CN102500360B - Method for preparing mesoporous tungsten oxide/carbon composite conductive materials - Google Patents
Method for preparing mesoporous tungsten oxide/carbon composite conductive materials Download PDFInfo
- Publication number
- CN102500360B CN102500360B CN2011103598579A CN201110359857A CN102500360B CN 102500360 B CN102500360 B CN 102500360B CN 2011103598579 A CN2011103598579 A CN 2011103598579A CN 201110359857 A CN201110359857 A CN 201110359857A CN 102500360 B CN102500360 B CN 102500360B
- Authority
- CN
- China
- Prior art keywords
- mesoporous
- preparation
- conducting material
- composite conducting
- tungsten
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
Landscapes
- Catalysts (AREA)
- Silicates, Zeolites, And Molecular Sieves (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for preparing mesoporous tungsten oxide/carbon composite conductive materials. The method comprises the following steps: taking mesoporous silicon dioxide that surface active agent is not removed as a template, tungsten salt as a tungsten source, and the surface active agent as a silicon source, and obtaining mesoporous WO3/C composite conductive materials throguh heat treatment in-situ carbonization under the protection of inert gas. According to the method provided by the invention, surface active agent is reutilized felicitously during the synthesis of mesoporous silica template, and the surface active agent is taken as the silicon source and then carbonized in situ through heat treatment under the protection of inert atmosphere, and is combined together with synchronogenically formed WO3.
Description
Technical field
The present invention relates to technical field of inorganic nanometer material, be specifically related to a kind of mesoporous WO
3The preparation method of/C composite conducting material.
Background technology
Tungsten oxide (WO
3) be a kind of important transition metal oxide, have performances such as excellent light, heat, electricity owing to it and be widely used in association areas such as photochemical catalyst, gas sensor and smart window.Particularly, WO
3Have special chemical property, can interact with hydrogen ion in the sour environment of low temperature Proton Exchange Membrane Fuel Cells and DMFC as electrode material forms a kind of hydrogen tungsten bronze type (H
XWO
3) compound, promote fuel oxidation and hydrionic releases such as anode hydrogen and methyl alcohol, thereby improve the performance of battery.
Mesoporous material since its unique high-specific surface area, regular mesopore orbit and controlled aperture size be widely used in field of nanometer material technology.In recent years, be that hard template prepares mesoporous inorganic metal oxide (for example tungsten oxide, manganese oxide, cobalt oxide, cerium oxide etc.) with the mesoporous silicon oxide, further expanded the range of application of mesoporous material.
Mesoporous WO
3Material has high specific area, regular pore passage structure and regulatable aperture size, has improved its catalytic activity greatly.The synthetic mesoporous WO with crystallization hole wall of hard template method preparation that particularly grew up in recent years
3Material not only has high electrochemical catalysis activity, also has high electro-catalysis stability, has broad application prospects in fields such as electrochemical catalysis.。
Yet, WO
3Be a kind of semiconducting compound, as electrode catalytic materials the time, its electric conductivity awaits improving, with the transfer of promotion electronics and the output of battery current.Bibliographical information is arranged, with WO
3Mode and precious metals pt with chemical deposition are carried on the activity carbon carrier altogether, can improve the catalytic activity (J. Chem. Soc., Faraday Trans. 1994,90,3089) of this electrode material.The applicant then attempts directly with mesoporous WO
3Material and conductive carbon black mix in the ultrasonic mode of machinery, form a kind of mesoporous WO
3/ C composite is to improve mesoporous WO
3Electric conductivity, thereby improved mesoporous WO greatly
3Electro catalytic activity (J. Mater. Chem., 2008,18,575 – 3580, CN 101181679A).But the mechanical ultrasonic mixing of above-mentioned usefulness improves mesoporous WO
3The method of electric conductivity is kept away the uneven distribution situation of unavoidable carbon, to such an extent as to influence mesoporous WO
3Catalytic activity.
Therefore, develop a kind of new preparation method, make conductive carbon black evenly be compound in mesoporous WO
3Prepare the WO with high conductivity and crystallization mesoporous wall structure in the duct
3/ C composite simultaneously can be regulated and control the carbon content of products obtained therefrom and for mesoporous WO
3Performance and the application of catalytic performance advantage have crucial effects.
