CN102205958B - Method for preparing fullerene internally embedded with nitride clusters - Google Patents
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- CN102205958B CN102205958B CN 201110114218 CN201110114218A CN102205958B CN 102205958 B CN102205958 B CN 102205958B CN 201110114218 CN201110114218 CN 201110114218 CN 201110114218 A CN201110114218 A CN 201110114218A CN 102205958 B CN102205958 B CN 102205958B
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- soccerballene
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- graphite
- urea
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Abstract
The invention provides a method for preparing fullerene internally embedded with nitride clusters. According to the method, fullerene internally embedded with nitride clusters is obtained by arc discharge with a hollow graphite rod filled with mixed powder as an anode and a graphite electrode as a cathode, wherein the mixed powder comprises rare earth oxides, urea and graphite powder; since solid urea is used as a nitrogen source, an electric arc furnace does not need reforming, the graphite rod does not need preheating, and the synthesis step is simple; meanwhile, the urea has wide sources and low price, therefore, the production cost of the fullerene internally embedded with nitride clusters is reduced. Experiments show that the fullerene internally embedded with nitride clusters, prepared from the scandium oxide, the urea and the graphite powder by using the method provided by the invention, has high selectivity up to 12%, and 2.9 g of graphite powder can be used for preparing 5mg of fullerene internally embedded with nitride clusters.
Description
Technical field
The invention belongs to the embed fullerene technical field, relate in particular to a kind of preparation method of embedded with nitride cluster soccerballene.
Background technology
Can wrap into various metal or metal atomic cluster in the carbon cage of soccerballene, form the compound that a class has special construction and character, this compounds is commonly called embed fullerene, generally uses M C
2nForm represents, wherein M represents metallic element.If because the embedded magnetic lanthanide series metal of master metal tool, embed fullerene has broad application prospects in fields such as biomedicine, the energy, physiology, laser, superconduction, Organic Ferromagnet, nonlinear optical material, information sciences.Wherein, the embedded with nitride cluster soccerballene of finding in 1999 is considered to the important breakthrough in embed fullerene field and becomes the study hotspot in soccerballene field.
Prior art discloses the preparation method of multiple embed fullerene, mainly comprise synchronous synthesis method and two step synthesis methods, wherein, synchronous synthesis method refers to wrap into one or more atoms and forms embed fullerene in the soccerballene forming process, such as arc discharge method, laser evaporation method etc.; Two step synthesis methods refer at first synthesize hollow soccerballene, and then under the condition of further opening cage or long-time high static pressure, by atom to be wrapped into and soccerballene collision or extruding, break through the fullerene cage wall and enter the method that the carbon cage forms embed fullerene, two step synthesis methods are mainly used in the alkali metal atom that rare gas element, non-metallic atom or atomic radius is less and wrap in the fullerene cage.
Embedded with nitride cluster soccerballene mainly adopts the arc discharge method preparation, namely utilizes graphite cathode and the hollow plumbago rod anode of having filled mix powder to pass through arc-over, and obtains embedded with nitride cluster soccerballene introduce nitrogenous source in discharge process after.In the preparation process of embedded with nitride cluster soccerballene, nitrogenous source directly affects productive rate and the selectivity of target product, at present generally with gases such as nitrogen or ammonias as nitrogenous source.As nitrogenous source, not only need in electric arc furnace, increase gas circuit with gas, and before arc-over, will carry out preheating to graphite rod, both increase the scrap build difficulty, increase again synthesis step, be unfavorable for a large amount of preparations of embedded with nitride cluster soccerballene.Prior art also discloses a kind of with the technology of isocyanic acid guanidine as nitrogenous source, the synthetic embedded with nitride cluster soccerballene of employing arc discharge method, the productive rate of the target product that obtains and selectivity and suitable take ammonia as nitrogenous source.Although the method need not to increase gas circuit in electric arc furnace, also can omit pre-heating step,, isocyanic acid guanidine price is high being difficult to obtain relatively, and the productive rate of the target product that obtains take the isocyanic acid guanidine as nitrogenous source is lower.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is to provide a kind of preparation method of embedded with nitride cluster soccerballene, and preparation method's raw material sources provided by the invention are extensive, and the productive rate of embedded with nitride cluster soccerballene is higher.
