treating the material subjected to chemical vapor deposition, and the nickel-iron-nitrogen-carbon Ni-Fe-N-C bi-metal single-atom porous material with the carrier material removed is obtained after centrifugal washing and drying.
Example 6
Commercial Graphene (GR) was placed as a carrier material in a plasma reaction chamber.
PtCl as solid metal salt 4 Dissolving in water to obtain 0.001mol/L solution, and separating PtCl 4 The solution is gasified by an atomizer at the flow rate of 0.02mL/min to obtain a gaseous metal precursor PtCl 4 。
PtCl as a gaseous metal precursor 4 Carbon source ethane and nitrogen source NH 3 The raw material gases were mixed in a volume ratio of 0.06:2:1, and introduced into the plasma reaction chamber at a flow rate of 10mL/min, and the total gas pressure of the raw material gases was 1.2bar.
And (3) opening plasma equipment at room temperature, regulating the voltage to be 30kV, regulating the current to be 30mA, starting to generate plasma, exciting the metal precursor, the carbon source and the nitrogen source to react, directly depositing on the surface of Graphene (GR), closing the equipment after the reaction time is 4 hours, and ending the reaction to obtain the Pt-N-C single-atom porous material.
Example 7
Commercial porous alumina was placed as a support material in a plasma reaction chamber.
RuCl as solid metal salt 3 Dissolving in water to obtain 0.002mol/L solution, and mixing RuCl 3 The solution was gasified by an atomizer at a flow rate of 0.02mL/min, and the gaseous metal precursor RuCl 3 。
RuCl as a gaseous metal precursor 3 Carbon source methane and nitrogen source N 2 The raw material gases were mixed in a volume ratio of 0.16:1:1, and introduced into the plasma reaction chamber at a flow rate of 10mL/min, and the total gas pressure of the raw material gases was 1.5bar.
And (3) opening the plasma equipment at room temperature, adjusting the voltage to be 20kV, adjusting the current to be 40mA, starting to generate plasma, exciting the metal precursor, the carbon source and the nitrogen source to react, directly depositing on the surface of the porous alumina, closing the equipment after the reaction time is 4 hours, and ending the reaction.
After the reaction is finished, 1mol/L nitric acid is used for treating the material subjected to chemical vapor deposition, and the ruthenium-nitrogen-carbon Ru-N-C monoatomic porous material with the carrier material removed is obtained after centrifugal washing and drying.
FIG. 2 is an EXAFS fitted spectrum of an Fe-N-C single-atom porous material of example 2. As can be seen from fig. 2: the chemical environment around the iron Fe atom is mainly iron-nitrogen Fe-N single atoms, the strength of the iron-iron Fe-Fe agglomerate particle is negligible relative to the iron-nitrogen Fe-N single atoms, which indicates that no iron Fe agglomerate particle exists, and the iron Fe in the material is proved to be in a single-atom state.
FIG. 3 is a graph showing the specific surface area of the Fe-N-C single-atom porous material of example 2, as can be seen from FIG. 3: the specific surface area of the Fe-N-C single-atom porous material of the Fe-N-C single-atom is 527m 2 And/g, the material has rich micro-mesoporous structure.
Fig. 4 is a HAADF-STEM diagram of the Pt-nitrogen-carbon Pt-N-C monatomic porous material of example 6, and as can be seen from fig. 4, the white bright point is a metal atom, and the diagram intuitively shows that the prepared Pt-nitrogen-carbon Pt-N-C monatomic porous material is a monatomic material.
Application example 1
The sheets obtained in examples 1 to 7 were usedThe atomic porous material catalyst is used for carrying out a methane anaerobic conversion reaction, and the composition of raw material gas in the methane anaerobic conversion reaction is as follows: n (N) 2 10% by volume and 90% by volume methane, and the specific methane anaerobic conversion reaction conditions and products are shown in table 1.
TABLE 1 anaerobic methane conversion reaction conditions and products in application example 1
Application example 2
The monoatomic porous material catalysts obtained in examples 1 to 7 were used for the methane anaerobic conversion reaction, respectively, and the composition of the raw material gas in the methane anaerobic conversion reaction was: n (N) 2 The volume fraction 90%, the methane volume fraction 10%, and the specific methane anaerobic conversion reaction conditions and products are shown in table 2.
