CN109216715A - It is a kind of rapidly and efficiently to improve the active method of business platinum ruthenium catalyst - Google Patents
It is a kind of rapidly and efficiently to improve the active method of business platinum ruthenium catalyst Download PDFInfo
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- CN109216715A CN109216715A CN201810872040.3A CN201810872040A CN109216715A CN 109216715 A CN109216715 A CN 109216715A CN 201810872040 A CN201810872040 A CN 201810872040A CN 109216715 A CN109216715 A CN 109216715A
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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
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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
- H01M4/9041—Metals or alloys
- H01M4/905—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC
- H01M4/9058—Metals or alloys specially used in fuel cell operating at high temperature, e.g. SOFC of noble metals or noble-metal based alloys
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- 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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Abstract
The present invention provides a kind of rapidly and efficiently raising active method of business platinum ruthenium catalyst, is related to catalyst technical field.The active method of business platinum ruthenium catalyst that rapidly and efficiently improves is mainly to select the acid of certain kind quickly to be handled according to its dissolubility business platinum ruthenium catalyst.The present invention overcomes the deficiencies in the prior art, effectively solves the problems, such as that the reunion of business PtRu catalyst activity component is more serious, promote activity, mithridatism and the stability of PtRu catalyst, and operating procedure is simple and convenient, the Pt and Ru of loss can be recycled simultaneously, reduce metallic pollution, safety and environmental protection.
Description
Technical field
The present invention relates to catalyst technical fields, and in particular to a kind of rapidly and efficiently raising business platinum ruthenium catalyst is active
Method.
Background technique
Platinum ruthenium (PtRu) synthetic material is a kind of catalyst for being mainly used in direct methanol fuel cell reaction, to first
Alcohol oxidation has higher electro catalytic activity.In bimetallic catalyst, PtRu elctro-catalyst is considered most promising at present
Fuel battery anode catalyst.Compared with pure Pt catalyst, it has preferable resisting CO poisoning ability and higher catalysis
Activity.In preparation PtRu/C method reported in the literature, colloid method be it is most common, mainly comprising the following three steps: platiniferous
The preparation of the colloid of ruthenium, such as organic metal object colloid or metal oxide colloids；On colloidal deposition to carbon carrier；The change of mixture
Learn reduction.This method can obtain very high dispersion degree, but preparation process is more complicated, therefore higher cost, efficiency are lower.Separately
One common method is infusion process, and the big advantage of the one of such methods is relatively to be suitble to large-scale production without filtering and washing,
And directly use chloride such as chloroplatinic acid (H2PtCl6) and ruthenic chloride (RuCl3), it is at low cost and prepare more convenient.
Presently commercially available business PtRu catalyst activity component is reunited active, more anti-than more serious and business PtRu catalyst
Toxicity and stablize poor, this generates larger limitation to the application of PtRu catalyst in a fuel cell.
Summary of the invention
In view of the shortcomings of the prior art, the present invention provides a kind of rapidly and efficiently raising active method of business platinum ruthenium catalyst,
It effectively solves the problems, such as that the reunion of business PtRu catalyst activity component is more serious, promotes activity, the mithridatism of PtRu catalyst
And stability, and operating procedure is simple and convenient, while can recycle the Pt and Ru of loss, reduces metallic pollution, safety and environmental protection.
In order to achieve the above object, technical solution of the present invention is achieved by the following technical programs:
A kind of rapidly and efficiently to improve the active method of business platinum ruthenium catalyst, the business platinum ruthenium that rapidly and efficiently improves is catalyzed
The active method of agent the following steps are included:
(1) choose business PtRu catalyst in processing acid in dispersed, stirring and dissolving for a period of time after, it is spare；
(2) substance after above-mentioned stirring is placed in autoclave, it is spare after being handled under high temperature；
(3) it by the PtRu catalyst natural cooling after above-mentioned high-temperature process, is dried after being used ethanol washing 3 times after cooling,
Obtain high activity business PtRu catalyst.
Preferably, it is chosen in step (1) sour for processing without the acid largely dissolved to business PtRu catalyst.
Preferably, processing acid used in this hair is with the mass ratio of business PtRu catalyst according to the sour type of processing and quotient
The difference of the type of industry PtRu catalyst and be changed.
Preferably, the time of step (2) high temperature processing is according to the type for using processing acid and business PtRu catalyst
It is different and changes, and handling the time should not be too long.
Preferably, lossy Pt and Ru during present invention acid processing business platinum ruthenium catalyst, need to add sodium borohydride
It is recycled.
The present invention provides a kind of rapidly and efficiently raising active method of business platinum ruthenium catalyst, compared with prior art advantage
It is:
Technical solution of the present invention can effectively improve activity, mithridatism and the stability of business PtRu catalyst.Pass through
Catalyst is carried out simple being after treatment that can be used, and the Pt and Ru of loss during processing can pass through addition
Sodium borohydride is recycled, not the loss of noble metal and relatively environment-friendly.Treatment conditions are relatively mild and the processing time is shorter, can
Make catalyst activity compared to untreated preceding 3 times of raising and improves 5 times or more compared to business Pt/C.