The invention provides a kind of preparation method of embedded with nitride cluster soccerballene, may further comprise the steps:
Take the hollow plumbago rod that is filled with mixed powder as anode, Graphite Electrodes as negative electrode, carry out arc-over, obtain embedded with nitride cluster soccerballene, wherein, described mixed powder comprises rare earth oxide, urea and Graphite Powder 99.
Preferably, the mol ratio of described rare earth oxide, urea and Graphite Powder 99 is 1: (1～6): (10～40).
Preferably, described rare earth oxide is one or more in Scium trioxide, gadolinium sesquioxide and the dysprosium oxide.
Preferably, described rare earth oxide is Scium trioxide.
Preferably, when carrying out described arc-over, the He atmospheric pressure is 300mbar～500mbar.
Preferably, when carrying out described arc-over, the electric current of welding machine is 50A～150A.
Compared with prior art, the present invention take urea as nitrogenous source, adopt arc discharge method to prepare embedded with nitride cluster soccerballene.In the process of carrying out arc-over, urea decomposition produces ammonia, be transformed in the process of soccerballene at Graphite Powder 99, ammonia reacts with rare-earth oxide first, generate the metal nitride cluster, then the metal nitride cluster is wrapped in the soccerballene forming process and is formed embedded with nitride cluster soccerballene in the Fullerene Carbon cage.It is nitrogenous source that the present invention adopts solid urea, need not electric arc furnace is transformed, and also need not graphite rod is carried out preheating, and synthesis step is simple.Simultaneously, urea wide material sources, low price can reduce the production cost of embedded with nitride cluster soccerballene.In addition, productive rate and the selectivity of the embedded with nitride cluster soccerballene for preparing of method provided by the invention are all higher.Experiment shows, take Scium trioxide, urea and Graphite Powder 99 as raw material, when adopting method provided by the invention to prepare embedded with nitride cluster soccerballene, the selectivity of embedded with nitride cluster soccerballene can reach 12%, 2.9g Graphite Powder 99 can prepare approximately 5mg embedded with nitride cluster soccerballene.
Description of drawings
Fig. 1 is the high-efficient liquid phase chromatogram of the reaction product of the embodiment of the invention 1 preparation;
Fig. 2 is the high-efficient liquid phase chromatogram of the reaction product of the embodiment of the invention 2 preparations;
Fig. 3 is the high-efficient liquid phase chromatogram of the reaction product of the embodiment of the invention 3 preparations;
Fig. 4 is the mass spectrum of the reaction product of the embodiment of the invention 3 preparations;
Fig. 5 is the high-efficient liquid phase chromatogram of the reaction product of the embodiment of the invention 6 preparations
Fig. 6 is the high-efficient liquid phase chromatogram of the reaction product of comparative example preparation of the present invention.
Embodiment
The invention provides a kind of preparation method of embedded with nitride cluster soccerballene, may further comprise the steps:
Take the hollow plumbago rod that is filled with mixed powder as anode, Graphite Electrodes as negative electrode, carry out arc-over, obtain embedded with nitride cluster soccerballene, wherein, described mixed powder comprises rare earth oxide, urea and Graphite Powder 99.
The present invention is take Graphite Powder 99 as raw material, take rare earth oxide as source metal, take urea as nitrogenous source, adopt arc discharge method to prepare embedded with nitride cluster soccerballene, preparation method provided by the invention need not electric arc furnace is transformed, also need not graphite rod is preheated, the embedded with nitride cluster soccerballene productive rate and the selectivity that obtain are all higher.
According to the present invention, at first in the hollow plumbago rod, fill mixed powder, described mixed powder comprises rare earth oxide, urea and Graphite Powder 99, and its middle rare earth provides carbon source for embedded with nitride cluster soccerballene provides nitrogenous source, Graphite Powder 99 for embedded with nitride cluster soccerballene for embedded with nitride cluster soccerballene provides source metal, urea.
In the present invention, described rare earth oxide is preferably one or more in Scium trioxide, gadolinium sesquioxide and the dysprosium oxide, more preferably Scium trioxide.
The present invention does not have particular restriction to described Graphite Powder 99, and commercially available Graphite Powder 99 gets final product.
In described mixed powder, the mol ratio of described rare earth oxide, urea and Graphite Powder 99 is preferably 1: (1～6): (10～40), more preferably 1: (2～5): (12～18) most preferably are 1: (3～4): (13～17).
