CN102553582A - 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
- Publication number
- CN102553582A CN102553582A CN2011103923306A CN201110392330A CN102553582A CN 102553582 A CN102553582 A CN 102553582A CN 2011103923306 A CN2011103923306 A CN 2011103923306A CN 201110392330 A CN201110392330 A CN 201110392330A CN 102553582 A CN102553582 A CN 102553582A
- Authority
- CN
- China
- Prior art keywords
- golden
- platinum
- carbon
- catalyst
- gold
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 76
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 56
- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 238000000034 method Methods 0.000 title claims abstract description 23
- 229910002710 Au-Pd Inorganic materials 0.000 title abstract 11
- 239000002131 composite material Substances 0.000 claims abstract description 45
- 239000000084 colloidal system Substances 0.000 claims abstract description 42
- 230000000694 effects Effects 0.000 claims abstract description 41
- 239000002105 nanoparticle Substances 0.000 claims abstract description 23
- 239000011943 nanocatalyst Substances 0.000 claims abstract description 15
- 238000006243 chemical reaction Methods 0.000 claims abstract description 12
- 230000004048 modification Effects 0.000 claims abstract description 11
- 238000012986 modification Methods 0.000 claims abstract description 11
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 149
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 111
- 229910052763 palladium Inorganic materials 0.000 claims description 54
- 239000000243 solution Substances 0.000 claims description 54
- 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 26
- JUWSSMXCCAMYGX-UHFFFAOYSA-N gold platinum Chemical compound [Pt].[Au] JUWSSMXCCAMYGX-UHFFFAOYSA-N 0.000 claims description 25
- 238000002360 preparation method Methods 0.000 claims description 23
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 20
- 238000011282 treatment Methods 0.000 claims description 18
- 238000003756 stirring Methods 0.000 claims description 16
- 229910052737 gold Inorganic materials 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- 239000002245 particle Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 9
- 239000003638 chemical reducing agent 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
- 239000002048 multi walled nanotube Substances 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
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 8
- 229930040373 Paraformaldehyde Natural products 0.000 claims description 5
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 5
- 229920002866 paraformaldehyde Polymers 0.000 claims description 5
- 229910052700 potassium Inorganic materials 0.000 claims description 5
- 239000011591 potassium Substances 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
- 230000008569 process Effects 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
- 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
- 239000011203 carbon fibre reinforced carbon Substances 0.000 claims description 2
- 239000012467 final product Substances 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
- 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
- 230000008901 benefit Effects 0.000 abstract description 2
- 238000010438 heat treatment Methods 0.000 description 11
- 239000000460 chlorine Substances 0.000 description 10
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 9
- 239000007800 oxidant agent Substances 0.000 description 4
- 230000001590 oxidative effect 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
- 239000002041 carbon nanotube Substances 0.000 description 3
- 229910021393 carbon nanotube Inorganic materials 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 229910052801 chlorine Inorganic materials 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 239000000956 alloy Substances 0.000 description 2
- 229910045601 alloy Inorganic materials 0.000 description 2
- 150000001875 compounds Chemical class 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
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000010304 firing Methods 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
Images
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 a kind of method of utilizing microwave modification gold platinum or golden palladium bimetal nano particle preparation carbon to carry high activity gold platinum or golden palladium catalyst, belong to the catalysis material technical field.
Background technology
Along with the fast development of nanometer technology of preparing and catalytic science, some researchers can improve the angle of catalyst activity and CO tolerance again and consider, bimetal Au/Pt, the AuPd nano particle of preparation high catalytic activity from reducing the catalyst cost.The physicochemical properties of discovering the bimetal Au/Pt nano particle in recent years not only change with the chemical composition of Au and Pt, but also change with the micro-structural of AuPt nano particle.For example; People such as Zhong Chuanjian (C J Zhong et al; Langmuir.2006; 22:2892) preparing the Au mass percent is that 65～85% carbon carries the AuPt nanocatalyst, through 500 ℃ of alloying heat treatments, in alkaline solution, the electro catalytic activity of methyl alcohol is surpassed the Pt/C and the PtRu/C catalyst of identical load amount; People such as Bryan Eichhorn (Eichhorn B. et al, Advanced Fuctional Materials, 2007,17:3099) reported that the AuPt alloy nano particle has more tolerance than the nano heterogeneous aggregation of AuPt to CO; Can prepare AuPt nano particle (Chi J H et al, the Journal of the electrochemical society of small particle diameter with chemical method while method of reducing
,2006,153:1812); Because the difference of the reduction potential of Au, Pt and Pd has caused the difference of rate of reduction; Structure such as can form graded alloy (type nucleocapsid) between Au and Pt and Au and the Pd and be separated, carbon carries Au Pt or Au Pd bimetallic catalyst also need could obtain catalytic activity preferably through high temperature solid-state heat treatment.But catalyst after conventional high-temperature heat treatment, can occur nano particle reunite grow up, local sintering and metal nanoparticle be from problems such as the carbon carrier surface come off.
