CN102133543B - Preparation of tin dioxide-carbon nitrogen composite material - Google Patents
Preparation of tin dioxide-carbon nitrogen composite material Download PDFInfo
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- CN102133543B CN102133543B CN 201010601450 CN201010601450A CN102133543B CN 102133543 B CN102133543 B CN 102133543B CN 201010601450 CN201010601450 CN 201010601450 CN 201010601450 A CN201010601450 A CN 201010601450A CN 102133543 B CN102133543 B CN 102133543B
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Abstract
The invention provides a tin dioxide-carbon nitrogen composite material, which belongs to the technical field of materials. In the invention, with tin dioxide as a matrix and pyrrole monomer as a modifier, the tin dioxide-carbon nitrogen composite material is obtained through graphitizing treatment. Synergistic action exists between the composite material and nanoparticles loaded thereon, to jointly promote the catalytic oxidation of alcohols and other micro-molecular fuels, and therefore the composite material can be applied to the preparation of a fuel cell catalyst as a novel high-performance catalyst carrier. A large number of experiments prove that the catalyst prepared by adopting the tin dioxide-carbon nitrogen composite material as the carrier, loaded with nanoparticles, has better catalytic activity and catalytic stability compared with those of the corresponding catalyst of the traditional carbon carrier, and has better anti-poisoning capability simultaneously.
Description
Technical field
The invention belongs to technical field of composite materials, relate to the preparation of a kind of tin ash-carbon nitrogen composite; The present invention also relates to this tin ash-carbon nitrogen composite simultaneously as the application of catalyst carrier in the preparation electrode catalyst of fuel cell.
Background technology
Because fuel battery energy provides the energy efficiently, environment is not polluted, so people hanker after applying it to such as automobile every aspects such as power station always in addition.In recent years, fuel cell has received great concern, although this technology has obtained develop rapidly, thinks large-scale commercial applications, and many technical bottlenecks also need to be resolved hurrily.Wherein important bottleneck mainly is that the cost that is applied to the catalyst of catalytic fuel remains high aspect catalyst, and catalyst stability is relatively poor, and anti-poisoning capability also needs problems such as further raising.
For realizing commercial applications, scientist solves these problems from two aspects.One, the catalyst nano particle on the improvement supported catalyst.It is good to put forth effort to seek anti-poisoning capability, and price is low, the class catalyst that catalytic efficiency is high, and as alloy catalyst, special appearance catalyst, nucleocapsid catalyst etc.Reduce the use amount of noble metal on the one hand, the performance of catalyst is further enhanced.Two, improve the carrier of supported catalyst nano particle.Nanoparticle catalysts such as platinum use for a long time and can run off at carrier surface, cause the catalytic capability of catalyst to reduce.Main cause is that traditional carrier is corroded easily, a little less than the interaction between carrier and the catalyst granules.In recent years, scientist be devoted to select and seek that specific area is big, good stability, surface contain active group, can have the carrier of synergistic effect preferably to the nano particle of load on it.To CNT, arrive novel carriers such as Graphene from traditional carbon dust again.The carrier that all is used as catalyst uses, and the carbon nitrogen carriers that present discovery is doped with the nitrogen element is a kind of very desirable fuel-cell catalyst high-performance carrier.
Summary of the invention
The purpose of this invention is to provide a kind of tin ash-carbon nitrogen composite.
Another object of the present invention provides a kind of method for preparing this tin ash-carbon nitrogen composite.
A further object of the invention, just providing a kind of is catalyst carrier with tin ash-carbon nitrogen composite material, prepares the method for electrode catalyst of fuel cell.
The preparation method of tin ash of the present invention-carbon nitrogen composite is that nano-stannic oxide is added to the water, ultrasonic dispersion under agitation; To the surfactant of 0.1 ~ 5 times of the pyrrole monomer that wherein adds 1 ~ 10 times of nano-stannic oxide quality and nano-stannic oxide quality, add the oxidizing agent solution of mass concentration 5 ~ 30 % then again, 0 ~ 5 ℃ of reaction 1 ~ 20 hour down; Suction filtration, washing, drying gets tin ash-carbon nitrogen composite precursor; At last with tin ash-carbon nitrogen composite precursor under nitrogen protection, handled 2 ~ 12 hours down in 200 ~ 1000 ℃, obtain tin ash-carbon nitrogen composite.
The preparation of tin ash of the present invention-carbon nitrogen composite, the particle diameter of described nano-stannic oxide is between 10 ~ 100 nm.
