CN112175333B - Preparation method and application of nanocomposite PMMA @ Fe-N-C - Google Patents
Preparation method and application of nanocomposite PMMA @ Fe-N-C Download PDFInfo
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- CN112175333B CN112175333B CN202011018100.9A CN202011018100A CN112175333B CN 112175333 B CN112175333 B CN 112175333B CN 202011018100 A CN202011018100 A CN 202011018100A CN 112175333 B CN112175333 B CN 112175333B
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Abstract
The invention provides a preparation method of a nano composite material PMMA @ Fe-N-C, which comprises the following steps: the preparation method comprises the steps of preparing an Fe-N-C carrier, dispersing the Fe-N-C carrier in PMMA dispersion liquid, performing ultrasonic treatment and stirring to obtain the nanocomposite PMMA @ Fe-N-C, and further provides application of removing oxygen in raw materials for preparing diamond, uniformly dispersing PMMA in gaps on the surface and in the interior of the Fe-N-C carrier to obtain the nanocomposite PMMA @ Fe-N-C.
Description
Technical Field
The invention belongs to the technical field of oxygen removal of diamond raw materials, and particularly relates to a preparation method and application of a nanocomposite PMMA @ Fe-N-C.
Background
The reduction technology used in the existing catalyst factory is to achieve the purpose of deoxidizing by using hydrogen and oxygen to react at high temperature and in a nitrogen atmosphere, and the method uses hydrogen which is prepared by pyrolyzing liquid ammonia, so that the used liquid ammonia and hydrogen are hazardous chemicals and have high cost and high requirements on equipment and environment, most importantly, the oxygen content is too high due to the poor treatment effect on the oxygen in the graphite powder which is one of the raw materials, so that the subsequent synthesis process is influenced, and the quality of diamond is further influenced. Therefore, a method which is safe and easy to handle and has an excellent reducing effect is urgently required.
Disclosure of Invention
The invention aims to solve the technical problem of providing a preparation method and application of a nanocomposite PMMA @ Fe-N-C aiming at the defects of the prior art, the method uniformly disperses PMMA in gaps on the surface and inside of an Fe-N-C carrier to obtain the nanocomposite @ PMMA @ Fe-N-C, and through the adsorption load of the Fe-N-C carrier, the contact chance of PMMA and oxygen is increased, and the effect of removing oxygen is improved.
In order to solve the technical problems, the invention adopts the technical scheme that: a preparation method of a nano composite material PMMA @ Fe-N-C comprises the following steps.
S1, dispersing the nano PMMA powder in purified water by ultrasonic for 1-2 h to obtain PMMA dispersion liquid with the mass fraction of 11%.
S2, dissolving ferric nitrate nonahydrate and zinc nitrate hexahydrate in methanol, and performing ultrasonic treatment for 0.5h to obtain a mixed solution A; dissolving 2-methylimidazole in methanol, and performing ultrasonic treatment for 0.5h to obtain a mixed solution B; and adding the mixed solution B into the mixed solution A, carrying out reflux reaction for 24 hours under the condition of an oil bath at the temperature of 60 ℃, and then carrying out centrifugal washing for 3-4 times by using ethanol to obtain a carrier precursor.
S3, drying the carrier precursor obtained in the S2 for 8 hours under the vacuum condition with the temperature of 60 ℃, and then carrying out heat treatment for 1 hour under the nitrogen atmosphere with the temperature of 1100 ℃ to obtain the Fe-N-C carrier.
S4, dispersing the Fe-N-C carrier obtained in the S3 in PMMA dispersion liquid obtained in the S1, performing ultrasonic treatment for 1-2 hours, and stirring for 6-7 hours at room temperature to obtain the nanocomposite PMMA @ Fe-N-C.
In the invention, PMMA is uniformly dispersed in the surface and the inner gaps of the Fe-N-C carrier, and the adsorption load of the Fe-N-C carrier increases the contact chance of PMMA and oxygen, thereby improving the effect of removing oxygen.
