CN103977841A - Method for preparing nitride/carbon nano tube-graphene ternary complex - Google Patents
Method for preparing nitride/carbon nano tube-graphene ternary complex Download PDFInfo
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- CN103977841A CN103977841A CN201410244703.9A CN201410244703A CN103977841A CN 103977841 A CN103977841 A CN 103977841A CN 201410244703 A CN201410244703 A CN 201410244703A CN 103977841 A CN103977841 A CN 103977841A
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Abstract
The invention discloses a method for preparing a nitride/carbon nano tube-graphene ternary complex, and relates to a preparation method for a graphene composite material, which aims to solve the problem of low catalysis activity of a catalyst after a carrier obtained by the conventional method is loaded with Pt. The preparation method comprises the steps of 1. preparing a graphite oxide solution and a polyethyleneimine solution; 2. adding the polyethyleneimine solution into the graphite oxide solution, dispersing collected solid-phase substances into water to obtain a modified graphite oxide solution; 3. adding a carbon nano tube aqueous solution into the modified graphite oxide solution, and adding polyacid or polyoxometalate to obtain a reaction suspension; 4. performing hydrothermal treatment on the reaction suspension to obtain a composite material; 5. putting the composite material into a muffle furnace for calcining; and 6. nitriding by putting the composite material into a tubular furnace for. The carbon nano tube in the ternary complex is well combined with graphite oxide; tungsten nitride on a composite carrier is high in dispersion property, and the catalysis activity and the stability of Pt are greatly improved.
Description
Technical field
The present invention relates to a kind of preparation method of graphene composite material.
Background technology
Nano composite material is the study hotspot of present material science.Composite not only has the independent character of its each part, the more important thing is interaction and impact between component, can cause complex to have new application performance.The synthetic new composite of design has great importance.
Transition metal nitride, because it has the characteristic such as stability, anti-CO gassing in " eka-platinium ", acid-alkali medium, is widely used in catalytic hydrogenation, dehydrogenation, isomerization, the fields such as fuel cell.Its application performance and its size, dispersiveness have substantial connection.For the performance that makes nitride is fully played, must be loaded on carrier.Electric conductivity, the form etc. of carrier has a great impact the application performance of resulting complex.Material with carbon element, such as Graphene and CNT have good physical and chemical performance, can serve as the matrix that builds nano complex.By compound to graphene oxide and nitride, can in certain scope, improve the application performance of nitride.But the electric conductivity of graphene oxide is poor, and easily assemble, introduce the good component of another electric conductivity very necessary.Compared with graphene oxide, the electric conductivity that CNT has had.Meanwhile, both are carbonaceous material, are beneficial to both combinations.
Meanwhile, the size of particulate and uniformity are very important factors that affects its catalytic performance, and little size and the distribution of homogeneous are very necessary for the performance that improves material.Heteropoly acid is the discrete polyanionic metal oxygen cluster of a class, because heteropoly acid has various types of molecular structures, approaches the size of nanometer, is the quality raw materials of preparation small size nitride.
Summary of the invention
The present invention seeks in order to solve the active low problem of catalyst after the carrier loaded Pt that existing preparation method obtains, and a kind of method of preparing nitride/CNT-Graphene ternary complex is provided.
The method that the present invention prepares nitride/CNT-Graphene ternary complex follows these steps to realize:
One, graphite oxide is distributed in deionized water, obtains graphite oxide solution, polymine is distributed in deionized water, obtain polyethyleneimine: amine aqueous solution;
Two, be 1:(1～10 by the mass ratio of polymine in graphite oxide in graphite oxide solution and polyethyleneimine: amine aqueous solution) polyethyleneimine: amine aqueous solution is joined in graphite oxide solution and stirred, filter and collect solid formation, after washing, be distributed to again the graphite oxide solution that obtains modification in deionized water;
Three, by the carbon nanotube dispersed of functionalization in deionized water, obtain carbon nano-tube aqueous solutions, carbon nano-tube aqueous solutions is joined in the graphite oxide solution of modification and mix, then add polyacid or multi-acid salt to stir 12～24 hours with the speed of 400～2000rpm, obtain reacting suspension;
Four, reaction suspension step 3 being obtained is transferred to hydrothermal treatment consists in teflon-lined water heating kettle, and suction filtration is collected solid formation, obtains composite after oven dry;
Five, composite step 4 being obtained is put into Muffle furnace and is calcined 2～8 hours with the temperature of 200～350 DEG C, obtains the complex after calcining;
Six, the complex after calcining is put into tube furnace again and pass into ammonia and carry out nitrogen treatment, then naturally cooling with stove, obtain nitride/CNT-Graphene ternary complex.
