CN101028922A - Production of doped aggregate cluster - Google Patents
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- CN101028922A CN101028922A CN 200710008602 CN200710008602A CN101028922A CN 101028922 A CN101028922 A CN 101028922A CN 200710008602 CN200710008602 CN 200710008602 CN 200710008602 A CN200710008602 A CN 200710008602A CN 101028922 A CN101028922 A CN 101028922A
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Abstract
A process for preparing the doped coacervated compound includes such steps as putting the mixture of BN and Ag in carbon rod, fixing it to positive electrode of an arc discharge apparatus, sealing the reaction cavity, vacuumizing, filling the mixture of He gas and N2, starting arc for reaction while cooling by water, cooling to ordinary temp, filling N2, taking the generated carbon ash, extracting in toluene, and evaporating toluene to obtain product.
Description
Technical field
The present invention relates to a kind of employing arc process at preparation C
60, C
70Etc. stablizing soccerballene and in the hope of forming mixed with fullerene (heterofullerene) and relevant cluster compound to the method for wherein introducing nitrogen (N), boron elements such as (B) in the classical cluster soccerballene process.
Background technology
The birth of soccerballene chemistry is based on C
60Find and further investigation, and C
60Discovery, then have benefited from the windfall of scientists to the research of interspace carbon compound.Early 1980s, Smally, Curl and Kroto have found the duster compound molecule that a series of even carbon atoms form on mass spectrum with laser evaporation graphite the time, and have successfully detected and compare C
58Strong 30 times C
60Thereby, drawn back the research prelude of soccerballene chemistry.Afterwards, they had proposed C
60Have the imagination of sealing cage structure, and analyze with the modern chemistry theory and to have made up ball caged molecule model.Owing to this model is to conceive out under the shape influence of U.S.'s globe building thing, and this buildings is Buckminster Fuller design, so the building scholar in order to commemorate that this is famous, and they are with C
60Called after bucky-ball (Buckyball) is afterwards directly with C
60Be commonly referred to as soccerballene (Fullerene) etc. the cage type molecule.And mixed with fullerene is meant that one or more carbon atoms are replaced the material that is generated by other atoms.Since soccerballene is found, the exploration of its synthetic method never had been interrupted.As the synthetic method of classics, and Kr tschmer (W.Kr tschmer, L.D.Lamb, K.Fostiropoulos, D.R.Huffman, Nature 1990, and 347:354) arc process is the main synthetic method of soccerballene and mixed with fullerene always.
Although up to the present, found out the synthetic method of multiple soccerballene in the world.But the investigators of soccerballene are attempting that always it is formed mechanism and are exploring, and explore the productive rate of arc process production soccerballene under the different condition.The formation condition that sounds out soccerballene is to kind and the size of dividing potential drop, power type, electric current and voltage, the diameter of positive and negative electrode and the dependency of a plurality of parameters such as profile, reaction cavity volumetrical size and catalyzer such as buffer gas, thereby according to the influence degree of these parameters to the productive rate size of soccerballene kind and various soccerballenes, it is formed mechanism reasonably infer and judge, go to explore the formation mechanism of soccerballene from the angle of physics and chemistry.And the study on the synthesis of mixed with fullerene also is the effective means that the research soccerballene forms mechanism.Synthetic and the sign of mixed with fullerene is the challenging research focus of tool in current soccerballene chemical research field.Because heteroatomic intervention changes the structure and the electronic property of pure carbon cage possibly, therefore these mixed with fullerene are being applied aspect superconduction, opto-electronic device and the Organic Ferromagnet probably, and may be widely used with the precursor that makes up nano material and other fullerene derivates as semi-conductor.In addition, heteroatomic doping can also make the oxidation-reduction quality of soccerballene be improved.Full carbon fullerene C with classics
60And C
70Compare, the desmotrope of mixed with fullerene is not only easier to be oxidized, and easier being reduced.For example, for the soccerballene C of double heteroatoms
58X
2, C
68X
2, C
58BN and C
68BN, along with the increase of distance between two heteroatomss, ionizing potential progressively descends and electron affinity progressively raises; Distance is big more between two heteroatomss, and the difference between system and desmotrope on redox property is just big more, and this result has illustrated the dependence of relative position between mixed with fullerene electronic property and heteroatoms once more.
