CN103887530A - Pt/(C-Pb) catalyst and preparation thereof - Google Patents

Pt/(C-Pb) catalyst and preparation thereof Download PDF

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Publication number
CN103887530A
CN103887530A CN201210563723.3A CN201210563723A CN103887530A CN 103887530 A CN103887530 A CN 103887530A CN 201210563723 A CN201210563723 A CN 201210563723A CN 103887530 A CN103887530 A CN 103887530A
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catalyst
preparation
carbon carrier
concentration
carbon
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孙公权
李光兰
姜鲁华
王素力
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Dalian Institute of Chemical Physics of CAS
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Dalian Institute of Chemical Physics of CAS
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/921—Alloys or mixtures with metallic elements
    • 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
    • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
    • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
    • B01J23/628—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with lead
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

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  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Catalysts (AREA)

Abstract

A Pt/(C-Pb) catalyst is provided. The mass of Pb in the catalyst is 0.05-10% of the total mass of the catalyst. The preparation method comprises the following steps of: pretreatment of a carbon carrier, preparation of a Pt/(C-Pb) catalyst precursor, and preparation of a Pt/(C-Pb) catalyst. Compared with traditional preparation methods, the preparation method, on one hand, reduces the using amount of Pb, which facilitates environment protection; on the other hand, adopts pretreatment of the carbon carrier, which facilitates the adsorption and uniform dispersion of lead ions and improves the lead utilization efficiency. More importantly, the Pt/(C-Pb) catalyst prepared by the method of the invention has high activity on micromolecular alcohol oxidation under alkaline conditions, and has good stability. The method for preparing the catalyst has the advantages of low catalyst preparation cost and simple process.

