CN110368970A - A kind of preparation method of the activated carbon supported tungsten carbide composite nano-powder as elctro-catalyst - Google Patents
A kind of preparation method of the activated carbon supported tungsten carbide composite nano-powder as elctro-catalyst Download PDFInfo
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- CN110368970A CN110368970A CN201910789777.3A CN201910789777A CN110368970A CN 110368970 A CN110368970 A CN 110368970A CN 201910789777 A CN201910789777 A CN 201910789777A CN 110368970 A CN110368970 A CN 110368970A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 102
- UONOETXJSWQNOL-UHFFFAOYSA-N tungsten carbide Chemical compound [W+]#[C-] UONOETXJSWQNOL-UHFFFAOYSA-N 0.000 title claims abstract description 49
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000011858 nanopowder Substances 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 20
- 239000003054 catalyst Substances 0.000 title claims abstract description 18
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 27
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000003610 charcoal Substances 0.000 claims abstract description 20
- 239000001257 hydrogen Substances 0.000 claims abstract description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 16
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 15
- 239000010937 tungsten Substances 0.000 claims abstract description 15
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000012298 atmosphere Substances 0.000 claims abstract description 10
- 230000004913 activation Effects 0.000 claims description 25
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 19
- 230000000694 effects Effects 0.000 claims description 18
- 238000003763 carbonization Methods 0.000 claims description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 10
- 229910017604 nitric acid Inorganic materials 0.000 claims description 10
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 9
- 229960001484 edetic acid Drugs 0.000 claims description 9
- 238000012216 screening Methods 0.000 claims description 9
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Natural products NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 7
- 229910002651 NO3 Inorganic materials 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 7
- 238000000498 ball milling Methods 0.000 claims description 7
- 239000007789 gas Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- 238000004321 preservation Methods 0.000 claims description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- PAWQVTBBRAZDMG-UHFFFAOYSA-N 2-(3-bromo-2-fluorophenyl)acetic acid Chemical compound OC(=O)CC1=CC=CC(Br)=C1F PAWQVTBBRAZDMG-UHFFFAOYSA-N 0.000 claims description 6
- 239000002671 adjuvant Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- 239000004471 Glycine Substances 0.000 claims description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004202 carbamide Substances 0.000 claims description 3
- 238000006555 catalytic reaction Methods 0.000 claims description 3
- 150000002431 hydrogen Chemical class 0.000 claims description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000001816 cooling Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 244000248349 Citrus limon Species 0.000 claims 2
- 235000005979 Citrus limon Nutrition 0.000 claims 2
- 239000002253 acid Substances 0.000 claims 1
- 125000003630 glycyl group Chemical group [H]N([H])C([H])([H])C(*)=O 0.000 claims 1
- 238000007873 sieving Methods 0.000 claims 1
- 239000000843 powder Substances 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 15
- 238000000034 method Methods 0.000 abstract description 13
- 239000002243 precursor Substances 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 2
- 239000008187 granular material Substances 0.000 abstract description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract 1
- 239000007791 liquid phase Substances 0.000 abstract 1
- 229910052760 oxygen Inorganic materials 0.000 abstract 1
- 239000001301 oxygen Substances 0.000 abstract 1
- 238000006722 reduction reaction Methods 0.000 abstract 1
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- KWYUFKZDYYNOTN-UHFFFAOYSA-M potassium hydroxide Inorganic materials [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 13
- 239000002994 raw material Substances 0.000 description 7
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 6
- 238000005406 washing Methods 0.000 description 6
- 229910021389 graphene Inorganic materials 0.000 description 5
- 230000009467 reduction Effects 0.000 description 5
- 239000000463 material Substances 0.000 description 3
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- QIJNJJZPYXGIQM-UHFFFAOYSA-N 1lambda4,2lambda4-dimolybdacyclopropa-1,2,3-triene Chemical compound [Mo]=C=[Mo] QIJNJJZPYXGIQM-UHFFFAOYSA-N 0.000 description 2
- 229910039444 MoC Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000004020 conductor Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- -1 Tungsten Carbides Chemical class 0.000 description 1
- 239000002250 absorbent Substances 0.000 description 1
- 230000002745 absorbent Effects 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 238000010411 cooking Methods 0.000 description 1
- 238000007598 dipping method Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 239000011964 heteropoly acid Substances 0.000 description 1
- 229920000404 heteropolyacid polymer Polymers 0.000 description 1
- 238000001802 infusion Methods 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910052750 molybdenum Inorganic materials 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 238000005554 pickling Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 238000010792 warming Methods 0.000 description 1
Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The preparation method of the invention discloses a kind of activated carbon supported tungsten carbide composite nano-powder as elctro-catalyst, it is that purple tungsten precursor powder is loaded using liquid phase method synthesizing activity charcoal first, then presoma is placed in the mixed atmosphere of methane and hydrogen and is carbonized to get activated carbon supported nanometer tungsten carbide composite nano-powder is arrived.Composite nano-powder load efficiency of the invention is high, load capacity is big, realizes tungsten carbide being uniformly distributed in active carbon duct, can inhibit growing up for tungsten carbide crystal grain；The porous structure of active carbon improves the specific surface area, transmittability and stability of composite granule, composite nano-powder oxygen reduction reaction with higher (ORR) catalytic performance and long-time stability.