The first mixed with fullerene C in 1991
60Materials chemistry and vitochemical new era have been started in the successful preparation of-xBx (x=1～6), and many underlying issues such as its stability, electronic property, one-tenth key characteristic all need to go to explore before us.In the same year, Pradeep etc. have reported and have contained part N
2Perhaps NH
3Under the He atmosphere of gas, during with arc process evaporation graphite, in the carbon ash, obtained C
59N.Nineteen ninety-five, the present inventor is evaporated the graphite rod of doping BN with arc process, and with methylbenzene extraction carbon ash, finds to have in the extracting solution existence of the assorted soccerballene of N in flight time mass spectrum, and has confirmed the doping of N atom with photoelectron spectrum.Peking University once attempted utilizing the assorted soccerballene of the synthetic B of arc process maroscopic quantity, and they have obtained being rich in the assorted soccerballene C of B
60And C
70The carbon ash, but separate and Purification is still a great difficult problem.Along with the successful preparation of the assorted soccerballene of maroscopic quantity B, the work of this respect is expected to obtain in the recent period certain progress.Simultaneously, other heteroatomss are doped to have also obtained success in the cage, nineteen ninety-five Stry etc. has obtained the assorted soccerballene C that Sauerstoffatom replaces experimentally
59O; Fye in 1997 etc. mix 3 SiC 2/graphite with laser gasification and have obtained CnSi
+(n=3～69), and inferred the structure of these sila soccerballenes; Branz in 1998 etc. utilize the method for photo-ionization C60Mx and C70Mx to obtain C
59-2nM and C
69-2nM (M=Fe, Co, Ni, Rh, mass signal Ir); Poblet in 1999 etc. utilize and swash sputter C60Mn[M=Pt, Ir (CO)
2] the method for film obtained C
59M
+, and think that it has and C
60Similar cage structure.In addition, mixed with fullerene can also obtain by the method for chemically modified except can obtaining by arc process and these physical methods of laser evaporation, especially aspect the assorted soccerballene of N synthetic.Nineteen ninety-five Mattay etc. has detected C
59NH
+And C
59NH
2 +, and from experimentally to C
59N proves conclusively, and Hirsch group utilizes the method for the fullerene derivate that dissociates to detect C in mass spectrum
59N
+And C
59N
+The peak; In the same year, Hummelen etc. have successfully prepared C
59Dimer (the C of N
59N)
21996, Nuber etc. synthesized and have separated (C
59N)
2(C
69N)
2, and successfully synthesize its adducts RC
59N closes RC
69N.Though the research work of mixed with fullerene has obtained certain progress, but the research in this field still only is in the starting stage, there are many problems to wait for that we carry out more deep exploration, as being doped in the carbon cage, go a greater variety of heteroatomss, enrich the kind of mixed with fullerene, strive obtaining new functional materials.On the other hand, the same with full carbon fullerene CHEMICAL DEVELOPMENT, the mixed with fullerene CHEMICAL DEVELOPMENT also rely on they macroscopic view preparation and separate purification.Therefore, seek suitable experimental technique and catalyzer, mixed with fullerene synthetic and the separation maroscopic quantity also is a job highly significant.So a kind of method that can effectively improve the mixed with fullerene productive rate just seems particularly important.
Summary of the invention
The object of the present invention is to provide a kind of preparation method that can obviously improve the doped aggregate cluster of productive rate.
Technical scheme of the present invention is in the process of arc process prepared in reaction mixed with fullerene, adds the mixture of blended boron nitride (BN) and silver powder (Ag) by a certain percentage in carbon-point.
The present invention includes following steps:
1) mixed uniformly BN and Ag mixture in proportion are positioned in the carbon-point, stand-by, press mass ratio BN: Ag=1: (0.1～0.5);
2) resistance to air loss of check reaction unit is fixed on the arc discharge device positive terminal to the carbon-point of putting into BN and Ag mixture, the capping cavity;
3) open all vacuum two logical pistons that link to each other with reactant gases in the induction trunk and the vacuum two logical pistons that link to each other with assist gas;
4) open the vacuum stop,threeway that links to each other with vacuum pump, begin system vacuumized until vacuum tightness being not less than 0.1Pa;
5) close the vacuum stop,threeway, open the vacuum two logical pistons that communicate with assist gas, open the air valve on the assist gas steel cylinder again, repeat this step at least 3 times;
6) in reaction cavity, put into He and N
2Mixed gas;
7) open water-cooled tube;
9) open arc welding machine, open arc initiation device simultaneously, the while at 60～90A, makes the starting the arc between two electrodes to current setting;
10) after the question response cavity is reduced to room temperature, close water coolant;
11) in reaction cavity, introduce N
2To normal pressure;
12) take out the carbon ash that reaction generates, weighing, as solvent, Soxhlet is extracted with toluene, and evaporation toluene gets target product.
