CN117943005A - Mono-atom and multi-atom transition metal co-doped carbon catalytic material and preparation method and application thereof - Google Patents
Mono-atom and multi-atom transition metal co-doped carbon catalytic material and preparation method and application thereof Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 156
- 239000000463 material Substances 0.000 title claims abstract description 94
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 86
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 78
- 230000003197 catalytic effect Effects 0.000 title claims abstract description 70
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 48
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- 239000002253 acid Substances 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 18
- 229910021524 transition metal nanoparticle Inorganic materials 0.000 claims abstract description 18
- -1 transition metal salt Chemical class 0.000 claims abstract description 17
- 238000005530 etching Methods 0.000 claims abstract description 15
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- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 22
- 238000002156 mixing Methods 0.000 claims description 21
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- 235000012828 Citrullus lanatus var citroides Nutrition 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 239000000243 solution Substances 0.000 claims description 12
- 239000003929 acidic solution Substances 0.000 claims description 11
- 238000005984 hydrogenation reaction Methods 0.000 claims description 11
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 6
- 150000002815 nickel Chemical class 0.000 claims description 4
- 235000017166 Bambusa arundinacea Nutrition 0.000 claims description 3
- 235000017491 Bambusa tulda Nutrition 0.000 claims description 3
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
- 240000007594 Oryza sativa Species 0.000 claims description 3
- 235000007164 Oryza sativa Nutrition 0.000 claims description 3
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- MBLBDJOUHNCFQT-LXGUWJNJSA-N aldehydo-N-acetyl-D-glucosamine Chemical compound CC(=O)N[C@@H](C=O)[C@@H](O)[C@H](O)[C@H](O)CO MBLBDJOUHNCFQT-LXGUWJNJSA-N 0.000 claims description 3
- 239000011425 bamboo Substances 0.000 claims description 3
- 150000001868 cobalt Chemical class 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- 150000002505 iron Chemical class 0.000 claims description 3
- 229910017604 nitric acid Inorganic materials 0.000 claims description 3
- 238000004321 preservation Methods 0.000 claims description 3
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- 244000082204 Phyllostachys viridis Species 0.000 claims 1
- 150000003624 transition metals Chemical class 0.000 abstract description 9
- 238000006555 catalytic reaction Methods 0.000 abstract description 8
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- 238000001035 drying Methods 0.000 description 28
- UEXCJVNBTNXOEH-UHFFFAOYSA-N Ethynylbenzene Chemical group C#CC1=CC=CC=C1 UEXCJVNBTNXOEH-UHFFFAOYSA-N 0.000 description 22
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- 239000002184 metal Substances 0.000 description 17
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 13
- 241000219109 Citrullus Species 0.000 description 11
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- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 8
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- 125000004429 atom Chemical group 0.000 description 7
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- 150000003839 salts Chemical class 0.000 description 4
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
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- 231100000053 low toxicity Toxicity 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
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- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 1
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- 229960000401 tranexamic acid Drugs 0.000 description 1
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Abstract
The invention belongs to the technical field of catalysis, and particularly relates to a single-atom and multi-atom transition metal co-doped carbon catalytic material, and a preparation method and application thereof. The activated carbon material and the transition metal salt are subjected to plasma calcination to obtain the carbon material loaded with the transition metal nano particles formed by multiple atoms, and then partial transition metal nano particles formed by multiple atoms are dispersed into single-atom transition metal through acid etching, so that the carbon catalytic material loaded with the transition metal nano particles formed by single-atom transition metal and multiple atoms simultaneously is obtained. Compared with monoatomic transition metal, the transition metal nano particles formed by multiple atoms have stronger binding force and stability with the carbon material, and are not easy to agglomerate in the catalysis process, so that the stability of the carbon catalysis material is improved. In addition, the activation treatment, the plasma calcination and the acid etching treatment can increase the porous structure of the surface of the carbon material, improve the specific surface area of the carbon material, and are beneficial to increasing active sites so as to improve the catalytic activity.
Description
Technical Field
The invention belongs to the technical field of catalysis, and particularly relates to a single-atom and multi-atom transition metal co-doped carbon catalytic material, and a preparation method and application thereof.
