CN111606316B - Biological enrichment preparation method of transition metal monoatomic carbon material - Google Patents
Biological enrichment preparation method of transition metal monoatomic carbon material Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
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- B01J35/647—
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B22F1/00—Metallic powder; Treatment of metallic powder, e.g. to facilitate working or to improve properties
- B22F1/05—Metallic powder characterised by the size or surface area of the particles
- B22F1/054—Nanosized particles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/02—Making metallic powder or suspensions thereof using physical processes
- B22F9/04—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling
- B22F2009/043—Making metallic powder or suspensions thereof using physical processes starting from solid material, e.g. by crushing, grinding or milling by ball milling
Abstract
The invention discloses a biological enrichment preparation method of a transition metal monoatomic carbon material, which comprises the following steps: preparing a liquid culture medium; inoculating fungus strains into a liquid culture medium, and performing shake culture; adding the transition metal complex into a liquid culture medium in the form of a solution or a dispersion; continuously culturing, pouring out the redundant liquid culture medium, washing with deionized water, freeze-drying, and naturally cooling when the dried sample is pyrolyzed in protective gas; adding the pyrolysis product into H2SO4Stirring and refluxing the solution, then centrifugally collecting, washing with deionized water to be neutral, and drying in vacuum to obtain the transition metal monoatomic carbon material. The transition metal monoatomic carbon material prepared by the method has the advantages of high transition metal monoatomic load, high specific surface area and the like, and can be widely applied to the fields of energy storage, catalysis, environmental protection and the like. The preparation method disclosed by the invention is simple in preparation process, convenient to operate, cheap, environment-friendly and easy for mass preparation.
Description
Technical Field
The invention belongs to preparation of transition metal monoatomic materials, and relates to a biological enrichment preparation method of transition metal monoatomic materials. The transition metal monatomic material prepared by the method is mainly suitable for the fields of energy storage, catalysis, environmental protection and the like.
Background
Atomic dispersion catalysts are receiving increasing attention in a variety of reactions due to their high atom utilization and controllable coordination environment. In electrochemistry, coordination of atom-dispersed transition metal atoms in metal-nitrogen-carbon materials to nitrogen is particularly attractive because isolated metal-nitrogen-carbon centers have been demonstrated to be highly active sites in various electrochemical reactions, particularly oxygen reduction reactions. Although metal-nitrogen-carbon monoatomic atoms have excellent activity and selectivity, the high surface energy of the monoatomic atoms presents challenges to chemical synthesis. Through the traditional direct pyrolysis process, metal species in the product are aggregated, and the single atom loading is low. To increase the loading of the monoatomic atoms, the pyrolysis process is often modified by the substitution of precursors. In general, the confinement of transition metals in a stable structure is an important factor in the synthesis of metal-nitrogen-carbon single atoms. Therefore, it is highly desirable to develop materials that contain a large number of sites that can confine transition metals to prevent the aggregation of metal species and increase the loading of individual atoms.
The biomass is a clean, cheap and environment-friendly material, contains a plurality of proteins and provides a rich place for limiting transition metal ions. Through conformational changes, proteins are able to bind to isolated metal ions, thereby preventing aggregation of individual atoms. In a living body, the uptake of metal ions promotes the formation of proteins, so that additional metal ions located in the living body coordinate with each other (referred to as a bio-enrichment phenomenon). Therefore, a single metal ion can be concentrated in a living body without aggregation. The phenomenon of biological enrichment makes organisms an ideal precursor for the preparation of atom dispersed metal-nitrogen-carbon materials.
At present, the developed preparation method of the monatomic material can be roughly divided into a pretreatment method and a post-treatment method. The pretreatment method is divided into a component separation method, a growth method, a solvothermal method, an arc discharge method and the like. These processes generally require harsh conditions and specific equipment, so that their widespread use is limited, and the low yields also make these processes difficult to industrialize; the post-treatment method is generally to pyrolyze or plasma treat the material in a heteroatom atmosphere or together with a heteroatom precursor at high temperature, and the post-treatment can control the doping amount and the morphology of the material, but inevitably adopts expensive or toxic precursor materials, so that the material is not suitable for practical application. Therefore, it is a trend of material development and research to find a preparation method of transition metal monatomic material that is cheap, suitable for mass production, and environmentally friendly.
Disclosure of Invention
The invention aims to overcome the problems that harsh conditions and specific equipment are generally required, expensive or toxic precursor materials are inevitably adopted, the traditional direct pyrolysis process product has the aggregation of metal species and low load of single atoms and the like, and provides a biological enrichment preparation method of transition metal single atoms. The invention introduces the transition metal complex in the growth process of the fungus, and the transition metal monoatomic organisms are enriched in hyphae after the fungus spores germinate. The hypha carbon fiber containing highly dispersed transition metal monoatomic hyphae is obtained by pyrolysis of transition metal-rich hyphae, and the material has the advantages of high transition metal monoatomic load, high specific surface area and the like, and can be widely applied to the fields of energy storage, catalysis, environmental protection and the like.