TABLE 2 anaerobic methane conversion reaction conditions and products in application example 2
As can be seen from tables 1-2, the single-atom porous material catalyst prepared by the preparation method provided by the invention has good catalytic performance for the anaerobic conversion reaction of methane. The results of application examples 1 and 2 show that the monoatomic porous material catalyst prepared by the preparation method provided by the invention can perform methane anaerobic conversion reaction on raw gas with methane content of 90% and 10%, and the monoatomic porous material catalyst prepared by the application can be used for preparing alkene, alkyne and arene by performing methane anaerobic conversion on methane with different concentrations; the results of example 1 and example 2 show that the catalytic efficiency and methane conversion of the monoatomic material with the support material removed are higher.
The foregoing is merely a preferred embodiment of the present invention and is not intended to limit the present invention in any way. It should be noted that modifications and adaptations to the present invention may occur to one skilled in the art without departing from the principles of the present invention and are intended to be comprehended within the scope of the present invention.
Claims (10)
1. The preparation method of the catalyst of the single-atom porous material is characterized by comprising the following steps:
placing a carrier material in a plasma reaction chamber of a plasma apparatus;
introducing raw material gas into a plasma reaction chamber, and performing chemical vapor deposition by using plasma to obtain the monoatomic porous material catalyst;
the raw material gas includes a reaction gas;
the reactant gas includes a gaseous metal precursor, a carbon source, and a nitrogen source.
2. The method of preparation of claim 1, wherein the support material comprises one or more of carbon nanotubes, activated carbon, graphene, porous silica, molecular sieves, and porous boron nitride; the specific surface area of the carrier material is more than or equal to 200m 2 /g。
3. The method of claim 1, wherein the active component of the gaseous metal precursor has the general formula MR x Wherein M is a metal element including one or more of Fe, co, ni, cu, zn, pd, ag, pt, au, ru, rh, ir, ti, al and Mo; r is a ligand, comprising one or more of carbonyl-C=O, halogen, carboxyl R ' -CO-O and acyl R ' -CO-, wherein R ' is H atom or straight-chain alkane or alkene group with 1-4 carbon atoms, x represents coordination number, and the position is connected with metal element.
4. The preparation method according to claim 1, wherein the carbon source is one or more of alkane, alkene and alkyne having 1 to 4 carbon atoms;
the nitrogen source comprises NH 3 、N 2 、N 2 O, NO and NO 2 One or more of the following;
the feed gas also includes a diluent gas that is one or more of an inert gas and/or hydrogen.
5. The method according to claim 4, wherein the volume ratio of the gaseous metal precursor, the carbon source, the nitrogen source and the diluent gas in the raw material gas is 0.001 to 1:0.01 to 3:0.01 to 3:0 to 3.
6. The method according to claim 1, wherein the total pressure of the raw material gas introduced into the plasma reaction chamber is 0.01 to 3bar, and the flow rate of the raw material gas introduced into the plasma reaction chamber is 1 to 100mL/min.
7. The method of claim 1, wherein the plasma is generated by dielectric barrier discharge, and wherein the parameters of the dielectric barrier discharge include: the voltage is 5-50 kV, the current is 10-100 mA, and the reaction time is 0.1-6 h.
8. The catalyst of the monatomic porous material prepared by the preparation method as claimed in any one of claims 1 to 7, wherein the catalyst of the monatomic porous material is a metal-nitrogen-carbon M-N-C monatomic material, M is a metal atom, N is a nitrogen atom, C is a carbon atom, and the metal atom comprises one or more of Fe, co, ni, cu, zn, pd, ag, pt, au, ru, rh, ir, ti, al and Mo.
9. Use of the catalyst of the monoatomic porous material according to claim 8, in a methane anaerobic conversion reaction, characterized by comprising the following steps:
under the action of a catalyst of a monoatomic porous material, the raw material gas carries out methane anaerobic conversion reaction;
the temperature of the anaerobic conversion reaction of methane is 750-1150 ℃;
the airspeed of the anaerobic conversion reaction of methane is 1000-50000 mL/gcat/h;
the feed gas comprises methane;
the methane accounts for 1-100% of the volume fraction of the raw material gas.
10. The use of claim 9, wherein the feed gas further comprises an assist gas;
the auxiliary gas comprises a chemically inert gas and/or a chemically non-inert gas;
the chemical inert gas is one or more of nitrogen, helium and argon; the chemical inert gas accounts for less than or equal to 99 percent of the volume fraction of the raw material gas;
the chemical non-inert gas is one or more of carbon monoxide, hydrogen, carbon dioxide, water, C2-4 monohydric alcohol, C2-4 alkane and C2-4 alkene; the chemical non-inert gas accounts for less than or equal to 10 percent of the volume fraction of the raw material gas.
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