Description
Technical field
The invention belongs to field of nanocomposite materials, and in particular to a kind of activated carbon supported tungsten carbide as elctro-catalyst
The preparation method of composite nano-powder.
Background technique
Since the catalytic activity of last century the fifties tungsten carbide eka-platinium is found, tungsten carbide is as precious metal catalyst
The potential substitute of agent becomes the emphasis of academia's research.However, just from the point of view of current result of study, the catalysis of tungsten carbide
Activity still has very big gap compared with the noble metals such as platinum.Restrict tungsten carbide catalytic activity principal element first is that tungsten carbide
Specific surface area very little, and easily reunite during the preparation process.A part of researcher attempts tungsten carbide being used as carrier,
The a small amount of noble metal of its area load, improves the catalytic activity of tungsten carbide.Another part researcher is then based on matrix-catalysis material
Cooking opinion proposes that Tungsten Carbides are formed composite material above, are passed through this using the material with high surface area as matrix
The tungsten carbide composite catalyst that kind method is prepared has high surface area, good dispersibility and electric conductivity, significantly improves carbon
Change the catalytic activity of tungsten.
Active carbon has pore structure abundant, biggish surface area, good chemical inertness and electric conductivity, if by active carbon
As carrier, the catalytic activity and stability of composite material can be improved, it has been reported that the electricity of WC/C p-nitrophenol is urged
Change the electro catalytic activity that activity is better than tungsten carbide and active carbon.Therefore, a kind of novel active carbon as elctro-catalyst is developed
Loading tungsten carbide nano-powder has important practical value.
In recent years, researcher both domestic and external has carried out the preparation of activated carbon supported tungsten carbide nano-powder and has largely ground
Study carefully, and achieves many achievements.Such as:
Horse Chunan etc. (Journal of Chemical Industry and Engineering, 2010,61 (05): 1313-1318.) will use nitric acid treatment active carbon and certain
After the ammonium metatungstate solution ultrasonic disperse of mass fraction, dipping, vacuum drying, it is placed in the tube furnace for being connected with methane and hydrogen,
Temperature is risen to 800 DEG C, keeps the temperature 8 hours, obtains WC/C nano-powder.This method is simple and easy, but the production time is longer, and institute
Obtaining product, there are also a small amount of W other than WC2C, purity are insufficient.
105562119 A of Chinese invention patent CN, which is disclosed, a kind of prepares graphene oxide-loaded molybdenum carbide or tungsten carbide
The method of catalyst.This method uses heteropoly acid containing molybdenum or tungsten, polymer conductor, graphene for raw material, is closed using one kettle way
At heteropoly acid-polymer conductor/redox graphene composite material.Then by gained composite material at 700 DEG C, nitrogen atmosphere
2~5 hours of lower heat treatment obtain reduced graphene load tungsten carbide or molybdenum carbide elctro-catalyst through cooling after pickling.It utilizes
The graphene oxide-loaded tungsten carbide of this method preparation has good catalytic performance, but required preparation time is longer and cost compared with
It is high.
To sum up, a kind of be simple and efficient, low cost activated carbon supported tungsten carbide composite nano-powder preparation process urgently
Exploitation.
Summary of the invention
The purpose of the present invention is to provide a kind of activated carbon supported tungsten carbide composite nano-powder as elctro-catalyst
Preparation method, it is intended to the good activated carbon supported carbonization of large specific surface area, catalytic performance can be obtained by the method being simple and efficient
Tungsten composite nano-powder.