To achieve these objects and other advantages in accordance with the present invention, there is provided a method for bio-enrichment preparation of a transition metal monatomic carbon material, comprising the steps of:
step one, preparing a culture medium: according to the raw material components and the proportion that each 100 ml of liquid culture medium contains 1-6 g of glucose, 0.25-1.25 g of peptone, 0.25-1.25 g of yeast powder and the balance of water, the raw materials of the components are uniformly mixed to dissolve solids, and the mixture is maintained for 15-20 minutes under the conditions that the pressure is 103.4 kilopascal vapor pressure and the temperature is 120 ℃ for sterilization to obtain the sterilized liquid culture medium; then 100 ml of sterilized liquid culture medium is added into a 250 ml conical flask;
inoculating fungus strains into 100 ml of liquid culture medium, and placing the liquid culture medium in a shaking table at the temperature of 26-30 ℃ to shake and culture the fungus strains for 0.5-1.5 days at the rotating speed of 150-200 r/min;
adding the transition metal complex into a liquid culture medium in the form of a solution or a dispersion liquid, and ensuring that the concentration of the transition metal complex in the liquid culture medium is 200-600 mg/L; after continuously culturing for 2-4 days, pouring out the redundant liquid culture medium, washing the liquid culture medium for 5 times by using deionized water, then carrying out freeze drying on the liquid culture medium, pyrolyzing the dried sample in protective gas, and then naturally cooling;
step four, adding 0.4-0.6 mol/L H into the pyrolysis product at the temperature of 75-85 DEG C2SO4Stirring and refluxing the solution for 8-12 hours, then centrifugally collecting, washing with deionized water to be neutral, and drying in vacuum at the temperature of 60-80 ℃ to obtain the transition metal monoatomic carbon material.
Preferably, the fungus strain is any one of a xylaria strain, a morchella strain, a pleurotus ostreatus strain, a agaricus bisporus strain and a shiitake mushroom strain.
Preferably, the transition metal complex is any one of a chitosan nickel complex, a chitosan cobalt complex, a chitosan iron complex, a chitosan manganese complex, a carboxymethyl chitosan nickel complex and a carboxymethyl chitosan cobalt complex.
Preferably, the preparation method of the chitosan nickel complex comprises the following steps: carrying out low-temperature plasma treatment on the water-soluble chitosan to obtain pretreated water-soluble chitosan; adding 5-10 parts by weight of pretreated water-soluble chitosan into 80-100 parts by weight of water, stirring for dissolving, then adding 1-3 parts by weight of citric acid, simultaneously adding ammonia water for adjusting the pH value to 5-6, heating to 50-60 ℃, adding 5-10 parts by weight of nickel salt, stirring for reacting for 60-90 min, irradiating the reacted material by adopting gamma rays under a vacuum condition, then precipitating for 12h at normal temperature by using ethanol, filtering, washing by using ethanol, and drying in vacuum; and ball-milling the dried product by using a nanosphere mill until the particle size is 100-500 nm to obtain the chitosan nickel complex.
Preferably, the gas for performing the low-temperature plasma treatment is Ar/O2The flow rate of the gas is 0.1-1L/min/cm2To putThe electric pressure is 10-30 Pa, the discharge power is 350-500W, the temperature is 45-55 ℃, and the discharge time is 5-8 min.
Preferably, the irradiation dose of the gamma ray irradiation is 50-80 KGy, and the irradiation dose rate is 10-20 KGy/h.
Preferably, in the third step, the freeze drying is carried out for 72-96 hours under the conditions of 80 ℃ below zero and 1.3-5 Pa of vacuum degree.
Preferably, in the third step, the protective gas is one of nitrogen, argon and argon-hydrogen mixed gas.
Preferably, in the third step, the temperature raising process of the pyrolysis is as follows: heating to 100-300 ℃ at the speed of 5-10 ℃/min, and keeping the temperature for 15 min; then heating to 400-500 ℃ at the speed of 1-2 ℃/min, and preserving heat for 30 min; then heating to 600-1000 ℃ at the speed of 1-2 ℃/min, and preserving heat for 30-60 min.
Preferably, in the third step, the concentration of the transition metal complex added in the form of a solution or a dispersion is 3-5 g/L.