The present invention does not have particular restriction to described hollow plumbago rod, and its diameter is preferably 5mm～10mm, more preferably 8mm; Its length is preferably 100mm～200mm, more preferably 120mm～180mm.
After described mixed powder was filled into described hollow plumbago rod, the graphite rod after the described filling is fixed on the anode rod of arc discharging device as anode, and was relative with negative electrode, then carries out arc-over, obtains embedded with nitride cluster soccerballene.The present invention is take Graphite Electrodes as negative electrode.
In the process of carrying out arc-over, blanketing gas is preferably He gas, and pressure is preferably 300mbar～500mbar, more preferably 350mbar～450mbar; The electric current of welding machine is preferably 50A～150A, more preferably 70A～120A.
According to the present invention, carry out arc-over and preferably include following steps: electric arc furnace is evacuated to 5Pa～10Pa, closes vacuum valve and mechanical pump; The turn-on flow rate meter is filled with 10mbarHe gas, again is evacuated to 5Pa～10Pa; After being filled with 300mbar～500mbar He gas, opening welding machine and discharge.
Can produce high temperature in arc discharge process, urea decomposes the generation ammonia under the effect of high temperature, and ammonia, rare earth oxide and Graphite Powder 99 react under High Pressure, generates embedded with nitride cluster soccerballene, comprises Sc
3N@C
80, Sc
3N@C
78, Sc
3N@C
70, Sc
3N@C
68And Sc
3N@C
82Deng.In described embedded with nitride cluster soccerballene, Sc
3N@C
80Be primary product, content is the highest, and therefore, the present invention is with Sc
3N@C
80Growing amount as the Main Basis that calculates embedded with nitride cluster soccerballene productive rate.
After obtaining embedded with nitride cluster soccerballene, described embedded with nitride cluster soccerballene is carried out liquid-phase chromatographic analysis and mass spectroscopy, the result shows, the selectivity of the embedded with nitride cluster soccerballene of method preparation provided by the invention can reach 12%, 2.9g Graphite Powder 99 and can prepare approximately 5mg embedded with nitride cluster soccerballene.
In order to further specify the present invention, below in conjunction with embodiment the preparation method of embedded with nitride cluster soccerballene provided by the invention is described in detail.
Below among each embodiment raw materials used being from the market buy.
Embodiment 1
Be that 8mm, length are to fill mixed powder in the hollow plumbago rod of 150mm to diameter, described mixed powder comprises 0.021mol (2.9g) Scium trioxide, 0.021mol urea (1.3g) and 0.315mol (3.8g) Graphite Powder 99; Graphite rod after the described filling is fixed on the anode rod in the electric arc furnace, and aligns with the negative electrode Graphite Electrodes as anode; Electric arc furnace is evacuated to 7.5Pa, then is filled with 400mbar He gas; Open welding machine, electric current is transferred to 100A, after the discharge, obtain reaction product.
Described reaction product is carried out efficient liquid phase chromatographic analysis, and the result is referring to Fig. 1, and Fig. 1 is the high-efficient liquid phase chromatogram of the reaction product of the embodiment of the invention 1 preparation, and wherein, the peak at 23min place is the peak value of embedded with nitride cluster soccerballene, i.e. Sc
3N@C
80, hence one can see that, and its selectivity is about 4.1%, and absolute mass is about 1.9mg.
Embodiment 2
Be that 8mm, length are to fill mixed powder in the hollow plumbago rod of 150mm to diameter, described mixed powder comprises 0.012mol (1.6g) Scium trioxide, 0.07mol urea (4.2g) and 0.18mol (2.2g) Graphite Powder 99; Graphite rod after the described filling is fixed on the anode rod in the electric arc furnace, and aligns with the negative electrode Graphite Electrodes as anode; Electric arc furnace is evacuated to 6.3Pa, then is filled with 400mbar He gas; Open welding machine, electric current is transferred to 100A, after the discharge, obtain reaction product.
Described reaction product is carried out efficient liquid phase chromatographic analysis, and the result is referring to Fig. 2, and Fig. 2 is the high-efficient liquid phase chromatogram of the reaction product of the embodiment of the invention 2 preparations, and wherein, the peak at 23min place is the peak value of embedded with nitride cluster soccerballene, i.e. Sc
3N@C
80, hence one can see that, and its selectivity is about 6.9%, and absolute mass is 2.2mg approximately.