Described surfactant is neopelex, octadecyl trimethylammonium bromide, softex kw, enuatrol, ammonium oleate, DTAB, dodecyl sodium sulfate or lauryl sodium sulfate.
Described oxidant chlorination iron or ammonium persulfate; The consumption of oxidant is 1 ~ 5 times of pyrrole monomer quality.
Tin ash-carbon nitrogen the composite of the present invention's preparation is even doping tin dioxide nano particles in the polypyrrole matrix.The mass percent of nano-stannic oxide particle in composite is 20 ~ 90 %.
The tin ash of the present invention preparation-carbon nitrogen composite active high, specific area is big, can produce well synergy with the active metal particles of load on it, can promote the catalytic activity of active metal particles.Oxide can improve the anti-poisoning capability of catalyst, and then the catalytic activity of raising catalyst, and the oxide-doped corrosion that in carrier, can effectively avoid and reduce electrolyte, therefore, tin ash-carbon nitrogen composite is the ideal carrier of preparation fuel-cell catalyst.
Characterize below by the tin ash-carbon nitrogen composite of the present invention's preparation of XRD figure and the catalyst of supporting Pt, and the performance of corresponding loaded Pt catalyst is tested.
Fig. 1 is the XRD figure of tin ash, tin ash-carbon nitrogen complexes carrier and tin ash-carbon nitrogen complexes carrier load platinum catalyst.Found out that by Fig. 1 corresponding peak has all appearred in the carbon nitrogen complex carrier of doped stannum oxide in XRD figure.At 37.9 °, 51.7 °, 54.0 °, 62.3 ° and 66.1 ° (101), (211), (220), (310) and (301) crystal faces that correspond to tin ash respectively.Behind tin ash-carbon nitrogen complexes carrier load platinum, four crystal faces (111) of face-centred cubic structure platinum have appearred, and (200), (220) and (311) illustrate that having active nano particle successfully loads on the novel carriers.
The corresponding catalyst of the supporting Pt of the present invention's preparation is at 0.5 M H
2SO
4/ CH
3CH
2Carry out the cyclic voltammetric test in the OH solution, confirmed the performance that it is excellent.Fig. 2 be tin ash modification type carrier, carbon nitrogen carriers, tin ash-carbon nitrogen complexes carrier and carbon carrier respectively behind the load 20 wt% platinum corresponding catalyst at 0.5 M H
2SO
4Catalysis ethanol cyclic voltammetric test in the solution.By among Fig. 2 as can be seen, under the situation of the identical carrying capacity of noble metal, the catalyst of tin ash-carbon nitrogen composite carrier load platinum has better current density than conventional carbon powder carrier load platinum catalyst and (is respectively 3.98 mA, 3.59 mA, conversion is respectively for the unit metal quality: 331 mA/mg, 299 mA/mg), illustrate that tin ash-carbon nitrogen complex carrier can promote the activity of noble metal, and can produce cooperative effect with it, acting in conjunction is in alcohol catalysis.
Fig. 3 is corresponding Catalyst for CO adsorption desorption test behind carbon carrier, carbon nitrogen carriers, tin ash-carbon nitrogen complex carrier and the tin ash modification type carrier difference load 20 wt% Pt.From the absorption area of Fig. 3 clearly as can be seen, the platinum of tin ash-carbon nitrogen composite carrier load has bigger electrochemistry specific area, and bigger specific surface is conducive to obtain better catalytic effect.
Fig. 4 is corresponding catalyst 0.5 M H under 0.6 V voltage behind tin ash modification type carrier, carbon nitrogen carriers, tin ash-carbon nitrogen complex carrier and the carbon carrier difference load 20 wt% Pt
2SO
4/ CH
3CH
2Timing testing current in the OH solution.As seen from Figure 4, prepared catalyst constantly reduces in time to the size of current of alcohol catalysis oxidation, but clearly: the catalyst of the novel carriers correspondence of preparation descends slow slightly than other catalyst.Behind timing testing current 1000 s, unit metal current density block diagram as shown in Figure 5.The oxidation peak current of the corresponding catalyst of tin ash-carbon nitrogen complex carrier is up to 52.45 mA/mg, and the corresponding catalyst of conventional carriers is 46.3 mA/mg, under the identical situation of correlated conditions such as noble metal carrying capacity, the corresponding catalyst of the supporting Pt of the present invention's preparation has bigger current density than the corresponding catalyst of conventional carriers carbon dust, illustrates that the tin ash-carbon nitrogen complex carrier of the present invention's preparation has better catalytic stability.