The invention at least comprises the following beneficial effects:
(1) in contrast to bacteria, most fungi exhibit a filamentous growth habit, which provides the ability to form hyphally-aggregated linear organs using exploratory or developmental growth strategies to protect fungal translocation; by adopting the invention, the fungus hypha is a clean, cheap and environment-friendly biomass material with a three-dimensional network structure, contains various proteins and provides a rich place for fixing transition metal ions. By using the allosteric effect of proteins, proteins can bind to isolated metal ions, thereby preventing aggregation of individual atoms. In the fungal hyphae, uptake of metal ions promotes the formation of proteins, such that additional metal ions located in the fungal hyphae coordinate with each other. Thus, a single metal ion can be bio-enriched in the fungal hyphae without aggregation, thereby forming a transition metal monatomic material; the problems that single atoms in the transition metal single atom material are easy to agglomerate, poor in dispersity and the like are solved;
(2) according to the invention, the adopted transition metal complex contains a nitrogen source and a transition metal source at the same time, and can be used as a nitrogen doping site of the carbon material on one hand; on the other hand, compared with metal ions, the transition metal complex has less toxicity to fungal hyphae, can fix more metal ions by protein, thereby improving the content of transition metal monoatomic substances, and has higher content of transition metal monoatomic substances compared with the traditional adsorption-pyrolysis method.
(3) The transition metal monoatomic carbon material prepared by the method has the advantages of high transition metal monoatomic load, high specific surface area and the like, and can be widely applied to the fields of energy storage, catalysis, environmental protection and the like.
(4) The preparation method disclosed by the invention is simple in preparation process, convenient to operate, cheap, environment-friendly and easy for mass preparation.
Additional advantages, objects, and features of the invention will be set forth in part in the description which follows and in part will become apparent to those having ordinary skill in the art upon examination of the following or may be learned from practice of the invention.
Description of the drawings:
FIG. 1 is an SEM image of a transition metal monatomic carbon material produced in example 1 of the present invention;
FIG. 2 is an SEM image of a transition metal monatomic carbon material produced in example 1 of the present invention;
FIG. 3 is a TEM image of a transition metal monatomic carbon material produced in example 1 of the present invention;
FIG. 4 is a TEM image of a transition metal monatomic carbon material produced in example 1 of the present invention.
The specific implementation mode is as follows:
the present invention is further described in detail below with reference to the attached drawings so that those skilled in the art can implement the invention by referring to the description text.
It will be understood that terms such as "having," "including," and "comprising," as used herein, do not preclude the presence or addition of one or more other elements or groups thereof.
Example 1:
a biological enrichment preparation method of a transition metal monoatomic carbon material comprises the following steps:
step one, preparing a culture medium: according to the raw material components and the proportion that each 100 ml of liquid culture medium contains 4g of glucose, 0.85 g of peptone, 0.85 g of yeast powder and the balance of water, the raw materials of the components are uniformly mixed to dissolve solids, and the mixture is maintained for 20 minutes under the conditions of the pressure of 103.4 kilopascals and the temperature of 120 ℃ for sterilization to obtain the sterilized liquid culture medium; then 100 ml of sterilized liquid culture medium is added into a 250 ml conical flask;
step two, inoculating 0.08g of carbon horn bacterium strains into 100 ml of liquid culture medium, and placing the carbon horn bacterium strains in a shaking table at the temperature of 28 ℃ to shake and culture the carbon horn bacterium strains for 1 day at the rotating speed of 180 rpm;
preparing 4g/L dispersion liquid (prepared by adopting sterile water) of the transition metal complex, and adding the dispersion liquid into a liquid culture medium to ensure that the concentration of the transition metal complex in the liquid culture medium is 400 mg/L; after continuously culturing for 3 days, pouring out the redundant liquid culture medium, washing the liquid culture medium for 5 times by using deionized water, then carrying out freeze drying on the liquid culture medium, carrying out pyrolysis on the dried sample in protective gas, and then naturally cooling the sample; the freeze drying is carried out for 96 hours under the conditions of 80 ℃ below zero and 1.3 Pa of vacuum degree; the protective gas is nitrogen; the temperature rise process of the pyrolysis is as follows: heating to 300 deg.C at a speed of 5 deg.C/min, and maintaining for 15 min; then heating to 500 ℃ at the speed of 1 ℃/min, and preserving heat for 30 min; then raising the temperature to 1000 ℃ at the speed of 2 ℃/min, and preserving the temperature for 60 min;