Description

A kind of Pt/ (C-Pb) catalyst and preparation thereof
Technical field
The present invention relates to a kind of alkaline medium small molecular alcohol oxidation catalyst, relate to specifically a kind of for alkaline fuel cell small molecular alcohol oxidized Pt/ (C-Pb) catalyst; The invention still further relates to the preparation method of above-mentioned Pt/ (C-Pb) catalyst.
Background technology
Direct alcohol fuel cell is the advantage such as energy conversion efficiency is high, environmental friendliness, sustainable generating because having, and arouses widespread concern.But current fuel cell commercialization still faces certain challenge, one of them is that anode Aalcohols fuel oxidizing process dynamic process is slow.At present, the most frequently used catalyst of alcohol fuel battery is Pt/C, although it has higher catalytic activity, but there is stronger suction-operated between the intermediate product class CO species of oxidation of alcohols and Pt, can make active sites be occupied and cause catalyst poisoning, catalytic activity and stability are reduced, thereby exploitation have higher resisting CO poison, high catalytic activity and stability, catalyst with low cost has important theory significance and using value.
Document (Journal of the American Chemical Society; 2004,126,4043-4049) adopt the method for high-temperature fusion that Pt metal and Pb are carried out to high-temperature fusion in the environment of sealed vacuum, after constant temperature 9-12 hour, be cooled to room temperature, carry out again long-time calcining and form pure intermetallic compound, finally can be cast as electrode and carry out electro-chemical test.Experimental result shows, such PtPb intermetallic compound has higher alcohols electrochemical oxidation activity.But this catalyst preparation cost is higher, preparation process needs the operating condition of high temperature high vacuum, and preparation time is longer, harsher to the condition control ratio of preparation process.
Document (Journal oftheAmerican Chemical Society; 2012,134,8655-8661) adopt the method for electronation and original position electro-deposition to prepare Pt 4the catalyst such as Pb/C, PtRuPb/C and Pt/C+Pb (II), Pt/C+Pb (IV), experimental result shows that the Pt/C+Pb (II), Pt/C+Pb (IV) catalyst that adopt the method for electro-deposition to prepare have higher catalysis ethanol oxidation electro catalytic activity in alkaline medium.But the electrolyte of preparation process need to contain Pb salt, the process that simultaneously needs to carry out electro-deposition, preparation process is loaded down with trivial details, and complex process, so experiment condition still needs further to optimize and improve.
In sum, reduce the preparation cost of leaded platinum based catalyst, process simplification has important actual application value for the development of direct alcohol fuel cell.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, object is to provide a kind of small molecular alcohol fuel electro-oxidizing-catalyzing agent that is applied to alcohol fuel battery and preparation method thereof.
For achieving the above object, the present invention adopts following concrete scheme to realize:
A kind of Pt/ (C-Pb) catalyst, in Pt/ (C-Pb) catalyst, Pb quality is the 0.05-10% of catalyst gross mass; Pt quality is the 1-85% of catalyst gross mass.
The preparation method of described Pt/ (C-Pb) catalyst, is characterized in that: comprises the following steps,
A) preliminary treatment of carbon carrier: by dispersed carbon dust to HNO 3in solution, after 70-120 ℃ of stirring and refluxing 0.5-6h, filter, washing, dry to obtain carbon carrier after treatment;
B) preparation of C-Pb catalyst precarsor: by step a) gained carbon carrier after treatment evenly spread to Pb (CH 3cOO) 2, Pb (CH 3cOO) 4, Pb (NO 3) 2in in one or both the aqueous solution, filter, must adsorb after dry the catalyst precarsor of Pb ion, C-Pb;
C) preparation of Pt/ (C-Pb) catalyst: Yu Shuizhong adds b) gained C-Pb catalyst precarsor and H of step 2ptCl 6, stir and regulate pH value to 7-9, after mixing, be warming up to 70-90 ℃, pass into reducing agent and react 0.5-5h, filtration, washing, the dry Pt/ (C-Pb) that to obtain.
Described carbon carrier is one or more the mixture in XC-72, BP2000, acetylene black, KB carbon dust, carbon nano-tube, graphite, Graphene.
HNO described in step a) 3concentration be 0.1-6M; The mass concentration of carbon dust in salpeter solution is 15.4gL -1.
Baking temperature described in step a) is 60-120 ℃.
The concentration of the ion of Pb described in step b) in the aqueous solution is 0.1mM-1M.
H described in step c) 2ptCl 6the concentration of the aqueous solution is 0.10-14.8mgmL -1.
Reducing agent described in step c) is formaldehyde, NaBH 4in one or more mixture; The concentration of described formaldehyde is 2-40%; Described NaBH 4concentration be 0.1mmolL -1-1molL -1.
Compared with traditional small molecular alcohol oxidation catalyst and method for preparing catalyst, tool of the present invention has the following advantages:
1. the present invention introduces a small amount of Pb in platinum based catalyst and has greatly improved electro-oxidizing-catalyzing activity and the stability of raw catalyst for small molecular alcohol fuel;
