CN113023690B - Metal nitride embedded fullerene and preparation method thereof - Google Patents
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Abstract
The invention discloses a metal nitride embedded fullerene and a preparation method thereof, wherein stable metal nitride is used as a nitrogen source, and the metal nitride embedded fullerene is prepared by an arc discharge method after being mixed with rare earth metal powder and graphite powder. In addition, the method does not need to add organic nitrogen compounds or nitric acid groups reported in documents to improve the yield, avoids the oxidation of the metal nitride embedded fullerene and ensures the purity of the metal nitride embedded fullerene. The technology of the invention is beneficial to the industrial production of the embedded fullerene, solves the problem of low yield of the embedded metal fullerene and promotes the research and application of the embedded fullerene.
Description
Technical Field
The invention belongs to the technical field of preparation of metal fullerene, and particularly relates to metal nitride embedded fullerene and a preparation method thereof.
Background
Fullerenes are hollow caged carbon molecules consisting of 12 five-membered rings and several six-membered rings. In the eighties of the twentieth century, for the first time, scientists discovered fullerenes, which have attracted countless scientists' attention in terms of unique structural and physicochemical characteristics. In recent years, the discovery of the endohedral metal fullerene continuously enriches the variety of fullerene families, and the endohedral metal fullerene has a more novel structure and more diverse properties. The main preparation method of fullerene and metal fullerene comprises the following steps: electron beam irradiation, laser irradiation evaporation graphite, arc discharge, etc. When preparing a large amount of fullerene and metal fullerene, the most widely used method is the arc discharge method.
In the family of endohedral metallo-fullerenes, metal nitride endohedral fullerenes have some special advantageous properties, such as high stability, excellent magnetic properties, quantum properties, relatively high yield, etc. In the scientific research field, the research on the excellent properties of the metal nitride embedded fullerene is more and more, and the metal nitride embedded fullerene has more and more application prospects in the fields of physical chemistry, materials, biopharmaceuticals, energy sources and the like, and becomes an important carbon nano material.
For example, metal nitride endohedral fullerene Y 3 N@C 80 Exhibit moderate quantum yields and long lifetime characteristics. The study of temperature-variable steady-state fluorescence spectrum shows that Y is above 60K 3 N@C 80 Exhibits thermally responsive delayed fluorescence with maximum emission at 120K and fluorescence enhancement. Below 60K, phosphorescence is observed. Further, Y 3 N@C 80 The fullerene thin-film device can be compounded with various materials (such as PFO) to make the emission range of the OLED device expanded to the red light range possible. Metal nitride embedded fullerene Sc 3 N@C 80 Is a thermoelectric material with great development potential. In 2016, a research team observes the embedded metal fullerene Sc by using a scanning tunnel microscope 3 N@C 80 The single-molecule heterojunction is connected with a gold electrode to be prepared, and research shows that the intensity and magnitude of a thermal energy signal of the single-molecule heterojunction greatly depend on molecular orientation and applied pressure. In combination with the theoretical calculation results, sc 3 N@C 80 The material is a material with double thermoelectric properties, shows positive thermoelectric properties and negative thermoelectric properties, proves the important role of transmission resonance in molecular heterojunction, and promotes the enrichment and development of thermoelectric materials. Metal nitride embedded fullerene M 3 N@C 80 Also plays an important role in organic photovoltaic devices. Metallic fullerene M 3 N@C 80 The derivative can be used as a novel acceptor material, and has a LUMO energy level close to that of a donor material poly (3-hexylthiophene-2, 5-diyl) (P3 HT)The exciton excitation energy can be better utilized, and the energy conversion efficiency of the organic photovoltaic device is greatly improved.
In 2009, ross and colleagues constructed Lu 3 N@C 80 Organic photovoltaic devices of PCBH, which exhibit a very high open circuit voltage (810 mV), this effect being greater than that of C 60 PCBM increased efficiency by about 4.2%. Metal nitride embedded fullerene Gd 3 N@C 80 Can be used as a high-efficiency nuclear magnetic contrast agent, and has even better effect than that of many other types of contrast agents. Gd (Gd) 3 N@C 80 Has high magnetic property, and is prepared by mixing Gd 3 N@C 80 The metal fullerene is embedded in a polymer colloidal particle with a core-shell structure and the capability of eliminating active oxygen quenching. Gd possessing PEG shell with biocompatibility 3 N@C 80 The nanoparticles also possess higher colloidal stability. Such Gd-based compounds 3 N@C 80 The nano-particle of the metal fullerene hardly has side effects, is a very efficient magnetic resonance imaging contrast agent, and has important application in the aspects of tumor diagnosis and tumor imaging.