Preferably, the nano PMMA powder in S1 has a particle size of 50 nm-60 nm.
Preferably, the amount ratio of the iron nitrate nonahydrate, the zinc nitrate hexahydrate and methanol in the mixed solution a in S2 is 439 mg: 3.39 g: 500 mL.
Preferably, the dosage ratio of the 2-methylimidazole to the methanol in the mixed solution B in the S2 is 3.94 g: 500 mL.
Preferably, the specific surface area of the Fe-N-C carrier in S3 is 640m 2/g-750 m 2/g; the average pore diameter of the Fe-N-C carrier is 100 nm-150 nm.
Preferably, the Fe-N-C carrier and PMMA dispersion in S4 are used in a ratio of 1 g: 9 mL.
The invention also provides application of the prepared nano composite material PMMA @ Fe-N-C, wherein the nano composite material PMMA @ Fe-N-C is used for removing oxygen in raw materials for preparing diamond, and the raw materials for preparing diamond are nickel-iron alloy powder and graphite powder.
Preferably, the method for removing oxygen in the raw material for preparing diamond is as follows.
Mixing nickel-iron alloy powder, graphite powder and a nano composite material PMMA @ Fe-N-C, heating the mixture from room temperature to 450 ℃ at a heating rate of 20 ℃/min in a nitrogen atmosphere, then monitoring the oxygen content of the raw materials, heating the mixture to 1000 ℃ at a heating rate of 5 ℃/min when the oxygen content is less than or equal to 500ppm, removing oxygen in the raw materials for preparing the diamond, and entering a subsequent diamond synthesis stage.
In the process that the temperature of PMMA (polymethyl methacrylate) in the nano composite material PMMA @ Fe-N-C is gradually increased to 450 ℃, depolymerization is carried out to generate a large amount of tert-butyl radicals and MMA (methyl methacrylate) monomers, wherein the tert-butyl radicals react with oxygen in a system to generate a main oxidation product methyl pyruvate, and then oxygen in graphite and nickel-iron alloy powder is removed, so that the aim of reducing and deoxidizing nickel is fulfilled by replacing hydrogen, when the temperature is continuously increased to 1000 ℃, PMMA in the system is carbonized and decomposed, and only Fe-N-C carriers, nickel-iron alloy powder and graphite powder exist in the system, so that the next step of synthesis is carried out, and diamond synthesis is carried out.
Preferably, the mass ratio of the nickel-iron alloy powder to the graphite powder to the nano composite material PMMA @ Fe-N-C is 1: 1.5*: 5*.
Compared with the prior art, the invention has the following advantages.
1. In the invention, PMMA is uniformly dispersed in the surface and the inner gaps of the Fe-N-C carrier to obtain the nanocomposite PMMA @ Fe-N-C, and the adsorption load of the Fe-N-C carrier increases the contact chance of PMMA and oxygen, thereby improving the effect of removing oxygen.
2. In the process that the temperature of PMMA (polymethyl methacrylate) in the nano composite material PMMA @ Fe-N-C is gradually increased to 450 ℃, depolymerization is carried out to generate a large amount of tert-butyl radicals and MMA (methyl methacrylate) monomers, wherein the tert-butyl radicals react with oxygen in a system to generate a main oxidation product methyl pyruvate, and then oxygen in graphite and nickel-iron alloy powder is removed, so that the aim of reducing and deoxidizing by replacing hydrogen is fulfilled, when the temperature is continuously increased to 1000 ℃, PMMA in the system is carbonized and decomposed, and only Fe-N-C carriers, nickel-iron alloy powder and graphite powder exist in the system, so that the next step of synthesis is carried out, and diamond synthesis is carried out.
