CN101671019A - Method for preparing mesoporous needle-shaped tungsten carbide - Google Patents
Method for preparing mesoporous needle-shaped tungsten carbide Download PDFInfo
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- CN101671019A CN101671019A CN200910153606A CN200910153606A CN101671019A CN 101671019 A CN101671019 A CN 101671019A CN 200910153606 A CN200910153606 A CN 200910153606A CN 200910153606 A CN200910153606 A CN 200910153606A CN 101671019 A CN101671019 A CN 101671019A
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Abstract
The invention discloses a method for preparing mesoporous needle-shaped tungsten carbide. The preparation method comprises the following steps of: controlling the ambient temperature to be 10-30 DEG C; adding deionized water into ammonium meta-tungstate and ammonium carbonate which has a mass ratio of 1:0.75-2, for preparing a precursor culture solution in which the total mass fraction of the ammonium meta-tungstate and the ammonium carbonate is 2.5-50 wt%; stirring the precursor culture solution for 1-15 minutes, then placing the precursor culture solution in an open system for 2-24 hours, and obtaining self-growing ammonium meta-tungstate needle-shaped crystal after centrifuging and drying; and carrying out one-step reduction and carbonization of the self-growing ammonium meta-tungstateneedle-shaped crystal in a hydrogen-rich atmosphere, and thus obtaining the mesoporous needle-shaped tungsten carbide. The mesoporous needle-shaped tungsten carbide prepared by the preparation methodis formed by the piling of nano-tungsten carbide grains, has controllable crystal length, well-developed aperatures, is simply prepared and operated and can be well used in the crystallization field.
Description
(1) technical field
The present invention relates to a kind of preparation method of wolfram varbide, relate in particular to the preparation method of the mesoporous needle-shaped tungsten carbide that forms by the nanometer tungsten carbide particle packing.
(2) background technology
Wolfram varbide (WC) is as a kind of base metal catalytic material of excellent property, and since the sixties in last century reported that it has good catalytic activity to cyclohexane dehydrogenation, ethyl benzene dehydrogenation preparation of styrene, the application potential of its catalysis aspect received much concern.Bibliographical information points out that (Pt) is similar for WC surface electrical sublayer and platinum, has the catalytic activity of class Pt in some reaction.WC not only possesses the characteristic of noble metal catalysts such as alternative platinum and good anti-poisoning capability, and also has very strong acid resistance and electro catalytic activity preferably.But one of main difficult problem that is faced in the present WC catalyst preparation process of the catalytic activity that how further to improve WC.
The porosity of catalyzer is to influence the principal element that catalyzer comprises base attributes such as specific surface area, gas-liquid spread mutually with pore size distribution, and how preparing the suitable catalyzer of space prosperity and pore size distribution becomes the precondition that its catalytic activity embodies.And the structure of presoma is formed and pattern will produce considerable influence to the tungsten carbide particle structure of later stage preparation, and the particle nanometer has become a main direction of the property that can embody materials such as nanometer size effect now.Thereby the prosperity of preparation hole, the appropriate mesoporous wolfram varbide of pore size distribution are research directions that potential using value is relatively arranged.
The nanometer tungsten carbide of today preparation isolating methods of organic polymers that adopt more, during not only can introduce organic molecule and in late phase reaction residual unnecessary carbon cause the catalyst activity surface to descend, also can in calcination process, cause hard aggregation.As to presoma granulation, doping, the structure of control presoma with become to be grouped into, and the method for finally not introducing other element can be controlled the particle hard aggregation in the carbonization process effectively.So how to being that the granulation of presoma and the processing of doping volatile salt seem particularly important with the ammonium metawolframate in preparation process.And ammonium metawolframate has advantages such as pollution-free, easy to use as the of paramount importance presoma of wolfram varbide, and is comparatively extensive in the application as the tungsten source.
The single stage method carbonization process can keep the structure of presoma ammonium metawolframate admirably, and in certain temperature programming process, progressively remove the volatilizable composition in the reaction particles, thereby reduce intergranular collision probability, obtain scattered, the tungsten carbide material of space prosperity.