2. catalyst of the present invention is compared with existing leaded platinum based catalyst, and Pb content is low, is conducive to environmental protection;
3. in this method preparation process, the preliminary treatment of carbon carrier is conducive to the absorption of lead ion and dispersed, improves plumbous utilization ratio;
4. adopt this method Kaolinite Preparation of Catalyst to have that preparation cost is cheap, technical process is simple, be conducive to the large-scale production of product.
Accompanying drawing explanation
Fig. 1 is for adopting the method for the invention to prepare the preparation process schematic diagram of Pt/ (C-Pb) catalyst.
Fig. 2 is the XRD spectra of embodiment 1,2 and comparative example 1,2 samples.
The sample preparing according to embodiment 1-2 and comparative example 1-2 is at N 2cV figure in saturated 1.0M NaOH electrolyte.
Fig. 3 is the electromicroscopic photograph of the sample for preparing according to embodiment 1-2, (a) embodiment 1, (b) embodiment 2.
Fig. 4 is that the sample for preparing according to embodiment 1-2 and comparative example 1-2 is at N 2saturated 1.0MNaOH+1.0M CH 3cV figure in OH electrolyte.
Fig. 5 is that the sample for preparing according to embodiment 1-2 and comparative example 1-2 is at N 2saturated 1.0MNaOH+1.0M CH 2oHCH 2instant current curve in OH electrolyte, electromotive force is constant in-0.2V.
Fig. 6 is that the sample for preparing according to embodiment 1-2 and comparative example 1-2 is at N 2saturated 1.0MNaOH+1.0M CH 3cH 2cV figure in OH electrolyte.
Fig. 7 is that the sample for preparing according to embodiment 1-2 and comparative example 1-2 is at N 2saturated 1.0MNaOH+1.0M CH 2oHCH 2cV figure in OH electrolyte.
Embodiment
Below in conjunction with embodiment, the present invention is explained in detail.Certainly the present invention is not limited in these specific embodiments.
Embodiment 1:20%Pt/ (C-0.65%Pb) (0.65% mass content that refers to active component Pb accounts for the mass content that 0.65%, 20% of catalyst gross mass refers to active component Pt and accounts for 20% of catalyst gross mass, and C refers to Vulcan XC-72)
First be scattered in 1.0L high purity water ultrasonic 2.0g VulcanXC-72, then add 379.4mgPb (CH 3cOO) 2to the aqueous solution, be uniformly dispersed.Above-mentioned solution is flooded under room temperature and stir 4h, filter, then 90 ° of C air atmospheres are dried solvent are removed, and obtain black powder.Get the above-mentioned black powder of 200mg and be distributed in 445mL high purity water, add 6.76mL7.4mgmL -1h 2ptCl 6ethylene glycol solution, ultrasonic being uniformly dispersed, by the pH value of the ethylene glycol solution regulator solution of 1M NaOH, to pH be 8, stir after 2-3h, be warming up to 80 ℃, add 55.6mL formalin (mass concentration is 30%), after reaction 2h, filter, wash, be dried, obtaining target product is 20%Pt/ (C+0.65%Pb) eelctro-catalyst.
(3.5% refers to that the mass content of active component Pb accounts for 3.5% of catalyst gross mass to embodiment 2:20%Pt/ (C-t-3.5%Pb), 20% refers to that the mass content of active component Pt accounts for 20% of catalyst gross mass, and C-t refers to Vulcan XC-72 5M HNO 3the dry carbon carrier obtaining of washing after 110 ℃ of backflow 6h of solution process)
First, 12g VulcanXC-72 is scattered in to 780ml5molL -1hNO 3in the aqueous solution, after 110 ℃ of reflow treatment 6h, filter, washing, dry to obtain pretreated carbon carrier, and this carbon carrier is labeled as to C-t.
Secondly, be scattered in 445mL high purity water ultrasonic 2.0g C-t, then add 379.4mgPb (CH 3cOO) 2to the aqueous solution, be uniformly dispersed.Above-mentioned solution is flooded under room temperature and stir 4h, filter, then 90 ° of C air atmospheres are dried solvent are removed, and obtain black powder.Get the above-mentioned black powder of 200mg and be distributed in 1.0L high purity water, add 6.76mL7.4mgmL -1h 2ptCl 6ethanolic solution, ultrasonic being uniformly dispersed, by the ethylene glycol solution regulator solution pH value of 1M NaOH, to pH value be 8 only, stir after 2-3h, be warming up to 80 ℃, add 55.6mL formalin (mass concentration is 30%), after reaction 2h, filter, wash, be dried, obtaining target product is 20%Pt/ (C+3.5%Pb) eelctro-catalyst.
Comparative example 1:20%Pt/C(20% refer to the mass content of active component Pt account for catalyst gross mass 20%)
Get the above-mentioned Vulcan XC-72 of 200mg powder and be distributed in 445mL high purity water, add 6.76mL7.4mgmL -1h 2ptCl 6ethylene glycol solution, ultrasonic being uniformly dispersed, by the pH value of the ethylene glycol solution regulator solution of 1M NaOH, to pH be 8, stir after 2-3h, be warming up to 80 ℃, add 55.6mL formalin (mass concentration is 30%), after reaction 2h, filter, wash, be dried, obtaining target product is 20%Pt/C eelctro-catalyst.
Comparative example 2:20%Pt/C-t(20% refers to that the mass content of active component Pt accounts for 20% of catalyst gross mass, and C-t refers to Vulcan XC-72 5MHNO 3the dry carrier obtaining of washing after 110 ℃ of backflow 6h of solution process)
First, 12g VulcanXC-72 is scattered in to 780ml5molL -1hNO 3in the aqueous solution, after 110 ℃ of reflow treatment 6h, filter, washing, dry to obtain pretreated carbon carrier, and this carbon carrier is labeled as to C-t.
