CN109734074A - A kind of interior packet metal nitride cluster fullerene and preparation method thereof - Google Patents
A kind of interior packet metal nitride cluster fullerene and preparation method thereof Download PDFInfo
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- CN109734074A CN109734074A CN201910097343.7A CN201910097343A CN109734074A CN 109734074 A CN109734074 A CN 109734074A CN 201910097343 A CN201910097343 A CN 201910097343A CN 109734074 A CN109734074 A CN 109734074A
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Abstract
The invention discloses a kind of interior packet metal nitride cluster fullerenes and preparation method thereof, are passed through air in direct-current arc furnace cavity, using air as nitrogen source, carry out arc erosion to the anode carbon-point of filling metal oxide powder and carbon dust, obtain former ash；Former ash is separated, interior packet metal nitride cluster fullerene is obtained.The present invention prepares interior packet metal nitride cluster fullerene under air system, the cost free of air will necessarily reduce the preparation cost of interior packet metal nitride cluster fullerene, meanwhile, without to the processing of electric arc furnaces chamber vacuum, without cleaning gas circuit, preparation efficiency is greatly improved；The maximum bright spot of preparation method of the present invention is the interior packet metal nitride cluster fullerene specific yield height being prepared, and solves the problems, such as packet metal nitride cluster fullerene development and application in this long-term restriction of low yield.
Description
Technical field
The invention belongs to fullerene preparation field, more particularly, to a kind of interior packet metal nitride cluster fullerene and its
Preparation method.
Background technique
Interior packet metal nitride cluster fullerene, as the metal-carbon hybrid material being found earliest in fullerene family,
Unique structure and chemical property make it have many potential applications in photoelectromagnetic, biology, energy field.Preparation is rich at present
The method for strangling alkene has flame combustion process, chemical synthesis, laser ablation method, chemical vapour deposition technique, direct current arc electric discharge.
In above method, only direct current arc electric discharge can be suitably used for preparing interior packet metal nitride cluster fullerene, i.e., in helium and
Anode carbon-point under nitrogen system using direct current arc ablation filled with metal oxide and carbon dust is to obtain containing interior gold filled
Belong to nitride cluster fullerene former ash, heated circumfluence method is extracted, chromatographic isolation obtains interior packet metal nitride cluster fullerene.It is practical
On, the separating step immobilization of interior packet metal nitride cluster fullerene, i.e. high performance liquid chromatography, and separation process is not
The yield of packet metal nitride cluster fullerene in influencing.Crucially, interior packet metal nitride cluster fullerene is prepared with single carbon-point
Process for, the content of interior packet metal nitride cluster fullerene then directly determines most in the single resulting former ash of carbon-point ablation
The total amount for the interior packet metal nitride cluster fullerene isolated can be extracted afterwards.
All the time, a large amount of working needle is unfolded to interior packet metal nitride cluster fullerene content in former ash is promoted, still
Frame is prepared all without departing from traditional helium nitrogen mixed gas system.Such as: regulation helium nitrogen ratios, size of current, sun
Metal oxide and carbon dust ratio in the carbon-point of pole.These regulations improve interior packet metal nitride cluster fullerene to a certain extent
Yield, but the variation of external environment can usually make these parameters fail, none blanket optimal conditions；In tradition
Under system, the absolute yield of packet metal nitride cluster fullerene is for a long time in low-level, preparation efficiency in single carbon-point
It is difficult to be promoted because of preparation link complex steps, these factors constrain the application of interior packet metal nitride cluster fullerene jointly
And industrialized production.Therefore, the restriction of these factors is eliminated, realizes the preparation of interior packet metal nitride cluster fullerene high yield,
It is the problem of this field urgent need to resolve.
Summary of the invention
Aiming at the above defects or improvement requirements of the prior art, the present invention provides a kind of interior packet metal nitride cluster fowlers
Thus alkene and preparation method thereof solves the prior art and is difficult to realize high yield, low cost, the interior packet nitride metal of efficient stable preparation
The technical issues of object cluster fullerene.
To achieve the above object, according to one aspect of the present invention, a kind of interior packet metal nitride cluster fullerene is provided
Preparation method, in turn include the following steps:
(1) it is passed through air in direct-current arc furnace cavity, using air as nitrogen source, to filling metal oxide powder and carbon
The anode carbon-point of powder carries out arc erosion, obtains former ash；
(2) former ash is separated, obtains interior packet metal nitride cluster fullerene.
Further, in the metal oxide powder filled in anode carbon-point in metallic atom and carbon dust carbon atom mole
Than being 1: 3-1: 50.