The finding that a metal nitride-embedded fullerene is produced by an arc discharge method involves accidentally mixing a small amount of air into a synthesis atmosphere during production of a metal fullerene, and thus, sc was found 3 N@C 80 And nitrogen in the air was found to be a nitrogen source. Thereafter, scientists added a small amount of nitrogen to prepare M 3 N@C 80 A metal fullerene. To date, this method is also the most common method for synthesizing metal nitride endohedral fullerenes. Subsequently, people also thought to improve M 3 N@C 80 And (3) synthesis conditions of metal fullerene. For example, dunsch et al, germany, studied the addition of NH in an arc discharge atmosphere 3 Preparation of Sc as Nitrogen Source 3 N@C 80 . Preparation of Sc by Steveson et al in the arc discharge method 3 N@C 80 Adding NH into the mixed raw material of metal graphite 4 NO 3 Or Cu (NO) 3 ) 2 ·2.5H 2 O is used as an additive in an attempt to increase the yield of metal nitride endohedral fullerenes. It has also been proposed to add nitrogen-containing organic compounds as a nitrogen source during the arc discharge process. Above is added with nitrate or nitrogenOrganic matter method although for Sc 3 N@C 80 The yield of the fullerene is promoted, but a large amount of toxic gas is generated, the environment is polluted, and particularly, the existence of organic matters and oxides can bring impurities which are not easy to remove to the fullerene and metal fullerene raw materials. In addition, the above methods are directed only to Sc 3 N@C 80 The yield of the fullerene is studied, and the method lacks universality and is not suitable for promoting the yield of the fullerene embedded in other metal nitrides.
Therefore, it is of great significance to research new techniques for improving the yield of metal nitride endohedral fullerenes. In view of the excellent and abundant characteristics of metal nitride endohedral fullerenes in many fields, the demand for metal nitride endohedral fullerenes is expected to increase, however, the yield of the conventional method for preparing metal nitride endohedral fullerenes by adding nitrogen gas is limited, and some improved methods for adding organic nitrogen or nitric acid groups bring about safety problems of impurities and the like, which greatly limit the development and wide application of the methods, so that how to effectively improve the yield of metal nitride endohedral fullerenes still remains a problem to be solved at present.
Disclosure of Invention
The invention aims to provide a metal nitride embedded fullerene and a preparation method thereof, and the preparation method effectively improves the yield of the metal nitride embedded fullerene, and is at least 1 time higher than that of the traditional preparation method.
In order to achieve the above objects, according to one aspect of the present invention, there is provided a method for preparing a metal nitride-embedded fullerene using a stable metal nitride as a nitrogen source, mixed with rare earth metal powder and graphite powder, and then prepared using an arc discharge method.
Further, the method comprises the following steps: s1, uniformly mixing stable metal nitride, rare earth metal powder and graphite powder, filling the mixture into a spectrum-level hollow graphite tube, and compacting; s2, fixing the compacted graphite tube at the anode of an electric arc furnace, vacuumizing the cavity of the electric arc furnace, filling helium, starting an electric welding machine to adjust current so as to discharge cathode and anode, and performing cluster self-assembly on the raw materials after high-temperature atomization to obtain carbon ash containing metal nitride embedded fullerene; and S3, extracting and separating the metal nitride embedded fullerene in the carbon ash to obtain the metal nitride embedded fullerene.
Further, the step of extracting comprises: dispersing the carbon ash in a solvent, and extracting for 12 hours preferably by using a Soxhlet extractor, so that the hollow fullerene and the metal nitride embedded fullerene in the carbon ash are fully dissolved in toluene to obtain an extracting solution containing the metal nitride embedded fullerene.
Further, the solvent is selected from one or more of toluene, dichlorobenzene, chlorobenzene and carbon disulfide. Preferably, the extract is separated by high performance liquid chromatography.