Summary of the invention
The problems referred to above in the face of the prior art existence, the inventor recognizes when utilizing the mesoporous silicon dioxide hard template method to prepare mesoporous tungsten oxide, surfactant in the silica template duct (containing the carbon chain polymerization thing) can be used as carbon source, namely, can utilize surfactant original position carbonization in the silica template duct to introduce carbon in mesoporous tungsten oxide material.
At this, the invention provides a kind of mesoporous WO
3The preparation method of/C composite conducting material; it is characterized in that; the mesoporous silicon oxide that described method comprises not removing surfactant is template, is the tungsten source, is carbon source with described surfactant with tungsten salt, under inert gas shielding through the carbonization of heat treatment original position to obtain described mesoporous WO
3/ C composite conducting material.
Surfactant when method of the present invention has reused the synthesizing mesoporous silicon dioxide mould material dexterously, with its as carbon source under inert atmosphere protection after Overheating Treatment by the original position carbonization, with the WO that forms simultaneously
3Original position is combined with each other, thereby has obtained the compound mesoporous WO of carbon original position
3/ C composite conducting material.The mesoporous WO that obtains like this
3In/C the composite conducting material, carbon can be dispersed in mesoporous WO
3The duct in, and this method also can avoid mesoporous silicon oxide in the step that the high-temperature calcination of removal of surfactant will be handled when the mould material, changing waste into valuable, the power saving that saves time, energy savings.
In the present invention, can control described heat treatment period to regulate and control described mesoporous WO
3The carbon content of/C composite conducting material and then regulate and control described mesoporous WO
3It is electrical that/C composite conducting material is led.Can be worth the adjustable mesoporous WO of carbon content and electric conductivity like this
3/ C composite conducting material.
Described heat treated temperature can be 350～500 ℃, and described heat treatment period can be 1～8 hour, and preferred 2～6 hours, more preferably 2～4 hours.Can obtain having the mesoporous WO of suitable carbon content and conductance like this
3/ C composite conducting material.The mesoporous WO that makes of the present invention for example
3The carbon content of/C composite conducting material can be 4～30wt%, is preferably 5～20wt%, and this moment, its corresponding conductance was 5.0 * 10
-3～7.8 * 10
-2Ω
-1.m
-1, more preferably 5～13wt%, this moment, its corresponding conductance was 5.0 * 10
-3～1.2 * 10
-2Ω
-1.m
-1
In the present invention, can described tungsten salt be poured in the mesopore orbit of described template by the mode of vacuum pouring (preferred vacuum nano cast).Like this, tungsten source presoma fully can be filled in the duct of mesoporous silicon oxide mould material, thereby reduced the few and inadequate factor of tungsten source presoma groundwater increment that the existence because of surfactant causes, improved the charging efficiency of tungsten source in mesopore silicon oxide template duct.
Again, described tungsten salt can adopt the tungsten salt that dissolves in ethanol, for example phosphotungstic acid.Like this, be easy to enter the mesopore orbit of silica template and adsorbed the meso-hole structure WO that is beneficial to by mesoporous material owing to ethanol
3/ C's is compound.
Method of the present invention also can comprise with strong acid or strong alkali aqueous solution (preferred hydrofluoric acid aqueous solution) removes described template.Like this, can make things convenient for, cheap mode removes template.
Synthesis technique of the present invention is simple, output is high, cost is low, efficient is high, easy suitability for industrialized production; Make mesoporous WO
3Carbon is evenly distributed in/C the composite conducting material, and meso-hole structure is regular, and carbon content and conductance are adjustable, can be used as the anode catalyst that eelctro-catalyst is applied to low-temperature fuel cell; The raising of its electric conductivity can greatly improve mesoporous WO
3Electro catalytic activity.
Description of drawings
Fig. 1 illustrates the mesoporous WO of illustrated embodiments of the invention preparation
3The wide-angle XRD diffraction pattern of/C composite conducting material;
Fig. 2 illustrates the mesoporous WO of illustrated embodiments of the invention preparation
3The little angle XRD diffraction pattern of/C composite conducting material;
Fig. 3～5 illustrate the mesoporous WO of illustrated embodiments of the invention preparation
3The FE-SEM photo of/C composite conducting material;
Fig. 6～9 illustrate the mesoporous WO of illustrated embodiments of the invention preparation
3The TEM photo of/C composite conducting material.