The method that the present invention is based on assembling is prepared nitride/CNT-Graphene ternary complex, tungsten nitride/CNT-Graphene the ternary complex obtaining have between component in conjunction with closely, the easily advantage such as regulation and control of the little and component of nitride size, apply its carrier as Pt metal, significantly promote catalytic activity and the stability of Pt, reduced the consumption of Pt.This nitride/CNT-Graphene ternary complex is 702.4mAmg as the mass ratio activity of the catalyst of carrier loaded Pt
-1 pt, be business Pt/C activity (184.5mA mg
-1 pt) 3.81 times, and when through the stability test of 15000s, residual current density is 29.13mA m
g-1
pt, but business Pt/C residual current density is only 0.85mA mg
-1 pt, illustrate that this ternary complex is better than business Pt/C as catalyst activity and the stability of carrier loaded Pt, for fuel cell commercialization from now on lays the foundation.
The present invention also comprises following beneficial effect in sum:
1, the coupling agent polymine that the present invention selects is a kind of organic macromolecule with higher cationic charge density, is beneficial to effective assembling of function ingredients and obtains the complex material of excellent performance;
2, the source metal of selecting is polyacid, has that size is little, a good stability, the various advantages such as regulation and control that are easy to of structure, is conducive to regulate and control the composition of nitride in complex, and then is easy to realize the regulation and control of complex application performance;
3, the present invention can realize by changing the parameters such as heat treatment time, material ratio the control of complex structure.
Brief description of the drawings
Fig. 1 is the transmission electron microscope figure of tungsten nitride/CNT-Graphene ternary complex of obtaining of embodiment mono-;
Fig. 2 is the infrared conversion collection of illustrative plates of the Fourier of tungsten nitride;
Fig. 3 is tungsten nitride particle diameter distribution map;
Fig. 4 is the cyclic voltammetry curve of three kinds of different catalysts, wherein 1-platinum-tungsten nitride/CNT-graphen catalyst, 2-platinum/carbon nano-tube-graphen catalyst, 3-business Pt/C catalyst;
Fig. 5 is ampere curve that clocks of three kinds of different catalysts, wherein 1-platinum-tungsten nitride/CNT-graphen catalyst, 2-platinum/carbon nano-tube-graphen catalyst, 3-business Pt/C catalyst.
Detailed description of the invention
Detailed description of the invention one: the method for present embodiment nitride/CNT-Graphene ternary complex
One, graphite oxide is distributed in deionized water, obtains graphite oxide solution, polymine is distributed in deionized water, obtain polyethyleneimine: amine aqueous solution;
Two, be 1:(1～10 by the mass ratio of polymine in graphite oxide in graphite oxide solution and polyethyleneimine: amine aqueous solution) polyethyleneimine: amine aqueous solution is joined in graphite oxide solution and stirred, filter and collect solid formation, after washing, be distributed to again the graphite oxide solution that obtains modification in deionized water;
Three, by the carbon nanotube dispersed of functionalization in deionized water, obtain carbon nano-tube aqueous solutions, carbon nano-tube aqueous solutions is joined in the graphite oxide solution of modification and mix, then add polyacid or multi-acid salt to stir 12～24 hours with the speed of 400～2000rpm, obtain reacting suspension;
Four, reaction suspension step 3 being obtained is transferred to hydrothermal treatment consists in teflon-lined water heating kettle, and suction filtration is collected solid formation, obtains composite after oven dry;
Five, composite step 4 being obtained is put into Muffle furnace and is calcined 2～8 hours with the temperature of 200～350 DEG C, obtains the complex after calcining;
Six, the complex after calcining is put into tube furnace again and pass into ammonia and carry out nitrogen treatment, then naturally cooling with stove, obtain nitride/CNT-Graphene ternary complex.