Further, metal is scandium, ytterbium, lutetium, erbium, gadolinium, terbium, yttrium, dysprosium, lanthanum, thulium, holmium, praseodymium, cerium in metal oxide powder
With any one in neodymium.
Further, the DC current of direct current electric arc furnace is 90A-125A during arc erosion.
Further, after being passed through air in direct-current arc furnace cavity in step (1), air pressure is in direct-current arc furnace cavity
1 Wan Pa -5, ten thousand pa.
Further, the specific implementation of step (2) are as follows:
Former ash is dissolved using organic solvent, mixed solution is obtained, after mixed solution is filtered, uses HPLC (colleges and universities' liquid phase
Chromatography) it is separated, obtain interior packet metal nitride cluster fullerene.
Further, step (2) further include: when using organic solvent dissolution former ash, ultrasound -180 minutes 10 minutes.Have
Solvent is carbon disulfide, toluene, chlorobenzene, o-dichlorohenzene or 1,2,4- trichloro-benzenes, preferably carbon disulfide, carbon disulfide valence
Lattice are cheap to be easy to get.
Further, step (2) further include: separated using HPLC, obtain empty fullerene, the empty fullerene
It include: C60、C70、C76、C78、C82And C84。
Further, interior packet metal nitride cluster fullerene is interior packet scandium metal nitride cluster fullerene, interior packet ytterbium metal
Nitride cluster fullerene, interior packet lutetium metal nitride cluster fullerene, interior packet erbium metal nitride cluster fullerene, interior packet gadolinium metal nitrogen
Compound cluster fullerene, interior packet terbium metal nitride cluster fullerene, interior packet yttrium metal nitride cluster fullerene, interior packet dysprosium nitride metal
Object cluster fullerene, interior packet lanthanum nitride cluster fullerene, interior packet thulium metal nitride cluster fullerene, interior packet holmium metal nitride
Cluster fullerene, interior packet praseodymium metal nitride cluster fullerene, interior packet ce metal nitride cluster fullerene and Nei Bao neodymium metal nitride
Any one in cluster fullerene.
It is another aspect of this invention to provide that providing a kind of interior packet metal nitride cluster fullerene, the interior packet metal nitrogen
Compound cluster fullerene is prepared by preparation method of the invention.
In general, through the invention it is contemplated above technical scheme is compared with the prior art, can obtain down and show
Beneficial effect:
(1) conventional method needs the vacuum degree of as high as possible electric arc furnaces inner chamber body, for intracavitary vacuum processing step and
Gas circuit cleaning step need to consume the plenty of time, and in the present invention, without being vacuum-treated, without cleaning gas circuit, time-saving and efficiency.Together
When, the cost free of air is compared compared with helium expensive in conventional method with nitrogen, and preparation cost of the present invention greatly reduces.Together
When, the interior packet metal nitride cluster fullerene content under air system after ablation carbon-point in gained former ash greatly improves；Then right
Former ash, which carries out separation, to be realized high yield, low cost, efficiently and stably prepares interior packet metal nitride cluster fullerene.
(2) during conventional method preparation former ash, inevitably drawback is packet nitride metal in prepared by each electric arc furnaces
The optimized parameter disunity of object cluster fullerene.It is harsh to the relative scale requirement of nitrogen and helium in its preparation process, it is small
Deviation influences greatly the interior packet metal nitride cluster fullerene content in last former ash, meanwhile, under optimal conditions parameter,
Do not allow that DC current flow used in electric arc is excited to deviate, does not allow the ratio of the metal powder and carbon dust in anode carbon-point
Deviation, low serious forgiveness are difficult to realize industrial production.And air system is initiated in the present invention, it is advantageous in that without considering
Regulation gas ratio this link in traditional preparation methods allows DC current flow to change, and also allows metal in anode carbon-point
The variation of the ratio of powder and carbon dust, the extremely strong feature of applicability provide technical support for industrial production.
(3) during arc erosion, the intracorporal air pressure of chamber is too low to will lead to interior packet metal nitride cluster fullerene in former ash
Yield decline, air pressure is excessively high to will lead to the damage of electric arc furnace cavity, and therefore, for the present invention during arc erosion, chamber is intracorporal
Air pressure is kept between 1 Wan Pa -5, ten thousand pa, can improve interior packet metal nitride in former ash while not damaging electric arc furnace cavity
The yield of cluster fullerene.