In BN and Ag mixture, press the best BN of mass ratio: Ag=1: 0.3.He that in reaction cavity, puts into and N
2The air pressure of mixed gas is preferably (4.8～5.5) * 10
4Pa, He and N
2Mixed gas is 1: 1 by volume.Open the arc initiation device after-current and preferably be adjusted to 80A, start stepper-motor, regulate two distance between electrodes and make the starting the arc between two electrodes, control two interelectrode distances between 1～2mm, make reaction continue to carry out.The carbon ash that reaction generates and toluene by quality than carbon ash: toluene≤50.
Because the present invention under arc-over, improves the productive rate of mixed with fullerene by add the mixture of blended boron nitride (BN) and silver powder (Ag) by a certain percentage in carbon-point in the process of arc process prepared in reaction mixed with fullerene significantly.
Description of drawings
Fig. 1 is the structural representation of the arc discharge device of the embodiment of the invention.
Fig. 2 is the structural representation of the carbon-point of the embodiment of the invention.
Fig. 3 is the mass spectrum of the embodiment of the invention.In Fig. 3, X-coordinate is mass-charge ratio m/z, and ordinate zou is intensity Relative Abundance.The mark of each molecular ion peak is followed successively by 265.3,267.3,269.3,281.4,283.4 from left to right, 317.4,359.3,371.3,411.2,447.1,476.1,515.2,580.4,608.2,650.6,697.5,720.5,721.4,722.4,751.3,812.0,840.4,880.4,922.5 and 976.6.
Fig. 4 is the short molecular ion peak enlarged view between 250～500 among Fig. 3.In Fig. 4, X-coordinate is mass-charge ratio m/z, and ordinate zou is intensity Relative Abundance.The mark of each molecular ion peak is followed successively by 265.5,267.5,277.6,278.6,281.6,301.7,317.6,318.6 from left to right, 331.5,342.5,367.6,383.5,395.4,408.5,420.4,434.4,444.4,462.4,484.2,494.4,502.5,535.6,545.2 and 562.1.
Fig. 5 is for being the molion figure of the embodiment of the invention.In Fig. 5, X-coordinate is mass-charge ratio m/z, and ordinate zou is intensity Relative Abundance.The mark of each molecular ion peak is followed successively by 202.5,227.5,277.5,301.5,339.5,353.4,354.4 from left to right, 375.3,432.5,479.1,542.1,721.3,771.2,910.2,1069.4,1119.8,1236.9,1367.6,1541.0,1782.9 and 1871.0.
Fig. 6 is the corresponding enlarged view of Fig. 5.In Fig. 6, X-coordinate is mass-charge ratio m/z, and ordinate zou is intensity RelativeAbundance.The mark of each molecular ion peak is followed successively by 164.0,165.6,166.5,179.9,202.7 from left to right, 215.6,227.6,240.6,254.5,265.4,277.6,301.6,302.6,305.6,328.5,339.7,340.6,353.6,356.5,380.7,407.7,429.6,431.5,449.4,481.4,495.9,519.4,531.3,556.4,579.4 and 621.2.
Fig. 7 is the part mass spectrum that the Appi of the embodiment of the invention makes from the source.In Fig. 7, X-coordinate is mass-charge ratio m/z, and ordinate zou is intensity I ntens.The mark of each molecular ion peak is followed successively by 154.2,166.2,180.2,191.2 from left to right, and 203.2,216.2,227.2,241.1,253.2,265.0,278.2,293.2,302.3,318.3,330.3,343.3,357.3,368.3,384.3 and 393.3.
Fig. 8 is one group of peak mass spectrum of 330.3 for the molecular ion peak among Fig. 7.In Fig. 8, X-coordinate is mass-charge ratio m/z, and ordinate zou is intensity I ntens.Molecular ion peak be labeled as 330.3.