Background
Transition metals (such as Fe, co, ni, mn and Cu) and nitrogen co-doped porous carbon catalysts (referred to as M-N-C) are an emerging family of materials with atomically dispersed metal species. Great attention has recently been paid to the abundant, low toxicity, excellent activity and stability of transition metals. The M-N-C catalyst is widely applied to energy storage and conversion, biomedicine, organic conversion, tranexamic acid and other catalytic reactions at present, and generally shows excellent catalytic performance.
Pyrolysis of N-containing organic ligand-metal complexes and/or carbon supports, or metal-organic frameworks, or mixtures of metal salts and renewable biomass under inert atmosphere is the most common method for preparing M-N-C catalysts. However, one key challenge of this synthetic approach is the high structural non-uniformity of the coexistence of complex metal sites, including the atomic dispersed metal species (M-Nx) and metal-containing metal Nanoparticles (NPs) and/or Nanoclusters (NCs), which makes it difficult to distinguish the nature of the catalytically active sites. To remove insoluble metal-containing NPs and/or NCs, a specific post-treatment process is required, acid etching or concentrated H 2O2, high temperature Cl 2 treatment, etc., after thermal decomposition, to finally form an atomic dispersed m—nx species, which has been widely accepted as a catalytically active site. Although, the catalyst of M-Nx species with dispersed atoms has high catalytic activity, and the M-Nx species with dispersed atoms has poor stability, and is easy to agglomerate in the catalytic process, thereby reducing the catalytic activity.
Disclosure of Invention
In view of the above, the present invention aims to provide a single-atom and multi-atom transition metal co-doped carbon catalytic material, a preparation method and an application thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a single-atom and multi-atom transition metal co-doped carbon catalytic material, which is characterized by comprising the following steps of:
Providing biomass carbon;
Mixing the biomass carbon with an alkaline solution, and performing activation treatment to obtain an activated carbon material;
Mixing the activated carbon material with a transition metal salt, and performing plasma calcination to obtain a calcination product, wherein the calcination product comprises a carbon carrier and a transition metal nanoparticle formed by polyatoms loaded on the surface of the carbon carrier;
And mixing the calcined product with an acidic solution, and carrying out acid etching treatment to obtain the single-atom and multi-atom transition metal co-doped carbon catalytic material.
Preferably, the alkaline solution comprises sodium hydroxide solution and/or potassium hydroxide solution; the concentration of the alkaline solution is 4-20 mmol/L.
Preferably, the transition metal salt comprises one or more of iron salt, nickel salt and cobalt salt.
Preferably, the power of the plasma calcination is 100-2000 w, the temperature is 400-800 ℃, the vacuum degree is 100-1000 Pa, and the heat preservation time is 0.1-0.6 h.
Preferably, the acidic solution comprises one or more of sulfuric acid, nitric acid and hydrochloric acid.
Preferably, the concentration of the acid solution is 1-10 mmol/L; the temperature of the acid etching treatment is 30-100 ℃ and the time is 2-20 h.
Preferably, the biomass carbon is prepared by calcining biomass; the biomass is one or more of shrimp shell, rice stem, bamboo cotyledon, lu Weicao and watermelon peel.
Preferably, the calcining temperature is 700-1200 ℃, and the heat preservation time is 3-20 h.
The invention also provides the single-atom and multi-atom transition metal co-doped carbon catalytic material prepared by the preparation method, which comprises a porous carbon material and transition metal nano particles formed by single-atom transition metal and multi-atom doped on the porous carbon material.
The invention also provides application of the single-atom and multi-atom transition metal co-doped carbon catalytic material in preparing a carbon-carbon double bond compound through hydrogenation of a carbon-carbon triple bond.
The invention provides a preparation method of a single-atom and multi-atom transition metal co-doped carbon catalytic material, which comprises the following steps: providing biomass carbon; mixing the biomass carbon with an alkaline solution, and performing activation treatment to obtain an activated carbon material; mixing the activated carbon material and transition metal salt, and performing plasma calcination to obtain a calcination product, wherein the calcination product comprises a carbon carrier and transition metal nano particles loaded on the surface of the carbon carrier; and mixing the calcined product with an acidic solution, and carrying out acid etching treatment to obtain the single-atom and multi-atom transition metal co-doped carbon catalytic material. The carbon material carrying the transition metal nano particles formed by multiple atoms is obtained by carrying out plasma calcination on the activated carbon material and the transition metal salt, and then partial transition metal nano particles formed by multiple atoms are dispersed into single-atom transition metal through acid etching, so that the carbon catalytic material carrying the transition metal nano particles formed by single-atom transition metal and multiple atoms at the same time is obtained. Compared with monoatomic transition metal, the transition metal nano particles formed by multiple atoms have stronger binding force and stability with the carbon material, and are not easy to agglomerate in the catalysis process, so that the stability of the carbon catalysis material is improved. In addition, the activation treatment, the plasma calcination and the acid etching treatment can increase the porous structure of the surface of the carbon material, improve the specific surface area of the carbon material, and are beneficial to increasing active sites so as to improve the catalytic activity. Therefore, the preparation method provided by the invention can be used for preparing the single-atom and multi-atom transition metal co-doped carbon catalytic material with excellent catalytic activity and stability.