Presoma preparation method used herein: room temperature is will mix through the soluble salt after the pre-treatment with single operation to be dissolved in the deionized water from the crystallization process of growing.This method major advantage is that required envrionment temperature is lower, need not other heating installations, and crystalline form, particle size are easily controlled.Its characteristics are that the Solid-Liquid Separation that obtains is obvious, and aftertreatment is simple, do not need vaporised liquid separately again, thereby have avoided the hard aggregation phenomenon in drying process.
In consulting document, and find no the bibliographical information similar approach and prepare granular precursor, and obtain the mesoporous needle-shaped tungsten carbide particle through carburising step as precursor.
(3) summary of the invention
The preparation method who the purpose of this invention is to provide a kind of mesoporous needle-shaped tungsten carbide (WC), this mesoporous needle-shaped tungsten carbide is formed by the nanometer tungsten carbide particle packing, and crystal length is controlled, and preparation manipulation is simple, and the hole prosperity can well be applied to catalytic field.
For solving the problems of the technologies described above, the technical solution used in the present invention is as follows:
A kind of preparation method of mesoporous needle-shaped tungsten carbide, specific as follows: in envrionment temperature is under 10～30 ℃ of conditions, is the presoma nutrient solution of 2.5～50wt% with mass ratio 1: 0.75～2 for ammonium metawolframate and volatile salt add the total mass mark that deionized water is mixed with ammonium metawolframate and volatile salt, stir after 1～15 minute and placed 2～24 hours in the system of opening wide, centrifugal, drying obtains from growing the ammonium metawolframate needle-like crystal; Gained promptly obtains mesoporous needle-shaped tungsten carbide from growing ammonium metawolframate needle-like crystal single stage method reduction and carbonization in the hydrogen rich gas atmosphere.
Presoma nutrient solution of the present invention can be prepared as follows: in envrionment temperature is under 10～30 ℃ of conditions, with ammonium metawolframate and volatile salt 1: 0.75～2 solid phase mixing of pressing mass ratio, ground 2～20 minutes, adding the total mass mark that deionized water is mixed with ammonium metawolframate and volatile salt then is the presoma nutrient solution of 2.5～50wt%.Preferred milling time is 3～10 minutes.
Presoma nutrient solution of the present invention also can be prepared as follows: in envrionment temperature is under 10～30 ℃ of conditions, with deionized water ammonium metawolframate and volatile salt are mixed with the aqueous solution respectively, be the presoma nutrient solution of 2.5～50wt% with two kinds of aqueous solution with the total mass mark that obtains ammonium metawolframate and volatile salt then, and the mass ratio of ammonium metawolframate and volatile salt is 1: 0.75～2 in the control presoma nutrient solution.
Among the present invention, the mass ratio of ammonium metawolframate and volatile salt is 1: 1～2 in the preferred presoma nutrient solution; The total mass mark of ammonium metawolframate and volatile salt is 5～30wt%, more preferably 5～20wt% in the preferred presoma nutrient solution.
Alr mode of the present invention can adopt glass stick stirring, mechanical stirring or sonic oscillation, and generally when using sonic oscillation, the ammonium metatungstate crystal particle that obtains at last is thinner, and size distribution is even; When using glass stick to stir, the ammonium metatungstate crystal particle that obtains at last is bigger; And the crystal grain size that obtains after mechanical stirring is handled is between the two.So those skilled in the art can select alr mode according to actual needs, with control ammonium metatungstate crystal particulate size.
Particularly, after ammonium metawolframate and volatile salt are ground, the disposable adding of deionized water, glass stick stir or mechanical stirring after leave standstill, crystallization, centrifugal and dry after promptly obtain even particle distribution, needle-like crystal that crystalline form is complete, after carbonization, can obtain mesoporous needle-shaped tungsten carbide.
When described presoma nutrient solution alr mode is selected sonic oscillation, can make the concentration distribution of ammonium metawolframate and volatile salt mixing solutions more even, make intermolecular distribution rule more, thereby rule obtains thinner crystal to make crystal be orientated more in process of growth, can obtain the littler complete fine acicular ammonium metatungstate crystal of crystalline form of length, thereby after carbonization is finished, obtain the littler mesoporous needle-shaped tungsten carbide of particle.