(4) in the present invention, in the obtained former ash of the single carbon-point of ablation, the interior packet metal nitride cluster that can be extracted is rich
The absolute yield for strangling alkene is high, the interior category covered with gold leaf compared in the resulting former ash of carbon-point ablation single under the optimal conditions in traditional preparation methods
Nitride cluster fullerene absolute yield promotes three times or more, moreover, the fullerene including empty fullerene extracted is total
Amount be one times of total amount under conventional method optimal conditions at most times, be more dexterously increase ground part be mostly in packet
Metal nitride cluster fullerene.
(5) for the present invention when using organic solvent dissolution former ash, ultrasonic extraction, extracting method is simple, compared to time-consuming 24
Hour ground conventional backflow heating extraction, is greatly improved extraction efficiency.The too short solute effect of ultrasonic time is poor, and ultrasonic time is too long
The structure of interior packet metal nitride cluster fullerene in former ash may be destroyed, so ultrasound of the invention 10-180 minutes, will not
While destroying the structure of interior packet metal nitride cluster fullerene in former ash, former ash is quickly and effectively dissolved.Compared to time-consuming 24
Hour ground conventional backflow heating extraction, is greatly improved extraction efficiency.
Detailed description of the invention
Fig. 1 is ablation under the air system direct current arc method that the embodiment of the present invention 1 provides and conventional method optimal conditions
It include the fullerene solute absolute mass pair of empty fullerene and Nei Bao metal nitride cluster fullerene acquired by three carbon-points
Than figure；
Fig. 2 is the air system direct current arc method that the embodiment of the present invention 1 provides and obtains under conventional method optimal conditions
Fullerene Comparative HPLC figure；
Fig. 3 is the air system direct current arc method and conventional method optimal conditions is lower is taken that the embodiment of the present invention 1 provides
The interior packet scandium metal nitride cluster fullerene Sc obtained3N@C80HPLC figure；
Fig. 4 is the air system direct current arc method and conventional method optimal conditions is lower is taken that the embodiment of the present invention 1 provides
The interior packet scandium metal nitride cluster fullerene Sc obtained3N@C80Mass spectrogram；
As Fig. 5 is the air system direct current arc method that the embodiment of the present invention 1 provides and is burnt under conventional method optimal conditions
Lose packet scandium metal nitride cluster fullerene Sc in three resulting wholes of carbon-point3N@C80It is dissolved in organic solvent under same volume
Saturated solution ultraviolet spectra comparison diagram；
Fig. 6 is ablation under the air system direct current arc method that the embodiment of the present invention 1 provides and conventional method optimal conditions
Main component empty fullerene C acquired by three carbon-points60, C70, interior packet scandium metal nitride cluster fowler Sc3N@C80Quality
Compare figure.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to the accompanying drawings and embodiments, right
The present invention is further elaborated.It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and
It is not used in the restriction present invention.As long as in addition, technical characteristic involved in the various embodiments of the present invention described below
Not constituting a conflict with each other can be combined with each other.
Conventional method prepares interior packet metal nitride cluster fullerene, and using High Purity Nitrogen as nitrogen source, helium is dielectric gas,
Two kinds of mixed gas of a certain proportion of nitrogen and helium are passed through in by vacuum treated repeatedly electric arc furnace cavity, are being mixed
Under gas system, former ash is obtained filled with the anode carbon-point of metal oxide and carbon dust using direct current arc ablation, using adding
Water bath reflux method has three in conjunction with the isolated interior packet metal nitride cluster fullerene of HPLC:
First, under the system, if two kinds of gas ratios in optimal preparation parameter, size of current, filling mixture ratio
Occur error during the preparation process, will lead to interior packet metal nitride cluster fullerene content in former ash and sharply reduce, and is optimal
Parameter general applicability is poor.
Second, it economically considers, a large amount of consumption of helium and nitrogen, which certainly will increase, in traditional preparation process is prepared into
This；Chamber vacuum processing, cleaning gas circuit and etc. and the reflux extraction that takes a long time necessarily reduce unit time production efficiency.
The specific yield of third, the interior packet metal nitride cluster fullerene under conventional method is usually lower.
These factors constrain the development and application of interior packet metal nitride cluster fullerene jointly.
Defect based on traditional preparation methods, the present invention provides a kind of preparation sides of interior packet metal nitride cluster fullerene
Method in turn includes the following steps:
(1) it is passed through air in direct-current arc furnace cavity, using air as nitrogen source, to filling metal oxide powder and carbon
The anode carbon-point of powder carries out arc erosion, obtains former ash；
(2) former ash is separated, obtains interior packet metal nitride cluster fullerene.