Further, the degree of vacuum in the chamber of the arc furnace chamber is reduced to 10Pa or less, and helium gas is charged at 50 to 300Torr, preferably at 200Torr. Preferably, the current is regulated to 100-150A; the current is preferably adjusted to 120A.
Preferably, the graphite tube is a spectral grade hollow graphite tube. More preferably, the graphite tube has an outer diameter of 8 to 12mm and an inner diameter of 6 to 10mm. Further preferably, the graphite tube has an outer diameter of 8mm and an inner diameter of 6mm.
Further, the stable metal nitride is one or more of zirconium nitride, aluminum nitride, iron nitride, and titanium nitride. Preferably zirconium nitride. Preferably, the rare earth metal powder is selected from one or more of Sc, Y, gd, ho, tb, lu, dy, er, tm and Zr.
Further, the mass ratio of the rare earth metal powder to the graphite powder in the raw materials is (2-4); the mass of the added stable metal nitride accounts for 10-100% of the mass of the rare earth metal powder, and the mass of the added stable metal nitride accounts for 10-60% of the mass of the rare earth metal powder.
Preferably, the metal powder and the graphite powder are mixed according to the mass ratio of 3.
Further, the stable metal nitride is powdery particles with the particle size of 50-200 meshes; the particle size of the rare earth metal powder and the graphite powder is less than or equal to 200 meshes; the particle size of the rare earth metal powder and the graphite powder is preferably less than or equal to 100 meshes.
According to another aspect of the invention, the metal nitride endohedral fullerene prepared by the method has a structure M 3 N@C 80 Which is a trimetallic nitride cluster embedded in C 80 The fullerene cage of (a); m represents one or more of rare earth metals Sc, Y, gd, ho, tb, lu, dy, er and Tm.
The invention has the beneficial effects that:
the invention adopts stable metal nitride as a nitrogen source, and prepares the metal nitride embedded fullerene by adopting an arc discharge method after mixing the stable metal nitride with rare earth metal powder and graphite powder, compared with the traditional preparation method under the nitrogen atmosphere, the method has the advantages that the yield of the metal nitride embedded fullerene is at least 1 time improved, the universality is realized, and the yield of various metal nitride embedded fullerenes can be improved. In addition, the method does not need to add organic nitrogen compounds or nitric acid groups reported in documents, avoids the oxidation of the metal nitride embedded fullerene, and ensures the high purity of the metal nitride embedded fullerene. The technology of the invention is beneficial to the industrialized production of the embedded fullerene, solves the problem of low yield of the embedded metal fullerene, and promotes the research and application of the embedded fullerene.
Drawings
FIG. 1 is a graph showing comparison between high performance liquid chromatograms of extracts prepared under two conditions of example 1 after separation using a Buckyprep column.
FIG. 2 is a mass spectrum of the peak of the extract prepared in example 1, which shows that the molecular weight of the main component is 1241, that is, Y, when the retention time of the extract is 40-46min in HPLC 3 N@C 80 。
FIG. 3 shows the Y-rich fraction obtained in the first separation in example 1 using a Buckyprep-M column 3 N@C 80 And performing high performance liquid chromatogram obtained by separating and purifying the chromatographic peak again.
Detailed Description
The present invention will be described in further detail with reference to the following drawings and examples. However, those skilled in the art will appreciate that the scope of the present invention is not limited to the following examples. In light of the present disclosure, those skilled in the art will recognize that many variations and modifications may be made to the embodiments described above without departing from the spirit and scope of the present invention.
According to the invention, the preparation method of the metal nitride embedded fullerene is provided, and the metal nitride embedded fullerene is prepared by adopting a stable metal nitride as a nitrogen source, mixing the stable metal nitride with rare earth metal powder and graphite powder and then adopting an arc discharge method.
The metal nitride is unstable, and the stable metal nitride in the present invention mainly refers to one or more of zirconium nitride, aluminum nitride, iron nitride and titanium nitride in a solid state. The solid nitrides provide nitrogen sources in the process of preparing metal nitride embedded fullerene by an arc discharge method, wherein metals cannot enter the fullerene, and only metals in rare earth metal powder mixed with the fullerene can enter fullerene cages.