Nitride/CNT-Graphene ternary complex that present embodiment prepares is by (mass ratio is 1:2) on the Graphene of the carbon nanotube loaded polyethylene imine beautify of a certain amount of functionalization,, then will load on taking silico-tungstic acid as the tungsten nitride in tungsten source on the complex carrier of CNT and Graphene (mass ratio is as 1:1) then.
The nitride of present embodiment gained and graphene oxide and carbon nanometer pipe ternary composite, have nitride good dispersion, and size is little, and carbon pipe and the advantage such as Graphene contacts, show the good catalytic performance that helps.Taking it as carrier material, support catalytic activity and the stability that can significantly strengthen Pt after Pt.
Detailed description of the invention two: what present embodiment was different from detailed description of the invention one is that step 1 is 1:(100～400 in mass ratio) graphite oxide is distributed in deionized water, obtain graphite oxide solution.Other step and parameter are identical with detailed description of the invention one.
Detailed description of the invention three: what present embodiment was different from detailed description of the invention one is that step 1 is 1:(50～200 in mass ratio) polymine is distributed in deionized water, obtain polyethyleneimine: amine aqueous solution.Other step and parameter are identical with detailed description of the invention one.
Detailed description of the invention four: what present embodiment was different from one of detailed description of the invention one to three is that the mixing speed described in step 2 is 400～2000rpm, and mixing time is 4～36 hours.Other step and parameter are identical with one of detailed description of the invention one to three.
Detailed description of the invention five: the mass ratio of the graphite oxide in the CNT in the carbon nano-tube aqueous solutions of the functionalization described in step 3 that what present embodiment was different from one of detailed description of the invention one to four is and the graphite oxide solution of modification is 1:(0.25～4).Other step and parameter are identical with one of detailed description of the invention one to four.
Detailed description of the invention six: what present embodiment was different from one of detailed description of the invention one to five is that the polyacid described in step 3 is silico-tungstic acid, silicomolybdic acid, phosphotungstic acid or phosphomolybdic acid; Described multi-acid salt is silicotungstic sodium, silicomolybdic acid sodium, sodium phosphotungstate or sodium phosphomolybdate.Other step and parameter are identical with one of detailed description of the invention one to five.
Detailed description of the invention seven: what present embodiment was different from one of detailed description of the invention one to six is that step 3 is 1:(0.25～3 by the total mass ratio of polyacid and graphite oxide and CNT) add polyacid.Other step and parameter are identical with one of detailed description of the invention one to six.
Detailed description of the invention eight: what present embodiment was different from one of detailed description of the invention one to seven is that step 3 is 1:(0.25～3 by the total mass ratio of multi-acid salt and graphite oxide and CNT) add multi-acid salt.Other step and parameter are identical with one of detailed description of the invention one to seven.
Detailed description of the invention nine: described in step 4 that what present embodiment was different from one of detailed description of the invention one to eight is, the temperature of hydrothermal treatment consists is 160～200 DEG C, and the hydro-thermal time is 8～24 hours.Other step and parameter are identical with one of detailed description of the invention one to eight.
Detailed description of the invention ten: the temperature of what present embodiment was different from one of detailed description of the invention one to nine is step 6 nitrogen treatment is 600～1000 DEG C, and nitridation time is 1～4 hour.Other step and parameter are identical with one of detailed description of the invention one to nine.