The embodiment of the present invention preferably, carbon in metallic atom and carbon dust in the metal oxide powder filled in anode carbon-point
The molar ratio of atom is 1: 3-1: 50.The partial size of metal oxide powder and carbon dust is -300 mesh of 200 mesh.Metal oxide powder
Middle metal is any one in scandium, ytterbium, lutetium, erbium, gadolinium, terbium, yttrium, dysprosium, lanthanum, thulium, holmium, praseodymium, cerium and neodymium.During arc erosion
The DC current of direct current electric arc furnace is 90A-125A.After being passed through air in direct-current arc furnace cavity in step (1), direct-current arc
Air pressure is 1 Wan Pa -5, ten thousand pa in furnace cavity.
The embodiment of the present invention preferably, the specific implementation of step (2) are as follows:
Former ash is dissolved using organic solvent, ultrasound -60 minutes 10 minutes obtains mixed solution, organic solvent is curing
Carbon, toluene, chlorobenzene, o-dichlorohenzene or 1,2,4- trichloro-benzenes, preferably carbon disulfide, carbon disulfide is cheap to be easy
It arrives.It after mixed solution is filtered, is separated using HPLC, obtains empty fullerene and Nei Bao metal nitride cluster fullerene.
The empty fullerene includes: C60、C70、C76、C78、C82And C84.Interior packet metal nitride cluster fullerene is interior packet scandium metal nitrogen
Compound cluster fullerene, interior packet ytterbium metal nitride cluster fullerene, interior packet lutetium metal nitride cluster fullerene, interior packet erbium nitride metal
Object cluster fullerene, interior packet gadolinium metal nitride cluster fullerene, interior packet terbium metal nitride cluster fullerene, interior packet yttrium metal nitride
Cluster fullerene, interior packet dysprosium metal nitride cluster fullerene, interior packet lanthanum nitride cluster fullerene, interior packet thulium metal nitride cluster
Fullerene, interior packet holmium metal nitride cluster fullerene, interior packet praseodymium metal nitride cluster fullerene, interior packet ce metal nitride cluster are rich
Strangle any one in alkene and Nei Bao neodymium metal nitride cluster fullerene.
It can be seen that direct current arc ablation anode carbon-point obtains the mistake of former ash under the pioneering air system of the present invention
The step for ratio of gas mixture regulation is then directly eliminated in journey, and allow to excite direct current size variation used in electric arc,
Allow filling mixture ratio to change, there is general applicability, is suitble to industrial mass production；Secondly, the cost free of air
The preparation cost of interior packet metal nitride cluster fullerene will necessarily be reduced, meanwhile, without being not necessarily to the processing of electric arc furnaces chamber vacuum
Gas circuit is cleaned, in conjunction with time-consuming extremely short ultrasonic extraction, preparation efficiency is greatly improved；Finally, be prepared using the present invention
Interior packet metal nitride cluster fullerene specific yield is high.In conjunction with the above advantage, the present invention is solved in this long-term restriction of low yield
The pain spot of packet metal nitride cluster fullerene development and application.
The process route of the preparation of anode carbon-point used in the ablation of direct current arc institute is as follows:
By taking scandium as an example, scandium oxide and carbon dust are filled into carbon according to 1: 3-1: 50 Sc/C molar ratio after mixing
It in stick, is then placed in tube furnace, calcines 10 hours for 1000 DEG C under protection of argon gas.Then, it can be used as anode carbon-point straight
Ablation in galvanic electricity electric arc.
Embodiment 1
Under air system, prepared anode carbon-point is mixed with the molar ratio 1: 5 of carbon to scandium and is burnt using direct current arc
Erosion, size of current 115A, arc furnace is intracavitary, and to be passed through air to intracavitary air pressure be 2.5 ten thousand pas.After anode carbon-point ablation,
Former ash is collected after cooling, is dissolved using carbon disulfide, and ultrasound 30 minutes is obtained by filtration filtrate and is replaced into toluene, through HPLC points
From obtaining interior packet scandium metal nitride cluster fullerene.
Embodiment 2
Under air system, prepared carbon-point is mixed using direct current arc ablation, electric current with carbon molar ratio 1: 9 to erbium
Size is 100A, and arc furnace is intracavitary, and to be passed through air to intracavitary air pressure be 2.5 ten thousand pas.It is to be cooled after anode carbon-point ablation
After collect former ash, dissolved using carbon disulfide, ultrasound 50 minutes, filtrate is obtained by filtration and is replaced into toluene, is separated through HPLC, obtains
Interior packet erbium metal nitride cluster fullerene.