3. The free radicals generated in the depolymerization process of PMMA in the nano composite material PMMA @ Fe-N-C at high temperature can be used as an oxygen scavenger, and the load of the Fe-N-C carrier on PMMA improves the contact area of PMMA and oxygen, avoids PMMA agglomeration, improves the stability of PMMA before depolymerization and does not influence the subsequent diamond synthesis process, Fe-N-C is used as the carrier, because the main component C of the carrier can be used as a carbon source for synthesizing diamond, Fe is used as a component in a catalyst for synthesizing diamond, nitrogen and diamond (the diamond is composed of carbon elements) are compatible because nitrogen and carbon have similar atomic size and valence electron layers, and the subsequent diamond synthesis is not influenced, the synthesis of diamond is not influenced when the Fe-N-C carrier enters the subsequent diamond synthesis stage at the later stage, when the nanocomposite PMMA @ Fe-N-C prepared by the embodiment is used for removing oxygen in raw materials for preparing diamond, liquid ammonia and hydrogen are not used, the operability is high, the oxygen removing effect is obvious, the oxygen in the final raw materials for preparing diamond is less than or equal to 500ppm, the oxygen removing effect is more obvious, and the operation safety is high.
Detailed Description
The present invention will be described in further detail with reference to examples.
Example 1
The preparation method of the nanocomposite PMMA @ Fe-N-C of the embodiment comprises the following steps.
S1, dispersing the nano PMMA powder with the particle size of 50 nm-60 nm in purified water by ultrasonic for 1h to obtain PMMA dispersion liquid with the mass fraction of 11%.
S2, 439mg of ferric nitrate nonahydrate and 3.39g of zinc nitrate hexahydrate are dissolved in 500mL of methanol, and ultrasonic treatment is carried out for 0.5h to obtain a mixed solution A; dissolving 3.94g of dimethyl imidazole in 500mL of methanol, and performing ultrasonic treatment for 0.5h to obtain a mixed solution B; and adding the mixed solution B into the mixed solution A, carrying out reflux reaction for 24 hours under the condition of an oil bath at the temperature of 60 ℃, and then carrying out centrifugal washing for 3 times by using ethanol to obtain a carrier precursor.
S3, drying the carrier precursor obtained in the S2 for 8 hours under the vacuum condition at the temperature of 60 ℃, and then carrying out heat treatment for 1 hour under the nitrogen atmosphere at the temperature of 1100 ℃ to obtain the Fe-N-C carrier with the specific surface area of 640m 2/g and the average pore diameter of 100 nm.
S4, dispersing the Fe-N-C carrier obtained in the S3 in PMMA dispersion liquid obtained in the S1, performing ultrasonic treatment for 1 hour, and stirring for 6 hours at room temperature to obtain the nanocomposite PMMA @ Fe-N-C.
The embodiment also provides application of the prepared nanocomposite PMMA @ Fe-N-C, wherein the nanocomposite PMMA @ Fe-N-C is used for removing oxygen in raw materials for preparing diamond; the raw materials for preparing the diamond are nickel-iron alloy powder and graphite powder; the method for removing oxygen in the raw materials for preparing the diamond comprises the following steps.
Mixing nickel-iron alloy powder, graphite powder and a nano composite material PMMA @ Fe-N-C, heating the temperature from room temperature to 450 ℃ at a heating rate of 20 ℃/min in a nitrogen atmosphere, then monitoring the oxygen content of the raw materials, heating the temperature to 1000 ℃ at a heating rate of 5 ℃/min when the oxygen content is less than or equal to 500ppm, removing oxygen in the raw materials for preparing the diamond, wherein the oxygen content of a final system is 500ppm, and then entering a subsequent diamond synthesis stage; the mass ratio of the nickel-iron alloy powder to the graphite powder to the nano composite material PMMA @ Fe-N-C is 1: 1.5*: 5*.
The oxygen content of the mixed material of the nickel-iron alloy powder and the graphite powder which are used as the raw materials for preparing the diamond reaches 2000ppm, and the oxygen content is reduced to 500ppm after the oxygen removal method of the nickel-iron alloy powder and the graphite powder is carried out by the nano composite material PMMA @ Fe-N-C prepared by the embodiment, so that the oxygen content of the raw materials for preparing the diamond can be effectively removed by the nano composite material PMMA @ Fe-N-C prepared by the embodiment, the safety is good, and the operation is simple.