Get the above-mentioned black powder of 200mg and be distributed in 445mL high purity water, add 6.76mL7.4mg mL -1h 2ptCl 6ethylene glycol solution, ultrasonic being uniformly dispersed, by the pH value of the ethylene glycol solution regulator solution of 1M NaOH, to pH be 8, stir after 2-3h, be warming up to 80 ℃, add 55.6mL formalin (mass concentration is 30%), after reaction 2h, filter, wash, be dried, obtaining target product is 20%Pt/C eelctro-catalyst.
Fig. 1 adopts the method for the invention to prepare the preparation process schematic diagram of Pt/C-Pb catalyst.First schematic diagram has described a rough surface of carbon carrier; Carbon carrier is at process HNO 3processing rear surface can be functionalized, and is combined with carboxyl (COO-), and carbon carrier is now marked as C-t; And carboxyl (COO-) is very favorable for the absorption of lead ion, therefore lead salt is added after above-mentioned carbon carrier after treatment, the adsorption capacity of lead ion can strengthen, and adsorbance can improve, and the lead ion of now absorption can be scattered in carbon carrier surface uniformly; Finally, at above-mentioned carbon carrier adsorption on the carbon carrier of lead ion, further support Pt, can obtain Pt/ (C-Pb) catalyst of low Pb content.
Fig. 2 is the XRD spectra of embodiment 1,2 and comparative example 1,2 samples.The PCPDF standard card of contrast Fig. 1 below can be found out, embodiment 1,2 and comparative example 1,2 samples all have the characteristic peak of Pt, 39.8,46.2,67.4,81.3 and 85.7 ° can belong to respectively (111) of Pt, (200), (220), the diffraction maximum of (311) and (222) crystal face.The particle diameter that calculates Pt in embodiment 1,2 and comparative example 1,2 samples by Scherrer formula is respectively 4.9,2.3,2.7 and 3.5nm.From XRD figure, do not find the signal peak of Pb, may have two reasons: the content of the one, Pb element is too low cannot detect signal; Another kind may be that the existence of Pb is unbodied, there is no corresponding signal peak so do not form in crystal structure XRD spectra.
Fig. 3 is the electromicroscopic photograph of the sample for preparing according to embodiment 1 and embodiment 2.From a figure, can see, by without in the prepared catalyst of acid-treated carbon carrier, metal nanoparticle disperses more even, and average grain diameter is in 4.7nm left and right; And by passing through in the prepared catalyst (b figure) of acid-treated carbon carrier, metal nanoparticle disperses also more even, average grain diameter is in 2.4nm left and right, particle diameter than the nano particle in embodiment 1 is little, and the acid treatment that carrier is described contributes to the dispersed of metallic and control that nanometer particle size is big or small.
Fig. 4 is that the sample for preparing according to embodiment 1-2 and comparative example 1-2 is at N 2saturated 1.0MNaOH+1.0M CH 3cV figure in OH electrolyte.Can find that by the contrast of comparative example 1 and 2 carrier carries out can improving after acid treatment the activity of catalyst methanol oxidation, the oxygen-containing functional group that reason may increase to acid treatment carrier surface is relevant.Can find to only have the sample that embodiment 2 prepares can promote the catalytic activity of catalyst to improve by the contrast of embodiment 1-2 and comparative example 1-2: initial oxidation current potential increases about 100mV, and peak current increases approximately 1 times.
Fig. 5 is that the sample for preparing according to embodiment 1-2 and comparative example 1-2 is at N 2saturated 1.0MNaOH+1.0M CH 3instant current curve in OH electrolyte, electromotive force is constant in-0.3V.Curve by comparative example 1 and 2 can find, carrier carries out acid treatment meeting and improve electroxidation activity and the stability of catalyst.Stability test by the 1800s that carries out at constant potential-0.3V can be found, the electroxidation activity of the sample that embodiment 2 prepares and stability, all apparently higher than other three kinds of catalyst, illustrate that this method can effectively improve catalytic activity and the stability of catalyst.
Fig. 6 is that the sample for preparing according to embodiment 1-2 and comparative example 1-2 is at N 2saturated 1.0MNaOH+1.0M CH 3cH 2cV figure in OH electrolyte.Can find that by the methanol oxidation current curve of embodiment 1-2 and comparative example 1-2 the carbon carrier absorption Pb after acid treatment can obviously improve the catalytic activity of catalyst afterwards, initial oxidation current potential be born and moved about 150mV, peak current increases by 3 times.
Fig. 7 is that the sample for preparing according to embodiment 1-2 and comparative example 1-2 is at N 2saturated 1.0MNaOH+1.0M CH 2oHCH 2cV figure in OH electrolyte.Can find that by the current curve of embodiment 1-2 and comparative example 1-2 catalysis oxidation of glycol the carbon carrier absorption Pb after acid treatment can obviously improve the catalytic activity of catalyst afterwards, initial oxidation current potential be born and moved about 300mV, peak current also increases to some extent.