Embodiment 3
Under air system, prepared carbon-point is mixed using direct current arc ablation, electricity with carbon molar ratio 1: 15 to lutetium
Stream size is 105A, and arc furnace is intracavitary, and to be passed through air to intracavitary air pressure be 20,000 pas.It is to be cooled after anode carbon-point ablation
After collect former ash, dissolved using carbon disulfide, ultrasound 60 minutes, filtrate is obtained by filtration and is replaced into toluene, is separated through HPLC, obtains
Interior packet lutetium metal nitride cluster fullerene.
Embodiment 4
Under air system, prepared carbon-point is mixed using direct current arc ablation, electricity with carbon molar ratio 1: 11 to scandium
Stream size is 110A, and arc furnace is intracavitary, and to be passed through air to intracavitary air pressure be 20,000 pas.It is to be cooled after anode carbon-point ablation
After collect former ash, using 1,2,4- trichloro-benzenes dissolve, ultrasound 70 minutes, filtrate is obtained by filtration and is replaced into toluene, is separated through HPLC,
Obtain interior packet scandium metal nitride cluster fullerene.
Embodiment 5
Under air system, prepared carbon-point is mixed using direct current arc ablation, electricity with carbon molar ratio 1: 20 to scandium
Stream size is 115A, and arc furnace is intracavitary, and to be passed through air to intracavitary air pressure be 20,000 pas.It is to be cooled after anode carbon-point ablation
After collect former ash, dissolved using chlorobenzene, ultrasound 2 hours, filtrate is obtained by filtration and is replaced into toluene, is separated through HPLC, obtains interior packet
Scandium metal nitride cluster fullerene.
Embodiment 6
Under air system, prepared carbon-point is mixed using direct current arc ablation, electricity with carbon molar ratio 1: 50 to scandium
Stream size is 120A, and it is 50,000 pas that air to chamber air pressure is passed through in furnace chamber.After anode carbon-point ablation, collect after cooling former
Ash is dissolved using toluene, ultrasound 3 hours.Filtrate is obtained by filtration to separate through HPLC, obtains interior packet scandium metal nitride cluster fowler
Alkene.
Embodiment 7
Under air system, prepared carbon-point is mixed using direct current arc ablation, electric current with carbon molar ratio 1: 3 to ytterbium
Size is 90A, and it is 10,000 pas that air to chamber air pressure is passed through in furnace chamber.After anode carbon-point ablation, former ash is collected after cooling,
It is dissolved using carbon disulfide, ultrasound 10 minutes is obtained by filtration filtrate and is replaced into toluene, filtrate is obtained by filtration and separates through HPLC, obtains
To interior packet ytterbium metal nitride cluster fullerene.
Embodiment 8
Under air system, prepared anode carbon-point is mixed with carbon molar ratio 1: 5 to gadolinium and uses direct current arc ablation,
Size of current is 115A, and arc furnace is intracavitary, and to be passed through air to intracavitary air pressure be 2.5 ten thousand pas.After anode carbon-point ablation, to
Former ash to be collected after cooling, is dissolved using carbon disulfide, ultrasound 30 minutes is obtained by filtration filtrate and is replaced into toluene, separates through HPLC,
Obtain interior packet gadolinium metal nitride cluster fullerene.
Embodiment 9
Under air system, prepared anode carbon-point is mixed with carbon molar ratio 1: 5 to terbium and uses direct current arc ablation,
Size of current is 115A, and arc furnace is intracavitary, and to be passed through air to intracavitary air pressure be 2.5 ten thousand pas.After anode carbon-point ablation, to
Former ash to be collected after cooling, is dissolved using carbon disulfide, ultrasound 30 minutes is obtained by filtration filtrate and is replaced into toluene, separates through HPLC,
Obtain interior packet terbium metal nitride cluster fullerene.
Embodiment 10
Under air system, prepared anode carbon-point is mixed with carbon molar ratio 1: 5 to yttrium and uses direct current arc ablation,
Size of current is 115A, and arc furnace is intracavitary, and to be passed through air to intracavitary air pressure be 2.5 ten thousand pas.After anode carbon-point ablation, to
Former ash to be collected after cooling, is dissolved using carbon disulfide, ultrasound 30 minutes is obtained by filtration filtrate and is replaced into toluene, separates through HPLC,
Obtain interior packet yttrium metal nitride cluster fullerene.
Embodiment 11
Under air system, prepared anode carbon-point is mixed with carbon molar ratio 1: 5 to dysprosium and uses direct current arc ablation,
Size of current is 115A, and arc furnace is intracavitary, and to be passed through air to intracavitary air pressure be 2.5 ten thousand pas.After anode carbon-point ablation, to
Former ash to be collected after cooling, is dissolved using carbon disulfide, ultrasound 30 minutes is obtained by filtration filtrate and is replaced into toluene, separates through HPLC,
Obtain interior packet dysprosium metal nitride cluster fullerene.