The specific embodiment
With reference to Figure of description, and further specify the present invention with the following embodiments, should be understood that Figure of description and following embodiment only are used for explanation the present invention, and unrestricted the present invention.
The present invention adopts the silicon dioxide hard template replica method of not removing surfactant to prepare mesoporous WO
3Material; with tungsten salt; preferably dissolve in the tungsten salt of ethanol; for example phosphotungstic acid is the tungsten source; adopt the method for vacuum pouring (preferred vacuum nano cast) the tungsten source to be poured in the mesopore orbit of silica template; and utilize surfactant in the mesopore orbit of silicon dioxide hard template as carbon source, under inert gas shielding, be combined with each other through the mesoporous tungsten oxide of heat treatment original position carbonization with carbon and formation, obtain carbon and be evenly distributed on mesoporous WO in the mesopore orbit
3/ C composite conducting material.
At first, according to document (Chem. Commun., 2003,35,2136; Science, 1998,279,548-552.) preparation mesopore silicon oxide mould material (SBA-15 of for example KIT-6 of three-dimensional cubic pore passage structure, or two-dimentional hexagonal structure) is removed surfactant, for example P without calcination processing then
123(polyoxypropylene-polyoxyethylene-polyoxypropylene) is directly as the following mesoporous WO of preparation
3The mesoporous silicon dioxide hard template of/C composite conducting material.
Then, with the mesoporous SiO of above-mentioned preparation
2Material places closed container, with vavuum pump it is vacuumized, and makes the mesopore orbit of silica mould material be in vacuum state; With the tungsten source, the tungsten salt (as phosphotungstic acid etc.) that preferably is soluble in absolute ethyl alcohol is dissolved in the absolute ethyl alcohol, it slowly is added drop-wise in the mesopore silicon oxide mould material that is in vacuum state then, tungsten salt alcoholic solution under atmospheric pressure is perfused in the SiO that is in vacuum state rapidly
2Mesopore orbit in, continue to vacuumize making ethanol volatilization in 10～50 minutes, and make tungsten salt precursor thing be poured into mesoporous SiO fully
2The duct in.
Then, with the mesoporous SiO that is mounted with tungsten salt of above-mentioned preparation
2Compound oven dry, for example in 40～120 ℃ of baking ovens dry 30～120 minutes.The mesoporous SiO that is loaded with tungsten salt after will drying then
2Compound places inert gas (as N
2, He, Ar, preferred N
2) protection under heat-treat so that the tungsten oxide original position of carbon and formation is compound.Wherein can regulate and control compound carbon content and then the control electrical conductivity of original position in the tungsten oxide mesopore orbit by the control heat treatment period.Experiment finds that if carbonization time is too short, then the presoma thermal decomposition of tungsten source is insufficient, is unfavorable for meso-hole structure WO
3Compound with carbon; Otherwise, if carbonization time is long, the carbon that original position forms will with WO
3The WO that reacts and cause forming
3By partial reduction.Find that after deliberation the proper heat treatment time (carbonization time) is 1～8 hour, preferred 2～6 hours, optimum carbonization time then was 2～4 hours, and at this moment, the presoma thermal decomposition of tungsten source is abundant, and simultaneously, the carbon original position of formation is incorporated into WO
3Mesopore orbit in.
At last, adopt strong acid or strong alkali aqueous solution, for example hydrofluoric acid aqueous solution handle above-mentioned preparation powder to remove silica template, separate then, wash and drying.
Mesoporous WO according to above technological process preparation
3The specific area of/C composite conducting material can be 100～130 m
2/ g, carbon content can be 4 ~ 30wt %, and electrical conductivity can be 1.8 * 10
-5～7.8 * 10
-2Ω
-1.m
-1Fig. 1 and Fig. 2 illustrate the mesoporous WO of the inventive method preparation respectively
3The wide-angle XRD diffraction pattern of/C composite conducting material and little angle XRD diffraction pattern, wherein a line is 6 hours sample of heat treatment, the b line is 4 hours sample of heat treatment, the c line is 2 hours sample of heat treatment, as can be seen from the figure, in the proper heat treatment time range, suitably increase heat treatment time and can increase the carbon content that makes product.Fig. 3～5 illustrate the mesoporous WO of the inventive method preparation
3The FE-SEM photo of/C composite conducting material; Fig. 6～9 illustrate the mesoporous WO that the present invention shows the method preparation
3The TEM photo of/C composite conducting material.As can be seen from the figure, in the proper heat treatment time range, suitably the shortening heat processing time can alleviate the carbonizing degree of surfactant, and the tablet of gained shows the comparatively mesopore orbit structure of rule.