Embodiment mono-: the method that the present embodiment is prepared nitride/CNT-Graphene ternary complex follows these steps to realize:
One, 0.08g graphite oxide standby Hummer legal system is distributed in 20ml deionized water, obtains graphite oxide solution, 0.08g polymine is distributed in 20ml deionized water, obtain polyethyleneimine: amine aqueous solution;
Two, be that 1:1 joins polyethyleneimine: amine aqueous solution in graphite oxide solution and stirs by the mass ratio of polymine in graphite oxide in graphite oxide solution and polyethyleneimine: amine aqueous solution, filter and collect solid formation, after washing, be distributed to again the graphite oxide solution that obtains modification in the ion that anhydrates;
Three, be distributed in deionized water ultrasonic the CNT of functionalization, obtain carbon nano-tube aqueous solutions, be that 1:2 joins carbon nano-tube aqueous solutions in the graphite oxide solution of modification and mixes by CNT and the mass ratio of graphite oxide, then be that 1:1 adds silico-tungstic acid by the total mass ratio of silico-tungstic acid and graphite oxide and CNT, speed with 500rpm stirs 24 hours, obtains reacting suspension;
Four, reaction suspension step 3 being obtained transfer to in teflon-lined water heating kettle with 180 DEG C of hydro-thermal 10h, suction filtration is collected solid formation, then drying obtains composite;
Five, composite step 4 being obtained is put into Muffle furnace and is calcined 5 hours with the temperature of 300 DEG C, obtains the complex after calcining;
Six, the complex after calcining is put into tube furnace again and pass into ammonia with 800 DEG C of nitrogenize 3h, then naturally cooling with stove, obtain tungsten nitride/CNT-Graphene ternary complex.
The CNT of the functionalization described in the present embodiment step 3 is that original CNT is placed in round-bottomed flask, in mass ratio for 3:1 adds sulfuric acid and nitric acid, after heating reflux reaction, obtains the CNT after acidifying through washing, oven dry.Then the CNT after the acidifying of 0.04g is dissolved in 20ml water, can obtains the carbon nano-tube aqueous solutions of functionalization.
The transmission electron microscope figure of tungsten nitride/graphene oxide-carbon nanometer pipe ternary composite prepared by the present embodiment as shown in Figure 1, as can be seen from the figure, CNT is combined with graphene oxide well, and on Graphene and CNT complex carrier, tungsten nitride presents good dispersiveness simultaneously.Fig. 1 shown tungsten nitride/CNT-Graphene ternary complex transmission electron micrograph, therefrom can find out, CNT is combined with Graphene well, simultaneously on Graphene and CNT complex carrier, tungsten nitride presents good dispersiveness.
Fig. 2 has shown the infrared conversion collection of illustrative plates of the Fourier of tungsten nitride, and the spacing of lattice that can calculate tungsten nitride from figure is that 0.25nm is tungsten nitride (100) crystal face.
Fig. 3 has shown tungsten nitride particle diameter distribution map, as can be seen from the figure the particle size of tungsten nitride is about 3nm, has proved to form the tungsten nitride/graphene-carbon nano tube composite material of small size, high dispersive.
Fig. 4 has shown that complex carries the cyclic voltammetry curve of the different catalysts after Pt, test process is that tungsten nitride/CNT of 100mg-Graphene ternary complex is dissolved in to the platinum acid chloride solution that then adds 5.4ml7.723mM in 23ml water, after ultrasonic 30min, adding concentration is that to regulate PH be 8 for 20% NaOH, and then add 0.039g sodium borohydride, stir after 2～3h, centrifugal, dryly can obtain platinum-tungsten nitride/CNT-graphen catalyst.In figure, curve 1 is the performance curve of platinum-tungsten nitride/CNT-graphen catalyst catalysis methanol oxidation, and curve 2 and curve 3 are control sample.Wherein shown in curve 2 for directly Pt being loaded on to the catalytic activity that there is no the catalyst of tungsten nitride on CNT and Graphene complex carrier, the catalytic activity that curve 3 is business Pt/C (the Johnson Matthey company) catalyst bought.This tungsten/CNT-Graphene ternary complex is 702.4mAmg as the mass ratio activity of the catalyst of carrier loaded Pt
-1 pt, be respectively platinum/carbon nano-tube-graphen catalyst (288.3mA mg
-1 pt) and business Pt/C activity (184.5mAmg
-1 pt) 2.44 times and 3.81 times.Illustrate that small size, high dispersive tungsten nitride just play an important role and ternary complex has optimum catalytic activity as the catalyst of carrier loaded Pt to catalytic activity.