Free radicals generated in the depolymerization process of PMMA in the nano composite material PMMA @ Fe-N-C at high temperature can be used as an oxygen scavenger, the load of the Fe-N-C carrier on PMMA improves the contact area of PMMA and oxygen, avoids PMMA agglomeration, improves the stability before depolymerization and does not influence the subsequent diamond synthesis process, Fe-N-C is used as the carrier, because the main component C of the carrier can be used as a carbon source for synthesizing diamond, Fe is used as a catalyst for synthesizing diamond, and because nitrogen and carbon have similar atomic size and valence electron layers, nitrogen is compatible with diamond (the diamond is composed of carbon elements) and does not influence the subsequent diamond synthesis, the Fe-N-C carrier does not influence the diamond synthesis when entering the subsequent diamond synthesis stage at the later stage, when the nanocomposite PMMA @ Fe-N-C prepared by the embodiment is used for removing oxygen in raw materials for preparing the diamond, liquid ammonia and hydrogen are not used, the operability is high, the oxygen removing effect is obvious, the oxygen content is reduced from 2000ppm to 500ppm, hydrogen or liquid ammonia is used for removing oxygen, the oxygen content in the raw materials for finally preparing the diamond is 1000ppm, the nanocomposite PMMA @ Fe-N-C prepared by the method has a more obvious effect when being used as an oxygen remover, and the operation safety is high.
Example 2
The preparation method of the nanocomposite PMMA @ Fe-N-C of the embodiment comprises the following steps.
S1, dispersing the nano PMMA powder with the particle size of 50 nm-60 nm in purified water by ultrasonic for 2h to obtain PMMA dispersion liquid with the mass fraction of 11%.
S2, 439mg of ferric nitrate nonahydrate and 3.39g of zinc nitrate hexahydrate are dissolved in 500mL of methanol, and ultrasonic treatment is carried out for 0.5h to obtain a mixed solution A; dissolving 3.94g of 2-methylimidazole in 500mL of methanol, and performing ultrasonic treatment for 0.5h to obtain a mixed solution B; and adding the mixed solution B into the mixed solution A, carrying out reflux reaction for 24 hours under the condition of an oil bath at the temperature of 60 ℃, and then carrying out centrifugal washing for 4 times by using ethanol to obtain a carrier precursor.
S3, drying the carrier precursor obtained in the S2 for 8 hours under the vacuum condition with the temperature of 60 ℃, and then carrying out heat treatment for 1 hour under the nitrogen atmosphere with the temperature of 1100 ℃ to obtain the Fe-N-C carrier with the specific surface area of 750 m2/g and the average pore diameter of 150 nm.
S4, dispersing the Fe-N-C carrier obtained in the S3 in PMMA dispersion liquid obtained in the S1, performing ultrasonic treatment for 2 hours, and stirring for 7 hours at room temperature to obtain the nanocomposite PMMA @ Fe-N-C.
The embodiment also provides application of the prepared nanocomposite PMMA @ Fe-N-C, wherein the nanocomposite PMMA @ Fe-N-C is used for removing oxygen in raw materials for preparing diamond; the raw materials for preparing the diamond are nickel-iron alloy powder and graphite powder; the method for removing oxygen in the raw materials for preparing the diamond comprises the following steps.
Mixing nickel-iron alloy powder, graphite powder and a nano composite material PMMA @ Fe-N-C, heating the temperature from room temperature to 450 ℃ at a heating rate of 20 ℃/min in a nitrogen atmosphere, then monitoring the oxygen content of the raw materials, heating the temperature to 1000 ℃ at a heating rate of 5 ℃/min when the oxygen content is less than or equal to 400ppm, removing oxygen in the raw materials for preparing the diamond, wherein the oxygen content of a final system is 400ppm, and then entering a subsequent diamond synthesis stage; the mass ratio of the nickel-iron alloy powder to the graphite powder to the nano composite material PMMA @ Fe-N-C is 1: 1.5*: 5*.