The invention provides a kind of simple, eco-friendly method prepare have good dispersion, carbon content and the adjustable mesoporous WO of conductance
3/ C composite conducting material.
Further exemplify embodiment below to describe example preparation technology of the present invention in detail.Should be understood that following embodiment is for the present invention is described better, and unrestricted the present invention.Although adopting the KIT-6 and the SBA-15 that do not remove surfactant in the following embodiments is template, should be understood that other any suitable silica templates of not removing surfactant also are suitable for.Although example phosphotungstic acid be the tungsten source, also be suitable for yet also should understand other tungsten salt that are soluble in ethanol commonly used, for example tungsten hexachloride.In addition, although only example remove template with hydrofluoric acid, yet should understand other strong acid or strong alkali aqueous solution also is suitable for, for example, sodium hydrate aqueous solution etc.
Embodiment 1
At first prepare the mesopore silicon oxide (KIT-6) of three-dimensional cubic meso-hole structure according to document, do not remove the surfactant P in the duct
123, directly used as mould material (to call the KIT-6 mould material in the following text).Get KIT-6 mould material 0.2 g and place airtight there-necked flask, vacuumize, make in the mesopore orbit of mould material to be in vacuum state.Get phosphotungstic acid 0.4 g and evenly be dissolved in the 5 mL absolute ethyl alcohols, then it slowly is added drop-wise in the there-necked flask, the alcoholic solution of tungsten salt is poured into rapidly in the mesopore orbit of mould material under atmospheric effect.Continue to vacuumize 30 min, make the ethanolic solution volatilization that tungsten salt precursor body fully is poured in the mesopore orbit of KIT-6 mould material.Then load is had the silica compound of tungsten salt to place 60 ℃ of baking ovens oven dry 30 min, resulting powder is put into the blanket of nitrogen stove, be raised to 400 ℃ and be incubated 2 h with the speed among the 2 ℃/min, whole carbonisation carries out under nitrogen atmosphere.The gained powder separates then then through 2 M HF solution removal templates, and washing and drying have just obtained target product.Prepared mesoporous WO
3Shown in c and the c among Fig. 2 among Fig. 1, its specific area is: 108 m respectively for the wide-angle of/C composite conducting material and little angle XRD diffraction pattern
2/ g (seeing the following form 1), its carbon content is that 5.6wt%(sees the following form 2), conductance is: 5.0 * 10
-3Ω
-1.m
-1(seeing the following form 2).
Embodiment 2
Get KIT-6 mould material 0.5 g and place airtight there-necked flask, vacuumize, make in the mesopore orbit of mould material to be in vacuum state.Get phosphotungstic acid 1.2 g and evenly be dissolved in the 10 ml absolute ethyl alcohols, then it slowly is added drop-wise in the there-necked flask, the alcoholic solution of tungsten salt is poured into rapidly in the mesopore orbit of mould material under atmospheric effect.Continue to vacuumize 30 min, make the ethanolic solution volatilization that tungsten salt precursor body fully is poured in the mesopore orbit of KIT-6 mould material.Then load there is the silica compound of tungsten salt to place 100 ℃ of baking oven oven dry 60 min, resulting powder is put into the blanket of nitrogen stove with the powder of gained, be raised to 400 ℃ and be incubated 4 h with the speed among the 2 ℃/min, whole carbonisation carries out under nitrogen atmosphere, and other are operated with embodiment 1.Shown in b and the b among Fig. 2 among Fig. 1, its specific area is: 110 m respectively for the wide-angle of resulting target product and little angle XRD diffraction pattern
2/ g (seeing the following form 1), its carbon content is that 13.4wt%(sees the following form 2), conductance is: 1.2 * 10
-2Ω
-1.m
-1(seeing the following form 2).