Churning time is generally at 1～15 minute among the present invention, and the proper extension churning time helps to obtain to disperse more uniform presoma nutrient solution in arbitrary alr mode.Preferably, the churning time that glass stick stirs is 10～15 minutes, and churned mechanically churning time is 5～12 minutes, and the time of sonic oscillation is 5～10 minutes.
Make nutrient solution in the system of opening wide, place 2～24 hours after the stirring to separate out crystal.Further, the storage period preferred 6～24 hour of the presoma nutrient solution that ultrasonic agitation obtains in opening wide system, more preferably 12～18 hours; The storage period preferred 4～20 hour of the presoma nutrient solution that mechanical stirring obtains in opening wide system, more preferably 8～16 hours; Glass stick stirs the storage period preferred 2～18 hour of presoma nutrient solution in the system of opening wide that obtains, more preferably 5～15 hours.
First preferred version that the present invention prepares ammonium metatungstate crystal is: earlier ammonium metawolframate and volatile salt were ground 3～10 minutes after than solid phase mixing with 1: 1～2 quality, add the aqueous solution that deionized water is mixed with 5～20wt%, sonic oscillation left standstill after 5～10 minutes 12～18 hours.Drying at room temperature after the centrifugation promptly gets described fine acicular crystal.
Second preferred version that the present invention prepares ammonium metatungstate crystal is: earlier ammonium metawolframate and volatile salt were ground 3～10 minutes after than solid phase mixing with 1: 1～2 quality, be mixed with the aqueous solution of 5～20wt%, glass stick stirs after 10～15 minutes and left standstill 2～18 hours, drying at room temperature after the centrifugation promptly gets described needle-like crystal.
The 3rd preferred version that the present invention prepares ammonium metatungstate crystal is: ammonium metawolframate and volatile salt are mixed with the aqueous solution with deionized water respectively, then two kinds of solution are mixed and obtain the aqueous solution that the total mass mark is 5～20wt%, wherein the mass ratio of ammonium metawolframate and volatile salt is 1: 1～2, glass stick stirred 10～15 minutes, quiet straight 8～24 hours, drying at room temperature after the centrifugation promptly gets the needle-like crystal of described more long grain.
The 4th preferred version that the present invention prepares ammonium metatungstate crystal is: earlier ammonium metawolframate and volatile salt were ground 3～10 minutes after than solid phase mixing with 1: 1～2 quality, be mixed with the aqueous solution of 5～20wt%, mechanical stirring left standstill after 5～12 minutes 8～16 hours, drying at room temperature after the centrifugation promptly gets described needle-like crystal.
The present invention carries out carbonizing treatment to the ammonium metatungstate crystal that makes under the hydrogen rich gas atmosphere, described hydrogen rich gas atmosphere is meant H
2Proportion is the mixed gas more than 50%, and the preferred described hydrogen rich gas atmosphere of the present invention is that volume ratio is 1: 1.1～2.5 CO and H
2Mixed atmosphere, more preferably volume ratio is 1: 1.5～2.0 CO and H
2Mixed atmosphere.
The present invention is concrete to recommend described carbonization to adopt following steps: the ammonium metawolframate needle-like crystal of will growing certainly places the high-temperature tubular Reaktionsofen, under the hydrogen rich gas atmosphere, kept 2～8 hours according to 2～10 ℃/min temperature programming to 700～900 ℃, the cooling back is taken out and is promptly got mesoporous needle-shaped tungsten carbide.Generally by before the hydrogen-rich gas, feed nitrogen earlier and throw out air in the tubular react furnace, close nitrogen then and feed hydrogen-rich gas again and carry out carbonization.
In carbonization process, preferably kept 3～6 hours with 3～7 ℃/min temperature programming to 750～820 ℃.