Fig. 9 is the figure as a result that is Ms-Ms of Fig. 8.In Fig. 9, X-coordinate is mass-charge ratio m/z, and ordinate zou is intensity I ntens.The mark of molecular ion peak is respectively 276.1 and 302.2.
Embodiment
Referring to Fig. 1, the arc discharge device that the embodiment of the invention adopts is by vacuum two logical pistons 1, U type pipe (interior dress mercury metal) 2, heavy wall vacuum rubber pipe 3, fluid-tight device 4, electrode cooling water inlet 5, electrode supply joint 6, electrode cooling water outlet 7, water coolant delivery line 8, reaction cooling bucket 9, electrode glass overcoat 10, red copper electrode 11, water shutoff soft rubber ball 12, tetrafluoroethylene cutting ferrule 13, ground (plug) 14, water coolant 15, metallic cavity 16, Graphite Electrodes (Graphite Electrodes headgear) 17, graphite rod 18, water coolant spillway 19, vacuum stop,threeway 20 and lead to vacuum pump 21 compositions such as grade.This device generates C
60And C
70Top condition such as table 1.Referring to Fig. 2, the length of carbon-point is 200mm, and external diameter is 8.00mm, and internal diameter is 3.00mm, and empty is 90.00mm deeply.The purity of BN is 99.9%, 200 order; The purity of silver powder is 99.9%, 200 order.
Table 1
| Cushion gas | Buffering air pressure (Pa) | Discharging current (A) |
| He | 24000～26000 | 80 |
During preparation mixed uniformly BN and Ag mixture in proportion are positioned in the carbon-point of arc discharge device, stand-by, press mass ratio BN: Ag=1: 0.3.The resistance to air loss of check reaction unit is fixed on the arc discharge device positive terminal to the carbon-point of putting into BN and Ag mixture, the capping cavity.Open all vacuum two logical pistons that link to each other with reactant gases in the induction trunk and the vacuum two logical pistons that link to each other with assist gas, open the vacuum stop,threeway that links to each other with vacuum pump, begin system vacuumized until vacuum tightness and be not less than 0.1Pa, close the vacuum stop,threeway, open the vacuum two logical pistons that communicate with assist gas, open the air valve on the assist gas steel cylinder again, repeat " closing the vacuum stop,threeway; open the vacuum two logical pistons that communicate with assist gas, open the air valve on the assist gas steel cylinder again " this step 3 time again.In reaction cavity, put into He and N
2Mixed gas is opened water-cooled tube, arc welding machine and arc initiation device, is current setting 80A simultaneously, makes the starting the arc between two electrodes.After the question response cavity is reduced to room temperature, close water coolant, in reaction cavity, introduce N
2To normal pressure, take out the carbon ash that reaction generates, weighing, as solvent, Soxhlet is extracted with toluene, and evaporation toluene gets target product.
He that in reaction cavity, puts into and N
2The air pressure of mixed gas is preferably 5.3 * 10
4Pa, He and N
2Mixed gas is 1: 1 by volume.Make between two electrodes after the starting the arc regulating two distance between electrodes, preferably control two interelectrode distances between 1～2mm, make reaction continue to carry out.The carbon ash that reaction generates and toluene by quality than carbon ash: toluene≤50.
Analysis of experimental data mainly according to APCI-MS (atmospheric pressure chemical ionization mass spectrum), is analyzed reaction product.The mass spectrum that Fig. 3 represents is to obtain under the reaction conditions of table 2, the 720.5th, and soccerballene C
60Molecular ion peak; And 265.3 are background peaks in the mass spectrum (what occur in the following mass spectra peak all are).After the short molecular ion peak between 250～500 amplifies as shown in Figure 4.According to the isotopic distribution of C, N, B unit prime element, can determine that these more weak molecular ion peaks are CxByNz class cluster compounds.And table 3 is another different reaction conditionss, and different with table 2 is to be mixed with a certain proportion of silver powder among the BN of use.Fig. 5 is the corresponding molion figure of this sample, and Fig. 6 is corresponding enlarged view.