Embodiment 12
Under air system, prepared anode carbon-point is mixed with carbon molar ratio 1: 5 to lanthanum and uses direct current arc ablation,
Size of current is 115A, and arc furnace is intracavitary, and to be passed through air to intracavitary air pressure be 2.5 ten thousand pas.After anode carbon-point ablation, to
Former ash to be collected after cooling, is dissolved using carbon disulfide, ultrasound 30 minutes is obtained by filtration filtrate and is replaced into toluene, separates through HPLC,
Obtain interior packet lanthanum nitride cluster fullerene.
Embodiment 13
Under air system, prepared anode carbon-point is mixed with carbon molar ratio 1: 5 to thulium and uses direct current arc ablation,
Size of current is 115A, and arc furnace is intracavitary, and to be passed through air to intracavitary air pressure be 2.5 ten thousand pas.After anode carbon-point ablation, to
Former ash to be collected after cooling, is dissolved using carbon disulfide, ultrasound 30 minutes is obtained by filtration filtrate and is replaced into toluene, separates through HPLC,
Obtain interior packet thulium metal nitride cluster fullerene.
Embodiment 14
Under air system, prepared anode carbon-point is mixed with carbon molar ratio 1: 5 to holmium and uses direct current arc ablation,
Size of current is 115A, and arc furnace is intracavitary, and to be passed through air to intracavitary air pressure be 2.5 ten thousand pas.After anode carbon-point ablation, to
Former ash to be collected after cooling, is dissolved using carbon disulfide, ultrasound 30 minutes is obtained by filtration filtrate and is replaced into toluene, separates through HPLC,
Obtain interior packet holmium metal nitride cluster fullerene.
Embodiment 15
Under air system, prepared anode carbon-point is mixed with carbon molar ratio 1: 5 to praseodymium and uses direct current arc ablation,
Size of current is 115A, and arc furnace is intracavitary, and to be passed through air to intracavitary air pressure be 2.5 ten thousand pas.After anode carbon-point ablation, to
Former ash to be collected after cooling, is dissolved using carbon disulfide, ultrasound 30 minutes is obtained by filtration filtrate and is replaced into toluene, separates through HPLC,
Obtain interior packet praseodymium metal nitride cluster fullerene.
Embodiment 16
Under air system, prepared anode carbon-point is mixed with carbon molar ratio 1: 5 to cerium and uses direct current arc ablation,
Size of current is 115A, and arc furnace is intracavitary, and to be passed through air to intracavitary air pressure be 2.5 ten thousand pas.After anode carbon-point ablation, to
Former ash to be collected after cooling, is dissolved using carbon disulfide, ultrasound 30 minutes is obtained by filtration filtrate and is replaced into toluene, separates through HPLC,
Obtain interior packet ce metal nitride cluster fullerene.
Embodiment 17
Under air system, prepared anode carbon-point is mixed with carbon molar ratio 1: 5 to neodymium and uses direct current arc ablation,
Size of current is 115A, and arc furnace is intracavitary, and to be passed through air to intracavitary air pressure be 2.5 ten thousand pas.After anode carbon-point ablation, to
Former ash to be collected after cooling, is dissolved using carbon disulfide, ultrasound 30 minutes is obtained by filtration filtrate and is replaced into toluene, separates through HPLC,
Obtain interior packet neodymium metal nitride cluster fullerene.
The content of interior packet metal nitride cluster fullerene directly determines in final in the every resulting former ash of carbon-point ablation
Packet metal nitride cluster fullerene absolute yield, former ash are extracted through organic solvent, and organic solvent extracting solution is filtered after filtration
Liquid removes the solvent in filtrate, weighs the quality of remaining fullerene solute, repeatedly weighs and be averaged, obtains comprising hollow richness
Strangle the fullerene solute absolute mass of all kinds of metal fullerenes of alkene.