Claims (8)

1. Pt/ (C-Pb) catalyst, is characterized in that: in Pt/ (C-Pb) catalyst, Pb quality is the 0.05-10% of catalyst gross mass; Pt quality is the 1-85% of catalyst gross mass.
2. a preparation method for Pt/ claimed in claim 1 (C-Pb) catalyst, is characterized in that: comprises the following steps,
A) preliminary treatment of carbon carrier: by dispersed carbon dust to HNO 3in solution, 70-120 ℃ of stirring and refluxing
After 0.5-6h, filter, washing, dry to obtain carbon carrier after treatment;
B) preparation of C-Pb catalyst precarsor: by step a) gained carbon carrier after treatment evenly spread to Pb (CH 3cOO) 2, Pb (CH 3cOO) 4, Pb (NO 3) 2in in one or both the aqueous solution, filter, must adsorb after dry the catalyst precarsor of Pb ion, C-Pb;
C) preparation of Pt/ (C-Pb) catalyst: Yu Shuizhong adds b) gained C-Pb catalyst precarsor and H of step 2ptCl 6, stir and regulate pH value to 7-9, after mixing, be warming up to 70-90 ℃, pass into reducing agent and react 0.5-5h, filtration, washing, the dry Pt/ (C-Pb) that to obtain.
3. the preparation method of Pt/ as claimed in claim 1 or 2 (C-Pb) catalyst, is characterized in that: described carbon carrier is one or more the mixture in XC-72, BP2000, acetylene black, KB carbon dust, carbon nano-tube, graphite, Graphene.
4. the preparation method of Pt/ as claimed in claim 2 (C-Pb) catalyst, is characterized in that: HNO described in step a) 3concentration be 0.1-6M; The mass concentration of carbon dust in salpeter solution is 15.4gL -1.
5. the preparation method of Pt/ as claimed in claim 2 (C-Pb) catalyst, is characterized in that: baking temperature described in step a) is 60-120 ℃.
6. the preparation method of Pt/ as claimed in claim 2 (C-Pb) catalyst, is characterized in that: the concentration of the ion of Pb described in step b) in the aqueous solution is 0.1mM-1M.
7. the preparation method of Pt/ as claimed in claim 2 (C-Pb) catalyst, is characterized in that: H described in step c) 2ptCl 6the concentration of the aqueous solution is 0.10-14.8mgmL -1.
8. the preparation method of Pt/ as claimed in claim 2 (C-Pb) catalyst, is characterized in that: reducing agent described in step c) is formaldehyde, NaBH 4in one or more mixture; The mass concentration of described formaldehyde is 2-40%; Described NaBH 4concentration be 0.1mmolL -1-1molL -1.
CN201210563723.3A 2012-12-21 2012-12-21 Pt/(C-Pb) catalyst and preparation thereof Pending CN103887530A (en)