In sum, exist between the tin ash-carbon nitrogen composite of the present invention preparation and the load nano particle on it and act synergistically, the common micromolecular catalytic oxidation of alcohols that promotes can be used as the novel high-performance support applications in the preparation of fuel-cell catalyst.Experimental results demonstrate, be nano particles such as carrier loaded Pt(or PtRu, PtSn, Pd with tin ash-carbon nitrogen composite) catalyst have better catalytic activity and catalytic stability than the corresponding catalyst of traditional carbon carrier load, have better anti-poisoning capability simultaneously.
Description of drawings
Fig. 1 is the XRD figure of corresponding catalyst behind tin ash, tin ash-carbon nitrogen complex carrier and tin ash-carbon nitrogen composite carrier load platinum.
Fig. 2 be tin ash modification type carrier, carbon nitrogen carriers, tin ash-carbon nitrogen complex carrier and carbon carrier respectively behind the load 20 wt% Pt corresponding catalyst at 0.5 M H
2SO
4Catalysis methanol cyclic voltammetric test in the solution.
Fig. 3 is corresponding Catalyst for CO adsorption desorption test behind carbon carrier, carbon nitrogen carriers, tin ash-carbon nitrogen complex carrier and the tin ash modification type carrier difference load 20 wt% Pt.
Fig. 4 is corresponding catalyst 0.5 M H under 0.6 V voltage behind tin ash modification type carrier, carbon nitrogen carriers, tin ash-carbon nitrogen complex carrier and the carbon carrier difference load 20 wt% Pt
2SO
4/ CH
3CH
2Timing testing current in the OH solution.
After Fig. 5 was tin ash modification type carrier, carbon nitrogen carriers, tin ash-carbon nitrogen complex carrier and carbon carrier difference load 20 wt% Pt, corresponding catalyst is 0.5 M H under 0.6 V voltage
2SO
4/ CH
3CH
2Behind timing testing current 1000 s in the OH solution, unit metal current density block diagram.
The specific embodiment
Be described further below by the preparation of specific embodiment to composite of the present invention, and be example with load platinum catalyticing anode oxidation of ethanol reaction, illustrate that composite that the present invention prepares is to the facilitation of catalytic nanometer particle.
Embodiment 1
(1) preparation of tin ash-carbon nitrogen composite
0.2 g nano-stannic oxide is joined in three distilled water, stir and ultrasonic down it is fully disperseed; Add pyrrole monomer 0.2 g, neopelex 2g successively, slowly drip the ferric chloride solution (containing iron chloride 0.46 g) of mass concentration 10 % then, 5 ℃ of stirring reaction 16 h; After reaction is finished, suction filtration, 70 ℃ of dryings get tin ash-carbon nitrogen composite material precursors.Tin ash-carbon nitrogen composite material precursors is placed tube furnace, under nitrogen protection, in 400 ℃ of heat treatments 6 hours, obtain tin ash-carbon nitrogen composite.
(2) preparation of loaded Pt catalyst
Chloroplatinic acid 68 mg are joined in the 100 ml round-bottomed flasks, add 35 ml ethylene glycol, and add magneton and stir, ultrasonicly more than 0.5 hour it is dissolved fully; Add 100 mg natrium citricums, be stirred to dissolving fully; Use PH=8 ~ 9 of 5 % KOH/EG solution regulator solutions then; Add tin ash-carbon nitrogen composite 100 mg of above-mentioned preparation, stirred 0.5 hour, ultrasonic 0.5 hour, 160 ℃ of back flow reaction 6 h; Suction filtration, with three water washings, 60 ℃ are dried to weight, obtain loaded Pt catalyst.
The catalyst of tin ash-carbon nitrogen composite carrier load platinum has bigger current density than conventional carbon powder carrier load platinum catalyst catalysis ethanol oxidation reaction, and (conversion reaches for the unit mass metal: 341 mA/mg), improve 14 %.
Embodiment 2:
(1) preparation of tin ash-carbon nitrogen composite
0.3 g nano-stannic oxide is joined in three distilled water, stir and ultrasonic down it is fully disperseed; Add pyrrole monomer 0.4 g successively, lauryl sodium sulfate 2.2 g slowly drip the ferric chloride solution (containing iron chloride 0.8g) of mass concentration 15 % then, and 0 ℃ down about reaction 12 h; After reaction is finished, suction filtration, 70 ℃ of dried overnight obtain tin ash-carbon nitrogen composite material precursors.Tin ash-carbon nitrogen composite material precursors is placed tube furnace, under nitrogen protection, in 500 ℃ of heat treatments 8 hours, obtain high-performance carrier tin ash-carbon nitrogen composite.