In addition, the invention utilizes biomass as a raw material to prepare the carbon material, and has wide sources and low price.
Drawings
FIG. 1 is a TEM image of a single-and multi-atom transition metal co-doped carbon catalytic material prepared in example 1 of the present invention.
Detailed Description
The invention provides a preparation method of a single-atom and multi-atom transition metal co-doped carbon catalytic material, which comprises the following steps:
Providing biomass carbon;
Mixing the biomass carbon with an alkaline solution, and performing activation treatment to obtain an activated carbon material;
Mixing the activated carbon material with a transition metal salt, and performing plasma calcination to obtain a calcination product, wherein the calcination product comprises a carbon carrier and a transition metal nanoparticle formed by polyatoms loaded on the surface of the carbon carrier;
And mixing the calcined product with an acidic solution, and carrying out acid etching treatment to obtain the single-atom and multi-atom transition metal co-doped carbon catalytic material.
The present invention is not limited to the specific source of the raw materials used, and may be commercially available products known to those skilled in the art, unless otherwise specified.
The invention provides biomass carbon.
In the present invention, the biomass carbon is preferably produced by calcining biomass.
In the invention, the biomass is preferably one or more of shrimp shell, rice stem, bamboo leaf, lu Weicao and watermelon peel, more preferably watermelon peel; when the biomass is the biomass, the ratio of the biomass of different types is not particularly limited, and the biomass can be mixed at random; the temperature of the calcination is preferably 700-1200 ℃, more preferably 800-1000 ℃; the holding time is preferably 3 to 20 hours, more preferably 8 to 10 hours.
According to the invention, biomass is calcined, and the biomass is carbonized at high temperature to obtain biomass carbon.
After biomass carbon is obtained, the biomass carbon and alkaline solution are mixed, and activation treatment is carried out to obtain an activated carbon material.
In the present invention, the alkaline solution preferably includes a sodium hydroxide solution and/or a potassium hydroxide solution, more preferably a potassium hydroxide solution; when the alkaline solutions are the above-mentioned several types, the invention has no special limitation on the proportion of different types of alkaline solutions, and the alkaline solutions can be mixed at random; the concentration of the alkaline solution is preferably 4 to 20mol/L, more preferably 7 to 9mol/L; the activation treatment time is preferably 16 to 36 hours, more preferably 22 to 26 hours.
In the present invention, the activation treatment is preferably performed by immersing the carbon material in an alkaline solution and stirring the same. The stirring process is not particularly limited, and the stirring process is selected according to actual needs.
According to the invention, through the activation treatment of the biomass carbon material, on one hand, the non-carbonized substances are cleaned, and on the other hand, the activation can be used for pore-forming on the surface of the carbon material, so that the specific surface area and the surface functional groups of the carbon material are increased.
After the activation treatment, the mixed solution obtained by the activation treatment is preferably filtered and dried in sequence to obtain the activated carbon material. The invention is not particularly limited in the filtering process, and the filtering process can be selected according to actual needs. In the present invention, the temperature of the drying is preferably 100 ℃, and the time of the drying is preferably 8 hours.
After the activated carbon material is obtained, the activated carbon material and the transition metal salt are mixed and subjected to plasma calcination to obtain a calcination product, wherein the calcination product comprises a carbon carrier and transition metal nano particles formed by multiple atoms loaded on the surface of the carbon carrier.