The above description is only for the preferred embodiment of the present invention, and is not intended to limit the present invention in any way. Any simple modification, change and equivalent changes of the above embodiments according to the technical essence of the invention are still within the protection scope of the technical solution of the invention.
Claims (8)
1. A preparation method of a nano composite material PMMA @ Fe-N-C is characterized by comprising the following steps:
s1, dispersing the nano PMMA powder in purified water by ultrasonic for 1-2 h to obtain PMMA dispersion liquid with the mass fraction of 11%;
s2, dissolving ferric nitrate nonahydrate and zinc nitrate hexahydrate in methanol, and performing ultrasonic treatment for 0.5h to obtain a mixed solution A; dissolving 2-methylimidazole in methanol, and performing ultrasonic treatment for 0.5h to obtain a mixed solution B; adding the mixed solution B into the mixed solution A, carrying out reflux reaction for 24 hours under the condition of an oil bath at the temperature of 60 ℃, and then carrying out centrifugal washing for 3-4 times by using ethanol to obtain a carrier precursor;
s3, drying the carrier precursor obtained in the S2 for 8 hours under the vacuum condition at the temperature of 60 ℃, and then carrying out heat treatment for 1 hour under the nitrogen atmosphere at the temperature of 1100 ℃ to obtain the Fe-N-C carrier; the specific surface area of the Fe-N-C carrier is 640m2/g～750m2(ii)/g; the average pore diameter of the Fe-N-C carrier is 100 nm-150 nm;
s4, dispersing the Fe-N-C carrier obtained in the S3 in PMMA dispersion liquid obtained in the S1, performing ultrasonic treatment for 1-2 hours, and stirring for 6-7 hours at room temperature to obtain the nanocomposite PMMA @ Fe-N-C.
2. The preparation method of the nanocomposite PMMA @ Fe-N-C as claimed in claim 1, wherein the nano PMMA powder in S1 has a particle size of 50nm to 60 nm.
3. The method for preparing a nanocomposite PMMA @ Fe-N-C as claimed in claim 1, wherein the amount ratio of the ferric nitrate nonahydrate, the zinc nitrate hexahydrate and the methanol in the mixed solution A in S2 is 439 mg: 3.39 g: 500 mL.
4. The method for preparing a nanocomposite PMMA @ Fe-N-C as claimed in claim 1, wherein the amount ratio of 2-methylimidazole and methanol in the mixed solution B in S2 is 3.94 g: 500 mL.
5. The method for preparing a nanocomposite PMMA @ Fe-N-C as claimed in claim 1, wherein the amount ratio of the Fe-N-C carrier to the PMMA dispersion in S4 is 1 g: 9 mL.
6. Use of a nanocomposite PMMA @ Fe-N-C according to any of claims 1-5 wherein the nanocomposite PMMA @ Fe-N-C is used to remove oxygen from diamond making feedstock which is nickel iron alloy powder and graphite powder.
7. Use of a nanocomposite PMMA @ Fe-N-C according to claim 6, wherein the method for removing oxygen from the raw material for diamond production comprises:
mixing nickel-iron alloy powder, graphite powder and a nano composite material PMMA @ Fe-N-C, heating the temperature from room temperature to 450 ℃ at a heating rate of 20 ℃/min in a nitrogen atmosphere, then monitoring the oxygen content of the raw materials, heating the temperature to 1000 ℃ at a heating rate of 5 ℃/min when the oxygen content is less than or equal to 500ppm, removing oxygen in the raw materials for preparing the diamond, and entering a subsequent diamond synthesis stage.
8. The use of the nanocomposite PMMA @ Fe-N-C as claimed in claim 7, wherein the mass ratio of the ferronickel powder to the graphite powder to the nanocomposite PMMA @ Fe-N-C is 1: 1.5: 5.
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