The present invention compared with prior art, its beneficial effect is embodied in:
1, the present invention has initiated the room temperature liquid phase from growing compound ammonium metatungstate crystal technology, in the crystal structure process, incorporated low temperature decomposable compound volatile salt, to make spontaneous minute hand shape ammonium metatungstate crystal, this crystal is the composite crystal of ammonium metawolframate and volatile salt; The structure and the pattern of the operative association ammonium metawolframate composite crystal after the liquid-phase system configuration finishes, and realization is to the control of crystalline structure and granularity, made full use of the characteristic of composite crystal then, in carbonization process, volatile salt in the ammonium metawolframate composite crystal at high temperature resolves into gas and forms the space, makes tungsten carbide particle be able to nano level and piles up, and obtains the needle-shaped tungsten carbide of meso-hole structure, significantly improve the void density of wolfram varbide, obtained the tungsten carbide particle of high-ratio surface.
2, carbonization process adopts the carbonization of temperature programming single stage method, and mixed gas is controlled, adopts rich hydrogen ratio, can not only effectively reduce wolfram varbide and become the phase temperature, and can improve microcosmic W/C atomic ratio, and obtained the wolfram varbide phase of the scarce carbon of microcosmic, make the wolfram varbide active surface increase and improve catalytic activity.
(4) description of drawings
Fig. 1 is embodiment 1 a needle-like presoma photo.
Fig. 2 is the AFM figure of embodiment 1 needle-like presoma surface three-dimensional structure.
Fig. 3 is embodiment 2 mesoporous needle-shaped tungsten carbide photos.
Fig. 4 is the AFM figure of embodiment 2 mesoporous needle-shaped tungsten carbide surface three-dimensional structures.
Fig. 5 is the surface topography SEM photo of original ammonium metawolframate.
(5) embodiment:
Following specific embodiment illustrates technical scheme of the present invention, but protection scope of the present invention is not limited thereto:
Embodiment 1
The temperature that controls environment is 10 ℃, get each 10g of ammonium metawolframate and volatile salt, putting into mortar mixes, grind after 3 minutes mixed powder is poured in the uncovered cultivation utensil, add the 200ml deionized water, glass stick stirred 3 minutes, left standstill centrifugation after 18 hours, with washed with de-ionized water three times, drying at room temperature.The gained ammonium metatungstate crystal is a needle-like long strip shape crystal.The ammonium metatungstate crystal that makes is taken pictures, and as seen from Figure 1, the gained crystal is a needle-like long strip shape crystal.And it is done AFM atomic power scan-probe analyze surface topography, as seen from Figure 2, smooth surface, crystallization ideal.Again with 1: 2 CO of volume ratio, H
2Gas mixture is a reduction and carbonization gas, is that temperature programming speed keeps carbonization in 4 hours to obtain mesoporous needle-shaped tungsten carbide under 800 ℃ of temperature with single stage method with 6 ℃/min, the mesoporous needle-shaped tungsten carbide mean length is 2.1mm, its surface irregularity as seen from Figure 4, bore dia about about 50nm, belongs to mesoporous scope greatly.
The temperature that controls environment is 10 ℃, get ammonium metawolframate 10g and volatile salt 5g, putting into mortar mixes, grind after 3 minutes mixed powder is poured in the uncovered cultivation utensil, add the 180ml deionized water, sonic oscillation 3 minutes leaves standstill centrifugation after 24 hours, with washed with de-ionized water three times, drying at room temperature.The gained ammonium metatungstate crystal is a needle-like long strip shape crystal.Again with 1: 2 CO of volume ratio, H
2Gas mixture is a reduction and carbonization gas, is that temperature programming speed keeps carbonization in 4 hours to obtain mesoporous needle-shaped tungsten carbide under 800 ℃ of temperature with single stage method with 6 ℃/min.The mesoporous needle-shaped tungsten carbide mean length is 1.2mm.