Embodiment 3
Get KIT-6 mould material 1.0 g and place airtight there-necked flask, vacuumize, make in the mesopore orbit of mould material to be in vacuum state.Get phosphotungstic acid 2.5 g and evenly be dissolved in the 20 ml absolute ethyl alcohols, then it slowly is added drop-wise in the there-necked flask, the alcoholic solution of tungsten salt is poured into rapidly in the mesopore orbit of mould material under atmospheric effect.Continue to vacuumize 30 min, make the ethanolic solution volatilization that tungsten salt precursor body fully is poured in the mesopore orbit of KIT-6 mould material.Then load there is the silica compound of tungsten salt to place 100 ℃ of baking oven oven dry 60 min, resulting powder is put into the blanket of nitrogen stove with the powder of gained, be raised to 450 ℃ and be incubated 6 h with the speed among the 2 ℃/min, whole carbonisation carries out under nitrogen atmosphere, and other are operated with embodiment 1.Shown in a and a among Fig. 2 among Fig. 1, its specific area is: 130 m respectively for the wide-angle of resulting target product and little angle XRD diffraction pattern
2/ g (seeing the following form 1), its carbon content is that 19.1wt%(sees the following form 2), conductance is pore size: 7.8 * 10
-2Ω
-1.m
-1(seeing the following form 2).
Embodiment 4
Get KIT-6 mould material 0.8 g and place airtight there-necked flask, with vacuumizing, make in the mesopore orbit of mould material to be in vacuum state.Get phosphotungstic acid 2.0 g and evenly be dissolved in the 15 ml absolute ethyl alcohols, then it slowly is added drop-wise in the there-necked flask, the alcoholic solution of tungsten salt is poured into rapidly in the mesopore orbit of mould material under atmospheric effect.Continue to vacuumize 30 min, make the ethanolic solution volatilization that tungsten salt precursor body fully is poured in the mesopore orbit of KIT-6 mould material.Then load there is the silica compound of tungsten salt to place 80 ℃ of baking oven oven dry 30 min, resulting powder is put into the blanket of nitrogen stove with the powder of gained, be raised to 500 ℃ and be incubated 6 h with the speed among the 2 ℃/min, whole carbonisation carries out under nitrogen atmosphere, and other are operated with embodiment 1.Resulting mesoporous WO
3The ESEM of/C composite conducting material (FE-SEM) photo shows the comparatively disk shape of rule as shown in Figure 3, and diameter is about 400 nm; Its corresponding transmission electron microscope (TEM) photo is shown in Fig. 6,7, and it is mesoporous appearance about 5 nm that diameter is arranged on the tablet of gained.
Embodiment 5
Get KIT-6 mould material 1.0 g and place airtight there-necked flask, vacuumize, make in the mesopore orbit of mould material to be in vacuum state.Get phosphotungstic acid 2.5 g and evenly be dissolved in the 20 ml absolute ethyl alcohols, then it slowly is added drop-wise in the there-necked flask, the alcoholic solution of tungsten salt is poured into rapidly in the mesopore orbit of mould material under atmospheric effect.Continue to vacuumize 30 min, make the ethanolic solution volatilization that tungsten salt precursor body fully is poured in the mesopore orbit of KIT-6 mould material.After then load being had the silica compound of tungsten salt to place the baking oven oven dry, resulting powder is put into the blanket of nitrogen stove with the powder of gained, in 500 ℃ of insulation 2 h, whole carbonisation carries out under nitrogen atmosphere, and other are operated with embodiment 1.Resultant mesoporous WO
3The stereoscan photograph of/C composite conducting material and transmission electron microscope photo are respectively as Fig. 4 and shown in Figure 8, and as can be seen, suitably the shortening heat processing time can alleviate the carbonizing degree of surfactant, and the tablet of gained shows the comparatively mesopore orbit structure of rule.
Embodiment 6
At first prepare the silica SBA-15 mould material (SBA-15) of two-dimentional hexagonal mesoporous structure according to document, do not remove the surfactant P in the duct
123, directly used as mould material (to call the SBA-15 mould material in the following text).Get SBA-15 mould material 1.0 g and place airtight there-necked flask, vacuumize, make in the mesopore orbit of mould material to be in vacuum state.Get phosphotungstic acid 2.5 g and evenly be dissolved in the 20 ml absolute ethyl alcohols, then it slowly is added drop-wise in the there-necked flask, the alcoholic solution of tungsten salt is poured into rapidly in the mesopore orbit of mould material under atmospheric effect.Continue to vacuumize 30 min, make the ethanolic solution volatilization that tungsten salt precursor body fully is poured in the mesopore orbit of KIT-6 mould material.After then load being had the silica compound of tungsten salt to place the baking oven oven dry, resulting powder is put into the blanket of nitrogen stove with the powder of gained, in 500 ℃ of insulation 2 h, whole carbonisation carries out under nitrogen atmosphere, and other are operated with embodiment 1.Resultant mesoporous WO
3The stereoscan photograph of/C composite conducting material and transmission electron microscope photo be respectively as Fig. 5 and shown in Figure 9, is the conductive mesoporous WO that mould material also can compositing conducting carbon black original position be compound in mesopore orbit with the SBA-15 that does not remove surfactant as can be seen
3/ C composite.