The present invention is to realize goal of the invention, is adopted the following technical scheme that:
The preparation method of the invention discloses a kind of activated carbon supported tungsten carbide composite nano-powder as elctro-catalyst,
It is characterized in that, carries out as follows:
(1) it by after active carbon ball milling, screening, is placed in nitric acid and is activated, obtain activity following activation charcoal；
(2) by ammonium metatungstate (NH4)6H2W12O40, ammonium nitrate NH4NO3, ethylenediamine tetra-acetic acid, adjuvant and activity following activation
Charcoal is added in deionized water, and magnetic agitation is uniform under room temperature, obtains mixed liquor；
(3) mixed liquor is placed in Muffle furnace, is warming up to 200 DEG C and 2~4h of heated at constant temperature, obtains activated carbon supported
Purple tungsten presoma；
(4) presoma is placed in tube furnace, is carbonized under the mixed atmosphere of methane and hydrogen, that is, obtained and be used as electricity
The activated carbon supported tungsten carbide composite nano-powder of catalyst.
Further, in step (1), the screening is carried out with the sieve of 200~400 mesh.
Further, it is 0.5~1.5mol/L that active carbon, which is placed in concentration, in step (1), after the activation will sieve
In nitric acid, 2~6h of heat preservation activation under the conditions of 75~95 DEG C of oil bath, cooled and filtered, washing are obtained to neutral, drying
Activity following activation charcoal.
Further, in step (2), the adjuvant is at least one of glycine, citric acid, urea and thiocarbamide.
Further, in step (2), the mass ratio of ammonium metatungstate and active carbon is 1~20:1, ammonium nitrate and ammonium metatungstate
Molar ratio be 12~36:1, the molar ratio of ethylenediamine tetra-acetic acid and ammonium metatungstate is 0.5~1:1, adjuvant and ammonium metatungstate
Molar ratio be 5~15:1.
Further, in step (2), the time of the stirring is 6~16h.
Further, in step (4), the temperature of the carbonization is 700~1000 DEG C, carbonization time is 2~4h, gas stream
Amount is 50~200mL/min.
Further, the volume ratio of methane and hydrogen is 20%:80% in step (4) described mixed atmosphere.
Compared with the prior art, the beneficial effects of the present invention are embodied in:
1, the present invention has the characteristics that process is short, at low cost using tungstates and active carbon as raw material.
2, the present invention is prepared for the presoma powder of activated carbon supported purple tungsten using infusion process and solution combustion synthetic method, bears
Carry that high-efficient, load capacity is big.
3, the present invention is added to active carbon during precursor preparation, and the porous structure of active carbon is conducive to reaction solution
Entrance, make reaction sufficiently carried out in duct, growing up for purple tungsten is limited, to limit tungsten carbide crystal grain in carbonisation
Grow up.
4, the present invention uses activated carbon supported tungsten carbide, and it is evenly dispersed on absorbent charcoal carrier to realize tungsten carbide, living
Property charcoal have high-specific surface area, form synergistic effect with tungsten carbide, improve the electronic conduction ability of composite granule, be conducive to
The transmission of reactant and intermediate product migrates, and is conducive to the stability for improving tungsten carbide powder.The activated carbon supported carbon prepared
Changing tungsten composite powder has good electric conductivity, catalytic activity and long-time stability.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of 1 gained precursor powder of embodiment；
Fig. 2 is the stereoscan photograph of the 1 activated carbon supported tungsten carbide composite nano-powder of gained of embodiment；
Fig. 3 is the TEM map of the 1 activated carbon supported tungsten carbide composite nano-powder of gained of embodiment.
Specific embodiment
It elaborates below with reference to embodiment to the present invention, following embodiments are under the premise of the technical scheme of the present invention
Implemented, the detailed implementation method and specific operation process are given, but protection scope of the present invention be not limited to it is following
Embodiment.
Embodiment 1
(1) by active carbon ball milling, excessively 200 meshes；Active carbon after screening is placed in the nitric acid that concentration is 1mol/L, 85
DEG C oil bath under the conditions of heat preservation activation 4h, cooled and filtered, washing obtain activity following activation to neutral, dry 5h at 120 DEG C
Charcoal.
(2) ammonium metatungstate ((NH is weighed according to stoichiometry4)6H2W12O40) 0.01mol, activity following activation charcoal 12g, nitre
Sour ammonium (NH4NO3) 0.24mol, ethylenediamine tetra-acetic acid 0.0072mol, glycine 0.072mol；Each raw material powder is dissolved in 50mL
In deionized water, magnetic agitation 8h under room temperature obtains mixed liquor；
(3) by mixed liquor in Muffle furnace 200 DEG C of heated at constant temperature 3h, before obtaining the needle-shaped activated carbon supported purple tungsten of porous nano
Drive body powder；
(4) precursor powder is placed in tube furnace, (flow of gas is under the mixed atmosphere of methane and hydrogen
150mL/min), 850 DEG C of carbonization 4h obtain the activated carbon supported tungsten carbide composite nano-powder for being used as elctro-catalyst.