Detailed description of the invention
Fig. 1 be Pt50Ru50/C before treatment after transmission electron microscope picture, (A) it is untreated and (B) processing after.
Fig. 2 be Ru 3p (A) andPt4f (B) before treatment after electron spectrum, (before) processing before and (after) at
After reason.
(A) is cyclic voltammetry curve of the sample in 0.5mol/L sulfuric acid before and after the processing in Fig. 3；(B) for before and after the processing with
And cyclic voltammetry curve of the business Pt/C in 0.5mol/L, 1mol/L methanol solution；It (C) is the expression activitiy of sample；(D) it is
The stability of sample.
Specific embodiment
In order to make the object, technical scheme and advantages of the embodiment of the invention clearer, below with reference to the embodiment of the present invention pair
Technical solution in the embodiment of the present invention is clearly and completely described, it is clear that described embodiment is a part of the invention
Embodiment, instead of all the embodiments.Based on the embodiments of the present invention, those of ordinary skill in the art are not making wound
Every other embodiment obtained under the premise of the property made labour, shall fall within the protection scope of the present invention.
Embodiment 1:
Rapidly and efficiently improve Pt50Ru50The active method of/C catalyst, comprising the following steps: by 50mg Pt50Ru50/ C is urged
Agent is scattered in 5mL glacial acetic acid, and stirring is transferred to the autoclave of 10mL and by reaction kettle at 120 degrees Celsius after ten minutes
Reason 2 hours.After natural cooling, with ethanol washing 3 times and dries stand-by, obtain high activity Pt50Ru50/ C catalyst.
Detect Pt50Ru50/ C catalyst acid catalytic activity component reunion situation before and after the processing and Pt50Ru50/ C catalyst
The increase and decrease situation of sour ru oxide and platinum oxide before and after the processing, as a result as shown in Figure 1 and Figure 2.
Wherein shown in Fig. 1, after acetic acid processing, more severe PtRu particle of reuniting originally becomes uniformly clear, particle
Spacing of lattice is rear almost the same before treatment.
Shown in Fig. 2, after acetic acid processing, the ru oxide in business PtRu catalyst increases and platinum oxide is reduced, this
A little ingredients are conducive to the increase of methanol oxidative activity and mithridatism.
With aqua regia dissolution 50mg Pt50Ru50/ C catalyst, by constituent content mensure, as a result as shown in the table, although having
Partial Pt and ruthenium loss, but the molar ratio (Molarratio) generally before and after catalyst treatment does not change.In addition, molten
The Pt and Ru for solving part can carry out recycling recycling by adding sodium borohydride.
Embodiment 2:
10uL Pt before and after the processing is taken respectively50Ru50It the ethanol solution (4mg/mL) of/C and is dripped to the business Pt/C of concentration
Platinum carbon electrode and naturally dry, with three-electrode system, (for silver chlorate/silver for reference electrode, platinum filament is the platinum containing sample to electrode
Carbon electrode is working electrode), activity is tested in 0.5mol/L, 1mol/L methanol solution, as a result as shown in Figure 3.
Wherein, Fig. 3 A shows the Pt after acetic acid treatment50Ru50Area of/C cyclic voltammetry curve the curve in -0.2-0.2V is aobvious
It writes and increases (increasing to 39.8 square metre/milligram platinum by 16.7)；Fig. 3 B shows that treated Pt50Ru50/ C is aoxidized in an acidic solution
With lower take-off potential and bigger current density when methanol.In addition, by utilizing peak value at peak value at 0.8V and 0.5V
Comparison, this value is increased to 2.1 by 1.7 before and after the processing, illustrates the mithridatism promotion of sample after processing；It can be sent out by the comparison of Fig. 3 C
Its existing activity is 3.3 times of untreated samples and is active 5 times of commercially available business Pt/C or more；Sample after Fig. 3 D surface treatment
The electric current of its Oxidation of Methanol is consistently greater than untreated and business Pt/C sample, its stabilization of surface is better than untreated samples and business
Pt/C。
It should be noted that, in this document, relational terms such as first and second and the like are used merely to a reality
Body or operation are distinguished with another entity or operation, are deposited without necessarily requiring or implying between these entities or operation
In any actual relationship or order or sequence.Moreover, the terms "include", "comprise" or its any other variant are intended to
Non-exclusive inclusion, so that the process, method, article or equipment including a series of elements is not only wanted including those
Element, but also including other elements that are not explicitly listed, or further include for this process, method, article or equipment
Intrinsic element.In the absence of more restrictions, the element limited by sentence "including a ...", it is not excluded that
There is also other identical elements in process, method, article or equipment including the element.