In the present invention, the transition metal salt preferably includes one or more of an iron salt, a nickel salt and a cobalt salt, more preferably a nickel salt, and most preferably nickel nitrate; when the transition metal salt is the above metal salts, the proportion of the different metal salts is not particularly limited, and the metal salts can be mixed at random; the mass ratio of the activated carbon material to the transition metal salt is preferably (3 to 8): 1, more preferably (4.2 to 5): 1.
In the present invention, the mixing process of the activated carbon material and the transition metal salt is preferably to mix the activated carbon material with an aqueous solution of the transition metal salt under stirring; the stirring time is preferably 6 hours; the stirring power is not particularly limited, and the stirring power is selected according to actual needs.
The invention preferably comprises drying the mixture obtained by mixing the activated carbon material and the transition metal salt prior to the plasma calcination; the temperature of the drying is preferably 80 ℃, and the time of the drying is preferably 8 hours.
In the present invention, the power of the plasma calcination is preferably 100 to 2000w, more preferably 200 to 1000w; the temperature is preferably 400 to 800 ℃, more preferably 500 to 700 ℃; the vacuum degree is preferably 100 to 1000Pa, more preferably 200 to 500Pa; the holding time is preferably 0.1 to 0.6 hours, more preferably 0.1 to 0.3 hours.
According to the invention, the mixed system of the activated carbon material and the transition metal salt is subjected to plasma calcination, so that on one hand, active metal ions in the transition metal salt are reduced at high temperature to obtain transition metal atoms, and on the other hand, the carbon material can be etched to obtain more pore structures, the specific surface area of the carbon material is increased, active metal sites are increased, and the catalytic activity is improved; the plasma calcination can reduce carbonization time and increase the pore structure of the carbon material.
After the calcination product is obtained, the calcination product is mixed with an acidic solution, and acid etching treatment is carried out to obtain the single-atom and multi-atom transition metal co-doped carbon catalytic material.
In the present invention, the acidic solution preferably includes one or more of sulfuric acid, nitric acid and hydrochloric acid, more preferably sulfuric acid; when the acid solutions are the above-mentioned several kinds, the invention has no special limitation on the proportion of different kinds of acid solutions, and the acid solutions can be mixed at random; the concentration of the acidic solution is preferably 1 to 10mol/L, more preferably 1 to 5mol/L; the temperature of the acid etching treatment is preferably 30 to 100 ℃, more preferably 70 to 90 ℃, and the time is preferably 2 to 20 hours, more preferably 10 to 15 hours.
In the present invention, the acid etching treatment is preferably performed by immersing the calcined product in an acidic solution.
Under high temperature calcination, ionic metals are mutually polymerized to form multi-atom nano particles, and the transition metal nano particles formed by the multi-atoms loaded on the carbon carrier through acid etching are partially dispersed into single-atom metals, so that active sites are increased, and the catalytic activity is improved.
The invention also provides the single-atom and multi-atom transition metal co-doped carbon catalytic material prepared by the preparation method, which comprises a porous carbon material and transition metal nano particles formed by single-atom transition metal and multi-atom doped on the porous carbon material.
In the present invention, the mass of the transition metal nanoparticle formed of the single-atom transition metal and the multi-atom is preferably 2 to 5% of the mass of the single-atom and multi-atom transition metal co-doped carbon catalytic material, and more preferably 2 to 3%.
The invention also provides application of the single-atom and multi-atom transition metal co-doped carbon catalytic material in preparing a carbon-carbon double bond compound through hydrogenation of a carbon-carbon triple bond.
In the present invention, the application is preferably the hydrogenation of phenylacetylene to produce styrene. In the embodiment of the invention, the specific process of preparing styrene by hydrogenating phenylacetylene comprises the steps of loading the monoatomic and polyatomic transition metal codoped carbon catalytic material into a high-pressure reaction kettle, taking ethanol as a solution, and carrying out hydrogenation reaction for 1h under the condition that the mass ratio of phenylacetylene to the monoatomic and polyatomic transition metal codoped carbon catalytic material is 20:1 under the reaction pressure of 0.2MPa hydrogen at the temperature of 60 ℃.
The technical solutions of the present invention will be clearly and completely described in conjunction with the embodiments of the present invention, but they should not be construed as limiting the scope of the present invention.