Heating using microwave is interior heating, has characteristics such as firing rate is fast, homogeneous heating, no thermograde, no hysteresis effect.At present; Heating using microwave is used for Preparation of Catalyst, mainly is to utilize heating using microwave to assist synthetic catalyst, promptly utilizes heating using microwave to promote the characteristics of metallic precursor reduction; Like people such as Zhong Qiling (ZHONG Qi Ling Acta Phys.-Chim. Sin.; 2007,23 (3): 429) with ethylene glycol be reducing agent, adopt microwave heating method to promote chloroplatinic acid (H
2PtCl
6) reduce and prepare the carbon supported catalyst that nano platinum particle is evenly distributed in carbon nano tube surface.The HTHP that utilizes microwave in high-pressure reaction pot, to produce is directly handled chemical co-reducing process synthetic golden platinum or golden palladium composite Nano colloid; Induce golden platinum or golden palladium bimetal nano particle generation modification in the colloid; The micro-structural of golden platinum or golden palladium bimetal nano particle is changed; Bimetal nano particle with microwave modification is deposited on the carbon carrier surface again; Omit the catalyst high temperature heat treatment step, can obtain highly active carbon and carry the bimetal nano catalyst, also avoided the reunion of nano particle to grow up simultaneously, local sintering and problem such as come off.
Summary of the invention
The objective of the invention is to overcome the deficiency of prior art; A kind of golden platinum or golden Pd nano particle that utilizes microwave modification is provided; And with modification gold platinum or golden Pd nano particle high-efficient carrier to carbon black or carbon nano tube surface, preparation carbon carries the preparation method of golden platinum of high activity or golden palladium nanocatalyst.
Technical scheme of the present invention is: the golden platinum or the golden palladium composite Nano colloid that at first are of a size of 3～10 nanometers with chemical coreduction method compound particle; And the composite Nano colloid changed in the high-pressure reaction pot; Make golden platinum or golden palladium composite Nano colloid in the retort in very short time, produce HTHP; After treating the colloidal sol cooling; Golden platinum of again microwave modification being crossed or golden palladium composite nanoparticle load to carbon black or carbon nanotube carrier surface as the catalyst activity component, obtain having highly active carbon and carry high activity gold platinum or golden palladium catalyst.Wherein the carbon concrete preparation process of carrying high activity gold platinum catalyst comprises as follows:
(1) be that 0.01～0.04wt% gold chloride and Pt (IV) content are in the mixed aqueous solution or ethanolic solution of 0.01～0.04wt% chloroplatinic acid at Au (III) content; Gold: the mass ratio of platinum is 1:0.25～4; The polyvinylpyrrolidone (PVP) that in this solution, adds concentration then and be 1wt% is cooked protective agent; Add the reducing agent that concentration is 0.1wt% again; Au (III) wherein: 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, stirs 0.5～1h by 60～300 rev/mins speed; Reaction temperature is 10～50 ℃, and obtaining particle size is 3 ~ 10 nm of gold platinum composite colloid solution;
(2) with the golden platinum composite colloid solution of step (1) gained at 2～6 standard atmospheric pressures (atm); Microwave frequency is under the condition of 915～2450MHz temperature to be heated to 100～250oC; Keep handling 1～8min, obtain the golden platinum composite colloid solution that microwave treatment is crossed; The high temperature high pressure process gold platinum or the golden palladium composite Nano colloid that utilize microwave in high-pressure reaction pot, to produce are induced golden platinum or golden palladium bimetal nano particle generation modification;
(3) carbon black or CNT being joined the microwave treatment that step (2) obtains crosses in the golden platinum composite colloid solution; Keep golden platinum: the mass ratio of carbon black is 1～30:100; Behind the ultrasonic Treatment 0.15h; Under 60～300 rev/mins speed, stir 2～24h, filter then, spend secondary water washing and wash to detecting Cl
-, dry 1～3h obtains high-activity carbon and carries golden platinum nano catalyst under 60 ℃ of vacuum conditions.
The implication of said Au (III) is the gold of trivalent, and the implication of Pt (IV) is the platinum of tetravalence, and the implication of Pd (IV) is the palladium of tetravalence.
The concentration of ethanolic solution is 50 mol %～95 mol % in the said step (1).
The concrete preparation method that said carbon carries high activity gold palladium catalyst is identical with the preparation method of golden platinum catalyst; With the Pt (IV) that contains in the step (1) is that the platinum acid chloride solution of 0.01～0.04wt% is changed to that to contain Pd (IV) be that the palladium chloride solution of 0.01～0.04wt% gets final product, and finally obtains high-activity carbon and carries golden palladium nanocatalyst.
Synthetic golden platinum or the employed reducing agent of golden palladium composite Nano colloid are sodium borohydride, potassium borohydride (KBH in the said step (2)
4), in the formaldehyde, paraformaldehyde, sodium thiosulfate, ethanol, ethylene glycol, citric acid, glucose, hydrazine hydrate any one, be commercially available.