wherein the transition metal complex is a chitosan nickel complex, and the preparation method comprises the following steps: carrying out low-temperature plasma treatment on the water-soluble chitosan to obtain pretreated water-soluble chitosan; adding 5g of pretreated water-soluble chitosan into 80g of water, stirring for dissolving, then adding 1g of citric acid, simultaneously adding ammonia water for adjusting the pH value to 5, heating to 50 ℃, adding 5g of nickel nitrate, stirring for reacting for 60min, irradiating the reacted material by adopting gamma rays under the vacuum condition, then precipitating for 12h at normal temperature by using ethanol, filtering, washing by using ethanol, and drying in vacuum; ball-milling the dried product by using a nanosphere mill until the particle size is 200nm to obtain a chitosan nickel complex; the gas for low-temperature plasma treatment is Ar/O2The flow rate of the gas is 0.2L/min/cm2Discharge of electricityThe pressure is 15Pa, the discharge power is 350W, the temperature is 45 ℃, and the discharge time is 5 min; the nickel salt is nickel nitrate; the irradiation dose of the gamma ray irradiation is 50KGy, and the irradiation dose rate is 10 KGy/h; the chitosan is pretreated by adopting low-temperature plasma so as to improve the active center on the surface of the chitosan and provide higher reactivity for chemical reaction; the mechanism of modifying the surface of the chitosan by the low-temperature plasma is that extremely unstable excited molecules, atoms, ions, free radicals and the like are formed in the atmosphere to activate the surface of the chitosan, so that the reaction activity of the chitosan is improved. The low-temperature plasma modification technology is simple to operate, an initiator is not needed, and the bulk performance of the polymer is not influenced;
step four, adding 0.5mol/L H into the pyrolysis product at the temperature of 80 DEG C2SO4Stirring and refluxing the solution for 8 hours, then centrifugally collecting, washing the solution to be neutral by using deionized water, and drying the solution in vacuum at the temperature of 60 ℃ to obtain the transition metal monoatomic carbon material; the specific surface area of the transition metal monoatomic carbon material prepared in this example was 855.65m2Per g, average pore diameter 2.35nm, content of monoatomic nickel: 5.1% (using ICP-AES test); the appearance and microstructure of the transition metal single-atom carbon material are characterized by SEM and TEM, and the diameter of the reticular skeleton of the transition metal single-atom carbon material reaches micro-nanometer level and has a porous structure.
Example 2:
a biological enrichment preparation method of a transition metal monoatomic carbon material comprises the following steps:
step one, preparing a culture medium: according to the raw material components and the proportion that each 100 ml of liquid culture medium contains 5g of glucose, 1g of peptone, 1g of yeast powder and the balance of water, the raw materials of the components are uniformly mixed to dissolve solids, and the mixture is maintained for 15 minutes under the conditions that the pressure is 103.4 kilopascal vapor pressure and the temperature is 120 ℃ for sterilization to obtain the sterilized liquid culture medium; then 100 ml of sterilized liquid culture medium is added into a 250 ml conical flask;
step two, inoculating 0.08g of carbon horn bacterium strains into 100 ml of liquid culture medium, and placing the carbon horn bacterium strains in a shaking table at the temperature of 28 ℃ to shake and culture the carbon horn bacterium strains for 1 day at the rotating speed of 180 rpm;
preparing a 5g/L dispersion liquid (prepared by adopting sterile water) of the transition metal complex, and adding the dispersion liquid into a liquid culture medium to ensure that the concentration of the transition metal complex in the liquid culture medium is 400 mg/L; after continuously culturing for 3 days, pouring out the redundant liquid culture medium, washing the liquid culture medium for 5 times by using deionized water, then carrying out freeze drying on the liquid culture medium, carrying out pyrolysis on the dried sample in protective gas, and then naturally cooling the sample; the freeze drying is carried out for 72 hours under the conditions of 80 ℃ below zero and 1.3 Pa of vacuum degree; the protective gas is nitrogen; the temperature rise process of the pyrolysis is as follows: heating to 300 deg.C at a speed of 10 deg.C/min, and maintaining for 15 min; then heating to 400 ℃ at the speed of 2 ℃/min, and preserving heat for 30 min; then heating to 800 ℃ at the speed of 1 ℃/min, and preserving heat for 60 min;
wherein the transition metal complex is a chitosan nickel complex, and the preparation method comprises the following steps: carrying out low-temperature plasma treatment on the water-soluble chitosan to obtain pretreated water-soluble chitosan; adding 10g of pretreated water-soluble chitosan into 100g of water, stirring for dissolving, then adding 3g of citric acid, simultaneously adding ammonia water for adjusting the pH value to 5.5, heating to 55 ℃, adding 10g of nickel chloride, stirring for reacting for 90min, irradiating the reacted materials by adopting gamma rays under the vacuum condition, then precipitating for 12h at normal temperature by using ethanol, filtering, washing by using ethanol, and drying in vacuum; ball-milling the dried product by using a nanosphere mill until the particle size is 200nm to obtain a chitosan nickel complex; the gas for low-temperature plasma treatment is Ar/O2The flow rate of the gas is 0.2L/min/cm2The discharge pressure is 20Pa, the discharge power is 350W, the temperature is 45 ℃, and the discharge time is 5 min; the nickel salt is nickel nitrate; the irradiation dose of gamma ray irradiation is 50KGy, and the irradiation dose rate is 20 KGy/h;
step four, adding 0.4mol/L H into the pyrolysis product at the temperature of 80 DEG C2SO4Stirring and refluxing the solution for 12 hours, then centrifugally collecting, washing the solution to be neutral by deionized water, and drying the solution in vacuum at the temperature of 60 ℃ to obtain the transition metal monoatomic carbon material. The specific surface area of the transition metal monoatomic carbon material prepared in this example was 862.58m2G, average pore diameter 2.28 nm. Content of monoatomic nickel: 5.8% (tested by ICP-AES).