Example 1
Drying watermelon peel in the sun, grinding into powder, and calcining at 1000 ℃ for 9 hours to obtain a carbon material; adding the carbon material into 8mol/L potassium hydroxide solution, stirring for 24 hours, filtering, and drying at 100 ℃ for 8 hours to obtain an activated carbon material; weighing 1g of the activated carbon material, adding 265mg of nickel nitrate hexahydrate, mixing and stirring for 6 hours, drying at 80 ℃ for 8 hours, calcining for 0.2 hours under the condition of 300W power, 700 ℃ and 300Pa vacuum degree under the plasma, and placing the obtained calcined product into 2mol/L sulfuric acid to etch for 12 hours at 80 ℃ to obtain the single-atom and multi-atom transition metal co-doped carbon catalytic material.
Example 2
Drying watermelon peel in the sun, grinding into powder, and calcining at 800 ℃ for 9 hours to obtain a carbon material; adding the carbon material into 8mol/L potassium hydroxide solution, stirring for 24 hours, filtering, and drying at 100 ℃ for 8 hours to obtain an activated carbon material; weighing 1g of the activated carbon material, adding 265mg of nickel nitrate hexahydrate, mixing and stirring for 6 hours, drying at 80 ℃ for 8 hours, calcining for 0.2 hours under the condition of 300W power, 700 ℃ and 300Pa vacuum degree under the plasma, and placing the obtained calcined product into 2mol/L sulfuric acid to etch for 12 hours at 80 ℃ to obtain the single-atom and multi-atom transition metal co-doped carbon catalytic material.
Example 3
Drying watermelon peel in the sun, grinding into powder, and calcining at 1000 ℃ for 9 hours to obtain a carbon material; adding the carbon material into 4mol/L potassium hydroxide solution, stirring for 24 hours, filtering, and drying at 100 ℃ for 8 hours to obtain an activated carbon material; weighing 1g of the activated carbon material, adding 265mg of nickel nitrate hexahydrate, mixing and stirring for 6 hours, drying at 80 ℃ for 8 hours, calcining for 0.2 hours under the condition of 300W power, 700 ℃ and 300Pa vacuum degree under the plasma, and placing the obtained calcined product into 2mol/L sulfuric acid to etch for 12 hours at 80 ℃ to obtain the single-atom and multi-atom transition metal co-doped carbon catalytic material.
Example 4
Drying watermelon peel in the sun, grinding into powder, and calcining at 1000 ℃ for 9 hours to obtain a carbon material; adding the carbon material into 8mol/L potassium hydroxide solution, stirring for 24 hours, filtering, and drying at 100 ℃ for 8 hours to obtain an activated carbon material; weighing 1g of the activated carbon material, adding 265mg of nickel nitrate hexahydrate, mixing and stirring for 6 hours, drying at 80 ℃ for 8 hours, calcining for 0.2 hours under the condition of 300W power, 400 ℃ and 300Pa vacuum degree under the plasma, and placing the obtained calcined product into 2mol/L sulfuric acid to etch for 12 hours at 80 ℃ to obtain the single-atom and multi-atom transition metal co-doped carbon catalytic material.
Example 5
Drying watermelon peel in the sun, grinding into powder, and calcining at 1000 ℃ for 9 hours to obtain a carbon material; adding the carbon material into 8mol/L potassium hydroxide solution, stirring for 24 hours, filtering, and drying at 100 ℃ for 8 hours to obtain an activated carbon material; weighing 1g of the activated carbon material, adding 265mg of nickel nitrate hexahydrate, mixing and stirring for 6 hours, drying at 80 ℃ for 8 hours, calcining for 0.2 hour under the condition of 300W power, 700 ℃ and 300Pa vacuum degree under the plasma, and placing the obtained calcined product in 6mol/L sulfuric acid to etch for 12 hours at 80 ℃ to obtain the single-atom and multi-atom transition metal co-doped carbon catalytic material.
Example 6
Drying watermelon peel in the sun, grinding into powder, and calcining at 1000 ℃ for 9 hours to obtain a carbon material; adding the carbon material into 8mol/L potassium hydroxide solution, stirring for 24 hours, filtering, and drying at 100 ℃ for 8 hours to obtain an activated carbon material; weighing 1g of the activated carbon material, adding 265mg of nickel nitrate hexahydrate, mixing and stirring for 6 hours, drying at 80 ℃ for 8 hours, calcining for 0.2 hour under the condition of 300W power, 700 ℃ and 300Pa vacuum degree under the plasma, and placing the obtained calcined product into 0.5mol/L sulfuric acid to etch for 12 hours at 80 ℃ to obtain the single-atom and multi-atom transition metal co-doped carbon catalytic material.