Through characterizing, in activated carbon supported tungsten carbide composite nano-powder obtained by the present embodiment the partial size of tungsten carbide be 20~
100nm, in 0.1molL-1Potassium hydroxide solution in hydrogen reduction take-off potential be 970mV, have preferable catalytic performance.
Embodiment 2
(1) by active carbon ball milling, excessively 250 meshes；Active carbon after screening is placed in the nitric acid that concentration is 1mol/L, 85
DEG C oil bath under the conditions of heat preservation activation 4h, cooled and filtered, washing obtain activity following activation to neutral, dry 5h at 120 DEG C
Charcoal.
(2) ammonium metatungstate ((NH is weighed according to stoichiometry4)6H2W12O40) 0.01mol, activity following activation charcoal 4g, nitre
Sour ammonium (NH4NO3) 0.24mol, ethylenediamine tetra-acetic acid 0.0072mol, glycine 0.072mol；Each raw material powder is dissolved in 50mL
In deionized water, magnetic agitation 8h under room temperature obtains mixed liquor；
(3) by mixed liquor in Muffle furnace 200 DEG C of heated at constant temperature 3h, before obtaining the needle-shaped activated carbon supported purple tungsten of porous nano
Drive body powder；
(4) precursor powder is placed in tube furnace, (flow of gas is under the mixed atmosphere of methane and hydrogen
150mL/min), 800 DEG C of carbonization 4h obtain the activated carbon supported tungsten carbide composite nano-powder for being used as elctro-catalyst.
Through characterizing, in activated carbon supported tungsten carbide composite nano-powder obtained by the present embodiment the partial size diameter of tungsten carbide be 35~
90nm,.In 0.1molL-1Potassium hydroxide solution in hydrogen reduction take-off potential be 1.10V, have preferable catalytic performance.
Embodiment 3
(1) by active carbon ball milling, excessively 400 meshes；Active carbon after screening is placed in the nitric acid that concentration is 1mol/L, 85
DEG C oil bath under the conditions of heat preservation activation 4h, cooled and filtered, washing obtain activity following activation to neutral, dry 5h at 120 DEG C
Charcoal.
(2) ammonium metatungstate ((NH is weighed according to stoichiometry4)6H2W12O40) 0.01mol, activity following activation charcoal 3g, nitre
Sour ammonium (NH4NO3) 0.24mol, ethylenediamine tetra-acetic acid 0.0072mol, citric acid 0.1mol；Each raw material powder is dissolved in 50mL
In ionized water, magnetic agitation 8h under room temperature obtains mixed liquor；
(3) by mixed liquor in Muffle furnace 200 DEG C of heated at constant temperature 3h, before obtaining the needle-shaped activated carbon supported purple tungsten of porous nano
Drive body powder；
(4) precursor powder is placed in tube furnace, (flow of gas is under the mixed atmosphere of methane and hydrogen
150mL/min), 800 DEG C of carbonization 3h obtain the activated carbon supported tungsten carbide composite nano-powder for being used as elctro-catalyst.
Through characterizing, in activated carbon supported tungsten carbide composite nano-powder obtained by the present embodiment the partial size of tungsten carbide be 40~
90nm, the hydrogen reduction take-off potential in the potassium hydroxide solution of 0.1molL-1 are 950mV, have preferable catalytic performance.
Embodiment 4
(1) by active carbon ball milling, excessively 400 meshes；Active carbon after screening is placed in the nitric acid that concentration is 1mol/L, 85
DEG C oil bath under the conditions of heat preservation activation 4h, cooled and filtered, washing obtain activity following activation to neutral, dry 5h at 120 DEG C
Charcoal.
(2) ammonium metatungstate ((NH is weighed according to stoichiometry4)6H2W12O40) 0.01mol, activity following activation charcoal 0.6g,
Ammonium nitrate (NH4NO3) 0.24mol, ethylenediamine tetra-acetic acid 0.0072mol, thiocarbamide 0.05mol；Each raw material powder is dissolved in 50mL
In ionized water, magnetic agitation 8h under room temperature obtains mixed liquor；
(3) by mixed liquor in Muffle furnace 200 DEG C of heated at constant temperature 3h, before obtaining the needle-shaped activated carbon supported purple tungsten of porous nano
Drive body powder；
(4) precursor powder is placed in tube furnace, (flow of gas is under the mixed atmosphere of methane and hydrogen
150mL/min), 850 DEG C of carbonization 2h obtain the activated carbon supported tungsten carbide composite nano-powder for being used as elctro-catalyst.