Table 2
| Buffer gas | Buffering air pressure (Pa) | Discharging current (A) | The material that mixes in the carbon-point |
| He | 2.6×10 4 | 80 | BN |
Table 3
| Buffer gas | Buffering air pressure (Pa) | Discharging current (A) | Mix in the carbon-point |
| He&N2 | 5.3×10 4(1∶1) | 80 | BN+Ag |
Can find the CxByNz intensity showed increased that occurs Fig. 3 from Fig. 6, this is the silver powder that adds of meaning just also, has played catalytic effect, improves the content of these doped aggregate clusters in the carbon ash.In order to explore the best proportioning of silver powder optimum content, can make further quantitative experiment, referring to Fig. 2, as calculated: the AB of reaction partly is about 90mm, AB section carbon-point quality 7.25g, carbon-point intermediary hole can add about 0.90gBN powder at most.Through the different proportionings of continuous debugging BN, find to work as M with Ag
BN: M
Ag=10: 3 o'clock, the intensity maximum of the doped aggregate cluster of generation.If BN is too much, can not give full play to the catalytic activity of Ag; If the content of Ag is too much, then influence the effect of arc-over, be difficult for striking and produce a large amount of ultraviolet rays.So, think M
BN: M
AgThe=10: the 3rd, the best proportioning under this condition.By the isotopic distribution of material in the mass spectrum, can determine necessarily to contain in this mixture the B element; Ultimate analysis shows in this mixture that the mass ratio of C and N is 8.96.For the more analysis of system, can use highly sensitive mass spectrograph to the synthetic material, and utilize Appi-MS (normal atmosphere Photoionization Mass Spectrometry) that the doped aggregate cluster of preparation is done further and determine.The part mass spectrum that Fig. 7 makes for the Appi ionizer.By mass spectrum 7, can find that almost total mass number differs between 11～14 between each adjacent molecular ion peak, that is to say that adjacent molion differs a B or C or N on the number of atom, this illustrates that these doped aggregate clusters are likely a series of mixture; These information, the mass spectrum texture ratio for preparing classical soccerballene to the arc-over of classics is more similar.And,, and utilize existing knowledge to infer the relevant nature of some mixed with fullerene about classical fullerene compound stability rule with its foundation relation between the two.In order to prove the relation between these clusters, to have chosen several groups of peaks, and it has been MS-MS (multi-stage ms), hope can be found the relation between them from the fragment of these materials.Fig. 8 is that to choose molecular ion peak be one group of peak of 330.3, and it is MS-MS, and its result as shown in Figure 9.From Fig. 7 and Fig. 8, can find 330.3 quasi-molecular ions, after the mass spectrum bombardment, successively occurred 302.2 and 276.1.From 330.3 to 302.2, molecular weight differs 28, can think to fall two N (M from order quasi-molecular ions (330.3) bombardment
N=14) atom; And from 302.2 to 276.1, quality differs 26, and this is to fall CN (M from fragment peak 302.2 bombardments
C+ M
N=26).Equally, bombardment molecular ion peak 368.3 can produce fragment peak 343.3 (BN is fallen in bombardment) and 318.3 (BN is fallen in bombardment); Bombard 227.2, can produce fragment peak 203.3 (2C is fallen in bombardment) equally and (BC) fallen in 180.2 bombardments, the molecular weight ratio that shows on all these and the mass spectrum is more identical.From these experiments.Can find that when some molecular ion peaks are bombarded it is always simultaneously hit two atoms (NN, CC, BB, CB, CN or BN), and reach next comparatively stable fragmention.This with to classical soccerballene (C
60Or C
70) when carrying out ion bombardment, " the magic number rule " of generation is closely similar.
Be positioned over BN and Ag mixture in the arc discharge device carbon-point, may be selected to be 1: 0.1 or 1: 0.5 by mass ratio BN: Ag.Close the vacuum stop,threeway, open the vacuum two logical pistons that communicate with assist gas, the step of opening the air valve on the assist gas steel cylinder again can repeat 4 times.In reaction cavity, put into He and N
2Mixed gas, open water-cooled tube, arc welding machine and arc initiation device after, can be current setting at 60A or 90A.He that in reaction cavity, puts into and N
2The air pressure of mixed gas can be 4.8 * 10
4Pa or 5.5 * 10
4Pa.