Embodiment 7
Get KIT-6 mould material 1.0 g and place airtight there-necked flask, vacuumize, make in the mesopore orbit of mould material to be in vacuum state.Get phosphotungstic acid 2.5 g and evenly be dissolved in the 20 ml absolute ethyl alcohols, then it slowly is added drop-wise in the there-necked flask, the alcoholic solution of tungsten salt is poured into rapidly in the mesopore orbit of mould material under atmospheric effect.Continue to vacuumize 30 min, make the ethanolic solution volatilization that tungsten salt precursor body fully is poured in the mesopore orbit of KIT-6 mould material.After then load being had the silica compound of tungsten salt to place the baking oven oven dry, resulting powder is put into the blanket of nitrogen stove with the powder of gained, in 500 ℃ of insulation 1 h, whole carbonisation carries out under nitrogen atmosphere, and other are operated with embodiment 1.Resultant mesoporous WO
3/ C composite conducting material, its carbon content is 4wt%.
Embodiment 8
Get KIT-6 mould material 1.0 g and place airtight there-necked flask, vacuumize, make in the mesopore orbit of mould material to be in vacuum state.Get phosphotungstic acid 2.5 g and evenly be dissolved in the 20 ml absolute ethyl alcohols, then it slowly is added drop-wise in the there-necked flask, the alcoholic solution of tungsten salt is poured into rapidly in the mesopore orbit of mould material under atmospheric effect.Continue to vacuumize 30 min, make the ethanolic solution volatilization that tungsten salt precursor body fully is poured in the mesopore orbit of KIT-6 mould material.After then load being had the silica compound of tungsten salt to place the baking oven oven dry, resulting powder is put into the blanket of nitrogen stove with the powder of gained, in 350 ℃ of insulation 8 h, whole carbonisation carries out under nitrogen atmosphere, and other are operated with embodiment 1.Resultant mesoporous WO
3/ C composite conducting material, its carbon content is 30wt%.
Comparative Examples
The mesoporous silicon oxide (KIT-6) that at first prepares the three-dimensional cubic meso-hole structure according to document, the surfactant P in 550 ℃ of calcining 5 h removal ducts
123, then used as mould material.Get this mould material 0.2 g and place airtight there-necked flask, vacuumize, make in the mesopore orbit of mould material to be in vacuum state.Getting phosphotungstic acid 0.4 g evenly is dissolved in the 5 ml absolute ethyl alcohols, it is poured in the mesopore orbit of mould material then, treats in baking oven, after the oven dry, resulting powder to be put into the blanket of nitrogen stove with the powder of gained, 450 ℃ of insulation 2 h, whole carbonisation carries out under nitrogen atmosphere.Other operations are with embodiment 1.Found that the specific area of prepared target product is: 83 m
2/ g (seeing the following form 1) does not have the original position composite carbon, and its conductance is: 1.8 * 10
-5Ω
-1.m
-1(seeing the following form 2).Illustrate that not have the original position of carbon compound, resulting target product is simple mesoporous WO
3, its electric conductivity is relatively poor, and conductance is lower.
Table 1
Referring to table 1 as can be known, with respect to Comparative Examples, utilize the surfactant original position heat of carbonization of template to handle, can increase specific area, in certain heat treatment time scope, heat treatment time proper extension, but hole diameter enlargement and pore volume.
Table 2
A: the resistance of sample;
B: the conductance of sample;
Referring to table 2 as can be known, with respect to Comparative Examples, utilize the surfactant original position heat of carbonization of template to handle original position and introduce carbon, greatly reduced the resistance of product and increased conductance.In certain heat treatment time scope, the heat treatment time proper extension can increase carbon content, reduces resistance and increase conductance.