Embodiment 3
The temperature that controls environment is 15 ℃, get ammonium metawolframate 10g and volatile salt 5g, putting into mortar mixes, grind after 3 minutes mixed powder is poured in the uncovered cultivation utensil, add the 180ml deionized water, sonic oscillation 3 minutes leaves standstill centrifugation after 24 hours, with washed with de-ionized water three times, drying at room temperature.The gained ammonium metatungstate crystal is a needle-like long strip shape crystal.Again with 1: 2 CO of volume ratio, H
2Gas mixture is a reduction and carbonization gas, is that temperature programming speed keeps carbonization in 2 hours to obtain mesoporous needle-shaped tungsten carbide under 800 ℃ of temperature with single stage method with 6 ℃/min.The mesoporous needle-shaped tungsten carbide mean length is 1.3mm.
Embodiment 4
The temperature that controls environment is 10 ℃, get ammonium metawolframate 2g and volatile salt 4g, putting into mortar mixes, grind after 3 minutes mixed powder is poured in the uncovered cultivation utensil, add the 30ml deionized water, sonic oscillation 3 minutes leaves standstill centrifugation after 22 hours, with washed with de-ionized water three times, drying at room temperature.The gained ammonium metatungstate crystal is a needle-like long strip shape crystal.Again with 1: 2 CO of volume ratio, H
2Gas mixture is a reduction and carbonization gas, is that temperature programming speed keeps carbonization in 4 hours to obtain mesoporous needle-shaped tungsten carbide under 800 ℃ of temperature with single stage method with 6 ℃/min.The mesoporous needle-shaped tungsten carbide mean length is 1.8mm.
Embodiment 5
The temperature that controls environment is 10 ℃, gets each 2g of ammonium metawolframate and volatile salt and joins respectively in the 8ml deionized water, is stirred to dissolving back and mixes, and glass stick stirred 3 minutes, leaves standstill 15 hours, and drying at room temperature after the centrifugation promptly gets the needle-like crystal of described more long grain.Again with 1: 2 CO of volume ratio, H
2Gas mixture is a reduction and carbonization gas, is that temperature programming speed keeps carbonization in 4 hours to obtain mesoporous needle-shaped tungsten carbide under 800 ℃ of temperature with single stage method with 4 ℃/min.The mesoporous needle-shaped tungsten carbide mean length is 2.2mm.
Embodiment 6
The temperature that controls environment is 30 ℃, gets each 2g of ammonium metawolframate and volatile salt and joins respectively in the 8ml deionized water, is stirred to dissolving back and mixes, and glass stick stirred 3 minutes, leaves standstill 15 hours, and drying at room temperature after the centrifugation promptly gets the needle-like crystal of described more long grain.Again with 1: 2 CO of volume ratio, H
2Gas mixture is a reduction and carbonization gas, is that temperature programming speed keeps carbonization in 4 hours to obtain mesoporous needle-shaped tungsten carbide under 800 ℃ of temperature with single stage method with 6 ℃/min.The mesoporous needle-shaped tungsten carbide mean length is 1.8mm.
Embodiment 7
The temperature that controls environment is 10 ℃, gets ammonium metawolframate 2g and volatile salt 2g, puts into mortar and mixes, grind after 4 minutes mixed powder is poured in the uncovered cultivation utensil, add the 36ml deionized water, mechanical stirring 5 minutes, leave standstill centrifugation after 8 hours, use washed with de-ionized water three times, drying at room temperature.The gained ammonium metatungstate crystal is a needle-like long strip shape crystal.With 1: 2 CO of volume ratio, H
2Gas mixture is a reduction and carbonization gas, is that temperature programming speed keeps carbonization in 4 hours to obtain mesoporous needle-shaped tungsten carbide under 800 ℃ of temperature with single stage method with 6 ℃/min.The mesoporous needle-shaped tungsten carbide mean length is 1.6mm.
Embodiment 8
The temperature that controls environment is 10 ℃, get ammonium metawolframate 2g and volatile salt 4g, putting into mortar mixes, grind after 10 minutes mixed powder is poured in the uncovered cultivation utensil, add the 14ml deionized water, mechanical stirring 15 minutes leaves standstill centrifugation after 16 hours, with washed with de-ionized water three times, drying at room temperature.The gained ammonium metatungstate crystal is a needle-like long strip shape crystal.Again with 1: 1.8 CO of volume ratio, H
2Gas mixture is a reduction and carbonization gas, is that temperature programming speed keeps carbonization in 4 hours to obtain mesoporous needle-shaped tungsten carbide under 800 ℃ of temperature with single stage method with 6 ℃/min.The mesoporous needle-shaped tungsten carbide mean length is 1.6mm.