Claims (7)
1. the preparation method of doped aggregate cluster is characterized in that the steps include:
1) mixed uniformly BN and Ag mixture in proportion are positioned in the carbon-point, stand-by, press mass ratio BN: Ag=1: 0.1～0.5;
2) resistance to air loss of check reaction unit is fixed on the arc discharge device positive terminal to the carbon-point of putting into BN and Ag mixture, the capping cavity;
3) open vacuum two logical pistons that link to each other with reactant gases in the induction trunk and the vacuum two logical pistons that link to each other with assist gas;
4) open the vacuum stop,threeway that links to each other with vacuum pump, begin system vacuumized until vacuum tightness being not less than 0.1Pa;
5) close the vacuum stop,threeway, open the vacuum two logical pistons that communicate with assist gas, open the air valve on the assist gas steel cylinder again, repeat this step at least 3 times;
6) in reaction cavity, put into He and N
2Mixed gas;
7) open water-cooled tube;
9) open arc welding machine, open arc initiation device simultaneously, the while at 60～90A, makes the starting the arc between two electrodes to current setting;
10) after the question response cavity is reduced to room temperature, close water coolant;
11) in reaction cavity, introduce N
2To normal pressure;
12) take out the carbon ash that reaction generates, weighing, as solvent, Soxhlet is extracted with toluene, and evaporation toluene gets target product.
2. the preparation method of doped aggregate cluster as claimed in claim 1 is characterized in that pressing mass ratio BN: Ag=1: 0.3 in BN and Ag mixture.
3. the preparation method of doped aggregate cluster as claimed in claim 1 is characterized in that the He and the N that put in reaction cavity
2The air pressure of mixed gas is (4.8～5.5) * 10
4Pa.
4. the preparation method of doped aggregate cluster as claimed in claim 1 is characterized in that He and N
2Mixed gas is 1: 1 by volume.
5. the preparation method of doped aggregate cluster as claimed in claim 1 is characterized in that described current setting is 80A.
6. the preparation method of doped aggregate cluster as claimed in claim 1 is characterized in that in step 9), makes between two electrodes after the starting the arc, regulates two distance between electrodes and makes the starting the arc between two electrodes, controls two interelectrode distances between 1～2mm, makes reaction continue to carry out.
7. the preparation method of doped aggregate cluster as claimed in claim 1, the carbon ash that it is characterized in that reacting generation and toluene by quality than carbon ash: toluene≤50.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108455559A (en) * | 2018-03-30 | 2018-08-28 | 桂林电子科技大学 | It is a kind of based on the nitrogen boron codope porous carbon materials and its preparation method and application for breaking BN keys |
| CN108483424A (en) * | 2018-04-28 | 2018-09-04 | 厦门大学 | A kind of fullerene electrical heating synthesizer |
| CN109115660A (en) * | 2018-08-23 | 2019-01-01 | 金华职业技术学院 | A kind of particle imaging method |
| CN111052429A (en) * | 2017-08-31 | 2020-04-21 | 松下知识产权经营株式会社 | P-type semiconductor film containing hetero fullerene and electronic device |
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| WO1998000363A1 (en) * | 1996-06-28 | 1998-01-08 | Hahn-Meitner-Institut Berlin Gmbh | PROCESS AND DEVICE FOR PRODUCING STABLE ENDOHEDRAL FULLERENES OF STRUCTURE Z@Cx, IN WHICH x ≥ 60 |
| CN100351174C (en) * | 2005-12-12 | 2007-11-28 | 西安交通大学 | Method for producing fullerene by temperature-controlling arc furnace |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111052429A (en) * | 2017-08-31 | 2020-04-21 | 松下知识产权经营株式会社 | P-type semiconductor film containing hetero fullerene and electronic device |
| CN111052429B (en) * | 2017-08-31 | 2023-07-04 | 松下知识产权经营株式会社 | P-type semiconductor film containing hetero fullerene and electronic device |
| CN108455559A (en) * | 2018-03-30 | 2018-08-28 | 桂林电子科技大学 | It is a kind of based on the nitrogen boron codope porous carbon materials and its preparation method and application for breaking BN keys |
| CN108455559B (en) * | 2018-03-30 | 2021-07-16 | 桂林电子科技大学 | BN bond breaking-based nitrogen-boron co-doped porous carbon material and preparation method and application thereof |
| CN108483424A (en) * | 2018-04-28 | 2018-09-04 | 厦门大学 | A kind of fullerene electrical heating synthesizer |
| CN109115660A (en) * | 2018-08-23 | 2019-01-01 | 金华职业技术学院 | A kind of particle imaging method |
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