Industrial applicability: the mesoporous WO of a kind of novelty provided by the invention
3The preparation method of/C composite conducting material utilizes the surfactant original position carbonization of template to form mesoporous WO
3/ C composite conducting material, row easy and simple to handle, easy, and changing waste into valuable, environmental friendliness, and also the raising of the product electric conductivity that makes can greatly improve mesoporous WO
3Electro catalytic activity, be suitable for sizable application in the anode catalyst of temp fuel battery.
Claims (12)
1. mesoporous WO
3The preparation method of/C composite conducting material is characterized in that, described method comprises:
Be template, be the tungsten source, be carbon source with described surfactant with tungsten salt with the mesoporous silicon oxide of not removing surfactant, under inert gas shielding through the carbonization of heat treatment original position; And
Remove silica to obtain described mesoporous WO with strong acid or strong alkali aqueous solution
3/ C composite conducting material, wherein, the mesoporous WO of gained
3The carbon content of/C composite conducting material is 4～30wt%.
2. preparation method according to claim 1 is characterized in that, controls described heat treatment period to regulate and control described mesoporous WO
3The carbon content of/C composite conducting material and then regulate and control described mesoporous WO
3The electric conductivity of/C composite conducting material.
3. preparation method according to claim 2 is characterized in that, described heat treated temperature is 350～500 ℃, and described heat treatment period is 1～8 hour.
4. preparation method according to claim 3 is characterized in that, described heat treatment period is 2～6 hours.
5. preparation method according to claim 4 is characterized in that, the mesoporous WO of gained
3The carbon content of/C composite conducting material is 5～20wt%, and its conductance is 5.0 * 10
-3～7.8 * 10
-2Ω
-1.m
-1
6. preparation method according to claim 4 is characterized in that, described heat treatment period is 2～4 hours.
7. preparation method according to claim 6 is characterized in that, the mesoporous WO of gained
3The carbon content of/C composite conducting material is 5～13wt%, and its conductance is 5.0 * 10
-3～1.2 * 10
-2Ω
-1.m
-1
8. according to each described preparation method in the claim 1～7, it is characterized in that the mode by vacuum pouring is poured into described tungsten salt in the mesopore orbit of described template.
9. preparation method according to claim 8 is characterized in that, the mode of pouring into a mould by vacuum nano is poured into described tungsten salt in the mesopore orbit of described template.
10. preparation method according to claim 8 is characterized in that, described tungsten salt is the tungsten salt that dissolves in ethanol.
11. preparation method according to claim 10 is characterized in that, described tungsten salt is phosphotungstic acid.
12. preparation method according to claim 1 is characterized in that, removes silica with hydrofluoric acid aqueous solution.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103598579A CN102500360B (en) | 2011-11-15 | 2011-11-15 | Method for preparing mesoporous tungsten oxide/carbon composite conductive materials |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011103598579A CN102500360B (en) | 2011-11-15 | 2011-11-15 | Method for preparing mesoporous tungsten oxide/carbon composite conductive materials |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102500360A CN102500360A (en) | 2012-06-20 |
| CN102500360B true CN102500360B (en) | 2013-08-14 |
Family
ID=46212527
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011103598579A Active CN102500360B (en) | 2011-11-15 | 2011-11-15 | Method for preparing mesoporous tungsten oxide/carbon composite conductive materials |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102500360B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103594722B (en) * | 2012-08-16 | 2016-08-03 | 中国科学院上海硅酸盐研究所 | Proton Exchange Membrane Fuel Cells |
| CN103730662B (en) * | 2012-10-10 | 2017-07-07 | 东莞东阳光科研发有限公司 | A kind of lithium ion battery negative silicon/carbon dioxide composite material and preparation method thereof |
| JP6162010B2 (en) * | 2013-09-19 | 2017-07-12 | 国立大学法人 新潟大学 | Method for producing mesoporous tungsten oxide, method for producing photocatalyst, and method for producing mesoporous tungsten oxide electrode |