Example 3:
a biological enrichment preparation method of a transition metal monoatomic carbon material comprises the following steps:
step one, preparing a culture medium: according to the raw material components and the proportion that each 100 ml of liquid culture medium contains 6 g of glucose, 1.25 g of peptone, 0.85 g of yeast powder and the balance of water, the raw materials of the components are uniformly mixed to dissolve solids, and the mixture is maintained for 20 minutes under the conditions of the pressure of 103.4 kilopascals and the temperature of 120 ℃ for sterilization to obtain the sterilized liquid culture medium; then 100 ml of sterilized liquid culture medium is added into a 250 ml conical flask;
step two, inoculating 0.1g of morchella strain into 100 ml of liquid culture medium, and placing the morchella strain in a shaking table at the temperature of 28 ℃ to shake and culture the morchella strain for 1 day at the rotating speed of 180 rpm;
preparing a 5g/L dispersion liquid (prepared by adopting sterile water) of the transition metal complex, and adding the dispersion liquid into a liquid culture medium to ensure that the concentration of the transition metal complex in the liquid culture medium is 450 mg/L; after continuously culturing for 3 days, pouring out the redundant liquid culture medium, washing the liquid culture medium for 5 times by using deionized water, then carrying out freeze drying on the liquid culture medium, carrying out pyrolysis on the dried sample in protective gas, and then naturally cooling the sample; the freeze drying is carried out for 96 hours under the conditions of 80 ℃ below zero and 1.3 Pa of vacuum degree; the protective gas is nitrogen; the temperature rise process of the pyrolysis is as follows: heating to 200 deg.C at a speed of 10 deg.C/min, and maintaining for 15 min; then heating to 400 ℃ at the speed of 2 ℃/min, and preserving heat for 30 min; then heating to 800 ℃ at the speed of 1 ℃/min, and preserving heat for 60 min;
wherein the transition metal complex is a chitosan nickel complex, and the preparation method comprises the following steps: carrying out low-temperature plasma treatment on the water-soluble chitosan to obtain pretreated water-soluble chitosan; adding 5g of pretreated water-soluble chitosan into 80g of water, stirring for dissolving, then adding 1g of citric acid, simultaneously adding ammonia water for adjusting the pH value to 5, heating to 50 ℃, adding 5g of nickel nitrate, stirring for reacting for 60min, and subjecting the reacted material to vacuum conditionIrradiating by gamma rays, then precipitating for 12h by using ethanol at normal temperature, filtering, washing by using ethanol, and drying in vacuum; ball-milling the dried product by using a nanosphere mill until the particle size is 200nm to obtain a chitosan nickel complex; the gas for low-temperature plasma treatment is Ar/O2The flow rate of the gas is 0.2L/min/cm2The discharge pressure is 15Pa, the discharge power is 350W, the temperature is 45 ℃, and the discharge time is 5 min; the nickel salt is nickel nitrate; the irradiation dose of the gamma ray irradiation is 50KGy, and the irradiation dose rate is 10 KGy/h;
step four, adding 0.5mol/L H into the pyrolysis product at the temperature of 80 DEG C2SO4Stirring and refluxing the solution for 8 hours, then centrifugally collecting, washing the solution to be neutral by deionized water, and drying the solution in vacuum at the temperature of 60 ℃ to obtain the transition metal monoatomic carbon material. The specific surface area of the transition metal monoatomic carbon material prepared in this example was 860.88m2G, average pore diameter 2.31 nm. Content of monoatomic nickel: 5.7% (tested by ICP-AES).