According to the present invention, zirconium nitride is preferably used as a raw material. The zirconium nitride has the advantages of stable chemical property, no decomposition, no explosion and no toxicity at normal temperature, cheap raw materials and greatly reduced cost when used for production. And the melting point of zirconium nitride is 2980 ℃, the melting point of graphite is 3652 ℃, the zirconium nitride can not be decomposed at the common temperature and can be simultaneously atomized at high temperature together with graphite and rare earth metal, so that the generation of the embedded fullerene is facilitated, the concentration of a nitrogen source in a high-temperature region is increased, and the yield of the embedded fullerene is further improved.
Preferably, the kind of the rare earth metal powder in the present invention is selected from one or more of Sc, Y, gd, ho, tb, lu, dy, er and Tm.
In the process of preparing the metal nitride embedded fullerene by the arc discharge method, stable metal nitride, rare earth metal powder and graphite powder are uniformly mixed and then filled into a graphite tube, and the raw materials are atomized at high temperature by the arc discharge method. The metal nitride has higher decomposition temperature, can be synchronously atomized with metal and graphite, is decomposed in an arc discharge area at high temperature to provide a nitrogen source, and the generated nitrogen atoms are combined with the rare earth metal clusters to form the metal nitride embedded fullerene after self-assembly, so that the solid nitrogen source participates in the generation of the metal nitride embedded fullerene. Compared with the traditional nitrogen atmosphere, the method for generating the nitrogen source in situ in real time is more efficient than the nitrogen atmosphere, and can concentrate the nitrogen source in an arc region, thereby greatly improving the yield of the fullerene embedded in the metal nitride.
According to the invention, the preparation method of the metal nitride endohedral fullerene is also provided, and comprises the following steps: s1, uniformly mixing stable metal nitride, rare earth metal powder and graphite powder, filling the mixture into a spectrum-level hollow graphite tube, and compacting the mixture; s2, fixing the compacted graphite tube at the anode of an electric arc furnace, vacuumizing the cavity of the electric arc furnace, filling helium, starting an electric welding machine to adjust current so that the anode and the cathode discharge, and performing cluster self-assembly on the raw materials after high-temperature atomization to obtain carbon ash containing metal nitride embedded fullerene; and S3, extracting and separating the metal nitride embedded fullerene in the carbon ash to obtain pure metal nitride embedded fullerene.
According to the invention, the step of extracting in step S3 comprises: dispersing carbon ash in a solvent, and extracting by using a Soxhlet extractor, wherein the solvent is selected from one or more of toluene, dichlorobenzene, chlorobenzene and carbon disulfide, and preferably extracting for 12 hours, so that the hollow fullerene and the metal nitride embedded fullerene in the carbon ash are fully dissolved in the solvent to obtain an extracting solution containing the hollow fullerene and the metal fullerene. Preferably, the extract is separated by high performance liquid chromatography.
The graphite tube used in the present invention is preferably a spectral-grade hollow graphite tube, but is not limited thereto as long as the function of the present invention can be achieved. Preferably, the graphite tube has an outer diameter of 8 to 12mm and an inner diameter of 6 to 10mm. Further preferably, the graphite tube has an outer diameter of 8mm and an inner diameter of 6mm.
In the invention, the vacuum degree in the chamber of the electric arc furnace is pumped to be below 10Pa, and helium is charged into the chamber at 50-300 Torr, preferably at 200Torr. The specific arc discharge operation is performed according to a conventional method. In the present invention, the arc discharge method turns on the welder at a current between 100 and 150A. The current of the welding bug is preferably adjusted to 120A.
According to the invention, the mass ratio of the metal powder to the graphite powder in the raw materials is 2-4. When the proportion is too large, the waste of rare earth metal can be caused; when the ratio is too small, the yield of the metal fullerene is reduced due to a low amount of the metal raw material. The proportion of the stable metal nitride added is within a certain range of values, and the more the addition is not more effective. The mass of the added stable metal nitride is preferably 10 to 100 percent of the mass of the rare earth metal powder. More preferably, the amount of the stable metal nitride added is 10 to 60% by mass of the rare earth metal powder.
