CN108499562A - A kind of pallium-on-carbon that anti-carbon monoxide poisons-tungsten dioxide elctro-catalyst and preparation method thereof - Google Patents
A kind of pallium-on-carbon that anti-carbon monoxide poisons-tungsten dioxide elctro-catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 66
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 48
- DZKDPOPGYFUOGI-UHFFFAOYSA-N tungsten dioxide Inorganic materials O=[W]=O DZKDPOPGYFUOGI-UHFFFAOYSA-N 0.000 title claims abstract description 47
- 229910002091 carbon monoxide Inorganic materials 0.000 title claims abstract description 24
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 92
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 44
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 42
- CMPGARWFYBADJI-UHFFFAOYSA-L tungstic acid Chemical compound O[W](O)(=O)=O CMPGARWFYBADJI-UHFFFAOYSA-L 0.000 claims abstract description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 72
- 239000000725 suspension Substances 0.000 claims description 60
- NGNBDVOYPDDBFK-UHFFFAOYSA-N 2-[2,4-di(pentan-2-yl)phenoxy]acetyl chloride Chemical compound CCCC(C)C1=CC=C(OCC(Cl)=O)C(C(C)CCC)=C1 NGNBDVOYPDDBFK-UHFFFAOYSA-N 0.000 claims description 25
- 239000001257 hydrogen Substances 0.000 claims description 19
- 229910052739 hydrogen Inorganic materials 0.000 claims description 19
- 239000007788 liquid Substances 0.000 claims description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007787 solid Substances 0.000 claims description 14
- 239000000843 powder Substances 0.000 claims description 8
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 239000008246 gaseous mixture Substances 0.000 claims description 4
- 239000011261 inert gas Substances 0.000 claims description 4
- 238000005245 sintering Methods 0.000 abstract description 28
- 238000000034 method Methods 0.000 abstract description 23
- 229910021607 Silver chloride Inorganic materials 0.000 abstract description 13
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 abstract description 13
- 239000003377 acid catalyst Substances 0.000 abstract description 11
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 6
- 238000007254 oxidation reaction Methods 0.000 abstract description 6
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000000463 material Substances 0.000 abstract description 3
- 239000011943 nanocatalyst Substances 0.000 abstract description 3
- 150000003057 platinum Chemical class 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 2
- 230000001590 oxidative effect Effects 0.000 abstract description 2
- 239000002245 particle Substances 0.000 abstract description 2
- 239000002574 poison Substances 0.000 abstract description 2
- 231100000614 poison Toxicity 0.000 abstract description 2
- 239000000243 solution Substances 0.000 description 45
- 239000000706 filtrate Substances 0.000 description 32
- 238000001914 filtration Methods 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 10
- 238000005406 washing Methods 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 8
- 239000002253 acid Substances 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 235000019441 ethanol Nutrition 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 230000008569 process Effects 0.000 description 6
- 239000012279 sodium borohydride Substances 0.000 description 6
- 229910000033 sodium borohydride Inorganic materials 0.000 description 6
- 239000007864 aqueous solution Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 239000007789 gas Substances 0.000 description 5
- SDLBJIZEEMKQKY-UHFFFAOYSA-M silver chlorate Chemical compound [Ag+].[O-]Cl(=O)=O SDLBJIZEEMKQKY-UHFFFAOYSA-M 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical class [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 4
- APIXVYLDKWFFQV-UHFFFAOYSA-N [W](=O)=O.[Pt] Chemical compound [W](=O)=O.[Pt] APIXVYLDKWFFQV-UHFFFAOYSA-N 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 238000004220 aggregation Methods 0.000 description 4
- 239000007795 chemical reaction product Substances 0.000 description 4
- 239000003153 chemical reaction reagent Substances 0.000 description 4
- 238000005352 clarification Methods 0.000 description 4
- 238000000840 electrochemical analysis Methods 0.000 description 4
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000007420 reactivation Effects 0.000 description 4
- 239000013049 sediment Substances 0.000 description 4
- 235000011121 sodium hydroxide Nutrition 0.000 description 4
- 229940126680 traditional chinese medicines Drugs 0.000 description 4
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 4
- 229910052721 tungsten Inorganic materials 0.000 description 4
- 239000010937 tungsten Substances 0.000 description 4
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
- 241000370738 Chlorion Species 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 239000006185 dispersion Substances 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 239000012047 saturated solution Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- GTKRFUAGOKINCA-UHFFFAOYSA-M chlorosilver;silver Chemical compound [Ag].[Ag]Cl GTKRFUAGOKINCA-UHFFFAOYSA-M 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 125000005909 ethyl alcohol group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229910003446 platinum oxide Inorganic materials 0.000 description 1
- CFQCIHVMOFOCGH-UHFFFAOYSA-N platinum ruthenium Chemical compound [Ru].[Pt] CFQCIHVMOFOCGH-UHFFFAOYSA-N 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229910001961 silver nitrate Inorganic materials 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000001291 vacuum drying Methods 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/56—Platinum group metals
- B01J23/64—Platinum group metals with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/652—Chromium, molybdenum or tungsten
- B01J23/6527—Tungsten
-
- 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 invention belongs to nanocatalyst preparing technical fields, and in particular to a kind of pallium-on-carbon tungsten dioxide elctro-catalyst and preparation method thereof that anti-carbon monoxide poisons.After preparation method provided by the invention is by the way that platinum salt, carbon carrier and tungstic acid to be sufficiently mixed, on the basis of disclosed microwave assisting method, it is prepared for pallium-on-carbon tungstic acid catalyst material, again by restoring sintering technology, tungstic acid is restored to lower valency, it is prepared for pallium-on-carbon tungsten dioxide elctro-catalyst, the oxidizing potential of carbon monoxide on a catalyst is greatly lowered, promotes the anti-carbon monoxide ability of catalyst.The particle diameter distribution of platinum has preferable utilization ratio in 4 rans in pallium-on-carbon tungsten dioxide elctro-catalyst provided by the invention.The pallium-on-carbon tungsten dioxide elctro-catalyst of the present invention is compared with oxidation current of the platinum carbon catalyst at 0.7V vs.Ag/AgCl, has more excellent anti-carbon monoxide oxidation susceptibility.
Description
Technical field
The invention belongs to nanocatalyst preparing technical fields, and in particular to a kind of pallium-on-carbon-that anti-carbon monoxide poisons
Tungsten dioxide elctro-catalyst and preparation method thereof.
Background technology
Platinum-based electrocatalyst is common electrocatalysis material, and dosage demand is very high in a fuel cell.In general, people use
Immersion reduction method prepares platinum carbon catalyst, and this method is suitble to large batch of production platinum carbon catalyst, but disadvantage is the grain of product
Diameter is larger.And the Chinese patent of Publication No. CN1775362A prepares platinum/carbon nano catalyst using microwave assisted techniques, is made
Catalyst grain size it is smaller, and have higher catalytic performance.
For the organic molecules fuel such as methanol, simple easily causes the strong of carbon monoxide intermediate using platinum catalyst
Absorption, so as to cause catalyst poisoning phenomenon.In order to solve this problem, the platinum-based electrocatalyst of bi-component, such as patent are often used
Number disclose a kind of platinum ruthenium catalyst of Ru as anti-carbon monoxide component, the catalyst for the Chinese patent of CN01118132.X
It can effectively catalytic CO aoxidize, mitigate catalyst poisoning phenomenon.Also document provides a kind of system of platinum-tungstic acid
Preparation Method, and the application in being aoxidized to methanol, but the highest that the tungstic acid used in this method is transition metal tungsten
Valence state, as reducible transition metal oxide, promoting catalysis still has the space (A.K.Shukla of promotion；
M.K.Ravikumar；et.al,Journal of Applied Electrochemistry 1995,25(6),528-532.).
Invention content
A kind of pallium-on-carbon poisoned the object of the present invention is to provide anti-carbon monoxide-tungsten dioxide elctro-catalyst and its preparation
Method.
To achieve the goals above, technical scheme of the present invention is specific as follows：
The present invention provides a kind of preparation method of the pallium-on-carbon that anti-carbon monoxide poisons-tungsten dioxide elctro-catalyst, including
Following steps：
Step 1：By carbon carrier with tungstic acid is polished is scattered in ethylene glycol, obtain the first suspension；
Step 2：Platinum acid chloride solution is added into the first suspension and pH adjusts liquid, obtains the second suspension；
Step 3：Second suspension is placed in microwave reactor, microwave reaction is carried out, obtains third suspension；
Step 4：Third suspension is filtered, is cleaned, it is dry, obtain solid powder；
Step 5：Solid powder is sintered in reducing atmosphere, obtains pallium-on-carbon-tungsten dioxide elctro-catalyst.
In the above-mentioned technical solutions, the carbon carrier is conductive carbon powder.
In the above-mentioned technical solutions, the mass ratio of platinum content and carbon carrier is (100~200) in the platinum acid chloride solution：
(300~400).
In the above-mentioned technical solutions, in the platinum acid chloride solution mass ratio of platinum content and tungstic acid be (100~
200)：(20~100).
In the above-mentioned technical solutions, the mass ratio of platinum content and carbon carrier is 100 in the platinum acid chloride solution：400, it is described
The mass ratio of platinum content and tungstic acid is 200 in platinum acid chloride solution：100, the mass ratio of the ethylene glycol and carbon carrier is
1000：10.
In the above-mentioned technical solutions, it is 10 that the pH, which adjusts liquid and adjusts the pH value of the second suspension,.
In the above-mentioned technical solutions, solid powder is restored using hydrogen and inert gas gaseous mixture in step 5, hydrogen
Volumn concentration is 5-20%.
In the above-mentioned technical solutions, the temperature restored in step 5 is 400-600 DEG C, and the time of reduction is 0.5-3 hours.
In the above-mentioned technical solutions, the temperature restored in step 5 is 500 DEG C, and the time of reduction is 1 hour.
The present invention also provides pallium-on-carbon-tungsten dioxide elctro-catalysts made from a kind of above-mentioned preparation method.
The beneficial effects of the invention are as follows：
The preparation method of the pallium-on-carbon that anti-carbon monoxide provided by the invention poisons-tungsten dioxide elctro-catalyst, pass through by
After platinum salt, carbon carrier and tungstic acid are sufficiently mixed, on the basis of disclosed microwave assisting method, it is prepared for-three oxygen of pallium-on-carbon
Change tungsten catalyst material.Again by restoring sintering technology, tungstic acid is restored to lower valency, is prepared for pallium-on-carbon-titanium dioxide
The oxidizing potential of carbon monoxide on a catalyst is greatly lowered in tungsten elctro-catalyst, promotes the anti-carbon monoxide ability of catalyst.
The catalyst of the present invention is subjected to transmission electron microscope characterization, obtains particle diameter distribution that result is platinum in 4 rans, tool
There is preferable utilization ratio.By the catalyst of the rotating disk electrode (r.d.e) analysis present invention to the oxidation effectiveness of carbon monoxide, obtain
As a result it is at 0.1V vs.Ag/AgCl there is oxidation current to generate carbon monoxide, with platinum carbon catalyst in 0.7V vs.Ag/
Oxidation current comparison under AgCl, has more excellent anti-carbon monoxide oxidation susceptibility.
Description of the drawings
Invention is further described in detail with reference to the accompanying drawings and detailed description.
Fig. 1 is pallium-on-carbon-transmission electron microscope of the tungsten dioxide elctro-catalyst under 20nm scales prepared by the embodiment of the present invention 1
Photo.
Fig. 2 is the X-ray diffractogram of pallium-on-carbon-tungsten dioxide elctro-catalyst prepared by the embodiment of the present invention 1.
Fig. 3 is after pallium-on-carbon-tungsten dioxide elctro-catalyst prepared by the embodiment of the present invention 1 is poisoned by carbon monoxide, in hydrogen
The cyclic voltammetry scan curve of restorability in gas saturated solution.
Fig. 4 is after pallium-on-carbon elctro-catalyst prepared by comparative example 1 is poisoned by carbon monoxide, to restore in hydrogen saturated solution
The cyclic voltammetry scan curve of performance.
Specific implementation mode
The present invention is described in detail below in conjunction with the accompanying drawings.
The preparation method of the pallium-on-carbon that anti-carbon monoxide provided by the invention poisons-tungsten dioxide elctro-catalyst first will
Carbon carrier with tungstic acid is polished is scattered in ethylene glycol, obtain the first suspension；Then it is added into the first suspension
Platinum acid chloride solution and pH adjust liquid, obtain the second suspension；Using technology is disclosed, platinum salt is restored using microwave method, is obtained
Third suspension, that is, pallium-on-carbon-tungstic acid.After filtering cleaning, pallium-on-carbon-titanium dioxide is made in reduction sintering under proper condition
Tungsten elctro-catalyst.
The preparation method of the pallium-on-carbon that anti-carbon monoxide provided by the invention poisons-tungsten dioxide elctro-catalyst specifically includes
Following steps：
Step 1：By carbon carrier with tungstic acid is polished is scattered in ethylene glycol, obtain the first suspension；
Step 2：Platinum acid chloride solution is added into the first suspension and pH adjusts liquid, obtains the second suspension；
Step 3：Second suspension is placed in microwave reactor, microwave reaction is carried out, obtains third suspension；
Step 4：Third suspension is filtered, is cleaned, it is dry, obtain solid powder；
Step 5：Solid powder is sintered in reducing atmosphere, obtains pallium-on-carbon-tungsten dioxide elctro-catalyst.
It is first that carbon carrier and tungstic acid is polished according to the present invention, it is scattered in the mixing of ethylene glycol and dispersant
In solvent, the first suspension is obtained；The present invention is not particularly limited dispersing mode, it is preferred to use the method for ultrasonic wave dispersion,
The time of the ultrasonic wave dispersion is preferably 1-3 hours, and more preferably 1.5-2 hours, the carbon carrier was this field skill
Carbon carrier known to art personnel, is not particularly limited, preferably conductive carbon powder.
According to the present invention, after obtaining the first suspension, platinum acid chloride solution is added into the first suspension and pH adjusts liquid,
It stirs at room temperature, preferred mixing time is 1-2 hours, obtains the second suspension；In the platinum acid chloride solution platinum content and
The mass ratio of carbon carrier is preferably (100~200)：(300~400), more preferably 100:400.The ethylene glycol and carbon carrier
Mass ratio be preferably (5000~10000)：(2~10), more preferably 1000：10.Platinum content in the platinum acid chloride solution
It is preferably (100~200) with tungstic acid mass ratio：(20~100), more preferably 200：100.
According to the present invention, above-mentioned second suspension is placed in microwave reactor, microwave reaction obtains third for a period of time
Suspension.Wherein chloroplatinic acid can be reduced to Platinum Nanoparticles, be dispersed in carbon carrier and tungstic acid by ethylene glycol as a kind of reducing agent
Surface.The microwave time is preferably 30-80 seconds, more preferably 50 seconds.Used microwave power is preferably 500-1000 watts.
According to the present invention, after stirring, obtained third suspension is filtered, after washing, drying, you can obtain carbon load
Platinum-tungstic acid compound.Present invention preferably uses the deionized waters that resistivity is 17M Ω cm~19M Ω cm to described
Reaction product carries out filtering and washing, washing to no chlorion, organic solvent-free.In the first time filtrate that the present invention is obtained to washing
Sodium borohydride solution is added, no black precipitate occurs, then shows to remain without chloroplatinic acid in reaction product.To what is washed
Silver nitrate solution is added in final filtrate, no precipitation occurs, then shows exist without chlorion in reaction product.By described by washing
The reaction product washed obtains pallium-on-carbon-tungstic acid catalyst after drying process well known to those skilled in the art.
According to the present invention, pallium-on-carbon-tungstic acid catalyst is placed in sintering processes in reducing atmosphere stove.Sintering atmosphere is
The volumn concentration of hydrogen and inert gas gaseous mixture, hydrogen is 5-20%, optimum condition 5%.It is preferred that sintering temperature is
400-600℃.Further preferably sintering temperature is 500 DEG C.Preferred reaction time is 0.5-3 hours, and further preferably the reaction time is 1 small
When.Sintering solid is ground, pallium-on-carbon-tungsten dioxide elctro-catalyst is obtained.
The present invention also provides pallium-on-carbon-tungsten dioxide elctro-catalysts made from a kind of above-mentioned preparation method.
The pallium-on-carbon that anti-carbon monoxide provided by the invention is poisoned with reference to specific embodiment-tungsten dioxide electro-catalysis
Agent and preparation method thereof is described in detail.Raw materials used in following embodiment is the general chemical bought from the market.
Embodiment 1
Chloroplatinic acid is dissolved in ethylene glycol, the platinum acid chloride solution that platiniferous is 0.01g/mL is formulated as.
1g sodium hydroxides are dissolved in 100mL ethylene glycol, are stirred 1 hour, pH is formulated as and adjusts liquid.
The tungsten trioxide nano powder of 2.5mg traditional Chinese medicines reagents production is produced with the U.S. 20mg Cabot (Cabot) company, quotient
The activated carbon that the name of an article is known as Vulcan XC-72 is ground 1 hour, and ultrasonic disperse 2 hours, obtains first after addition 20mL ethylene glycol
Suspension.Platinum acid chloride solution 0.5mL and pH is added into first suspension after being uniformly dispersed and adjusts liquid 1mL, adjusts solution
PH is 10, after stirring 2 hours, obtains the second suspension.Second suspension is placed in microwave reactor, under 800W power,
Microwave reaction 80 seconds, obtains third suspension.Above-mentioned third suspension is taken out with the deionized water that resistivity is 18.2M Ω cm
Filter washing obtains the first filtrate after filtering, sodium borohydride 0.01g/mL aqueous solutions are added in the first filtrate, and filtrate clarification is without heavy
It forms sediment.After filtering is cleaned multiple times, the silver chlorate that mass concentration is 0.01g/mL is added in final filtrate, filtrate is clarified without precipitation.
Filtrate is dried in vacuo at 80 DEG C, obtains pallium-on-carbon-tungstic acid catalyst.
Pallium-on-carbon-tungstic acid catalyst is placed in sintering processes in reducing atmosphere stove.Sintering atmosphere is hydrogen and inertia
The volumn concentration of gas mixture, hydrogen is 5%, and sintering temperature is 500 DEG C, and after reacting 1 hour, sintering solid is ground
Mill, obtains pallium-on-carbon-tungsten dioxide elctro-catalyst.
By the pallium-on-carbon-tungsten dioxide elctro-catalyst ultrasonic disperse in ethyl alcohol, suspension is obtained；By the suspension
It is applied to after being dried on copper mesh, carries out electron-microscope scanning, be as a result that pallium-on-carbon-tungsten dioxide prepared by embodiment 1 is electric referring to Fig. 1, Fig. 1
Transmission electron microscope photo of the catalyst under 20nm scales, it is seen that grain size is about within the scope of 3-5nm, and Pt nano-particles are carried in carbon
It is uniformly dispersed on body, no clustering phenomena.The pallium-on-carbon-tungsten dioxide elctro-catalyst is subjected to XRD characterization, as a result referring to Fig. 2,
Demonstrate the crystal structure of platinum and tungsten dioxide.
It is produced to 1mL absolute ethyl alcohols and 50 μ L Aldrich, 5mg is added in the Nafion solution that mass concentration is 5%
The pallium-on-carbon-tungsten dioxide elctro-catalyst, ultrasonic disperse 30 minutes, obtains solution；Take solution drop coating described in 10 μ L in glass carbon
On electrode, after room temperature is dried, membrane electrode is obtained；Using silver-silver chloride electrode as reference electrode, platinized platinum as three to electrode
Electrode system is first passed through carbon monoxide 10 minutes in the solution at 0.02V, will be catalyst poisoning, is then passed through in the solution
Pure hydrogen carries out cyclic voltammetry scan test, sweep speed 50mV/s.As a result it is pallium-on-carbon-tungsten dioxide referring to Fig. 3, Fig. 3
Recovery capability cyclic voltammetry scan curve of the elctro-catalyst in sulfuric acid solution.It is generated just at 0.1-0.15V vs.Ag/AgCl
Electric current restores catalytic capability at 0.4-0.5vs.Ag/AgCl.
Embodiment 2
Chloroplatinic acid is dissolved in ethylene glycol, the platinum acid chloride solution that platiniferous is 0.01g/mL is formulated as.
1g sodium hydroxides are dissolved in 100mL ethylene glycol, are stirred 1 hour, pH is formulated as and adjusts liquid.
The tungsten trioxide nano powder of 5mg traditional Chinese medicines reagents production is produced with the U.S. 20mg Cabot (Cabot) company, commodity
The activated carbon of entitled Vulcan XC-72 is ground 1 hour, and ultrasonic disperse 2 hours, it is outstanding to obtain first after addition 20mL ethylene glycol
Turbid.Platinum acid chloride solution 0.5mL and pH is added into first suspension after being uniformly dispersed and adjusts liquid 1mL, adjusts pH value of solution
It is 10, after stirring 2 hours, obtains the second suspension.Second suspension is placed in microwave reactor, it is micro- under 800W power
Wave reacts 80 seconds, obtains third suspension.Above-mentioned third suspension is filtered with the deionized water that resistivity is 18.2M Ω cm
Washing, obtains the first filtrate after filtering, sodium borohydride 0.01g/mL aqueous solutions are added in the first filtrate, and filtrate clarification is without heavy
It forms sediment.It is that 0.01g/mL silver chlorates are added in final filtrate by mass concentration, filtrate is clarified without precipitation after filtering is cleaned multiple times.It will
Filtrate drying is dried in vacuo at 80 DEG C, obtains pallium-on-carbon-tungstic acid catalyst.
Pallium-on-carbon-tungstic acid catalyst is placed in sintering processes in reducing atmosphere stove.Sintering atmosphere is hydrogen and inertia
Gas mixture, hydrogen content 10%.Sintering temperature is 400 DEG C, after reacting 0.5 hour, sintering solid is ground, carbon is obtained
Carry platinum-tungsten dioxide elctro-catalyst.
By the pallium-on-carbon-tungsten dioxide elctro-catalyst ultrasonic disperse in ethyl alcohol, electron-microscope scanning method with embodiment 1,
No aggregation it can be seen that grain size about within the scope of 3-5nm, is evenly distributed.
For electrochemical test method with embodiment 1, gained is that pallium-on-carbon-tungsten dioxide elctro-catalyst is extensive in sulfuric acid solution
Reactivation power cyclic voltammetry scan curve.Positive current is generated at 0.15-0.2V vs.Ag/AgCl, in 0.45-0.55vs.Ag/
Restore catalytic capability under AgCl.
Embodiment 3
Chloroplatinic acid is dissolved in ethylene glycol, the platinum acid chloride solution that platiniferous is 0.01g/mL is formulated as.
1g sodium hydroxides are dissolved in 100mL ethylene glycol, are stirred 1 hour, pH is formulated as and adjusts liquid.
The tungsten trioxide nano powder of 2mg traditional Chinese medicines reagents production is produced with the U.S. 30mg Cabot (Cabot) company, commodity
The activated carbon of entitled Vulcan XC-72 is ground 1 hour, and ultrasonic disperse 2 hours, it is outstanding to obtain first after addition 20mL ethylene glycol
Turbid.Platinum acid chloride solution 1.0mL and pH is added into first suspension after being uniformly dispersed and adjusts liquid 1mL, adjusts pH value of solution
It is 10, after stirring 2 hours, obtains the second suspension.Second suspension is placed in microwave reactor, it is micro- under 800W power
Wave reacts 80 seconds, obtains third suspension.Above-mentioned third suspension is filtered with the deionized water that resistivity is 18.2M Ω cm
Washing, obtains the first filtrate after filtering, sodium borohydride 0.01g/mL aqueous solutions are added in the first filtrate, and filtrate clarification is without heavy
It forms sediment.After filtering is cleaned multiple times, silver chlorate 0.01g/mL is added in final filtrate, filtrate is clarified without precipitation.By filtrate 80
DEG C vacuum drying, obtain pallium-on-carbon-tungstic acid catalyst.
Pallium-on-carbon-tungstic acid catalyst is placed in sintering processes in reducing atmosphere stove.Sintering atmosphere is hydrogen and inertia
Gas mixture, hydrogen content 20%.Sintering temperature is 600 DEG C, and after reacting 3 hours, sintering solid is ground, and obtains carbon load
Platinum-tungsten dioxide elctro-catalyst.
By the pallium-on-carbon-tungsten dioxide elctro-catalyst ultrasonic disperse in ethyl alcohol, electron-microscope scanning method with embodiment 1,
No aggregation it can be seen that grain size about within the scope of 3-5nm, is evenly distributed.
For electrochemical test method with embodiment 1, gained is that pallium-on-carbon-tungsten dioxide elctro-catalyst is extensive in sulfuric acid solution
Reactivation power cyclic voltammetry scan curve.Positive current is generated at 0.15-0.2V vs.Ag/AgCl, in 0.55-0.6vs.Ag/
Restore catalytic capability under AgCl.
Embodiment 4
Chloroplatinic acid is dissolved in ethylene glycol, the platinum acid chloride solution that platiniferous is 0.01g/mL is formulated as.
1g sodium hydroxides are dissolved in 100mL ethylene glycol, are stirred 1 hour, pH is formulated as and adjusts liquid.
The tungsten trioxide nano powder of 5mg traditional Chinese medicines reagents production is produced with the U.S. 30mg Cabot (Cabot) company, commodity
The activated carbon of entitled Vulcan XC-72 is ground 1 hour, and ultrasonic disperse 2 hours, it is outstanding to obtain first after addition 20mL ethylene glycol
Turbid.Platinum acid chloride solution 2.0mL and pH is added into first suspension after being uniformly dispersed and adjusts liquid 1mL, adjusts pH value of solution
It is 10, after stirring 2 hours, obtains the second suspension.Second suspension is placed in microwave reactor, it is micro- under 800W power
Wave reacts 80 seconds, obtains third suspension.Above-mentioned third suspension is filtered with the deionized water that resistivity is 18.2M Ω cm
Washing, obtains the first filtrate after filtering, sodium borohydride 0.01g/mL aqueous solutions are added in the first filtrate, and filtrate clarification is without heavy
It forms sediment.It is that 0.01g/mL silver chlorates are added in final filtrate by mass concentration, filtrate is clarified without precipitation after filtering is cleaned multiple times.It will
Filtrate is dried in vacuo at 80 DEG C, obtains pallium-on-carbon-tungstic acid catalyst.
Pallium-on-carbon-tungstic acid catalyst is placed in sintering processes in reducing atmosphere stove.Sintering atmosphere is hydrogen and inertia
Gas mixture, hydrogen content 5%.Sintering temperature is 500 DEG C, and after reacting 1 hour, sintering solid is ground, and obtains carbon load
Platinum-tungsten dioxide elctro-catalyst.
By the pallium-on-carbon-tungsten dioxide elctro-catalyst ultrasonic disperse in ethyl alcohol, electron-microscope scanning method with embodiment 1,
No aggregation it can be seen that grain size about within the scope of 3-5nm, is evenly distributed.
For electrochemical test method with embodiment 1, gained is that pallium-on-carbon-tungsten dioxide elctro-catalyst is extensive in sulfuric acid solution
Reactivation power cyclic voltammetry scan curve.Positive current is generated at 0.1-0.15V vs.Ag/AgCl, in 0.45-0.5vs.Ag/
Restore catalytic capability under AgCl.
Comparative example 1
As a comparison, carbon supported platinum catalyst is prepared using microwave method, wherein not containing tungstic acid.
Chloroplatinic acid is dissolved in ethylene glycol, the platinum acid chloride solution that platiniferous is 0.01g/mL is formulated as.
1g sodium hydroxids are dissolved in 100mL ethylene glycol, are stirred 1 hour, pH is formulated as and adjusts liquid.
The production of the U.S. 20mg Cabot (Cabot) company, trade name is small for the activated carbon grinding 1 of Vulcan XC-72
When, ultrasonic disperse 2 hours after 20mL ethylene glycol is added, obtains the first suspension.After being uniformly dispersed into first suspension
Platinum acid chloride solution 0.4mL and pH is added and adjusts liquid 1mL, it is 10 to adjust pH value of solution, after stirring 2 hours, obtains the second suspension.It will
Second suspension is placed in microwave reactor, and under 800W power, microwave reaction 80 seconds obtains third suspension.With resistivity
For 18.2M Ω cm deionized water by above-mentioned third suspension filtering and washing, the first filtrate is obtained after filtering, by sodium borohydride
0.01g/mL aqueous solutions are added in the first filtrate, and filtrate is clarified without precipitation.It is 0.01g/ by mass concentration after filtering is cleaned multiple times
ML silver chlorates are added in final filtrate, and filtrate is clarified without precipitation.Filtrate is dried in vacuo at 80 DEG C, obtains pallium-on-carbon catalysis
Agent.
It is compared as flow, carbon supported platinum catalyst is placed in sintering processes in reducing atmosphere stove.Sintering atmosphere be hydrogen and
Inert gas gaseous mixture, hydrogen content 5%.Sintering temperature is 500 DEG C, after reacting 1 hour, sintering solid is ground, is obtained
Treated pallium-on-carbon elctro-catalyst.
By the pallium-on-carbon-tungsten dioxide elctro-catalyst ultrasonic disperse in ethyl alcohol, electron-microscope scanning method with embodiment 1,
No aggregation it can be seen that grain size about within the scope of 3-5nm, is evenly distributed.
For electrochemical test method with embodiment 1, gained is that pallium-on-carbon-tungsten dioxide elctro-catalyst is extensive in sulfuric acid solution
Reactivation power cyclic voltammetry scan curve.As shown in figure 4, positive current is generated at 0.6-0.7V vs.Ag/AgCl, in 0.7-
Restore catalytic capability under 0.8vs.Ag/AgCl.
Comparative sample conclusion illustrates that the reduction sintered catalyst of platinum-tungsten dioxide can aoxidize under more low potential
Carbon.Pallium-on-carbon produced by the invention-tungsten dioxide elctro-catalyst has good anti-carbon monoxide performance.
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of preparation method of the pallium-on-carbon that anti-carbon monoxide poisons-tungsten dioxide elctro-catalyst, which is characterized in that including with
Lower step：
Step 1：By carbon carrier with tungstic acid is polished is scattered in ethylene glycol, obtain the first suspension；
Step 2：Platinum acid chloride solution is added into the first suspension and pH adjusts liquid, obtains the second suspension；
Step 3：Second suspension is placed in microwave reactor, microwave reaction is carried out, obtains third suspension；
Step 4：Third suspension is filtered, is cleaned, it is dry, obtain solid powder；
Step 5：Solid powder is sintered in reducing atmosphere, obtains pallium-on-carbon-tungsten dioxide elctro-catalyst.
2. preparation method according to claim 1, which is characterized in that the carbon carrier is conductive carbon powder.
3. preparation method according to claim 1, which is characterized in that platinum content and carbon carrier in the platinum acid chloride solution
Mass ratio is (100~200)：(300~400).
4. preparation method according to claim 1, which is characterized in that platinum content and tungstic acid in the platinum acid chloride solution
Mass ratio be (100~200)：(20~100).
5. preparation method according to claim 1, which is characterized in that platinum content and carbon carrier in the platinum acid chloride solution
Mass ratio is 100：400, the mass ratio of platinum content and tungstic acid is 200 in the platinum acid chloride solution：100, the ethylene glycol
Mass ratio with carbon carrier is 1000：10.
6. preparation method according to claim 1, which is characterized in that the pH adjusts the pH value that liquid adjusts the second suspension
It is 10.
7. preparation method according to claim 1, which is characterized in that use hydrogen and inert gas gaseous mixture in step 5
Solid powder is restored, the volumn concentration of hydrogen is 5-20%.
8. preparation method according to claim 1, which is characterized in that the temperature restored in step 5 is 400-600 DEG C, also
The former time is 0.5-3 hours.
9. preparation method according to claim 1, which is characterized in that the temperature restored in step 5 is 500 DEG C, reduction
Time is 1 hour.
10. pallium-on-carbon-tungsten dioxide elctro-catalyst made from a kind of any one preparation method of claim 1-9.
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