Example 4:
a biological enrichment preparation method of a transition metal monoatomic carbon material comprises the following steps:
step one, preparing a culture medium: according to the raw material components and the proportion that each 100 ml of liquid culture medium contains 4g of glucose, 0.85 g of peptone, 0.85 g of yeast powder and the balance of water, the raw materials of the components are uniformly mixed to dissolve solids, and the mixture is maintained for 20 minutes under the conditions of the pressure of 103.4 kilopascals and the temperature of 120 ℃ for sterilization to obtain the sterilized liquid culture medium; then 100 ml of sterilized liquid culture medium is added into a 250 ml conical flask;
step two, inoculating 0.08g of carbon horn bacterium strains into 100 ml of liquid culture medium, and placing the carbon horn bacterium strains in a shaking table at the temperature of 28 ℃ to shake and culture the carbon horn bacterium strains for 1 day at the rotating speed of 180 rpm;
preparing 4g/L dispersion liquid (prepared by adopting sterile water) of the transition metal complex, and adding the dispersion liquid into a liquid culture medium to ensure that the concentration of the transition metal complex in the liquid culture medium is 400 mg/L; after continuously culturing for 3 days, pouring out the redundant liquid culture medium, washing the liquid culture medium for 5 times by using deionized water, then carrying out freeze drying on the liquid culture medium, carrying out pyrolysis on the dried sample in protective gas, and then naturally cooling the sample; the freeze drying is carried out for 96 hours under the conditions of 80 ℃ below zero and 1.3 Pa of vacuum degree; the protective gas is nitrogen; the temperature rise process of the pyrolysis is as follows: heating to 300 deg.C at a speed of 5 deg.C/min, and maintaining for 15 min; then heating to 500 ℃ at the speed of 1 ℃/min, and preserving heat for 30 min; then raising the temperature to 1000 ℃ at the speed of 2 ℃/min, and preserving the temperature for 60 min;
wherein the transition metal complex is a chitosan nickel complex, and the preparation method comprises the following steps: adding 5g of water-soluble chitosan into 80g of water, stirring for dissolving, then adding 1g of citric acid, simultaneously adding ammonia water for adjusting the pH value to 5, heating to 50 ℃, adding 5g of nickel nitrate, stirring for reacting for 60min, irradiating the reacted material by adopting gamma rays under the vacuum condition, then precipitating for 12h at normal temperature by using ethanol, filtering, washing by using ethanol, and drying in vacuum; ball-milling the dried product by using a nanosphere mill until the particle size is 200nm to obtain a chitosan nickel complex; the nickel salt is nickel nitrate; the irradiation dose of the gamma ray irradiation is 50KGy, and the irradiation dose rate is 10 KGy/h;
step four, adding 0.5mol/L H into the pyrolysis product at the temperature of 80 DEG C2SO4Stirring and refluxing the solution for 8 hours, then centrifugally collecting, washing the solution to be neutral by deionized water, and drying the solution in vacuum at the temperature of 60 ℃ to obtain the transition metal monoatomic carbon material. The specific surface area of the transition metal monoatomic carbon material prepared in this example was 705.64m2G, average pore diameter 2.95 nm. Content of monoatomic nickel: 4.2% (tested by ICP-AES).
Example 5:
a biological enrichment preparation method of a transition metal monoatomic carbon material comprises the following steps:
step one, preparing a culture medium: according to the raw material components and the proportion that each 100 ml of liquid culture medium contains 4g of glucose, 0.85 g of peptone, 0.85 g of yeast powder and the balance of water, the raw materials of the components are uniformly mixed to dissolve solids, and the mixture is maintained for 20 minutes under the conditions of the pressure of 103.4 kilopascals and the temperature of 120 ℃ for sterilization to obtain the sterilized liquid culture medium; then 100 ml of sterilized liquid culture medium is added into a 250 ml conical flask;
step two, inoculating 0.08g of carbon horn bacterium strains into 100 ml of liquid culture medium, and placing the carbon horn bacterium strains in a shaking table at the temperature of 28 ℃ to shake and culture the carbon horn bacterium strains for 1 day at the rotating speed of 180 rpm;
preparing 4g/L dispersion liquid (prepared by adopting sterile water) of the transition metal complex, and adding the dispersion liquid into a liquid culture medium to ensure that the concentration of the transition metal complex in the liquid culture medium is 400 mg/L; after continuously culturing for 3 days, pouring out the redundant liquid culture medium, washing the liquid culture medium for 5 times by using deionized water, then carrying out freeze drying on the liquid culture medium, carrying out pyrolysis on the dried sample in protective gas, and then naturally cooling the sample; the freeze drying is carried out for 96 hours under the conditions of 80 ℃ below zero and 1.3 Pa of vacuum degree; the protective gas is nitrogen; the temperature rise process of the pyrolysis is as follows: heating to 300 deg.C at a speed of 5 deg.C/min, and maintaining for 15 min; then heating to 500 ℃ at the speed of 1 ℃/min, and preserving heat for 30 min; then raising the temperature to 1000 ℃ at the speed of 2 ℃/min, and preserving the temperature for 60 min;