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110198781A (en) * 2016-08-26 2019-09-03 阿里尔科技创新公司 Catalyst, its preparation based on tin and the fuel cell using it
CN112993279A (en) * 2021-02-22 2021-06-18 昆明贵研新材料科技有限公司 High-batch consistency preparation method for preparing carbon-supported noble metal catalyst by liquid phase reduction
US11264623B2 (en) 2017-08-24 2022-03-01 Ariel Scientific Innovations Ltd. Palladium-tin shell electrocatalysts, the preparation thereof, and using the same for fuel cells

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05286958A (en) * 1992-04-07 1993-11-02 Tosoh Corp Production of gamma-butyrolactone
CN1712394A (en) * 2004-06-24 2005-12-28 华东理工大学 Production of pyruvate from hydroxy-acetone in biomass pyrolytic water-phase product
CN101185900A (en) * 2007-12-12 2008-05-28 哈尔滨工业大学 Method for preparing direct alcohols fuel cell anode catalyst

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH05286958A (en) * 1992-04-07 1993-11-02 Tosoh Corp Production of gamma-butyrolactone
CN1712394A (en) * 2004-06-24 2005-12-28 华东理工大学 Production of pyruvate from hydroxy-acetone in biomass pyrolytic water-phase product
CN101185900A (en) * 2007-12-12 2008-05-28 哈尔滨工业大学 Method for preparing direct alcohols fuel cell anode catalyst

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
YANYAN FENG等: "Ethylene glycol, 2-propanol electrooxidation in alkaline medium on the ordered intermetallic PtPb surface", 《ELECTROCHIMICA ACTA》 *
YIYIN HUANG等: "Microwave synthesis and electrochemical performance of a PtPb alloy catalyst for methanol and formic acid oxidation", 《ELECTROCHIMICA ACTA》 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110198781A (en) * 2016-08-26 2019-09-03 阿里尔科技创新公司 Catalyst, its preparation based on tin and the fuel cell using it
US11233247B2 (en) * 2016-08-26 2022-01-25 Ariel Scientific Innovations Ltd. Tin-based catalysts, the preparation thereof, and fuel cells using the same
CN110198781B (en) * 2016-08-26 2023-08-29 阿里尔科技创新公司 Tin-based catalyst, preparation thereof, and fuel cell using the same
US11264623B2 (en) 2017-08-24 2022-03-01 Ariel Scientific Innovations Ltd. Palladium-tin shell electrocatalysts, the preparation thereof, and using the same for fuel cells
US11682772B2 (en) 2017-08-24 2023-06-20 Ariel Scientific Innovations Ltd. Electrocatalysts, the preparation thereof, and using the same for fuel cells
CN112993279A (en) * 2021-02-22 2021-06-18 昆明贵研新材料科技有限公司 High-batch consistency preparation method for preparing carbon-supported noble metal catalyst by liquid phase reduction

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Application publication date: 20140625