(2) preparation of loaded Pt catalyst
Chloroplatinic acid 61 mg are joined in the 100 ml round-bottomed flasks, add 30 ml ethylene glycol, and add magneton and stir, ultrasonicly more than 0.5 hour it is dissolved fully; Add 95 mg natrium citricums, be stirred to dissolving fully; Use the PH=11 of 5 % KOH/EG solution regulator solutions then; Add tin ash-carbon nitrogen composite 80 mg of above-mentioned preparation, stirred 0.5 hour, ultrasonic 0.5 hour, 120 ℃ of back flow reaction 8 h; Suction filtration, with three water washings, 60 ℃ are dried to weight, obtain loaded Pt catalyst.
The catalyst of tin ash-carbon nitrogen composite carrier load platinum has bigger current density than conventional carbon powder carrier load platinum catalyst catalysis ethanol oxidation reaction, and (conversion reaches for the unit mass metal: 347 mA/mg), improve 16 %.
Embodiment 3:
(1) preparation of tin ash-carbon nitrogen composite
0.2 g nano-stannic oxide is joined in three distilled water, stir and ultrasonic it is fully disperseed; Add pyrrole monomer 0.2 g successively, dodecyl sodium sulfate 2.1 g; Slowly drip the ferric chloride solution (containing iron chloride 0.46g) of mass concentration 15 % then, react about 8h down at 0 ℃; After reaction is finished, suction filtration, 70 ℃ of dried overnight obtain tin ash-carbon nitrogen composite material precursors.Tin ash-carbon nitrogen composite material precursors is placed tube furnace, under nitrogen protection, in 800 ℃ of heat treatments 6 hours, obtain high-performance carrier tin ash-carbon nitrogen composite.
(2) preparation of loaded Pt catalyst
The catalyst of tin ash-carbon nitrogen composite carrier load platinum has bigger current density than conventional carbon powder carrier load platinum catalyst catalysis ethanol oxidation reaction, and (conversion reaches for the unit mass metal: 323 mA/mg), improve 8 %.
Embodiment 4:
(1) preparation of tin ash-carbon nitrogen composite
0.2 g nano-stannic oxide is joined in three distilled water, stir and ultrasonic it is fully disperseed; Add pyrrole monomer 0.3 g successively, octadecyl trimethylammonium bromide 2.2 g slowly drip the ferric chloride solution (containing iron chloride 0.58g) of mass concentration 25% again, in 4 ℃ of reaction 10 h, after reaction is finished, suction filtration, 70 ℃ of dried overnight get tin ash-carbon nitrogen composite material precursors.Then tin ash-carbon nitrogen composite material precursors is placed tube furnace, under nitrogen protection, in 600 ℃ of following heat treatments 5 hours, obtain high-performance carrier tin ash-carbon nitrogen complex carrier.
(2) preparation of loaded Pt catalyst
Chloroplatinic acid 48 mg are joined in the 100 ml round-bottomed flasks, add 35 ml ethylene glycol, and add magneton and stir, ultrasonicly more than 0.5 hour it is dissolved fully; Add 60 mg natrium citricums, be stirred to dissolving fully; Use the PH=9 of 5 % KOH/EG solution regulator solutions then; Add tin ash-carbon nitrogen composite 70 mg of above-mentioned preparation, stirred 0.5 hour, ultrasonic 0.5 hour, 140 ℃ of back flow reaction 6 h; Suction filtration, with three water washings, 30 ℃ are dried to weight, obtain loaded Pt catalyst.
The catalyst of tin ash-carbon nitrogen composite carrier load platinum has bigger current density than conventional carbon powder carrier load platinum catalyst catalysis ethanol oxidation reaction, and (conversion reaches for the unit mass metal: 326 mA/mg), improve 9 %.
Embodiment 5:
(1) preparation of tin ash-carbon nitrogen composite
0.2 g nano-stannic oxide is joined in three distilled water, stir and ultrasonicly make its dispersion; Once add pyrrole monomer 0.25 g, DTAB 2.1 g slowly drip the ammonium persulfate solution (containing ammonium persulfate 0.5 g) of mass concentration 10 % again, 2 ℃ are reacted 10 h down, after reaction is finished, and suction filtration, 70 ℃ of dried overnight get tin ash-carbon nitrogen composite material precursors.Then tin ash-carbon nitrogen composite material precursors is placed tube furnace, under nitrogen protection, in 700 ℃ of heat treatments 5 hours, obtain high-performance carrier tin ash-carbon nitrogen compound.