wherein the transition metal complex is a chitosan nickel complex, and the preparation method comprises the following steps: carrying out low-temperature plasma treatment on the water-soluble chitosan to obtain pretreated water-soluble chitosan; adding 5g of pretreated water-soluble chitosan into 80g of water, stirring for dissolving, then adding 1g of citric acid, simultaneously adding ammonia water for adjusting the pH value to 5, heating to 50 ℃, adding 5g of nickel nitrate, stirring for reacting for 60min, and naturally standing for 5 h; then precipitating with ethanol at normal temperature for 12h, filtering, washing with ethanol, and vacuum drying; ball-milling the dried product by using a nanosphere mill until the particle size is 200nm to obtain a chitosan nickel complex; the gas for low-temperature plasma treatment is Ar/O2The flow rate of the gas is 0.2L/min/cm2The discharge pressure is 15Pa, the discharge power is 350W, the temperature is 45 ℃, and the discharge time is 5 min; the nickel salt is nickel nitrate; the chitosan is pretreated by adopting low-temperature plasma so as to improve the active center on the surface of the chitosan and provide higher reactivity for chemical reaction; the mechanism of the low-temperature plasma for modifying the surface of the chitosan is the formation in the atmosphereThe surface of the chitosan is activated by extremely unstable excited molecules, atoms, ions, free radicals and the like, and the reactivity of the chitosan is improved. The low-temperature plasma modification technology is simple to operate, an initiator is not needed, and the bulk performance of the polymer is not influenced;
step four, adding 0.5mol/L H into the pyrolysis product at the temperature of 80 DEG C2SO4Stirring and refluxing the solution for 8 hours, then centrifugally collecting, washing the solution to be neutral by deionized water, and drying the solution in vacuum at the temperature of 60 ℃ to obtain the transition metal monoatomic carbon material. The specific surface area of the transition metal monoatomic carbon material prepared in this example was 718.64m2G, average pore diameter 2.78 nm. Content of monoatomic nickel: 4.5% (tested by ICP-AES).
Example 6:
a biological enrichment preparation method of a transition metal monoatomic carbon material comprises the following steps:
step one, preparing a culture medium: according to the raw material components and the proportion that each 100 ml of liquid culture medium contains 4g of glucose, 0.85 g of peptone, 0.85 g of yeast powder and the balance of water, the raw materials of the components are uniformly mixed to dissolve solids, and the mixture is maintained for 20 minutes under the conditions of the pressure of 103.4 kilopascals and the temperature of 120 ℃ for sterilization to obtain the sterilized liquid culture medium; then 100 ml of sterilized liquid culture medium is added into a 250 ml conical flask;
step two, inoculating 0.08g of carbon horn bacterium strains into 100 ml of liquid culture medium, and placing the carbon horn bacterium strains in a shaking table at the temperature of 28 ℃ to shake and culture the carbon horn bacterium strains for 1 day at the rotating speed of 180 rpm;
preparing 4g/L dispersion liquid (prepared by adopting sterile water) of the transition metal complex, and adding the dispersion liquid into a liquid culture medium to ensure that the concentration of the transition metal complex in the liquid culture medium is 400 mg/L; after continuously culturing for 3 days, pouring out the redundant liquid culture medium, washing the liquid culture medium for 5 times by using deionized water, then carrying out freeze drying on the liquid culture medium, carrying out pyrolysis on the dried sample in protective gas, and then naturally cooling the sample; the freeze drying is carried out for 96 hours under the conditions of 80 ℃ below zero and 1.3 Pa of vacuum degree; the protective gas is nitrogen; the temperature rise process of the pyrolysis is as follows: heating to 300 deg.C at a speed of 5 deg.C/min, and maintaining for 15 min; then heating to 500 ℃ at the speed of 1 ℃/min, and preserving heat for 30 min; then raising the temperature to 1000 ℃ at the speed of 2 ℃/min, and preserving the temperature for 60 min;
wherein the transition metal complex is a chitosan nickel complex, and the preparation method comprises the following steps: adding 5g of water-soluble chitosan into 80g of water, stirring for dissolving, then adding 1g of citric acid, simultaneously adding ammonia water for adjusting the pH value to 5, heating to 50 ℃, adding 5g of nickel nitrate, stirring for reacting for 60min, and naturally standing for 5 h; then precipitating with ethanol at normal temperature for 12h, filtering, washing with ethanol, and vacuum drying; ball-milling the dried product by using a nanosphere mill until the particle size is 200nm to obtain a chitosan nickel complex; the voltage of the low-temperature plasma is 100V, the vacuum degree is 120Pa, and the processing time is 5 min; the nickel salt is nickel nitrate;
step four, adding 0.5mol/L H into the pyrolysis product at the temperature of 80 DEG C2SO4Stirring and refluxing the solution for 8 hours, then centrifugally collecting, washing the solution to be neutral by deionized water, and drying the solution in vacuum at the temperature of 60 ℃ to obtain the transition metal monoatomic carbon material. The specific surface area of the transition metal monoatomic carbon material prepared in this example was 628.67m2G, average pore diameter 3.12 nm. Content of monoatomic nickel: 3.8% (tested by ICP-AES).