Embodiment 9
The temperature that controls environment is 10 ℃, get ammonium metawolframate 2g and volatile salt 2g, putting into mortar mixes, grind after 10 minutes mixed powder is poured in the uncovered cultivation utensil, add the 14ml deionized water, glass stick stirred 15 minutes, left standstill centrifugation after 5 hours, with washed with de-ionized water three times, drying at room temperature.The gained ammonium metatungstate crystal is a needle-like long strip shape crystal.Again with 1: 2 CO of volume ratio, H
2Gas mixture is a reduction and carbonization gas, is that temperature programming speed keeps carbonization in 6 hours to obtain mesoporous needle-shaped tungsten carbide under 800 ℃ of temperature with single stage method with 6 ℃/min.The mesoporous needle-shaped tungsten carbide mean length is 1.7mm.
Embodiment 10
The temperature that controls environment is 10 ℃, get ammonium metawolframate 2g and volatile salt 4g, putting into mortar mixes, grind after 10 minutes mixed powder is poured in the uncovered cultivation utensil, add the 14ml deionized water, glass stick stirred 15 minutes, left standstill centrifugation after 15 hours, with washed with de-ionized water three times, drying at room temperature.The gained ammonium metatungstate crystal is a needle-like long strip shape crystal.Again with 1: 2 CO of volume ratio, H
2Gas mixture is a reduction and carbonization gas, is that temperature programming speed keeps carbonization in 4 hours to obtain mesoporous needle-shaped tungsten carbide under 800 ℃ of temperature with single stage method with 6 ℃/min.The mesoporous needle-shaped tungsten carbide mean length is 2.2mm.
Embodiment 11
The temperature that controls environment is 10 ℃, get ammonium metawolframate 2g and volatile salt 2g, putting into mortar mixes, grind after 10 minutes mixed powder is poured in the uncovered cultivation utensil, add the 14ml deionized water, sonic oscillation 15 minutes leaves standstill centrifugation after 12 hours, with washed with de-ionized water three times, drying at room temperature.The gained ammonium metatungstate crystal is a needle-like long strip shape crystal.Again with 1: 2 CO of volume ratio, H
2Gas mixture is a reduction and carbonization gas, is that temperature programming speed keeps carbonization in 4 hours to obtain mesoporous needle-shaped tungsten carbide under 800 ℃ of temperature with single stage method with 6 ℃/min.The mesoporous needle-shaped tungsten carbide mean length is 1.2mm.
Embodiment 12
The temperature that controls environment is 10 ℃, get ammonium metawolframate 2g and volatile salt 4g, putting into mortar mixes, grind after 10 minutes mixed powder is poured in the uncovered cultivation utensil, add the 14ml deionized water, sonic oscillation 15 minutes leaves standstill centrifugation after 18 hours, with washed with de-ionized water three times, drying at room temperature.The gained ammonium metatungstate crystal is a needle-like long strip shape crystal.Again with 1: 2 CO of volume ratio, H
2Gas mixture is a reduction and carbonization gas, is that temperature programming speed keeps carbonization in 2 hours to obtain mesoporous needle-shaped tungsten carbide under 800 ℃ of temperature with single stage method with 6 ℃/min.The mesoporous needle-shaped tungsten carbide mean length is 1.3mm.
Embodiment 13: the comparative example
The ammonium metawolframate raw material is made scanning electron microscope analysis, and as seen from Figure 5, the ammonium metawolframate raw material presents irregular, the solid lumphy structure that volume is bigger.With the ammonium metawolframate that does not process is raw material, with 1: 2 CO of volume ratio, H
2Gas mixture is a reduction and carbonization gas, is that temperature programming speed keeps carbonization in 4 hours to obtain tungsten carbide particle under 800 ℃ of temperature with single stage method with 6 ℃/min.Its specific surface area sees Table 1.