Fig. 5 has shown ampere curve that clocks of different catalysts, and as can be seen from the figure, in the time of the stability test through 15000s, the residual current density of platinum-tungsten nitride/CNT-graphen catalyst is 29.13mA mg
-1 pt, but platinum/carbon nano-tube-graphen catalyst and business Pt/C residual current density are only 3.67mA mg
-1 ptand 0.85mAmg
-1 pt, illustrate that this ternary complex has the highest stability as carrier loaded Pt.
Embodiment bis-: the method that the present embodiment is prepared nitride/CNT-Graphene ternary complex follows these steps to realize:
One, 0.08g graphite oxide standby Hummer legal system is distributed in 20ml deionized water, obtains graphite oxide solution, 0.04g polymine is distributed in 10ml deionized water, obtain polyethyleneimine: amine aqueous solution;
Two, be that 1:1 joins polyethyleneimine: amine aqueous solution in graphite oxide solution and stirs by the mass ratio of polymine in graphite oxide in graphite oxide solution and polyethyleneimine: amine aqueous solution, filter and collect solid formation, after washing, obtain the graphite oxide solution of modifying;
Three, be distributed in deionized water ultrasonic the CNT after acidifying, obtain carbon nano-tube aqueous solutions, be that 1:2 joins carbon nano-tube aqueous solutions in the graphite oxide solution of modification and mixes by CNT and the mass ratio of graphite oxide, then be that 1:1 adds phosphomolybdic acid by the total mass ratio of phosphomolybdic acid and graphite oxide and CNT, speed with 500rpm stirs 24 hours, obtains reacting suspension;
Four, reaction suspension step 3 being obtained transfer to in teflon-lined water heating kettle with 180 DEG C of hydro-thermal 10h, suction filtration is collected solid formation, then drying obtains composite;
Five, composite step 4 being obtained is put into Muffle furnace and is calcined 5 hours with the temperature of 300 DEG C, obtains the complex after calcining;
Six, the complex after calcining is put into tube furnace again and pass into ammonia with 800 DEG C of nitrogenize 3h, then naturally cooling with stove, obtain molybdenum nitride/CNT-Graphene ternary complex.
The present invention has prepared nitride/CNT-Graphene tri compound body method by a kind of effective method, tungsten nitride/graphene-carbon nano tube the nano composite material obtaining, there is CNT and be combined with Graphene closely, the feature such as nitride good dispersion, size on CNT and Graphene is little.The ternary complex that this method obtains, can be used as the carrier of Pt metal, significantly promoted catalytic activity and the stability of Pt, reduced the consumption of Pt, thereby reduce fuel fuel battery anode catalyst cost, provide a kind of effective way for realizing fuel cell commercialization.