While embodiments of the invention have been described above, it is not limited to the applications set forth in the description and the embodiments, which are fully applicable in various fields of endeavor to which the invention pertains, and further modifications may readily be made by those skilled in the art, it being understood that the invention is not limited to the details shown and described herein without departing from the general concept defined by the appended claims and their equivalents.
Claims (8)
1. A biological enrichment preparation method of a transition metal monoatomic carbon material is characterized by comprising the following steps:
step one, preparing a culture medium: according to the raw material components and the proportion that each 100 ml of liquid culture medium contains 1-6 g of glucose, 0.25-1.25 g of peptone, 0.25-1.25 g of yeast powder and the balance of water, the raw materials of the components are uniformly mixed to dissolve solids, and the mixture is maintained for 15-20 minutes under the conditions that the pressure is 103.4 kilopascal vapor pressure and the temperature is 120 ℃ for sterilization to obtain the sterilized liquid culture medium; then 100 ml of sterilized liquid culture medium is added into a 250 ml conical flask;
step two, inoculating 0.05-0.1 g of fungus strains into 100 ml of liquid culture medium, and placing the liquid culture medium in a shaking table at 26-30 ℃ to shake and culture the fungus strains for 0.5-1.5 days at the rotating speed of 150-200 r/min;
adding the transition metal complex into a liquid culture medium in the form of a solution or a dispersion liquid, and ensuring that the concentration of the transition metal complex in the liquid culture medium is 200-600 mg/L; after continuously culturing for 2-4 days, pouring out the redundant liquid culture medium, washing the liquid culture medium for 5 times by using deionized water, then carrying out freeze drying on the liquid culture medium, pyrolyzing the dried sample in protective gas, and then naturally cooling;
step four, adding 0.4-0.6 mol/L H into the pyrolysis product at the temperature of 75-85 DEG C2SO4Stirring and refluxing the solution for 8-12 hours, then centrifugally collecting, washing with deionized water to be neutral, and drying in vacuum at the temperature of 60-80 ℃ to obtain the transition metal monoatomic carbon material;
the transition metal complex is a chitosan nickel complex; the preparation method of the chitosan nickel complex comprises the following steps: carrying out low-temperature plasma treatment on the water-soluble chitosan to obtain pretreated water-soluble chitosan; adding 5-10 parts by weight of pretreated water-soluble chitosan into 80-100 parts by weight of water, stirring for dissolving, then adding 1-3 parts by weight of citric acid, simultaneously adding ammonia water for adjusting the pH value to 5-6, heating to 50-60 ℃, adding 5-10 parts by weight of nickel salt, stirring for reacting for 60-90 min, irradiating the reacted material by adopting gamma rays under a vacuum condition, then precipitating for 12h at normal temperature by using ethanol, filtering, washing by using ethanol, and drying in vacuum; and ball-milling the dried product by using a nanosphere mill until the particle size is 100-500 nm to obtain the chitosan nickel complex.
2. The method for producing a transition metal monoatomic carbon material according to claim 1, wherein the fungus strain is any one of a xylaria strain, a morchella strain, a pleurotus ostreatus strain, a agaricus bisporus strain, and a shiitake mushroom strain.
3. The method for producing a transition metal monoatomic carbon material according to claim 1, wherein the gas subjected to the low-temperature plasma treatment is Ar/O2The flow rate of the gas is 0.1-1L/min/cm2The discharge pressure is 10-30 Pa, the discharge power is 350-500W, the temperature is 45-55 ℃, and the discharge time is 5-8 min; the nickel salt is nickel nitrate or nickel chloride.
4. The method for bio-enrichment preparation of a transition metal monatomic carbon material as claimed in claim 1, wherein the irradiation dose of the gamma ray irradiation is 50 to 80KGy, and the irradiation dose rate is 10 to 20 KGy/h.
5. The method for preparing a transition metal monatomic carbon material according to claim 1, wherein in the third step, the freeze-drying is performed for 72 to 96 hours under the conditions of a temperature of 80 ℃ below zero and a vacuum degree of 1.3 to 5 Pa.
6. The method for preparing the transition metal monatomic carbon material according to claim 1, wherein in the third step, the protective gas is one of nitrogen, argon, and an argon-hydrogen mixed gas.
7. The method for preparing the transition metal monatomic carbon material according to claim 1, wherein in the third step, the temperature rise process of the pyrolysis is as follows: heating to 100-300 ℃ at the speed of 5-10 ℃/min, and keeping the temperature for 15 min; then heating to 400-500 ℃ at the speed of 1-2 ℃/min, and preserving heat for 30 min; then heating to 600-1000 ℃ at the speed of 1-2 ℃/min, and preserving heat for 30-60 min.
8. The method for producing a transition metal monatomic carbon material according to claim 1, wherein in the third step, the concentration of the transition metal complex added in the form of a solution or a dispersion is 3 to 5 g/L.
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