Through characterizing, the partial size of tungsten carbide is 20~60nm in activated carbon supported tungsten carbide nano-powder obtained by the present embodiment,
In 0.1molL-1Potassium hydroxide solution in hydrogen reduction take-off potential be 1.05V, have preferable catalytic performance.
Embodiment 5
(1) by active carbon ball milling, excessively 200 meshes；Active carbon after screening is placed in the nitric acid that concentration is 1mol/L, 85
DEG C oil bath under the conditions of heat preservation activation 4h, cooled and filtered, washing obtain activity following activation to neutral, dry 5h at 120 DEG C
Charcoal.
(2) ammonium metatungstate ((NH is weighed according to stoichiometry4)6H2W12O40) 0.01mol, activity following activation charcoal 2.5g,
Ammonium nitrate (NH4NO3) 0.24mol, ethylenediamine tetra-acetic acid 0.0072mol, urea 0.072mol；Each raw material powder is dissolved in 50mL
In deionized water, magnetic agitation 8h under room temperature obtains mixed liquor；
(3) by mixed liquor in Muffle furnace 200 DEG C of heated at constant temperature 3h, before obtaining the needle-shaped activated carbon supported purple tungsten of porous nano
Drive body powder；
(4) precursor powder is placed in tube furnace, (flow of gas is under the mixed atmosphere of methane and hydrogen
150mL/min), 900 DEG C of carbonization 2h obtain the activated carbon supported tungsten carbide composite nano-powder for being used as elctro-catalyst.
Through characterizing, the partial size of tungsten carbide is 15~50nm in activated carbon supported tungsten carbide nano-powder obtained by the present embodiment,
In 0.1molL-1Potassium hydroxide solution in hydrogen reduction take-off potential be 943mV, have preferable catalytic performance.
The foregoing is merely illustrative of the preferred embodiments of the present invention, is not intended to limit the invention, all in essence of the invention
Made any modifications, equivalent replacements, and improvements etc., should all be included in the protection scope of the present invention within mind and principle.
Claims (8)
1. a kind of preparation method of the activated carbon supported tungsten carbide composite nano-powder as elctro-catalyst, is characterized in that, by such as
Lower step carries out:
(1) it by after active carbon ball milling, screening, is placed in nitric acid solution and is activated, obtain activity following activation charcoal；
(2) by ammonium metatungstate (NH4)6H2W12O40, ammonium nitrate NH4NO3, ethylenediamine tetra-acetic acid, adjuvant and activity following activation charcoal add
Enter in deionized water, magnetic agitation is uniform under room temperature, obtains mixed liquor；
(3) mixed liquor is placed in Muffle furnace, is gradually heated to 200 DEG C and 2~4h of heated at constant temperature, obtains activated carbon supported
Purple tungsten presoma；
(4) presoma is placed in tube furnace, is carbonized under the mixed atmosphere of methane and hydrogen, that is, obtained and be used as electro-catalysis
The activated carbon supported tungsten carbide composite nano-powder of agent.
2. preparation method according to claim 1, it is characterised in that: in step (1), the screening is with 200~400 mesh
Sieve carry out.
3. preparation method according to claim 1, it is characterised in that: in step (1), the activation is active after sieving
Charcoal is placed in the nitric acid that concentration is 0.5~1.5mol/L, 2~6h of heat preservation activation under the conditions of 75~95 DEG C of oil bath, after cooling
It is filtered, washed to neutral, drying, i.e. acquisition activity following activation charcoal.
4. preparation method according to claim 1, it is characterised in that: in step (2), the adjuvant is glycine, lemon
At least one of lemon acid, urea and thiocarbamide.
5. preparation method according to claim 1, it is characterised in that: in step (2), the quality of ammonium metatungstate and active carbon
Than for 1~20:1, the molar ratio of ammonium nitrate and ammonium metatungstate is the molar ratio of 12~36:1, ethylenediamine tetra-acetic acid and ammonium metatungstate
Molar ratio for 0.5~1:1, adjuvant and ammonium metatungstate is 5~15:1.
6. preparation method according to claim 1, it is characterised in that: in step (2), time of the stirring is 6~
16h。
7. preparation method according to claim 1, it is characterised in that: in step (4), the temperature of the carbonization is 700~
1000 DEG C, carbonization time be 2~4h, gas flow is 50~200mL/min.
8. preparation method according to claim 1, it is characterised in that: methane and hydrogen in step (4) described mixed atmosphere
Volume ratio be 20%:80%.
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