As can be found from Table 1, after handling from the complex crystallization method of growing, the wolfram varbide that obtains much larger than common raw material of the specific surface area of the wolfram varbide particulate that obtains with identical carbonization method again.With embodiment 2 contrasts, different nutrient solution treatment processs can exert an influence to final nano particle size, thereby obtained different specific surface areas.
The specific surface area of the different samples of table 1
Embodiment 14: Application Example
Anode catalyst with fuel cell is an application example, and the mesoporous WC sample of embodiment 1 preparation and the bulk sample of embodiment 7 preparations are carried out noble metal support, is the platinum source with the Platinic chloride, carries out liquid phase-pickling process load with 10% for theoretical precious metal carrying capacity.Found that two samples that obtain under the same terms again, the mesoporous wolfram varbide of needle-like are nano-platinum particle in the load effectively, its test platinum carrying capacity is 8.8%, and bulk sample then charge capacity has only 1.5%.And load the mesoporous WC sample of platinum carry out having embodied satisfactory stability and anti-poisoning capability in the methanol oxidation test process, it is more smooth and easy to compare its mass transfer of blocky sample, thereby embodies better properties.
Claims (10)
1, a kind of preparation method of mesoporous needle-shaped tungsten carbide, it is characterized in that described preparation method is: the temperature that controls environment is 10～30 ℃, with mass ratio is that to add the total mass mark that deionized water is mixed with ammonium metawolframate and volatile salt be the presoma nutrient solution of 2.5～50wt% for 1: 0.75～2 ammonium metawolframate and volatile salt, stir after 1～15 minute and placed 2～24 hours in the system of opening wide, centrifugal, drying obtains from growing the ammonium metawolframate needle-like crystal; Gained promptly obtains mesoporous needle-shaped tungsten carbide from growing ammonium metawolframate needle-like crystal single stage method reduction and carbonization in the hydrogen rich gas atmosphere.
2, the preparation method of mesoporous needle-shaped tungsten carbide as claimed in claim 1, it is characterized in that preparing as follows of described presoma nutrient solution: in envrionment temperature is under 10～30 ℃ of conditions, with ammonium metawolframate and volatile salt 1: 0.75～2 solid phase mixing of pressing mass ratio, ground 2～20 minutes, adding the total mass mark that deionized water is mixed with ammonium metawolframate and volatile salt then is the presoma nutrient solution of 2.5～50wt%.
3, the preparation method of mesoporous needle-shaped tungsten carbide as claimed in claim 1, it is characterized in that preparing as follows of described presoma nutrient solution: in envrionment temperature is under 10～30 ℃ of conditions, with deionized water ammonium metawolframate and volatile salt are mixed with the aqueous solution respectively, be the presoma nutrient solution of 2.5-50wt% with two kinds of aqueous solution with the total mass mark that obtains ammonium metawolframate and volatile salt then, and the mass ratio of ammonium metawolframate and volatile salt is 1: 0.75～2 in the control presoma nutrient solution.
4,, it is characterized in that described alr mode adopts glass stick stirring, mechanical stirring or sonic oscillation as the preparation method of the described mesoporous needle-shaped tungsten carbide of one of claim 1～3.
5, the preparation method of mesoporous needle-shaped tungsten carbide as claimed in claim 4, it is characterized in that describedly preparing according to following steps: earlier ammonium metawolframate and volatile salt were ground 3～10 minutes after than solid phase mixing with 1: 1～2 quality from the ammonium metawolframate needle-like crystal of growing, add the aqueous solution that deionized water is mixed with 5～20wt%, sonic oscillation left standstill after 5～10 minutes 12～18 hours, drying at room temperature after the centrifugation promptly derives from growth ammonium metawolframate needle-like crystal.