(2) preparation of loaded Pt catalyst
Chloroplatinic acid 70 mg are joined in the 100 ml round-bottomed flasks, add 35 ml ethylene glycol, and add magneton and stir, ultrasonicly more than 0.5 hour it is dissolved fully; Add 120 mg natrium citricums, be stirred to dissolving fully; Use the PH=13 of 5 % KOH/EG solution regulator solutions then; Add tin ash-carbon nitrogen composite 106 mg of above-mentioned preparation, stirred 0.5 hour, ultrasonic 0.5 hour, 160 ℃ of back flow reaction 5 h; Suction filtration, with three water washings, 50 ℃ are dried to weight, obtain loaded Pt catalyst.
The catalyst of tin ash-carbon nitrogen composite carrier load platinum has bigger current density than conventional carbon powder carrier load platinum catalyst catalysis ethanol oxidation reaction, and (conversion reaches for the unit mass metal: 348 mA/mg), improve 16.3 %.
Embodiment 6:
(1) preparation of tin ash-carbon nitrogen composite
0.2 g nano-stannic oxide is joined in three distilled water, stir and ultrasonic it is fully disperseed; Add pyrrole monomer 0.23 g successively, ammonium oleate 2.1 g slowly drip the ammonium persulfate solution (containing ammonium persulfate 0.575g) of mass concentration 25 % again, 0 ℃ of reaction 8 h, after reaction is finished, suction filtration, 70 ℃ of dried overnight get tin ash-carbon nitrogen composite material precursors.Then tin ash-carbon nitrogen composite material precursors is placed tube furnace, under nitrogen protection, in 1000 ℃ of heat treatments 2 hours, obtain high-performance carrier tin ash-carbon nitrogen compound.
(2) preparation of loaded Pt catalyst
Chloroplatinic acid 54 mg are joined in the 100 ml round-bottomed flasks, add 35 ml ethylene glycol, and add magneton and stir, ultrasonicly more than 0.5 hour it is dissolved fully; Add 70 mg natrium citricums, be stirred to dissolving fully; Use PH=8 ~ 9 of 5 % KOH/EG solution regulator solutions then; Add tin ash-carbon nitrogen composite 65 mg of above-mentioned preparation, stirred 0.5 hour, ultrasonic 0.5 hour, 160 ℃ of back flow reaction 8 h; Suction filtration, with three water washings, 50 ℃ are dried to weight, obtain loaded Pt catalyst.
The catalyst of tin ash-carbon nitrogen composite carrier load platinum has bigger current density than conventional carbon powder carrier load platinum catalyst catalysis ethanol oxidation reaction, and (conversion reaches for the unit mass metal: 329 mA/mg), improve 10 %.
Embodiment 7:
(1) preparation of tin ash-carbon nitrogen composite
0.2 g nano-stannic oxide is joined in three distilled water, stir and ultrasonic it is fully disperseed; Add pyrrole monomer 0.2 g successively, enuatrol 2.2 g slowly drip the ammonium persulfate solution (containing ammonium persulfate 0.42 g) of mass concentration 30 % again, at 4 ℃ of reaction 10 h; After reaction is finished, suction filtration, 70 ℃ of dried overnight get tin ash-carbon nitrogen composite material precursors.Then tin ash-carbon nitrogen composite material precursors is placed tube furnace, under nitrogen protection, in 850 ℃ of heat treatments 8 hours, obtain high-performance carrier tin ash-carbon nitrogen compound.
(2) preparation of loaded Pt catalyst
Chloroplatinic acid 71 mg are joined in the 100 ml round-bottomed flasks, add 35 ml ethylene glycol, and add magneton and stir, ultrasonicly more than 0.5 hour it is dissolved fully; Carry adding 110 mg natrium citricums, be stirred to dissolving fully; Use the PH=10 of 5 % KOH/EG solution regulator solutions then; Add the tin ash-carbon nitrogen composite 95mg of above-mentioned preparation, stirred 0.5 hour, ultrasonic 0.5 hour, 160 ℃ of back flow reaction 4 h; Suction filtration, with three water washings, 50 ℃ are dried to weight, obtain loaded Pt catalyst.