The above embodiments are merely illustrative of the technical solutions of the present invention, rather than its limitations；Although with reference to the foregoing embodiments
Invention is explained in detail, those skilled in the art should understand that: it still can be to aforementioned each implementation
Technical solution documented by example is modified or equivalent replacement of some of the technical features；And these modification or
Replacement, the spirit and scope for technical solution of various embodiments of the present invention that it does not separate the essence of the corresponding technical solution.
Claims (5)
1. a kind of rapidly and efficiently improve the active method of business platinum ruthenium catalyst, which is characterized in that described rapidly and efficiently to improve quotient
The active method of industry platinum ruthenium catalyst the following steps are included:
(1) choose business PtRu catalyst in processing acid in dispersed, stirring and dissolving for a period of time after, it is spare；
(2) substance after above-mentioned stirring is placed in autoclave, it is spare after being handled under high temperature；
(3) it by the PtRu catalyst natural cooling after above-mentioned high-temperature process, dries, obtains high after being used ethanol washing 3 times after cooling
Active business PtRu catalyst.
2. a kind of rapidly and efficiently raising active method of business platinum ruthenium catalyst as described in claim 1, it is characterised in that: step
Suddenly it is chosen in (1) sour for processing without the acid largely dissolved to business PtRu catalyst.
3. a kind of rapidly and efficiently raising active method of business platinum ruthenium catalyst as described in claim 1, it is characterised in that: this
The mass ratio of processing acid and business PtRu catalyst used in hair is according to the type of processing acid and the kind of business PtRu catalyst
The difference of class and be changed.
4. a kind of rapidly and efficiently raising active method of business platinum ruthenium catalyst as described in claim 1, it is characterised in that: step
Suddenly the time of (2) high temperature processing changes according to using processing acid different from the type of business PtRu catalyst, and handles
Time is unsuitable too long.
5. a kind of rapidly and efficiently raising active method of business platinum ruthenium catalyst as described in claim 1, it is characterised in that: this
Lossy Pt and Ru during invention acid processing business platinum ruthenium catalyst, need to add sodium borohydride and be recycled.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005104275A1 (en) * | 2004-04-22 | 2005-11-03 | Nippon Steel Corporation | Fuel cell and gas diffusion electrode for fuel cell |
| CN104148058A (en) * | 2014-04-04 | 2014-11-19 | 西北师范大学 | Method for improving activity of carbon-supported platinum based catalyst |
| CN104174411A (en) * | 2014-07-07 | 2014-12-03 | 中国科学院过程工程研究所 | Method for improving catalytic oxidization activity of VOCs catalyst |
| CN105633422A (en) * | 2016-03-21 | 2016-06-01 | 北京化工大学 | Method for massively preparing platinum-based dealloyed electrocatalyst for cathode of fuel cell |
| CN106582634A (en) * | 2016-11-16 | 2017-04-26 | 盘锦格林凯默科技有限公司 | Highly active ruthenium-carbon catalyst modified by transition metal atoms and preparation method thereof |
| CN107684925A (en) * | 2017-10-26 | 2018-02-13 | 阜阳师范学院 | A kind of modified g C of acid3N4Photochemical catalyst and its preparation and application |
| CN108315564A (en) * | 2017-12-28 | 2018-07-24 | 核工业北京化工冶金研究院 | The method that a kind of molten carrier recycles platinum from aluminium-based catalyst |
-
2018
- 2018-08-02 CN CN201810872040.3A patent/CN109216715A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2005104275A1 (en) * | 2004-04-22 | 2005-11-03 | Nippon Steel Corporation | Fuel cell and gas diffusion electrode for fuel cell |
| CN104148058A (en) * | 2014-04-04 | 2014-11-19 | 西北师范大学 | Method for improving activity of carbon-supported platinum based catalyst |
| CN104174411A (en) * | 2014-07-07 | 2014-12-03 | 中国科学院过程工程研究所 | Method for improving catalytic oxidization activity of VOCs catalyst |
| CN105633422A (en) * | 2016-03-21 | 2016-06-01 | 北京化工大学 | Method for massively preparing platinum-based dealloyed electrocatalyst for cathode of fuel cell |
| CN106582634A (en) * | 2016-11-16 | 2017-04-26 | 盘锦格林凯默科技有限公司 | Highly active ruthenium-carbon catalyst modified by transition metal atoms and preparation method thereof |
| CN107684925A (en) * | 2017-10-26 | 2018-02-13 | 阜阳师范学院 | A kind of modified g C of acid3N4Photochemical catalyst and its preparation and application |
| CN108315564A (en) * | 2017-12-28 | 2018-07-24 | 核工业北京化工冶金研究院 | The method that a kind of molten carrier recycles platinum from aluminium-based catalyst |
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