Embodiment 3
Be that 8mm, length are to fill mixed powder in the hollow plumbago rod of 150mm to diameter, described mixed powder comprises 0.018mol (2.5g) Scium trioxide, 0.036mol urea (2.2g) and 0.27mol (3.3g) Graphite Powder 99; Graphite rod after the described filling is fixed on the anode rod in the electric arc furnace, and aligns with the negative electrode Graphite Electrodes as anode; Electric arc furnace is evacuated to 6.3Pa, then is filled with 400mbar He gas; Open welding machine, electric current is transferred to 100A, after the discharge, obtain reaction product.
Described reaction product is carried out efficient liquid phase chromatographic analysis, and the result is referring to Fig. 3, and Fig. 3 is the high-efficient liquid phase chromatogram of the reaction product of the embodiment of the invention 3 preparations, and wherein, the peak at 23min place is the peak value of embedded with nitride cluster soccerballene, i.e. Sc
3N@C
80, hence one can see that, and its selectivity is about 4.4%, and absolute mass is about 2.0mg.
Described reaction product is carried out mass spectroscopy, and the result is referring to Fig. 4, and Fig. 4 is the mass spectrum of the reaction product of the embodiment of the invention 3 preparations, and wherein, the peak at m/Z=1109 place is Sc
3N@C
80Peak value, the peak at m/Z=1085 place is Sc
3N@C
78Peak value, the peak at m/Z=989 place is Sc
3N@C
70Peak value, the peak at m/Z=965 place is Sc
3N@C
68Peak value, the peak at m/Z=1133 place is Sc
3N@C
82Peak value.
Embodiment 4
Be that 8mm, length are to fill mixed powder in the hollow plumbago rod of 150mm to diameter, described mixed powder comprises 0.017mol (2.4g) Scium trioxide, 0.0425mol urea (2.6g) and 0.255mol (3.0g) Graphite Powder 99; Graphite rod after the described filling is fixed on the anode rod in the electric arc furnace, and aligns with the negative electrode Graphite Electrodes as anode; Electric arc furnace is evacuated to 4.6Pa, then is filled with 400mbar He gas; Open welding machine, electric current is transferred to 120A, after the discharge, obtain reaction product.
Described reaction product is carried out efficient liquid phase chromatographic analysis, and the result shows, embedded with nitride cluster soccerballene Sc
3N@C
80Selectivity be about 6.9%, absolute mass is about 3.8mg.
Be that 8mm, length are to fill mixed powder in the hollow plumbago rod of 150mm to diameter, described mixed powder comprises 0.016mol (2.2g) Scium trioxide, 0.048mol urea (2.9g) and 0.24mol (2.9g) Graphite Powder 99; Graphite rod after the described filling is fixed on the anode rod in the electric arc furnace, and aligns with the negative electrode Graphite Electrodes as anode; Electric arc furnace is evacuated to 5.4Pa, then is filled with 400mbar He gas; Open welding machine, electric current is transferred to 80A, after the discharge, obtain reaction product.
Described reaction product is carried out efficient liquid phase chromatographic analysis, and the result shows, embedded with nitride cluster soccerballene Sc
3N@C
80Selectivity be about 9.6%, absolute mass is about 2.3mg.
Embodiment 6
Be that 8mm, length are to fill mixed powder in the hollow plumbago rod of 150mm to diameter, described mixed powder comprises 0.016mol (2.2g) Scium trioxide, 0.048mol urea (2.9g) and 0.24mol (2.9g) Graphite Powder 99; Graphite rod after the described filling is fixed on the anode rod in the electric arc furnace, and aligns with the negative electrode Graphite Electrodes as anode; Electric arc furnace is evacuated to 6.3Pa, then is filled with 400mbar He gas; Open welding machine, electric current is transferred to 100A, after the discharge, obtain reaction product.
Described reaction product is carried out efficient liquid phase chromatographic analysis, and the result is referring to Fig. 5, and Fig. 5 is the high-efficient liquid phase chromatogram of the reaction product of the embodiment of the invention 6 preparations, and wherein, the peak at 23min place is the peak value of embedded with nitride cluster soccerballene, i.e. Sc
3N@C
80, hence one can see that, and its selectivity is about 12%, and absolute mass is about 5mg.