Claims (9)
1. prepare a method for nitride/CNT-Graphene ternary complex, it is characterized in that following these steps to realizing:
One, graphite oxide is distributed in deionized water, obtains graphite oxide solution, polymine is distributed in deionized water, obtain polyethyleneimine: amine aqueous solution;
Two, be 1:(1～10 by the mass ratio of polymine in graphite oxide in graphite oxide solution and polyethyleneimine: amine aqueous solution) polyethyleneimine: amine aqueous solution is joined in graphite oxide solution and stirred, filter and collect solid formation, after washing, be distributed to again the graphite oxide solution that obtains modification in the aqueous solution;
Three, by the carbon nanotube dispersed of functionalization in deionized water, obtain carbon nano-tube aqueous solutions, carbon nano-tube aqueous solutions is joined in the graphite oxide solution of modification and mix, then add polyacid or multi-acid salt to stir 12～24 hours with the speed of 400～2000rpm, obtain reacting suspension;
Four, reaction suspension step 3 being obtained is transferred to hydrothermal treatment consists in teflon-lined water heating kettle, and suction filtration is collected solid formation, obtains composite after oven dry;
Five, composite step 4 being obtained is put into Muffle furnace and is calcined 2～8 hours with the temperature of 200～350 DEG C, obtains the complex after calcining;
Six, the complex after calcining is put into tube furnace again and pass into ammonia and carry out nitrogen treatment, then naturally cooling with stove, obtain nitride/CNT-Graphene ternary complex.
2. a kind of method of preparing nitride/CNT-Graphene ternary complex according to claim 1, it is characterized in that step 1 is 1:(100～400 in mass ratio) graphite oxide is distributed in deionized water, obtain graphite oxide solution.
3. a kind of method of preparing nitride/CNT-Graphene ternary complex according to claim 1, it is characterized in that step 1 is 1:(50～200 in mass ratio) polymine is distributed in deionized water, obtain polyethyleneimine: amine aqueous solution.
4. a kind of method of preparing nitride/CNT-Graphene ternary complex according to claim 1, is characterized in that the mixing speed described in step 2 is 400～2000rpm, and mixing time is 4～36 hours.
5. a kind of method of preparing nitride/CNT-Graphene ternary complex according to claim 1, is characterized in that the mass ratio of the graphite oxide in the graphite oxide solution of CNT in the carbon nano-tube aqueous solutions of the functionalization described in step 3 and modification is 1:(0.25～4).
6. a kind of method of preparing nitride/CNT-Graphene ternary complex according to claim 1, is characterized in that the polyacid described in step 3 is silico-tungstic acid, silicomolybdic acid, phosphotungstic acid or phosphomolybdic acid; Described multi-acid salt is silicotungstic sodium, silicomolybdic acid sodium, sodium phosphotungstate or sodium phosphomolybdate.
7. a kind of method of preparing nitride/CNT-Graphene ternary complex according to claim 1, is characterized in that step 3 is 1:(0.25～3 by the total mass ratio of polyacid and graphite oxide and CNT) add polyacid.
8. a kind of method of preparing nitride/CNT-Graphene ternary complex according to claim 1, is characterized in that the temperature of hydrothermal treatment consists is 160～200 DEG C described in step 4, and the hydro-thermal time is 8～24 hours.
9. a kind of method of preparing nitride/CNT-Graphene ternary complex according to claim 1, the temperature that it is characterized in that step 6 nitrogen treatment is 600～1000 DEG C, nitridation time is 1～4 hour.
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| CN108786887A (en) * | 2018-06-20 | 2018-11-13 | 上海电力学院 | A kind of catalyst and preparation method for photocatalytic water splitting hydrogen manufacturing |
| CN111659430A (en) * | 2020-05-07 | 2020-09-15 | 黑龙江大学 | Preparation method of low-platinum composite material for hydrogen production by acidic electrolyzed water |
| CN112086651A (en) * | 2020-09-21 | 2020-12-15 | 哈尔滨理工大学 | Synthetic method of WN-rGO nano particles and microbial fuel cell constructed by same |
| CN114156593A (en) * | 2021-11-30 | 2022-03-08 | 电子科技大学 | Diaphragm functional material for improving performance of lithium metal battery, preparation and application |
| CN114156593B (en) * | 2021-11-30 | 2022-08-02 | 电子科技大学 | Diaphragm functional material for improving performance of lithium metal battery, preparation and application |
| CN114447351A (en) * | 2022-01-19 | 2022-05-06 | 黑龙江大学 | Pt @ WN/rGO catalyst for resisting CO poisoning of fuel cell |
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