Control group is that conventional method optimal conditions in direct current arc discharge process, makes under helium nitrogen mixed system
Nitrogen source is provided with nitrogen, helium is as dielectric gas, and helium, argon gas are as purge gas.First to all gas circuits of electric arc furnaces and
Electric arc furnace cavity is cleaned, and using the method for being continually fed into argon gas, is passed through in argon gas to electric arc furnace cavity air pressure every time 20,000
Pa vacuumizes electric arc furnace cavity after being kept for one minute, repeatedly for three times, next, gentle using helium cleaning electric arc furnace cavity
Road is equally passed through air pressure in argon gas to electric arc furnace cavity and vacuumizes after being kept for one minute to electric arc furnace cavity in 20,000 pas.Thereafter,
Optimal atmosphere needed for being passed through preparation, continues to be passed through 0.5 ten thousand pa of nitrogen, air pressure reaches in electric arc furnace cavity after being passed through 20,000 pa of helium
2.5 ten thousand pas are electrically excited arc erosion anode carbon-point using 110A direct current, and metal is former in scandium oxide and carbon dust in anode carbon-point
Son and carbon atom molar ratio are 1:17, collect former ash after ablation, carry out separation and Extraction to former ash.
As Fig. 1 is the air system direct current arc method that the embodiment of the present invention 1 provides and is burnt under conventional method optimal conditions
Lose the comparison of fullerene solute absolute mass acquired by three carbon-points, the fullerene solute that air system direct current arc method obtains
Obtained fullerene solute gross mass under the far extra conventional method optimal conditions of gross mass.
Contained fullerene type in fullerene solute is judged using HPLC analytical technology, if Fig. 2 is that the embodiment of the present invention 1 mentions
Fullerene solute mainly organizes HPLC comparison diagram under the air system direct current arc method and conventional method optimal conditions of confession, according to out
Peak time is consistent, judges that component is consistent.Next main component C is separated using HPLC isolation technics60, C70, Sc3N@C80。HPLC
Technology combination mass-spectrometric technique can clearly determine the purity and fullerene type of component.
Fig. 3 is the air system direct current arc method and conventional method optimal conditions is lower is taken that the embodiment of the present invention 1 provides
The interior packet scandium metal nitride cluster fullerene Sc obtained3N@C80HPLC figure, as can be seen from the figure air system of the invention is straight
Sc is prepared in galvanic electricity arc process3N@C80Concentration be apparently higher than conventional method.
Fig. 4 is the air system direct current arc method and conventional method optimal conditions is lower is taken that the embodiment of the present invention 1 provides
The interior packet scandium metal nitride cluster fullerene Sc obtained3N@C80Mass spectrogram, mass spectrogram show molecular mass be 1108, thus judge
Air system direct current arc method and conventional method generate interior packet scandium metal nitride cluster fullerene Sc3N@C80And purity category
In chromatographically pure.
By UV-vis absorption spectrum technology, absolute magnitude how much difference of identical solute in same volume saturated solution
It is reflected in the height difference on ultraviolet absorpting spectrum for ordinate intensity, if Fig. 5 is the air system that the embodiment of the present invention 1 provides
Interior packet scandium metal nitride cluster fullerene acquired by three carbon-points of ablation under direct current arc method and conventional method optimal conditions
Sc3N@C80It is dissolved in the saturated solution ultraviolet spectra comparison diagram of organic solvent under same volume, it can be with air visible in detail
The interior packet scandium metal nitride cluster fullerene Sc that system direct current arc method obtains3N@C80Institute under the far extra conventional method of absolute magnitude
Obtain interior packet scandium metal nitride cluster fullerene Sc3N@C80Absolute magnitude.
Quality versus is more intuitively expressed in order to obtain, if Fig. 6 is the air system direct current that the embodiment of the present invention 1 provides
Main component empty fullerene C acquired by three carbon-points of ablation under arc process and conventional method optimal conditions60, C70, interior packet scandium
Metal nitride cluster fullerene Sc3N@C80Quality compare figure, what air system direct current arc method visible in detail obtained
Interior packet scandium metal nitride cluster fullerene Sc3N@C80Acquired interior packet scandium metal nitrogen under the far extra conventional method optimal conditions of quality
Compound cluster fullerene Sc3N@C80Quality, and orient, only internal packet scandium metal nitride cluster is rich in the solute of a variety of fullerenes
Strangle alkene Sc3N@C80Content promoted amplitude promoted three times more than.