The catalyst of tin ash-carbon nitrogen composite carrier load platinum has bigger current density than conventional carbon powder carrier load platinum catalyst catalysis ethanol oxidation reaction, and (conversion reaches for the unit mass metal: 306 mA/mg), improve 2.3 %.
Embodiment 8:
(1) preparation of tin ash-carbon nitrogen composite
0.21 g nano-stannic oxide is joined in three distilled water, stir and ultrasonicly make its dispersion; Add pyrrole monomer 0.24 g successively, softex kw 2.1 g slowly drip the ammonium persulfate solution (containing ammonium persulfate 0.528g) of mass concentration 15 % then, at 2 ℃ of reaction 12 h down; After reaction is finished, suction filtration, 40 ℃ of dried overnight get tin ash-carbon nitrogen composite material precursors.Then tin ash-carbon nitrogen composite material precursors is placed tube furnace, under nitrogen protection, in 500 ℃ of heat treatments 6 hours, obtain high-performance carrier tin ash-carbon nitrogen compound.
(2) preparation of loaded Pt catalyst
Chloroplatinic acid 63 mg are joined in the 100 ml round-bottomed flasks, add 35 ml ethylene glycol, and add magneton and stir, ultrasonicly more than 0.5 hour it is dissolved fully; Carry adding 110 mg natrium citricums, be stirred to dissolving fully; Use PH=8 ~ 9 of 5 % KOH/EG solution regulator solutions then; Add tin ash-carbon nitrogen composite 90 mg of above-mentioned preparation, stirred 0.5 hour, ultrasonic 0.5 hour, 120 ℃ of back flow reaction 10 h; Suction filtration, with three water washings, 60 ℃ are dried to weight, obtain loaded Pt catalyst.
The catalyst of tin ash-carbon nitrogen composite carrier load platinum has bigger current density than conventional carbon powder carrier load platinum catalyst catalysis ethanol oxidation reaction, and (conversion reaches for the unit mass metal: 351 mA/mg), improve 17.3 %.
Claims (3)
1. the preparation method of tin ash-carbon nitrogen composite is that nano-stannic oxide is added to the water, ultrasonic dispersion under agitation; To the surfactant of 0.1 ~ 5 times of the pyrrole monomer that wherein adds 1 ~ 10 times of nano-stannic oxide quality and nano-stannic oxide quality, add the oxidizing agent solution that mass concentration is 5 ~ 30 % then again, 0 ~ 5 ℃ of reaction 1 ~ 20 hour down; Suction filtration, washing, drying gets tin ash-carbon nitrogen composite precursor; At last with tin ash-carbon nitrogen composite precursor under nitrogen protection, handled 2 ~ 12 hours down in 200 ~ 1000 ℃, obtain tin ash-carbon nitrogen composite; Described oxidant is iron chloride or ammonium persulfate; The consumption of oxidant is 1 ~ 5 times of pyrrole monomer quality.
2. the preparation method of tin ash-carbon nitrogen composite according to claim 1, it is characterized in that: the particle diameter of described nano-stannic oxide is between 10 ~ 100 nm.
3. the preparation method of tin ash-carbon nitrogen composite according to claim 1, it is characterized in that: described surfactant is neopelex, octadecyl trimethylammonium bromide, softex kw, enuatrol, ammonium oleate, DTAB, dodecyl sodium sulfate or lauryl sodium sulfate.
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| CN103730638B (en) * | 2013-10-12 | 2016-09-07 | 吉林大学 | A kind of preparation method of nitrogen-doped carbon material |
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| CN107764871B (en) * | 2017-01-11 | 2020-08-25 | 郑州大学 | For NOXPPy/SnO with high selectivity2Nanotube composite gas sensitive material |
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| CN101209855A (en) * | 2007-12-21 | 2008-07-02 | 中国科学院长春应用化学研究所 | Method for preparing tin oxide nanocrystalline coated by organic ligand |
| CN101912791A (en) * | 2010-08-13 | 2010-12-15 | 西北师范大学 | Silicon/carbon dioxide composite material as well as preparation and application thereof |
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| CN101209855A (en) * | 2007-12-21 | 2008-07-02 | 中国科学院长春应用化学研究所 | Method for preparing tin oxide nanocrystalline coated by organic ligand |
| CN101912791A (en) * | 2010-08-13 | 2010-12-15 | 西北师范大学 | Silicon/carbon dioxide composite material as well as preparation and application thereof |
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| Title |
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| 杨同欢等.碳包覆纳米SnO2锂离子电池负极材料合成及其性能研究.《无机材料学报》.2009,第24卷(第01期),147-151. * |
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