Comparative example 1
Be that 8mm, length are to fill mixed powder in the hollow plumbago rod of 150mm to diameter, described mixed powder comprises 0.007mol (1.0g) Scium trioxide, 0.037mol guanidinium isothiocyanate (4.3g) and 0.24mol (2.7g) Graphite Powder 99; Graphite rod after the described filling is fixed on the anode rod in the electric arc furnace, and aligns with the negative electrode Graphite Electrodes as anode; Electric arc furnace is evacuated to 5.6Pa, then is filled with 400mbar He gas; Open welding machine, electric current is transferred to 100A, after the discharge, obtain reaction product.
Described reaction product is carried out efficient liquid phase chromatographic analysis, and the result is referring to Fig. 6, and Fig. 6 is the high-efficient liquid phase chromatogram of the reaction product of comparative example preparation of the present invention, and wherein, the peak at 23min place is the peak value of embedded with nitride cluster soccerballene, i.e. Sc
3N@C
80, hence one can see that, and its selectivity is about 3.9%, and absolute mass is about 1.4mg.
By comparative example 1 as can be known, selectivity and the productive rate of the embedded with nitride cluster soccerballene that method provided by the invention prepares are all higher, and raw material sources are extensive, cheap.
The above only is preferred implementation of the present invention; should be pointed out that for those skilled in the art, under the prerequisite that does not break away from the principle of the invention; can also make some improvements and modifications, these improvements and modifications also should be considered as protection scope of the present invention.
Claims (5)
1. the preparation method of an embedded with nitride cluster soccerballene may further comprise the steps:
Take the hollow plumbago rod that is filled with mixed powder as anode, Graphite Electrodes as negative electrode, carry out arc-over, obtain embedded with nitride cluster soccerballene, wherein, described mixed powder comprises rare earth oxide, urea and Graphite Powder 99, and the mol ratio of described rare earth oxide, urea and Graphite Powder 99 is 1:(1 ~ 6): (10 ~ 40).
2. preparation method according to claim 1 is characterized in that, described rare earth oxide is one or more in Scium trioxide, gadolinium sesquioxide and the dysprosium oxide.
3. preparation method according to claim 2 is characterized in that, described rare earth oxide is Scium trioxide.
4. preparation method according to claim 1 is characterized in that, when carrying out described arc-over, the He atmospheric pressure is 300mbar～500mbar.
5. preparation method according to claim 1 is characterized in that, when carrying out described arc-over, the electric current of welding machine is 50A ~ 150A.
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| CN104129775B (en) * | 2014-07-16 | 2015-12-30 | 苏州大学 | A kind of preparation method of embedded scandium oxide compound cluster soccerballene |
| CN109734074B (en) * | 2019-01-31 | 2020-09-18 | 华中科技大学 | Fullerene internally coated with metal nitride clusters and preparation method thereof |
| CN113023690B (en) * | 2019-12-25 | 2023-01-24 | 中国科学院化学研究所 | Metal nitride embedded fullerene and preparation method thereof |
| CN114130386B (en) * | 2021-11-26 | 2024-02-20 | 合肥智慧环境研究院 | Fullerene embedded manganese-cerium alloy catalyst and preparation method and application thereof |
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| CN1572724A (en) * | 2003-06-16 | 2005-02-02 | 索尼株式会社 | Nitrogen-containing carbonaceous material and process for production thereof |
| CN1671620A (en) * | 2002-07-22 | 2005-09-21 | 德累斯顿协会莱布尼茨固体材料研究所 | Method for the production of endohedral fullerenes |
| US20090022648A1 (en) * | 2004-08-04 | 2009-01-22 | Rikizo Hatakeyama | Induction fullerene producing device and producing method and induction fullerene |
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| CN1671620A (en) * | 2002-07-22 | 2005-09-21 | 德累斯顿协会莱布尼茨固体材料研究所 | Method for the production of endohedral fullerenes |
| CN1572724A (en) * | 2003-06-16 | 2005-02-02 | 索尼株式会社 | Nitrogen-containing carbonaceous material and process for production thereof |
| US20090022648A1 (en) * | 2004-08-04 | 2009-01-22 | Rikizo Hatakeyama | Induction fullerene producing device and producing method and induction fullerene |
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