By taking scandium as an example, usually contain in the former ash that under traditional preparation system prepared by arc discharge method from C60, C70, C76, C78,
C84Equal empty fullerenes and Sc3N@C78, Sc3N@C80Packet metal nitride cluster fullerene, interior packet metal nitride cluster fowler Deng in
Alkene leads to yield and is typically well below empty fullerene, therefore is unable to satisfy scientific research demand, it is more difficult to meet industrial application.Packet in other
Metal iridium, lutetium, erbium nitride cluster fullerenes yields are even more to be in extremely low level.And the present invention is used, former ash obtained by ablation carbon-point
In equally containing from C60, C70, C76, C78, C84Equal empty fullerenes and Sc3N@C78, Sc3N@C80Packet metal nitride cluster is rich Deng in
Alkene is strangled, and when single carbon-point provides ground carbon source total amount unchangeably, pointedly significantly promotes interior packet metal nitride
Cluster fullerene Sc3N@C80Yield without increasing empty fullerene ground yield, meanwhile, the present invention be suitable for interior packet metal scandium, ytterbium,
Lutetium, erbium, gadolinium, terbium, dysprosium, lanthanum, thulium, holmium, praseodymium, cerium, neodymium nitride cluster fowler will fully meet each scientific research to various interior categories covered with gold leaf
Nitride cluster fullerene demand, makes it possible industrialized production also.
As it will be easily appreciated by one skilled in the art that the foregoing is merely illustrative of the preferred embodiments of the present invention, not to
The limitation present invention, any modifications, equivalent substitutions and improvements made within the spirit and principles of the present invention should all include
Within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of interior packet metal nitride cluster fullerene, which is characterized in that in turn include the following steps:
(1) it is passed through air in direct-current arc furnace cavity, using air as nitrogen source, to filling metal oxide powder and carbon dust
Anode carbon-point carries out arc erosion, obtains former ash；
(2) former ash is separated, obtains interior packet metal nitride cluster fullerene.
2. a kind of preparation method of interior packet metal nitride cluster fullerene as described in claim 1, which is characterized in that the sun
The molar ratio of carbon atom is 1: 3-1: 50 in metallic atom and carbon dust in the metal oxide powder filled in the carbon-point of pole.
3. a kind of preparation method of interior packet metal nitride cluster fullerene as claimed in claim 1 or 2, which is characterized in that institute
It is any one in scandium, ytterbium, lutetium, erbium, gadolinium, terbium, yttrium, dysprosium, lanthanum, thulium, holmium, praseodymium, cerium and neodymium for stating metal in metal oxide powder
Kind.
4. a kind of preparation method of interior packet metal nitride cluster fullerene as claimed in claim 1 or 2, which is characterized in that institute
The DC current for stating direct current electric arc furnace during arc erosion is 90A-125A.
5. a kind of preparation method of interior packet metal nitride cluster fullerene as claimed in claim 1 or 2, which is characterized in that institute
It states after being passed through air in direct-current arc furnace cavity in step (1), air pressure is 1 Wan Pa -5, ten thousand pa in direct-current arc furnace cavity.
6. a kind of preparation method of interior packet metal nitride cluster fullerene as claimed in claim 1 or 2, which is characterized in that institute
State the specific implementation of step (2) are as follows:
Former ash is dissolved using organic solvent, mixed solution is obtained, after mixed solution is filtered, is separated, obtained using HPLC
Interior packet metal nitride cluster fullerene.
7. a kind of preparation method of interior packet metal nitride cluster fullerene as claimed in claim 6, which is characterized in that the step
Suddenly (2) further include: when using organic solvent dissolution former ash, ultrasound -180 minutes 10 minutes.
8. a kind of preparation method of interior packet metal nitride cluster fullerene as claimed in claim 6, which is characterized in that the step
Suddenly (2) further include: separated using HPLC, obtain empty fullerene, the empty fullerene includes: C60、C70、C76、C78、
C82And C84。
9. a kind of preparation method of interior packet metal nitride cluster fullerene as claimed in claim 1 or 2, which is characterized in that institute
State interior packet metal nitride cluster fullerene be interior packet scandium metal nitride cluster fullerene, interior packet ytterbium metal nitride cluster fullerene,
It is interior packet lutetium metal nitride cluster fullerene, interior packet erbium metal nitride cluster fullerene, interior packet gadolinium metal nitride cluster fullerene, interior
Packet terbium metal nitride cluster fullerene, interior packet yttrium metal nitride cluster fullerene, interior packet dysprosium metal nitride cluster fullerene, interior packet
Lanthanum nitride cluster fullerene, interior packet thulium metal nitride cluster fullerene, interior packet holmium metal nitride cluster fullerene, interior packet praseodymium
It is any in metal nitride cluster fullerene, interior packet ce metal nitride cluster fullerene and Nei Bao neodymium metal nitride cluster fullerene
It is a kind of.
10. a kind of interior packet metal nitride cluster fullerene, which is characterized in that the interior packet metal nitride cluster fullerene is by right
It is required that a kind of preparation method of any interior packet metal nitride cluster fullerene of 1-9 is prepared.
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