In a preferred embodiment of the invention, the rare earth metal powder and the graphite powder are mixed according to the mass ratio of 3 to 1, the mass of the added metal nitride is 20% of that of the rare earth metal powder, and the yield of the metal nitride embedded fullerene obtained according to the ratio is high.
According to the invention, the metal nitride is in the form of powder particles having a particle size of 50 to 200 mesh. The grain diameter of the rare earth metal powder and the graphite powder is less than or equal to 200 meshes, and the grain diameter of the rare earth metal powder and the graphite powder is preferably less than or equal to 100.
The invention also provides metal nitride embedded fullerene which is prepared by adopting the method and has the structure of M 3 N@C 80 Which is a trimetal nitride cluster embedded in C 80 The fullerene cage of (a). Wherein M represents one or more of metals Sc, Y, gd, ho, tb, lu, dy, er and Tm.
The present invention will be described below with reference to specific examples, but the present invention is not limited thereto. The experimental methods used in the following examples are all conventional methods unless otherwise specified; reagents, materials and the like used in the following examples are commercially available unless otherwise specified.
Example 1
Taking the addition mass fraction of 20% ZrN as an example:
1) First, a spectral-grade hollow graphite tube having an outer diameter of 8mm and an inner diameter of 6mm was prepared. Uniformly mixing rare earth yttrium powder (Y) and graphite powder according to the mass ratio of 3.
2) The mixed powder was filled into a spectral grade hollow graphite tube and compacted, and the filled and compacted graphite rod was fixed to the anode of an electric arc furnace with a jacket. The vacuum degree in the electric arc furnace chamber is pumped to below 10Pa, and helium gas is charged into the electric arc furnace chamber for 200Torr. Turning on the electric welder, adjusting current to 120A, and adjusting appropriate distance to discharge between cathode and anode to obtain carbon ash containing abundant fullerene and metal fullerene.
3) And (3) extracting the carbon ash prepared in the step for 12 hours in a Soxhlet extractor by using toluene as a solvent, so that the hollow fullerene and the metal nitride embedded fullerene in the carbon ash are fully dissolved in the toluene, and obtaining toluene extracting solution containing the hollow fullerene and the metal nitride embedded fullerene.
4) Separating the extract obtained in the above step by high performance liquid chromatography to obtain metal nitride embedded fullerene, and identifying each peak by MALDI-TOF mass spectrometer.
5) Metal nitride endohedral fullerene, M, prepared in example 1 3 N@C 80 The yield is about eight parts per million; the purity was about 99%.
Comparative example 1
To charge 20Torr N 2 Experimental conditions of (2) are as examples
1) First, a spectral-grade hollow graphite tube having an outer diameter of 8mm and an inner diameter of 6mm was prepared. Uniformly mixing yttrium powder (Y) and graphite powder according to the mass ratio of 3.
2) The filled and compacted graphite tube is fixed to the anode of an electric arc furnace with a jacket. The degree of vacuum in the chamber of the arc furnace was reduced to 10Pa or less, and 20Torr nitrogen gas and 180Torr helium gas were introduced. And starting the electric welding machine, adjusting the current to 120A, and adjusting a proper distance to discharge the cathode and the anode. The extraction procedure was the same as in example 1.
For the extracts of example 1 and comparative example 1:
separating the extractive solution with Buckyprep (fullerene column) as chromatographic column and toluene as mobile phase at flow rate of 15ml/min, and separating the extractive solutions under the two conditions with Buckyprep column as high performance liquid chromatogram shown in figure 1.
Collecting the effluent of each peak, and determining molecular weight with mass spectrometer, as shown in FIG. 2, mass spectrum data of chromatographic peak with retention time of 40-44min shows that the main component of the chromatographic peak is Y at the retention time 3 N@C 80 And less of an empty fullerene.
For more accurate analysis of Y 3 N@C 80 The sample with the retention time of 40-44min is separated again by using a Buckyprep-M column, the mobile phase is toluene, the flow rate is 12ml/min, and pure Y is obtained 3 N@C 80 As shown in FIG. 3, Y 3 N@C 80 Retention time on Buckyprep-M30-36 min, assay Y 3 N@C 80 Area of peak at position for comparison of Y 3 N@C 80 The yield of (2).