| CN105047914B (en) * | 2015-05-28 | 2017-11-17 | 东南大学 | A kind of lithium ion battery negative material molybdenum disulfide/carbon and preparation method thereof |
| CN107442105B (en) * | 2017-07-24 | 2019-11-22 | 苏州大学 | It can be used for preparing tungsten manganese calcium/mesoporous tungsten trioxide compound and preparation method thereof of light anode |
| CN108417788B (en) * | 2018-01-29 | 2020-08-25 | 昆明理工大学 | Preparation method of chromium and silver bimetal doped nano tungsten oxide @ porous carbon negative electrode material |
| CN110931808A (en) * | 2019-11-11 | 2020-03-27 | 中国科学院上海硅酸盐研究所 | Pd-WO3Anode electrocatalyst of/C proton exchange membrane fuel cell and its preparing method and use |
| CN111847517A (en) * | 2020-07-09 | 2020-10-30 | 长春工业大学 | Ordered mesoporous carbon composite material directly introduced with tungsten trioxide by hard template method and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101181679B (en) * | 2007-11-02 | 2012-09-05 | 中国科学院上海硅酸盐研究所 | Meso-porous C/WO3 electro-catalyst and preparation method thereof |
| CN101913597B (en) * | 2010-09-14 | 2012-03-07 | 武汉理工大学 | Tungsten oxide nano-wire and porous carbon nano composite structural material |
-
2011
- 2011-11-15 CN CN2011103598579A patent/CN102500360B/en active Active
Also Published As
| Publication number | Publication date |
|---|---|
| CN102500360A (en) | 2012-06-20 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102500360B (en) | Method for preparing mesoporous tungsten oxide/carbon composite conductive materials | |
| Zhu et al. | Hard-template synthesis of three-dimensional interconnected carbon networks: rational design, hybridization and energy-related applications | |
| CN107946560B (en) | Carbon-limited domain metal or metal oxide composite nano-structure material and preparation method and application thereof | |
| CN105826527B (en) | A kind of porous silicon-carbon composite and its preparation method and application | |
| CN107399729A (en) | A kind of bimetallic MOFs nitrogenous graphitized carbon material | |
| Jiao et al. | Non-precious transition metal single-atom catalysts for the oxygen reduction reaction: progress and prospects | |
| CN103035899A (en) | Method for performing carbon coating modification on nano-powder by adopting water-soluble polymer | |
| CN108172782B (en) | Preparation method and application of carbon-coated porous cobaltous oxide nano material with shell-core structure | |
| CN106025244A (en) | Nickel selenide/graphene/carbon nanotube composite material and preparation method thereof | |
| CN104174422A (en) | High nitrogen doped graphene and fullerene-like molybdenum selenide hollow-ball nanocomposite and preparation method thereof | |
| Zeng et al. | Synergistic performance of nitrogen and sulfur co-doped Ti3C2TX for electrohydrogenation of N2 to NH3 | |
| CN108101119B (en) | Preparation method of iron oxide nanosheet material | |
| CN109499495B (en) | Zinc oxide/zinc hydroxide aerogel and preparation method thereof | |
| CN114023948B (en) | Silicon-carbon negative electrode material, preparation method thereof and lithium ion battery | |
| CN112725819A (en) | Tungsten-molybdenum-based nitrogen carbide nano material and preparation method and application thereof | |
| Shinde et al. | An overview of self-grown nanostructured electrode materials in electrochemical supercapacitors | |
| CN109207958B (en) | A kind of preparation method of the phosphating sludge nano-chip arrays structure perpendicular to substrate grown | |
| CN111068717A (en) | Ruthenium simple substance modified sulfur-doped graphene two-dimensional material and preparation and application thereof | |
| CN102698741B (en) | Method for preparing grapheme platinum nanocomposite material by using argon plasma | |
| CN115036516A (en) | Cobalt and nitrogen co-doped hollow tubular porous carbon composite material and preparation method and application thereof | |
| Liu et al. | Ultrafast and stable lithium storage enabled by the electric field effect in layer-structured tablet-like NH4TiOF3 mesocrystals | |
| CN106602080B (en) | It is a kind of based on cetyl trimethylammonium bromide be carbon material pore creating material three-dimensional porous Fe-N-C catalyst and preparation method | |
| CN108545721A (en) | The preparation method and its resulting materials of a kind of three-dimensional grapheme hollow ball of high stable state and application | |
| CN116889884A (en) | Preparation method and application of CS-CSS/NHC heterogeneous nanocube | |
| CN114855210B (en) | Molten salt method in-situ synthesis carbon-based single-atom nanosheet and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant |