CN102553582B - Method for preparing carbon supported Au-Pt or Au-Pd catalyst - Google Patents
Method for preparing carbon supported Au-Pt or Au-Pd catalyst Download PDFInfo
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- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 75
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 36
- 229910002710 Au-Pd Inorganic materials 0.000 title abstract 11
- 239000002131 composite material Substances 0.000 claims abstract description 43
- 230000000694 effects Effects 0.000 claims abstract description 38
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 147
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 98
- 239000000243 solution Substances 0.000 claims description 55
- 229910052763 palladium Inorganic materials 0.000 claims description 48
- 239000010931 gold Substances 0.000 claims description 33
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 31
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 31
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 31
- 239000006229 carbon black Substances 0.000 claims description 25
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 19
- 238000002360 preparation method Methods 0.000 claims description 18
- 230000008569 process Effects 0.000 claims description 18
- 238000011282 treatment Methods 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 13
- 229910052737 gold Inorganic materials 0.000 claims description 13
- 239000002245 particle Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 9
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 9
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 8
- BBKFSSMUWOMYPI-UHFFFAOYSA-N gold palladium Chemical compound [Pd].[Au] BBKFSSMUWOMYPI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003223 protective agent Substances 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical group O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- 239000012279 sodium borohydride Substances 0.000 claims description 5
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 5
- 239000007864 aqueous solution Substances 0.000 claims description 4
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 3
- 239000008103 glucose Substances 0.000 claims description 3
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 3
- 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 2
- FFBHFFJDDLITSX-UHFFFAOYSA-N benzyl N-[2-hydroxy-4-(3-oxomorpholin-4-yl)phenyl]carbamate Chemical compound OC1=C(NC(=O)OCC2=CC=CC=C2)C=CC(=C1)N1CCOCC1=O FFBHFFJDDLITSX-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 claims description 2
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 claims description 2
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 2
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims 1
- 229910021641 deionized water Inorganic materials 0.000 claims 1
- WXHIJDCHNDBCNY-UHFFFAOYSA-N palladium dihydride Chemical compound [PdH2] WXHIJDCHNDBCNY-UHFFFAOYSA-N 0.000 claims 1
- 239000002105 nanoparticle Substances 0.000 abstract description 21
- 230000004048 modification Effects 0.000 abstract description 9
- 238000012986 modification Methods 0.000 abstract description 9
- 239000000084 colloidal system Substances 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000126 substance Substances 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 3
- 239000000460 chlorine Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000002048 multi walled nanotube Substances 0.000 description 7
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 4
- 229910052700 potassium Inorganic materials 0.000 description 4
- 239000011591 potassium Substances 0.000 description 4
- 230000009467 reduction Effects 0.000 description 4
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 229910002849 PtRu Inorganic materials 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 238000005275 alloying Methods 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
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- 238000004519 manufacturing process Methods 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 150000002941 palladium compounds Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
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Abstract
The invention relates to a method for preparing a carbon supported Au-Pt or Au-Pd catalyst by modifying Au-Pt or Au-Pd bimetal nanoparticles with microwaves, belonging to the technical field of catalytic materials. High pressure and high temperature generated by microwaves in a high-pressure reaction tank are utilized to treat an Au-Pt or Au-Pd composite nano colloid synthesized by a chemical coreduction method so as to induce the modification of the Au-Pt or Au-Pd bimetal nanoparticles; and the microwave-modified bimetal nanoparticles are deposited on the surface of the carbon support, thereby obtaining the carbon supported Au-Pt or Au-Pd catalyst with high activity. The carbon supported Au-Pt or Au-Pd catalyst has high electrocatalytic activity; the supporting rate of the Au-Pt or Au-Pd bimetal is high; the supporting amount of the Au-Pt or Au-Pd is controllable; and the method can be used for preparing the carbon supported Au-Pt or Au-Pd nano catalyst of which the mass ratio of Au-Pt or Au-Pd to carbon is 1-20%. The method provided by the invention has the advantages of low cost, simple technique and low facility request, and has wide industrial application prospects.
Description
Technical field
The present invention relates to and a kind ofly utilize microwave modification gold platinum or golden palladium bimetal nano particles to prepare carbon to carry high activity gold platinum or the method for golden palladium catalyst, belong to catalysis material technical field.
Background technology
Along with the fast development of nano fabrication technique and catalytic science, some researchers are from reducing catalyst cost, and the angle that can improve again catalyst activity and CO tolerance is considered, prepares the bimetal Au/Pt of high catalytic activity, AuPd nano particle.Research in recent years finds that the physicochemical properties of bimetal Au/Pt nano particle not only change with the chemical composition of Au and Pt, but also changes with the micro-structural of AuPt nano particle.Such as, the people such as Zhong Chuanjian (C J Zhong et al, Langmuir.2006,22:2892) prepare Au mass percent be 65 ~ 85% carbon carry AuPt nanocatalyst, through 500 DEG C of alloying heat treatments, the electro catalytic activity of methyl alcohol is exceeded to Pt/C and the PtRu/C catalyst of identical load amount in alkaline solution; The people (Eichhorn B. et al, Advanced Fuctional Materials, 2007,17:3099) such as Bryan Eichhorn report AuPt alloy nano particle than the nano heterogeneous aggregation of AuPt has more tolerance to CO; AuPt nano particle (Chi J H et al, the Journal of the electrochemical society of small particle diameter can be prepared with method of reducing while of chemical method
,2006,153:1812); Difference due to the reduction potential of Au, Pt and Pd result in the difference of rate of reduction, the structure such as can form graded alloy (class nucleocapsid) between Au and Pt and Au and Pd and be separated, carbon carries Au Pt or Au Pd bimetallic catalyst also needs could obtain good catalytic activity by high temperature solid-state heat treatment.But catalyst is after conventional high-temperature heat treatment, there will be nano particle reunite grow up, local sintering and metal nanoparticle be from problems such as carbon support come off.
Heating using microwave is interior heating, have that firing rate is fast, homogeneous heating, without thermograde, without features such as hysteresis effects.At present, heating using microwave is used for catalyst preparing, heating using microwave is mainly utilized to assist synthetic catalyst, namely heating using microwave is utilized to promote the feature of metallic precursor reduction, as the people such as Zhong Qiling (ZHONG Qi Ling Acta Phys.-Chim. Sin., 2007,23 (3): 429) take ethylene glycol as reducing agent, adopt microwave heating method to promote chloroplatinic acid (H
2ptCl
6) reduction prepares the carbon supported catalyst that nano platinum particle is evenly distributed in carbon nano tube surface.The HTHP utilizing microwave to produce in high-pressure reaction pot directly processes the golden platinum of chemical co-reducing process synthesis or golden palladium composite Nano colloid, golden platinum or golden palladium bimetal nano particles generation modification in inducing colloidal, the micro-structural of golden platinum or golden palladium bimetal nano particles is changed, again the bimetal nano particles of microwave modification is deposited on carbon support, eliminate catalyst high temperature heat treatment step, highly active carbon can be obtained and carry bimetal nano catalyst, the reunion that simultaneously also avoid nano particle is grown up, local sintering and the problem such as to come off.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art, there is provided a kind of and utilize the golden platinum of microwave modification or golden Pd nano particle, and by modification gold platinum or golden Pd nano particle high-efficient carrier to carbon black or carbon nano tube surface, prepare the preparation method that carbon carries the golden platinum of high activity or golden palladium nanocatalyst.
Technical scheme of the present invention is: be first of a size of the golden platinum of 3 ~ 10 nanometers or golden palladium composite Nano colloid with chemical coreduction method compound particle, and composite Nano colloid is proceeded in high-pressure reaction pot, the golden platinum in retort or golden palladium composite Nano colloid is made to produce HTHP within very short time, after colloidal sol cooling, the golden platinum crossed by microwave modification again or golden palladium composite nanoparticle are as catalyst activity component, load to carbon black or carbon nanotube carrier surface, obtain that there is highly active carbon and carry high activity gold platinum or golden palladium catalyst.Wherein carbon carry high activity gold platinum catalyst concrete preparation process comprise as follows:
(1) being 0.01 ~ 0.04wt% gold chloride and Pt(IV at Au (III) content) content is in the mixed aqueous solution of 0.01 ~ 0.04wt% chloroplatinic acid or ethanolic solution, gold: the mass ratio of platinum is 1:0.25 ~ 4, then add the polyvinylpyrrolidone (PVP) that concentration is 1wt% in this solution and cook protective agent, add the reducing agent that concentration is 0.1wt% again, wherein Au (III): polyvinylpyrrolidone: the mass ratio of reducing agent is 1:2 ~ 5:0.1 ~ 0.5, Pt(IV): polyvinylpyrrolidone: the mass ratio of reducing agent is 0.25 ~ 4:2 ~ 5:0.1 ~ 0.5, 0.5 ~ 1h is stirred by the speed of 60 ~ 300 revs/min, reaction temperature is 10 ~ 50 DEG C, obtaining particle size is 3 ~ 10 nm of gold platinum composite colloidal solution,
(2) by the golden platinum composite colloidal solution of step (1) gained 2 ~ 6 standard atmospheric pressures (atm), microwave frequency is by heating temperatures to 100 ~ 250oC under the condition of 915 ~ 2450MHz, keep process 1 ~ 8min, obtain the golden platinum composite colloidal solution that microwave treatment is crossed; The high temperature high pressure process gold platinum utilizing microwave to produce in high-pressure reaction pot or golden palladium composite Nano colloid, induce golden platinum or golden palladium bimetal nano particles generation modification;
(3) carbon black or CNT being joined the microwave treatment that step (2) obtains crosses in golden platinum composite colloidal solution, keep golden platinum: the mass ratio of carbon black is 1 ~ 30:100, after ultrasonic wave process 0.15h, 2 ~ 24h is stirred under the speed of 60 ~ 300 revs/min, then filter, spend intermediate water washing to detecting Cl
-, under 60 DEG C of vacuum conditions, dry 1 ~ 3h, obtains high-activity carbon and carries golden platinum nano catalyst.
The implication of described Au (III) is the gold of trivalent, Pt(IV) implication be the platinum of tetravalence, Pd(IV) implication be the palladium of tetravalence.
In described step (1), the concentration of ethanolic solution is 50 mol % ~ 95 mol %.
The concrete preparation method that described carbon carries high activity gold palladium catalyst is identical with the preparation method of golden platinum catalyst, by in step (1) containing Pt(IV) be that the platinum acid chloride solution of 0.01 ~ 0.04wt% is changed to containing Pd(IV) be the palladium chloride solution of 0.01 ~ 0.04wt%, finally obtain high-activity carbon and carry golden palladium nanocatalyst.
The reducing agent that in described step (2), the golden platinum of synthesis or golden palladium composite Nano colloid use is sodium borohydride, potassium borohydride (KBH
4), any one in formaldehyde, paraformaldehyde, sodium thiosulfate, ethanol, ethylene glycol, citric acid, glucose, hydrazine hydrate, be commercially available.
The carrier of described catalyst is carbon black or multi-walled carbon nano-tubes, and active component is golden platinum through microwave modification or golden palladium composite nanoparticle.
Described carbon black is commercially available Vulcan XC-72 carbon black, and CNT is commercially available multi-walled carbon nano-tubes, and carbon pipe caliber is 20 ~ 60 nanometers.
Compared to the prior art, the present invention has the following advantages or good effect:
1, the activity of catalyst is high: the golden platinum of microwave high-temperature HIGH PRESSURE TREATMENT chemistry co-reducing process synthesis or golden palladium compound
Nano-colloid, makes to change as the golden platinum of catalyst activity component or the micro-structural of golden palladium composite nanoparticle, the catalytic activity of carbon supported catalyst is significantly improved;
2, load capacity is controlled: the mass ratio can preparing golden platinum or golden palladium and carbon carries golden platinum or golden palladium nanocatalyst at the carbon of 1 ~ 20% scope;
3, method cost is low, technique is simple, low for equipment requirements, there is good prospects for commercial application.
Accompanying drawing explanation
Fig. 1 is that after the carbon multi-wall nano tube loaded microwave treatment of the embodiment of the present invention 1 preparation, golden platinum composite nanoparticle TEM schemes.
Detailed description of the invention
The invention will be further described to use embodiment below.
Embodiment 1: the concrete preparation process that carbon carries high activity gold platinum catalyst comprises as follows:
(1) being 0.01wt% gold chloride and Pt(IV at Au (III) content) content is in the mixed aqueous solution solution of 0.01wt% chloroplatinic acid, gold: the mass ratio of platinum is 1:0.25, then add the polyvinylpyrrolidone (PVP) that concentration is 1wt% in this solution and cook protective agent, add the sodium borohydride that concentration is 0.1wt% again, wherein Au (III): polyvinylpyrrolidone: the mass ratio of sodium borohydride is 1:2:0.1, Pt(IV): polyvinylpyrrolidone: the mass ratio of sodium borohydride is 0.25:2:0.1, 1h is stirred by the speed of 60 revs/min, reaction temperature is 10 DEG C, obtaining particle size is 3 ~ 10 nm of gold platinum composite colloidal solution (as shown in Figure 1),
(2) by the golden platinum composite colloidal solution of step (1) gained 2 standard atmospheric pressures (atm), microwave frequency be under the condition of 2450MHz by heating temperatures to 100oC, keep process 8min, obtain the golden platinum composite colloidal solution that microwave treatment is crossed;
(3) Vulcan XC-72 carbon black being joined the microwave treatment that step (2) obtains crosses in golden platinum composite colloidal solution, keep golden platinum: the mass ratio of carbon black is 1:100, after ultrasonic wave process 0.15h, 24h is stirred under the speed of 60 revs/min, then filter, spend intermediate water washing to detecting Cl
-, dry 2h under 60 DEG C of vacuum conditions, obtains golden platinum: the mass ratio of carbon black is that the high-activity carbon of 1:100 carries golden platinum nano catalyst.
Embodiment 2
The concrete preparation process that carbon carries high activity gold platinum catalyst comprises as follows:
(1) being 0.03wt% gold chloride and Pt(IV at Au (III) content) content is in the mixed aqueous solution solution of 0.02wt% chloroplatinic acid, gold: the mass ratio of platinum is 1:2, then add the polyvinylpyrrolidone (PVP) that concentration is 1wt% in this solution and cook protective agent, add the potassium borohydride that concentration is 0.1wt% again, wherein Au (III): polyvinylpyrrolidone: the mass ratio of potassium borohydride is 1:4:0.2, Pt(IV): polyvinylpyrrolidone: the mass ratio of potassium borohydride is 2:4:0.2, 0.8h is stirred by the speed of 100 revs/min, reaction temperature is 40 DEG C, obtaining particle size is 3 ~ 8 nm of gold platinum composite colloidal solution,
(2) by the golden platinum composite colloidal solution of step (1) gained 3 standard atmospheric pressures (atm), microwave frequency be under the condition of 2000MHz by heating temperatures to 200oC, keep process 1min, obtain the golden platinum composite colloidal solution that microwave treatment is crossed;
(3) multi-walled carbon nano-tubes (carbon pipe caliber is 20 ~ 60 nanometers) being joined the microwave treatment that step (2) obtains crosses in golden platinum composite colloidal solution, keep golden platinum: the mass ratio of carbon black is 1:10, after ultrasonic wave process 0.15h, 12h is stirred under the speed of 100 revs/min, then filter, spend intermediate water washing to detecting Cl
-, dry 1h under 60 DEG C of vacuum conditions, obtains golden platinum: the mass ratio of carbon black is that the high-activity carbon of 1:10 carries golden platinum nano catalyst.
Embodiment 3
The concrete preparation process that carbon carries high activity gold platinum catalyst comprises as follows:
(1) being 0.04wt% gold chloride and Pt(IV at Au (III) content) content is in the mixed ethanol solution (concentration is 95%) of 0.01wt% chloroplatinic acid, gold: the mass ratio of platinum is 1:4, then add the polyvinylpyrrolidone (PVP) that concentration is 1wt% in this solution and cook protective agent, add the formaldehyde that concentration is 0.1wt% again, wherein Au (III): polyvinylpyrrolidone: the mass ratio of formaldehyde is 1:5:0.5, Pt(IV): polyvinylpyrrolidone: the mass ratio of formaldehyde is 4:5:0.5, 0.8h is stirred by the speed of 300 revs/min, reaction temperature is 40 DEG C, obtaining particle size is 3 ~ 7 nm of gold platinum composite colloidal solution,
(2) by the golden platinum composite colloidal solution of step (1) gained 6 standard atmospheric pressures (atm), microwave frequency be under the condition of 915MHz by heating temperatures to 250oC, keep process 6min, obtain the golden platinum composite colloidal solution that microwave treatment is crossed;
(3) multi-walled carbon nano-tubes (carbon pipe caliber is 20 ~ 60 nanometers) being joined the microwave treatment that step (2) obtains crosses in golden platinum composite colloidal solution, keep golden platinum: the mass ratio of carbon black is 3:10, after ultrasonic wave process 0.15h, 2h is stirred under the speed of 300 revs/min, then filter, spend intermediate water washing to detecting Cl
-, dry 3h under 60 DEG C of vacuum conditions, obtains golden platinum: the mass ratio of carbon black is that the high-activity carbon of 3:10 carries golden platinum nano catalyst.
Embodiment 4:
The concrete preparation process that carbon carries high activity gold palladium catalyst comprises as follows:
(1) being 0.02wt% gold chloride and Pt(IV at Au (III) content) content is in the mixed ethanol solution (concentration is 80%) of 0.01wt% chlorine palladium acid, gold: the mass ratio of palladium is 1:4, then add the polyvinylpyrrolidone (PVP) that concentration is 1wt% in this solution and cook protective agent, add the paraformaldehyde that concentration is 0.1wt% again, wherein Au (III): polyvinylpyrrolidone: the mass ratio of paraformaldehyde is 1:3:0.5, Pt(IV): polyvinylpyrrolidone: the mass ratio of paraformaldehyde is 4:3:0.5, 0.8h is stirred by the speed of 100 revs/min, reaction temperature is 30 DEG C, obtaining particle size is 3 ~ 10 nm of gold palladium composite colloidal solution,
(2) by the golden palladium composite colloidal solution of step (1) gained 4 standard atmospheric pressures (atm), microwave frequency be under the condition of 1950MHz by heating temperatures to 190oC, keep process 7min, obtain the golden palladium composite colloidal solution that microwave treatment is crossed;
(3) multi-walled carbon nano-tubes (carbon pipe caliber is 20 ~ 60 nanometers) being joined the microwave treatment that step (2) obtains crosses in golden palladium composite colloidal solution, keep golden platinum: the mass ratio of carbon black is 1:50, after ultrasonic wave process 0.15h, 2h is stirred under the speed of 300 revs/min, then filter, spend intermediate water washing to detecting Cl
-, dry 3h under 60 DEG C of vacuum conditions, obtains golden palladium: the mass ratio of carbon black is that the high-activity carbon of 1:50 carries golden palladium nanocatalyst.
Embodiment 5:
The concrete preparation process that carbon carries high activity gold palladium catalyst comprises as follows:
(1) being 0.03wt% gold chloride and Pt(IV at Au (III) content) content is in the mixed ethanol solution (concentration is 50%) of 0.02wt% chlorine palladium acid, gold: the mass ratio of palladium is 1:4, then add the polyvinylpyrrolidone (PVP) that concentration is 1wt% in this solution and cook protective agent, add the hypo that concentration is 0.1wt% again, wherein Au (III): polyvinylpyrrolidone: the mass ratio of hypo is 1:4:0.2, Pt(IV): polyvinylpyrrolidone: the mass ratio of hypo is 4:4:0.2, 0.8h is stirred by the speed of 100 revs/min, reaction temperature is 40 DEG C, obtaining particle size is 3 ~ 8 nm of gold palladium composite colloidal solution,
(2) by the golden palladium composite colloidal solution of step (1) gained 3 standard atmospheric pressures (atm), microwave frequency be under the condition of 2000MHz by heating temperatures to 200oC, keep process 1min, obtain the golden palladium composite colloidal solution that microwave treatment is crossed;
(3) multi-walled carbon nano-tubes (carbon pipe caliber is 20 ~ 60 nanometers) being joined the microwave treatment that step (2) obtains crosses in golden platinum composite colloidal solution, keep golden palladium: the mass ratio of carbon black is 1:10, after ultrasonic wave process 0.15h, 12h is stirred under the speed of 100 revs/min, then filter, spend intermediate water washing to detecting Cl
-, dry 1h under 60 DEG C of vacuum conditions, obtains golden palladium: the mass ratio of carbon black is that the high-activity carbon of 1:10 carries golden palladium nanocatalyst.
Embodiment 6
The concrete preparation process that carbon carries high activity gold palladium catalyst comprises as follows:
(1) being 0.02wt% gold chloride and Pt(IV at Au (III) content) content is in the mixed ethanol solution (concentration is 60%) of 0.04wt% chlorine palladium acid, gold: the mass ratio of palladium is 1:4, then add the polyvinylpyrrolidone (PVP) that concentration is 1wt% in this solution and cook protective agent, add the ethanol that concentration is 0.1wt% again, wherein Au (III): polyvinylpyrrolidone: the mass ratio of ethanol is 1:4:0.2, Pt(IV): polyvinylpyrrolidone: the mass ratio of ethanol is 4:4:0.2, 0.8h is stirred by the speed of 100 revs/min, reaction temperature is 40 DEG C, obtaining particle size is 3 ~ 8 nm of gold palladium composite colloidal solution,
(2) by the golden palladium composite colloidal solution of step (1) gained 3 standard atmospheric pressures (atm), microwave frequency be under the condition of 2000MHz by heating temperatures to 200oC, keep process 1min, obtain the golden palladium composite colloidal solution that microwave treatment is crossed;
(3) Vulcan XC-72 carbon black being joined the microwave treatment that step (2) obtains crosses in golden platinum composite colloidal solution, keep golden palladium: the mass ratio of carbon black is 1:10, after ultrasonic wave process 0.15h, 12h is stirred under the speed of 100 revs/min, then filter, spend intermediate water washing to detecting Cl
-, dry 1h under 60 DEG C of vacuum conditions, obtains golden palladium: the mass ratio of carbon black is that the high-activity carbon of 1:10 carries golden palladium nanocatalyst.
Embodiment 7:
The concrete preparation process that the present embodiment carbon carries high activity gold platinum catalyst is identical with embodiment 1, the difference is that the reducing agent in step (1) is ethylene glycol.
Embodiment 8:
The concrete preparation process that the present embodiment carbon carries high activity gold platinum catalyst is identical with embodiment 2, the difference is that the reducing agent in step (1) is citric acid.
Embodiment 9:
The concrete preparation process that the present embodiment carbon carries high activity gold platinum catalyst is identical with embodiment 3, the difference is that the reducing agent in step (1) is glucose.
Embodiment 10:
The concrete preparation process that the present embodiment carbon carries high activity gold platinum catalyst is identical with embodiment 5, the difference is that the reducing agent in step (1) is hydrazine hydrate.
Claims (3)
1. prepare the method that carbon carries high activity gold platinum or golden palladium catalyst, it is characterized in that carbon carries the concrete preparation process of high activity gold platinum catalyst through as follows:
(1) being 0.01 ~ 0.04wt% gold chloride and Pt(IV at Au (III) content) content is in the mixed aqueous solution of 0.01 ~ 0.04wt% chloroplatinic acid or ethanolic solution, gold: the mass ratio of platinum is 1:0.25 ~ 4, then adding concentration is in this solution that the polyvinylpyrrolidone of 1wt% cooks protective agent, add the reducing agent that concentration is 0.1wt% again, wherein Au (III): polyvinylpyrrolidone: the mass ratio of reducing agent is 1:2 ~ 5:0.1 ~ 0.5, Pt(IV): polyvinylpyrrolidone: the mass ratio of reducing agent is 0.25 ~ 4:2 ~ 5:0.1 ~ 0.5, 0.5 ~ 1h is stirred by the speed of 60 ~ 300 revs/min, reaction temperature is 10 ~ 50 DEG C, obtain the golden platinum composite colloidal solution that particle size is 3 ~ 10 nanometers,
(2) by the golden platinum composite colloidal solution of step (1) gained at 2 ~ 6 standard atmospheric pressures, microwave frequency is by heating temperatures to 100 ~ 250oC under the condition of 915 ~ 2450MHz, keep process 1 ~ 8min, obtain the golden platinum composite colloidal solution that microwave treatment is crossed;
(3) carbon black or CNT are joined in the golden platinum composite colloidal solution that microwave treatment that step (2) obtains crosses, keep golden platinum: the mass ratio of carbon black is 1 ~ 30:100, after ultrasonic wave process 0.15h, 2 ~ 24h is stirred under the speed of 60 ~ 300 revs/min, then filter, with secondary deionized water washing to detecting Cl
-, under 60 DEG C of vacuum conditions, dry 1 ~ 3h, obtains high-activity carbon and carries golden platinum nano catalyst;
The concrete preparation method that carbon carries high activity gold palladium catalyst is identical with the preparation method of golden platinum catalyst, difference be by step (1) containing Pt(IV) be that the platinum acid chloride solution of 0.01 ~ 0.04wt% is changed to containing Pd(II) be the palladium chloride solution of 0.01 ~ 0.04wt%, finally obtain high-activity carbon and carry golden palladium nanocatalyst;
Synthesize that the reducing agent that golden platinum or the nano combined colloidal solution of golden palladium uses is sodium borohydride, in formaldehyde, paraformaldehyde, sodium thiosulfate, ethanol, citric acid, glucose, hydrazine hydrate any one.
2. the carbon of preparing according to claims 1 carries high activity gold platinum or the method for golden palladium catalyst, it is characterized in that: in described step (1), the concentration of ethanolic solution is 50 mol% ~ 95 mol %.
3. the carbon of preparing according to claims 1 carries high activity gold platinum or the method for golden palladium catalyst, it is characterized in that: described carbon black is commercially available Vulcan XC-72 carbon black.
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