Y obtained under two sets of experimental conditions of example 1 and comparative example 1 3 N@C 80 As a result of comparative studies, it was found from the data of high performance liquid chromatography that Y in example 1 (conditions for adding 20% by mass of ZrN) was comparable to that in comparative example 1 (experimental conditions for 20Torr nitrogen gas) 3 N@C 80 Is significantly increased, and the addition mass fraction of 20% of Y can be estimated from the peak area 3 N@C 80 The yield ratio increased 1.5 times with 20Torr nitrogen conditions.
Claims (20)
1. A preparation method of metal nitride embedded fullerene adopts stable metal nitride as a nitrogen source, and is prepared by mixing with rare earth metal powder and graphite powder and then adopting an arc discharge method; the stable metal nitride is zirconium nitride.
2. The method of claim 1, comprising the steps of:
s1, uniformly mixing the stable metal nitride, the rare earth metal powder and the graphite powder, filling the mixture into a spectrum-level hollow graphite tube, and compacting the mixture;
s2, fixing the compacted graphite tube at the anode of an electric arc furnace, vacuumizing the cavity of the electric arc furnace, filling helium, starting an electric welding machine to adjust current so that the anode and the cathode discharge, and performing cluster self-assembly on the raw materials after high-temperature atomization to obtain carbon ash containing the metal nitride embedded fullerene; and
s3, extracting and separating the metal nitride embedded fullerene in the carbon ash to obtain the metal nitride embedded fullerene.
3. The method of claim 2, wherein the step of extracting comprises: and dispersing the carbon ash in a solvent, and extracting by adopting a Soxhlet extractor to fully dissolve the hollow fullerene and the metal nitride embedded fullerene in the carbon ash in the solvent to obtain an extracting solution containing the metal nitride embedded fullerene.
4. The method of claim 3, wherein the extraction is performed for 12 hours using a Soxhlet extractor.
5. The method according to claim 3, wherein the solvent is selected from one or more of toluene, dichlorobenzene, chlorobenzene, and carbon disulfide.
6. The method according to claim 3, wherein the extract is separated by high performance liquid chromatography.
7. The preparation method of claim 2, wherein the degree of vacuum in the chamber of the arc furnace is reduced to below 10Pa, and helium gas is filled in the chamber at 50-300Torr.
8. The method of claim 2, wherein helium gas is introduced at 200Torr.
9. The method according to claim 2, wherein the current is adjusted to 100 to 150A.
10. The method of claim 9, wherein the current is adjusted to 120A.
11. The method of claim 2, wherein the graphite tube is a spectral grade hollow graphite tube.
12. The production method according to claim 2, wherein the graphite tube has an outer diameter of 8 to 12mm and an inner diameter of 6 to 10mm.
13. The method of claim 12, wherein the graphite tube has an outer diameter of 8mm and an inner diameter of 6mm.
14. The method according to claim 1, wherein the rare earth metal powder is one or more selected from the group consisting of Sc, Y, gd, ho, tb, lu, dy, er, tm, and Zr.
15. The preparation method according to any one of claims 1 to 13, wherein the mass ratio of the rare earth metal powder to the graphite powder in the raw materials is 2 to 1; the mass of the added stable metal nitride accounts for 10-100% of the mass of the rare earth metal powder.
16. The method of claim 15, wherein the stable metal nitride is present in an amount of 10 to 60% by mass based on the rare earth metal powder.
17. The production method according to claim 1, wherein the metal powder and the graphite powder are mixed in a ratio of 3 to 1 by mass, and the mass of the added stable metal nitride is 20% of the mass of the rare earth metal powder.
18. The production method according to any one of claims 1 to 13, wherein the stable metal nitride is a powdery granule having a particle diameter of 50 to 200 mesh; the particle size of the rare earth metal powder and the graphite powder is less than or equal to 200 meshes.
19. The production method according to any one of claims 1 to 13, characterized in that the particle size of the rare earth metal powder and graphite powder is 100 mesh or less.
20. A metal nitride endohedral fullerene produced by the method of any one of claims 1 to 19 having the structure M 3 N@C 80 Which is a trimetallic nitride cluster embedded in C 80 The fullerene cage of (a); m represents one or more of rare earth metals Sc, Y, gd, ho, tb, lu, dy, er and Tm.
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