6, the preparation method of mesoporous needle-shaped tungsten carbide as claimed in claim 4, it is characterized in that describedly preparing according to following steps: earlier ammonium metawolframate and volatile salt were ground 3～10 minutes after than solid phase mixing with 1: 1～2 quality from the ammonium metawolframate needle-like crystal of growing, be mixed with the aqueous solution of 5～20wt%, glass stick stirs after 10～15 minutes and left standstill 2～18 hours, drying at room temperature after the centrifugation promptly gets described from growing the ammonium metawolframate needle-like crystal.
7, the preparation method of mesoporous needle-shaped tungsten carbide as claimed in claim 4, it is characterized in that the described ammonium metawolframate needle-like crystal of growing certainly prepares according to following steps: ammonium metawolframate and volatile salt are mixed with the aqueous solution with deionized water respectively, then two kinds of solution are mixed and obtain the aqueous solution that the total mass mark is 5～20wt%, wherein the mass ratio of ammonium metawolframate and volatile salt is 1: 1～2, glass stick stirred 10～15 minutes, left standstill 8～24 hours, drying at room temperature after the centrifugation promptly gets described from growing the ammonium metawolframate needle-like crystal.
8, the preparation method of mesoporous needle-shaped tungsten carbide as claimed in claim 4, it is characterized in that describedly preparing according to following steps: earlier ammonium metawolframate and volatile salt were ground 3～10 minutes after than solid phase mixing with 1: 1～2 quality from the ammonium metawolframate needle-like crystal of growing, be mixed with the aqueous solution of 5～20wt%, mechanical stirring left standstill after 5～12 minutes 8～16 hours, drying at room temperature after the centrifugation promptly gets described from growing the ammonium metawolframate needle-like crystal.
9,, it is characterized in that described hydrogen rich gas atmosphere is that volume ratio is 1: 1.1～2.5 CO and H as the preparation method of the described mesoporous needle-shaped tungsten carbide of one of claim 1～3
2Mixed atmosphere.
10, as the preparation method of the described mesoporous needle-shaped tungsten carbide of one of claim 1～3, it is characterized in that described carbonization employing following steps: the ammonium metawolframate needle-like crystal of will growing certainly places the high-temperature tubular Reaktionsofen, under the hydrogen rich gas atmosphere, kept 2～8 hours according to 2～10 ℃/min temperature programming to 700～900 ℃, the cooling back is taken out and is promptly got mesoporous needle-shaped tungsten carbide.
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Cited By (3)
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|---|---|---|---|---|
| CN105948052A (en) * | 2016-06-03 | 2016-09-21 | 宁波检验检疫科学技术研究院 | Flaky nano tungsten carbide and preparation method and application thereof |
| CN109678157A (en) * | 2019-03-04 | 2019-04-26 | 合肥工业大学 | A kind of preparation method of high catalytic activity nanometer tungsten carbide |
| CN113215566A (en) * | 2021-05-07 | 2021-08-06 | 常州市天河电器有限公司 | High-strength wear-resistant enclosed steel frame and processing technology thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1277611C (en) * | 2004-10-13 | 2006-10-04 | 浙江工业大学 | Tungsten carbide catalyst and its preparation method and special retort |
| CN101362095B (en) * | 2008-09-18 | 2010-09-15 | 浙江工业大学 | Tungsten carbide and titanium dioxide composite catalyst and preparation method thereof |
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2009
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105948052A (en) * | 2016-06-03 | 2016-09-21 | 宁波检验检疫科学技术研究院 | Flaky nano tungsten carbide and preparation method and application thereof |
| CN105948052B (en) * | 2016-06-03 | 2018-08-10 | 宁波检验检疫科学技术研究院 | A kind of flake nano carbonization tungsten and its preparation and application |
| CN109678157A (en) * | 2019-03-04 | 2019-04-26 | 合肥工业大学 | A kind of preparation method of high catalytic activity nanometer tungsten carbide |
| CN109678157B (en) * | 2019-03-04 | 2022-05-10 | 合肥工业大学 | Preparation method of nano tungsten carbide with high catalytic activity |
| CN113215566A (en) * | 2021-05-07 | 2021-08-06 | 常州市天河电器有限公司 | High-strength wear-resistant enclosed steel frame and processing technology thereof |
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| CN101671019B (en) | 2011-06-29 |
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