The carrier of said catalyst is carbon black or multi-walled carbon nano-tubes, and active component is through the golden platinum of microwave modification or golden palladium composite nanoparticle.
Said 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.
Compare with prior art, the present invention has following advantage or good effect:
1, activity of such catalysts is high: golden platinum or golden palladium that microwave high-temperature HIGH PRESSURE TREATMENT chemistry co-reducing process synthesizes are compound
Nano-colloid makes as the golden platinum of catalyst activity component or the micro-structural of golden palladium composite nanoparticle to change, and the catalytic activity of carbon supported catalyst is significantly improved;
2, load capacity is controlled: the mass ratio that can prepare golden platinum or golden palladium and carbon carries golden platinum or golden palladium nanocatalyst at the carbon of 1～20% scope;
3, the method cost is low, technology is simple, low for equipment requirements, have better industrial application prospect.
Description of drawings
Fig. 1 is golden platinum composite nanoparticle TEM figure after the carbon multi-wall nano tube loaded microwave treatment of the embodiment of the invention 1 preparation.
The specific embodiment
With embodiment the present invention is described further below.
Embodiment 1: the concrete preparation process that carbon carries high activity gold platinum catalyst comprises as follows:
(1) be that 0.01wt% gold chloride and Pt (IV) content are in the mixed aqueous solution solution of 0.01wt% chloroplatinic acid at Au (III) content; Gold: the mass ratio of platinum is 1:0.25; The polyvinylpyrrolidone (PVP) that in this solution, adds concentration then and be 1wt% is cooked protective agent, and 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; Stir 1h by 60 rev/mins speed, reaction temperature is 10 ℃, and obtaining particle size is 3～10 nm of gold platinum composite colloid solution (as shown in Figure 1);
(2) with the golden platinum composite colloid solution of step (1) gained at 2 standard atmospheric pressures (atm), microwave frequency is under the condition of 2450MHz temperature to be heated to 100oC, keeps handling 8min, obtains the golden platinum composite colloid solution that microwave treatment is crossed;
(3) Vulcan XC-72 carbon black being joined the microwave treatment that step (2) obtains crosses in the golden platinum composite colloid solution; Keep golden platinum: the mass ratio of carbon black is 1:100; Behind the ultrasonic Treatment 0.15h; Under 60 rev/mins speed, stir 24h, filter then, spend secondary water washing and wash to detecting Cl
-, dry 2h under 60 ℃ 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) be that 0.03wt% gold chloride and Pt (IV) content are in the mixed aqueous solution solution of 0.02wt% chloroplatinic acid at Au (III) content; Gold: the mass ratio of platinum is 1:2; The polyvinylpyrrolidone (PVP) that in this solution, adds concentration then and be 1wt% is cooked protective agent, and 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; Stir 0.8h by 100 rev/mins speed, reaction temperature is 40 ℃, and obtaining particle size is 3～8 nm of gold platinum composite colloid solution;
(2) with the golden platinum composite colloid solution of step (1) gained at 3 standard atmospheric pressures (atm), microwave frequency is under the condition of 2000MHz temperature to be heated to 200oC, keeps handling 1min, obtains the golden platinum composite colloid 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 the golden platinum composite colloid solution; Keep golden platinum: the mass ratio of carbon black is 1:10; Behind the ultrasonic Treatment 0.15h; Under 100 rev/mins speed, stir 12h, filter then, spend secondary water washing and wash to detecting Cl
-, dry 1h under 60 ℃ 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) be that 0.04wt% gold chloride and Pt (IV) content are in the mixed ethanol solution (concentration is 95%) of 0.01wt% chloroplatinic acid at Au (III) content; Gold: the mass ratio of platinum is 1:4; The polyvinylpyrrolidone (PVP) that in this solution, adds concentration then and be 1wt% is cooked protective agent, and 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; Stir 0.8h by 300 rev/mins speed, reaction temperature is 40 ℃, and obtaining particle size is 3～7 nm of gold platinum composite colloid solution;
(2) with the golden platinum composite colloid solution of step (1) gained at 6 standard atmospheric pressures (atm), microwave frequency is under the condition of 915MHz temperature to be heated to 250oC, keeps handling 6min, obtains the golden platinum composite colloid 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 the golden platinum composite colloid solution; Keep golden platinum: the mass ratio of carbon black is 3:10; Behind the ultrasonic Treatment 0.15h; Under 300 rev/mins speed, stir 2h, filter then, spend secondary water washing and wash to detecting Cl
-, dry 3h under 60 ℃ 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) be that 0.02wt% gold chloride and Pt (IV) content are in the mixed ethanol solution (concentration is 80%) of 0.01wt% chlorine palladium acid at Au (III) content; Gold: the mass ratio of palladium is 1:4; The polyvinylpyrrolidone (PVP) that in this solution, adds concentration then and be 1wt% is cooked protective agent, and 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; Stir 0.8h by 100 rev/mins speed, reaction temperature is 30 ℃, and obtaining particle size is 3～10 nm of gold palladium composite colloid solution;
(2) with the golden palladium composite colloid solution of step (1) gained at 4 standard atmospheric pressures (atm), microwave frequency is under the condition of 1950MHz temperature to be heated to 190oC, keeps handling 7min, obtains the golden palladium composite colloid 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 the golden palladium composite colloid solution; Keep golden platinum: the mass ratio of carbon black is 1:50; Behind the ultrasonic Treatment 0.15h; Under 300 rev/mins speed, stir 2h, filter then, spend secondary water washing and wash to detecting Cl
-, dry 3h under 60 ℃ 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) be that 0.03wt% gold chloride and Pt (IV) content are in the mixed ethanol solution (concentration is 50%) of 0.02wt% chlorine palladium acid at Au (III) content; Gold: the mass ratio of palladium is 1:4; The polyvinylpyrrolidone (PVP) that in this solution, adds concentration then and be 1wt% is cooked protective agent, and 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; Stir 0.8h by 100 rev/mins speed, reaction temperature is 40 ℃, and obtaining particle size is 3～8 nm of gold palladium composite colloid solution;
(2) with the golden palladium composite colloid solution of step (1) gained at 3 standard atmospheric pressures (atm), microwave frequency is under the condition of 2000MHz temperature to be heated to 200oC, keeps handling 1min, obtains the golden palladium composite colloid 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 the golden platinum composite colloid solution; Keep golden palladium: the mass ratio of carbon black is 1:10; Behind the ultrasonic Treatment 0.15h; Under 100 rev/mins speed, stir 12h, filter then, spend secondary water washing and wash to detecting Cl
-, dry 1h under 60 ℃ 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) be that 0.02wt% gold chloride and Pt (IV) content are in the mixed ethanol solution (concentration is 60%) of 0.04wt% chlorine palladium acid at Au (III) content; Gold: the mass ratio of palladium is 1:4; The polyvinylpyrrolidone (PVP) that in this solution, adds concentration then and be 1wt% is cooked protective agent, and 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; Stir 0.8h by 100 rev/mins speed, reaction temperature is 40 ℃, and obtaining particle size is 3～8 nm of gold palladium composite colloid solution;
(2) with the golden palladium composite colloid solution of step (1) gained at 3 standard atmospheric pressures (atm), microwave frequency is under the condition of 2000MHz temperature to be heated to 200oC, keeps handling 1min, obtains the golden palladium composite colloid solution that microwave treatment is crossed;
(3) Vulcan XC-72 carbon black being joined the microwave treatment that step (2) obtains crosses in the golden platinum composite colloid solution; Keep golden palladium: the mass ratio of carbon black is 1:10; Behind the ultrasonic Treatment 0.15h; Under 100 rev/mins speed, stir 12h, filter then, spend secondary water washing and wash to detecting Cl
-, dry 1h under 60 ℃ 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 present embodiment carbon carries high activity gold platinum catalyst is identical with embodiment 1, the difference is that the oxidant in the step (1) is an ethylene glycol.
Embodiment 8:
The concrete preparation process that present embodiment carbon carries high activity gold platinum catalyst is identical with embodiment 2, the difference is that the oxidant in the step (1) is a citric acid.
Embodiment 9:
The concrete preparation process that present embodiment carbon carries high activity gold platinum catalyst is identical with embodiment 3, the difference is that the oxidant in the step (1) is a glucose.
Embodiment 10:
The concrete preparation process that present embodiment carbon carries high activity gold platinum catalyst is identical with embodiment 5, the difference is that the oxidant in the step (1) is a hydrazine hydrate.
Claims (6)
1. one kind prepares the method that carbon carries high activity gold platinum or golden palladium catalyst, it is characterized in that carbon carries the concrete preparation process process of high activity gold platinum catalyst as follows:
(1) be that 0.01～0.04wt% gold chloride and Pt (IV) content are in the mixed aqueous solution or ethanolic solution of 0.01～0.04wt% chloroplatinic acid at Au (III) content; Gold: the mass ratio of platinum is 1:0.25～4; The polyvinylpyrrolidone that in this solution, adds concentration then and be 1wt% is cooked protective agent; Add the reducing agent that concentration is 0.1wt% again; Au (III) wherein: 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, stirs 0.5～1h by 60～300 rev/mins speed; Reaction temperature is 10～50 ℃, and obtaining particle size is the golden platinum composite colloid solution of 3 ~ 10 nanometers;
(2) with the golden platinum composite colloid solution of step (1) gained at 2～6 standard atmospheric pressures, microwave frequency is under the condition of 915～2450MHz temperature to be heated to 100～250oC, keeps handling 1～8min, obtains the golden platinum composite colloid solution that microwave treatment is crossed;
(3) carbon black or CNT being joined the microwave treatment that step (2) obtains crosses in the golden platinum composite colloid solution; Keep golden platinum: the mass ratio of carbon black is 1～30:100; Behind the ultrasonic Treatment 0.15h; Under 60～300 rev/mins speed, stir 2～24h, filter then, spend secondary water washing and wash to detecting Cl
-, dry 1～3h obtains high-activity carbon and carries golden platinum nano catalyst under 60 ℃ of vacuum conditions.
2. prepare the method that carbon carries high activity gold platinum or golden palladium catalyst according to claims 1 are described; It is characterized in that: the concrete preparation method that said carbon carries high activity gold palladium catalyst is identical with the preparation method of golden platinum catalyst; With the Pt (IV) that contains in the step (1) is that the platinum acid chloride solution of 0.01～0.04wt% is changed to that to contain Pd (IV) be that the palladium chloride solution of 0.01～0.04wt% gets final product, and finally obtains high-activity carbon and carries golden palladium nanocatalyst.
3. prepare the method that carbon carries high activity gold platinum or golden palladium catalyst according to claims 1 are described, it is characterized in that: the concentration of ethanolic solution is 50 mol%～95 mol % in the said step (1).
4. the method for carrying high activity gold platinum or golden palladium catalyst according to the described microwave modification gold platinum of claims 1 or golden palladium bimetal nano particle preparation carbon is characterized in that: in the said step (1) synthetic golden platinum or the employed reducing agent of golden palladium composite Nano colloid be in sodium borohydride, potassium borohydride, formaldehyde, paraformaldehyde, sodium thiosulfate, ethanol, ethylene glycol, citric acid, glucose, the hydrazine hydrate any one.
5. prepare the method that carbon carries high activity gold platinum or golden palladium catalyst according to claims 1 are described, it is characterized in that: the carrier of said catalyst is carbon black or multi-walled carbon nano-tubes, and active component is through the golden platinum of microwave modification or golden palladium composite nanoparticle.
6. prepare the method that carbon carries high activity gold platinum or golden palladium catalyst according to claims 1 are described, it is characterized in that: said 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.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110392330.6A CN102553582B (en) | 2011-12-01 | 2011-12-01 | Method for preparing carbon supported Au-Pt or Au-Pd catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110392330.6A CN102553582B (en) | 2011-12-01 | 2011-12-01 | Method for preparing carbon supported Au-Pt or Au-Pd catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102553582A true CN102553582A (en) | 2012-07-11 |
| CN102553582B CN102553582B (en) | 2015-01-28 |
Family
ID=46400982
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201110392330.6A Expired - Fee Related CN102553582B (en) | 2011-12-01 | 2011-12-01 | Method for preparing carbon supported Au-Pt or Au-Pd catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102553582B (en) |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102896328A (en) * | 2012-10-30 | 2013-01-30 | 西安交通大学 | Method for continuously preparing colloid PdM (M=Pt, Au) alloy nano particles |
| CN102935519A (en) * | 2012-11-06 | 2013-02-20 | 南京理工大学 | Precious metal nano-particle preparation method based on modified collagen |
| CN102976879A (en) * | 2012-11-30 | 2013-03-20 | 清华大学 | Supported PtAu catalyst and method for catalytic reduction of olefinic bonds or acetylenic bonds by using same |
| CN103007929A (en) * | 2012-12-07 | 2013-04-03 | 上海华谊（集团）公司 | Pd-based catalyst prepared through colloid deposition, preparation method and application |
| CN104923303A (en) * | 2015-05-18 | 2015-09-23 | 昆明理工大学 | Method for preparing loaded noble metal nanocatalyst by modification treatment of carbon nanotubes with hydrogen fluoride and thiophenol |
| CN104941688A (en) * | 2015-05-18 | 2015-09-30 | 昆明理工大学 | Method for preparing carbon-loaded Au@Pd or Au@Pd catalyst by adopting carbon nano tube modified by HF and thiophenol |
| CN106346020A (en) * | 2016-11-16 | 2017-01-25 | 皖西学院 | Preparation method of platinum-palladium bi-metal nano-particles |
| CN106607020A (en) * | 2016-11-29 | 2017-05-03 | 南京东焱氢能源科技有限公司 | Preparation method for high-activity palladium-carbon catalyst |
| CN106607018A (en) * | 2015-10-23 | 2017-05-03 | 中国石油化工股份有限公司 | Low carbon alkane dehydrogenation catalyst, and preparation method and applications thereof |
| CN106748644A (en) * | 2016-12-10 | 2017-05-31 | 山东元利科技股份有限公司 | A kind of method that dimethyl adipate gas phase hydrogenation produces 1,6 hexylene glycols |
| CN106902817A (en) * | 2017-04-11 | 2017-06-30 | 辽宁大学 | A kind of method of activated carbon nano-tube supported palladium nano-particle catalyst and its application |
| CN107195917A (en) * | 2017-06-02 | 2017-09-22 | 浙江大学台州研究院 | A kind of AuPdNWs superfine nano forest elctro-catalysts of the vertical-growth on FTO glass and preparation method thereof |
| CN108686704A (en) * | 2018-05-23 | 2018-10-23 | 陕西理工大学 | A kind of metallic catalyst preparation method |
| CN108906039A (en) * | 2018-03-05 | 2018-11-30 | 浙江工业大学 | A kind of low-load amount Au catalyst and preparation method thereof and its application in catalysis oxidation toluene |
| CN109126822A (en) * | 2018-09-25 | 2019-01-04 | 中南大学 | A kind of carbon nanotube-gold copper composite material and preparation method and application |
| CN109248681A (en) * | 2018-09-06 | 2019-01-22 | 南京蔚岚环境技术研究院有限公司 | A kind of carbon monoxide oxidation catalyst and preparation method thereof and coat method of the catalyst on carrier |
| CN109622036A (en) * | 2018-12-25 | 2019-04-16 | 南开大学 | A kind of preparation method for the Au-based catalyst preparing vinyl chloride for acetylene hydrochlorination method |
| CN110568043A (en) * | 2019-08-26 | 2019-12-13 | 宁德师范学院 | Pt @ Au/C bimetallic nano material and method for detecting glucose by using same |
| CN110947381A (en) * | 2018-09-27 | 2020-04-03 | 湖南大学 | Carbon black limited nano gold catalyst and preparation method thereof |
| CN111082074A (en) * | 2019-11-28 | 2020-04-28 | 安徽元琛环保科技股份有限公司 | Porous platinum fuel cell catalyst and preparation method thereof |
| CN111420656A (en) * | 2020-05-06 | 2020-07-17 | 北京化工大学 | Catalyst for preparing isooctanoic acid by selective oxidation of isooctanol and preparation method thereof |
| CN111889136A (en) * | 2019-05-05 | 2020-11-06 | 中国科学院青岛生物能源与过程研究所 | Method for preparing catalyst carrier loaded with first metal and second metal |
| CN112086648A (en) * | 2020-08-18 | 2020-12-15 | 山东理工大学 | Method for synthesizing AuPd @ C material for oxygen reduction reaction electrocatalysis |
| CN112442706A (en) * | 2020-11-06 | 2021-03-05 | 四川大学 | Electrocatalytic reduction of CO2Supported gold platinum alloy electrode and preparation method thereof |
| CN114512687A (en) * | 2020-10-23 | 2022-05-17 | 中国石油化工股份有限公司 | Carbon-supported noble metal nano catalyst and preparation method and application thereof |
| CN114749172A (en) * | 2022-04-21 | 2022-07-15 | 清华大学 | Continuous preparation method of carbon nano material loaded with small-particle-size noble metal |
Families Citing this family (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109453767A (en) * | 2019-01-21 | 2019-03-12 | 郴州高鑫铂业有限公司 | A kind of Pd-Au/C bimetallic catalyst and its preparation method and application |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101436670A (en) * | 2007-11-12 | 2009-05-20 | 汉能科技有限公司 | Fuel battery cathode catalyst and preparation method thereof |
-
2011
- 2011-12-01 CN CN201110392330.6A patent/CN102553582B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101436670A (en) * | 2007-11-12 | 2009-05-20 | 汉能科技有限公司 | Fuel battery cathode catalyst and preparation method thereof |
Non-Patent Citations (3)
| Title |
|---|
| NADAGOUDA N. MALLIKARJUNA ET AL.: "Microwave-Assisted Shape-Controlled Bulk Synthesis of Noble Nanocrystals and Their Catalytic Properties", 《CRYSTAL GROWTH & DESIGN》, vol. 7, 22 February 2007 (2007-02-22) * |
| WEIXIA TU ET AL.: "Rapid synthesis of nanoscale colloidal metal clusters by microwave irradiation", 《J. MATER. CHEM.》, vol. 10, 4 August 2000 (2000-08-04) * |
| 温河丽 等: "碳载金铂双金属催化剂催化活性研究", 《贵金属》, vol. 32, no. 1, 28 February 2011 (2011-02-28) * |
Cited By (39)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102896328A (en) * | 2012-10-30 | 2013-01-30 | 西安交通大学 | Method for continuously preparing colloid PdM (M=Pt, Au) alloy nano particles |
| CN102935519A (en) * | 2012-11-06 | 2013-02-20 | 南京理工大学 | Precious metal nano-particle preparation method based on modified collagen |
| CN102976879A (en) * | 2012-11-30 | 2013-03-20 | 清华大学 | Supported PtAu catalyst and method for catalytic reduction of olefinic bonds or acetylenic bonds by using same |
| CN102976879B (en) * | 2012-11-30 | 2015-01-21 | 清华大学 | Supported PtAu catalyst and method for catalytic reduction of olefinic bonds or acetylenic bonds by using same |
| CN103007929B (en) * | 2012-12-07 | 2018-01-12 | 上海华谊（集团）公司 | The Pd bases catalyst of colloidal deposition method preparation, preparation method and application |
| CN103007929A (en) * | 2012-12-07 | 2013-04-03 | 上海华谊（集团）公司 | Pd-based catalyst prepared through colloid deposition, preparation method and application |
| CN104941688A (en) * | 2015-05-18 | 2015-09-30 | 昆明理工大学 | Method for preparing carbon-loaded Au@Pd or Au@Pd catalyst by adopting carbon nano tube modified by HF and thiophenol |
| CN104923303A (en) * | 2015-05-18 | 2015-09-23 | 昆明理工大学 | Method for preparing loaded noble metal nanocatalyst by modification treatment of carbon nanotubes with hydrogen fluoride and thiophenol |
| CN104941688B (en) * | 2015-05-18 | 2017-08-25 | 昆明理工大学 | The method that carbon carries Au@Pd or Au@Pt catalyst is prepared using HF and the common modification CNT of benzenethiol |
| CN106607018A (en) * | 2015-10-23 | 2017-05-03 | 中国石油化工股份有限公司 | Low carbon alkane dehydrogenation catalyst, and preparation method and applications thereof |
| CN106607018B (en) * | 2015-10-23 | 2019-07-23 | 中国石油化工股份有限公司 | A kind of catalyst for dehydrogenation of low-carbon paraffin and preparation method and application |
| CN106346020A (en) * | 2016-11-16 | 2017-01-25 | 皖西学院 | Preparation method of platinum-palladium bi-metal nano-particles |
| CN106607020A (en) * | 2016-11-29 | 2017-05-03 | 南京东焱氢能源科技有限公司 | Preparation method for high-activity palladium-carbon catalyst |
| CN106748644A (en) * | 2016-12-10 | 2017-05-31 | 山东元利科技股份有限公司 | A kind of method that dimethyl adipate gas phase hydrogenation produces 1,6 hexylene glycols |
| CN106748644B (en) * | 2016-12-10 | 2019-12-03 | 山东元利科技股份有限公司 | A kind of method of dimethyl adipate gas phase hydrogenation production 1,6- hexylene glycol |
| CN106902817A (en) * | 2017-04-11 | 2017-06-30 | 辽宁大学 | A kind of method of activated carbon nano-tube supported palladium nano-particle catalyst and its application |
| CN106902817B (en) * | 2017-04-11 | 2019-07-02 | 辽宁大学 | A kind of method and its application of activated carbon nano-tube supported palladium nano-particle catalyst |
| CN107195917A (en) * | 2017-06-02 | 2017-09-22 | 浙江大学台州研究院 | A kind of AuPdNWs superfine nano forest elctro-catalysts of the vertical-growth on FTO glass and preparation method thereof |
| CN108906039A (en) * | 2018-03-05 | 2018-11-30 | 浙江工业大学 | A kind of low-load amount Au catalyst and preparation method thereof and its application in catalysis oxidation toluene |
| CN108686704A (en) * | 2018-05-23 | 2018-10-23 | 陕西理工大学 | A kind of metallic catalyst preparation method |
| CN109248681A (en) * | 2018-09-06 | 2019-01-22 | 南京蔚岚环境技术研究院有限公司 | A kind of carbon monoxide oxidation catalyst and preparation method thereof and coat method of the catalyst on carrier |
| CN109126822B (en) * | 2018-09-25 | 2021-05-07 | 中南大学 | Carbon nanotube-gold copper alloy composite material and preparation method and application thereof |
| CN109126822A (en) * | 2018-09-25 | 2019-01-04 | 中南大学 | A kind of carbon nanotube-gold copper composite material and preparation method and application |
| CN110947381A (en) * | 2018-09-27 | 2020-04-03 | 湖南大学 | Carbon black limited nano gold catalyst and preparation method thereof |
| CN110947381B (en) * | 2018-09-27 | 2021-04-02 | 湖南大学 | Carbon black limited nano gold catalyst and preparation method thereof |
| CN109622036A (en) * | 2018-12-25 | 2019-04-16 | 南开大学 | A kind of preparation method for the Au-based catalyst preparing vinyl chloride for acetylene hydrochlorination method |
| EP3965927A4 (en) * | 2019-05-05 | 2023-01-18 | Qingdao Institute of Bioenergy and Bioprocess Technology, Chinese Academy of Sciences | Method for preparing catalyst support loaded with a first metal and a second metal |
| CN111889136A (en) * | 2019-05-05 | 2020-11-06 | 中国科学院青岛生物能源与过程研究所 | Method for preparing catalyst carrier loaded with first metal and second metal |
| WO2020224483A1 (en) * | 2019-05-05 | 2020-11-12 | Qingdao Institute Of Bioenergy And Bioprocess Technology Chinese Academy Of Sciences | Method for preparing catalyst support loaded with a first metal and a second metal |
| CN111889136B (en) * | 2019-05-05 | 2022-02-01 | 中国科学院青岛生物能源与过程研究所 | Method for preparing catalyst carrier loaded with first metal and second metal |
| CN110568043A (en) * | 2019-08-26 | 2019-12-13 | 宁德师范学院 | Pt @ Au/C bimetallic nano material and method for detecting glucose by using same |
| CN110568043B (en) * | 2019-08-26 | 2022-02-01 | 宁德师范学院 | Pt @ Au/C bimetallic nano material and method for detecting glucose by using same |
| CN111082074A (en) * | 2019-11-28 | 2020-04-28 | 安徽元琛环保科技股份有限公司 | Porous platinum fuel cell catalyst and preparation method thereof |
| CN111420656A (en) * | 2020-05-06 | 2020-07-17 | 北京化工大学 | Catalyst for preparing isooctanoic acid by selective oxidation of isooctanol and preparation method thereof |
| CN112086648A (en) * | 2020-08-18 | 2020-12-15 | 山东理工大学 | Method for synthesizing AuPd @ C material for oxygen reduction reaction electrocatalysis |
| CN114512687A (en) * | 2020-10-23 | 2022-05-17 | 中国石油化工股份有限公司 | Carbon-supported noble metal nano catalyst and preparation method and application thereof |
| CN114512687B (en) * | 2020-10-23 | 2023-11-28 | 中国石油化工股份有限公司 | Carbon-supported noble metal nano catalyst and preparation method and application thereof |
| CN112442706A (en) * | 2020-11-06 | 2021-03-05 | 四川大学 | Electrocatalytic reduction of CO2Supported gold platinum alloy electrode and preparation method thereof |
| CN114749172A (en) * | 2022-04-21 | 2022-07-15 | 清华大学 | Continuous preparation method of carbon nano material loaded with small-particle-size noble metal |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102553582B (en) | 2015-01-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102553582B (en) | Method for preparing carbon supported Au-Pt or Au-Pd catalyst | |
| Chang et al. | The tunable and highly selective reduction products on Ag@ Cu bimetallic catalysts toward CO2 electrochemical reduction reaction | |
| Hu et al. | Synthesis of Pt–rare earth metal nanoalloys | |
| Zhang et al. | Recent advances in palladium-based electrocatalysts for fuel cell reactions and hydrogen evolution reaction | |
| Wen et al. | Plasmonic Au@ Pd nanoparticles supported on a basic metal–organic framework: Synergic boosting of H2 production from formic acid | |
| Wei et al. | Bimetallic nanoparticles meet polymeric carbon nitride: Fabrications, catalytic applications and perspectives | |
| Zhang et al. | Effects of acid treatment of Pt− Ni alloy nanoparticles@ graphene on the kinetics of the oxygen reduction reaction in acidic and alkaline solutions | |
| CN102553579B (en) | Preparation method of high-dispersity supported nano metal catalyst | |
| EP3027308B1 (en) | Method for forming noble metal nanoparticles on a support | |
| CN104043481B (en) | A kind of functionalization graphene supports the preparation method of noble metal nanocrystalline composite catalyst | |
| Jiang et al. | Effect of pyridinic-and pyrrolic-nitrogen on electrochemical performance of Pd for formic acid electrooxidation | |
| Qin et al. | Pd-Au/C catalysts with different alloying degrees for ethanol oxidation in alkaline media | |
| CN104646025B (en) | A kind of preparation method of hollow Pt/Ni alloys and graphene aerogel composite | |
| KR20150039768A (en) | Method of preparing a catalytic structure | |
| KR20110060589A (en) | Synthesis methods of core-shell nanoparticles on a carbon support | |
| Sharada et al. | Synthesis of palladium nanoparticles using continuous flow microreactor | |
| Ren et al. | Electro-oxidation of methanol on SnO2-promoted Pd/MWCNTs catalysts in alkaline solution | |
| Zhou et al. | Facet effect of Pt nanocrystals on catalytical properties toward glycerol oxidation reaction | |
| CN108126695A (en) | A kind of functionalized carbon nano-tube supported palladium nanocatalyst and its preparation and application | |
| CN105845948B (en) | A kind of preparation method of flower-shaped copper/cupric oxide Micron-nano composites carried noble metal fuel-cell catalyst | |
| CN105642311A (en) | Carbon-based non-noble metal @ noble metal core-shell nano catalyst and preparation method thereof by taking MOFs (Metal-Organic Framework) as template | |
| Kim et al. | Metal alloy hybrid nanoparticles with enhanced catalytic activities in fuel cell applications | |
| Sui et al. | Boosting methanol oxidation reaction with Au@ AgPt yolk-shell nanoparticles | |
| Ding et al. | Two-dimensional palladium nanosheet intercalated with gold nanoparticles for plasmon-enhanced electrocatalysis | |
| CN105680054A (en) | Preparation method for supported hollow-structured alloy catalyst for low-temperature fuel cell |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150128 Termination date: 20201201 |