Example 7
Drying watermelon peel in the sun, grinding into powder, and calcining at 1000 ℃ for 9 hours to obtain a carbon material; adding the carbon material into 8mol/L potassium hydroxide solution, stirring for 24 hours, filtering, and drying at 100 ℃ for 8 hours to obtain an activated carbon material; weighing 1g of the activated carbon material, adding 215mg of nickel nitrate hexahydrate, mixing and stirring for 6 hours, drying at 80 ℃ for 8 hours, calcining for 0.2 hours under the condition of 300W of power, 700 ℃ of temperature and 300Pa of vacuum degree under the plasma, and placing the obtained calcined product into 2mol/L sulfuric acid to etch for 12 hours at 80 ℃ to obtain the single-atom and multi-atom transition metal co-doped carbon catalytic material.
Comparative example 1
Drying watermelon peel in the sun, grinding into powder, and calcining at 1000 ℃ for 9 hours to obtain a carbon material; adding the carbon material into 8mol/L potassium hydroxide solution, stirring for 24 hours, filtering, and drying at 100 ℃ for 8 hours to obtain an activated carbon material; 1g of the activated carbon material is weighed, 265mg of nickel nitrate hexahydrate is added, mixed and stirred for 6 hours, then dried at 80 ℃ for 8 hours, and then calcined for 0.2 hour under the condition that the power is 300W, the temperature is 700 ℃ and the vacuum degree is 300Pa under the plasma, so as to obtain the metal doped carbon catalytic material.
Application examples 1 to 7
Loading the single-atom and multi-atom transition metal co-doped carbon catalytic materials obtained in examples 1-7 into a high-pressure reaction kettle respectively, taking ethanol as a solution, and carrying out hydrogenation reaction on phenylacetylene and the single-atom and multi-atom transition metal co-doped carbon catalytic materials for 1h under the condition that the mass ratio of the phenylacetylene to the single-atom and multi-atom transition metal co-doped carbon catalytic materials is 20:1 at the temperature of 60 ℃ and the reaction pressure of 0.2MPa hydrogen, so as to obtain styrene through hydrogenation of the phenylacetylene.
Comparative application example 1
Loading the metal doped carbon catalytic material obtained in the comparative example 1 into a high-pressure reaction kettle, taking ethanol as a solution, and carrying out hydrogenation reaction for 1h under the condition that the temperature is 60 ℃ and the reaction pressure of 0.2MPa hydrogen and the mass ratio of phenylacetylene to the single-atom and multi-atom transition metal co-doped carbon catalytic material is 20:1, so as to obtain styrene through hydrogenation of phenylacetylene.
Performance testing
(1) The specific surface areas of the single-atom and multi-atom transition metal co-doped carbon catalytic materials obtained in examples 1 to 7 were measured, and the results are shown in table 1.
TABLE 1 specific surface area of the Mono-and polyatomic transition Metal Co-doped carbon catalytic Material obtained in examples 1 to 7 and the Metal doped carbon catalytic Material obtained in comparative example 1
| Sample of | Specific surface area m 2/g |
| Comparative example 1 | 683.1 |
| Example 1 | 983.5 |
| Example 2 | 734.3 |
| Example 3 | 722.6 |
| Example 4 | 892.6 |
| Example 5 | 912.1 |
| Example 6 | 938.4 |
| Example 7 | 975.2 |
As can be seen from Table 1, the specific surface area of the single-atom and multi-atom transition metal co-doped carbon catalytic material prepared by the method can reach 983.5m 2/g, which is far higher than the specific surface area (683.1 m 2/g) of the metal doped carbon catalytic material in comparative example 1, and the single-atom and multi-atom transition metal co-doped carbon catalytic material prepared by the method has high specific surface area, is beneficial to increasing active sites, and thus improves catalytic activity.
(2) The conversion and selectivity of phenylacetylene to styrene in application examples 1 to 7 and comparative application example 1 were measured, and the results are shown in Table 2.
TABLE 2 conversion and Selectivity of styrene by hydrogenation of phenylacetylene in application examples 1 to 7 and comparative application example 1
| Sample of | Conversion/% | Selectivity/% |
| Comparative application example 1 | 55.2 | 85.3 |
| Application example 1 | 97.6 | 95.2 |
| Application example 2 | 85.6 | 91.3 |
| Application example 3 | 78.3 | 90.3 |
| Application example 4 | 74.6 | 88.5 |
| Application example 5 | 88.9 | 93.6 |
| Application example 6 | 80.1 | 86.3 |
| Application example 7 | 70.1 | 94.2 |
As can be seen from Table 2, the conversion rate of styrene prepared by hydrogenation of phenylacetylene catalyzed by the single-atom and multi-atom transition metal co-doped carbon catalytic material prepared by the invention reaches 97.6%, and the selectivity reaches 95.2%, which shows that the single-atom and multi-atom transition metal co-doped carbon catalytic material prepared by the invention has excellent catalytic efficiency and selectivity.
(3) The catalytic stability of the single-and multi-atom transition metal co-doped carbon catalytic materials and the metal-doped carbon catalytic materials obtained in example 1 are shown in table 3.
TABLE 3 catalytic stability of the monatomic and polyatomic transition metal co-doped carbon catalytic materials and metal-doped carbon catalytic materials obtained in example 1
As can be seen from Table 3, the single-atom and multi-atom transition metal co-doped carbon catalytic material prepared by the invention still has excellent conversion rate and selectivity after 8 times of catalysis, which indicates that the single-atom and multi-atom transition metal co-doped carbon catalytic material prepared by the invention has excellent catalytic stability.
(4) The single-and multi-atom transition metal co-doped carbon catalytic material prepared in example 1 was tested using a transmission electron microscope and the results are shown in fig. 1.
As can be seen from FIG. 1, the single-atom and multi-atom transition metal co-doped carbon catalytic material prepared by the invention has various metal particle sizes dispersed therein, and has metal particles of single-atom level and nanoparticle clusters.
Although the foregoing embodiments have been described in some, but not all, embodiments of the invention, according to which one can obtain other embodiments without inventiveness, these embodiments are all within the scope of the invention.
Claims (10)
1. The preparation method of the single-atom and multi-atom transition metal co-doped carbon catalytic material is characterized by comprising the following steps of:
Providing biomass carbon;
Mixing the biomass carbon with an alkaline solution, and performing activation treatment to obtain an activated carbon material;
Mixing the activated carbon material with a transition metal salt, and performing plasma calcination to obtain a calcination product, wherein the calcination product comprises a carbon carrier and a transition metal nanoparticle formed by polyatoms loaded on the surface of the carbon carrier;
And mixing the calcined product with an acidic solution, and carrying out acid etching treatment to obtain the single-atom and multi-atom transition metal co-doped carbon catalytic material.
2. The preparation method according to claim 1, wherein the alkaline solution comprises a sodium hydroxide solution and/or a potassium hydroxide solution; the concentration of the alkaline solution is 4-20 mmol/L.
3. The method of claim 1, wherein the transition metal salt comprises one or more of an iron salt, a nickel salt, and a cobalt salt.
4. The preparation method according to claim 1, wherein the power of the plasma calcination is 100-2000 w, the temperature is 400-800 ℃, the vacuum degree is 100-1000 Pa, and the heat preservation time is 0.1-0.6 h.
5. The method of claim 1, wherein the acidic solution comprises one or more of sulfuric acid, nitric acid, and hydrochloric acid.
6. The method according to claim 1 or 5, wherein the concentration of the acidic solution is 1 to 10mmol/L; the temperature of the acid etching treatment is 30-100 ℃ and the time is 2-20 h.
7. The method of claim 1, wherein the biomass carbon is produced by calcining biomass; the biomass is one or more of shrimp shell, rice stem, bamboo cotyledon, lu Weicao and watermelon peel.
8. The method according to claim 7, wherein the calcination temperature is 700 to 1200 ℃ and the holding time is 3 to 20 hours.
9. The carbon catalytic material co-doped with single-atom and multi-atom transition metals prepared by the preparation method according to any one of claims 1 to 8, which is characterized by comprising a porous carbon material and transition metal nanoparticles formed by single-atom transition metals and multi-atom transition metals doped on the porous carbon material.
10. Use of the single-atom and multi-atom transition metal co-doped carbon catalytic material according to claim 9 for preparing carbon-carbon double bond compounds by hydrogenation of carbon-carbon triple bonds.
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