CN102139219B - Method for preparing carrier loaded Pt-Cu Nanocube catalyst - Google Patents
Method for preparing carrier loaded Pt-Cu Nanocube catalyst Download PDFInfo
- Publication number
- CN102139219B CN102139219B CN201110029583.7A CN201110029583A CN102139219B CN 102139219 B CN102139219 B CN 102139219B CN 201110029583 A CN201110029583 A CN 201110029583A CN 102139219 B CN102139219 B CN 102139219B
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- nanocube
- catalyst
- preparation
- carrier
- surfactant
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- 229910018883 Pt—Cu Inorganic materials 0.000 title claims abstract description 33
- 239000003054 catalyst Substances 0.000 title claims abstract description 28
- 238000000034 method Methods 0.000 title claims abstract description 14
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 15
- 238000002360 preparation method Methods 0.000 claims abstract description 13
- 239000002904 solvent Substances 0.000 claims abstract description 13
- 238000005406 washing Methods 0.000 claims abstract description 11
- 239000004094 surface-active agent Substances 0.000 claims abstract description 10
- 239000002002 slurry Substances 0.000 claims description 7
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- CXRFDZFCGOPDTD-UHFFFAOYSA-M Cetrimide Chemical compound [Br-].CCCCCCCCCCCCCC[N+](C)(C)C CXRFDZFCGOPDTD-UHFFFAOYSA-M 0.000 claims description 4
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 4
- 229910010413 TiO 2 Inorganic materials 0.000 claims description 2
- 125000000217 alkyl group Chemical group 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 238000007306 functionalization reaction Methods 0.000 claims description 2
- 229910052736 halogen Inorganic materials 0.000 claims description 2
- 150000002367 halogens Chemical class 0.000 claims description 2
- 150000002500 ions Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 abstract description 6
- 238000003786 synthesis reaction Methods 0.000 abstract description 6
- 239000000446 fuel Substances 0.000 abstract description 5
- 239000002184 metal Substances 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 5
- 239000002243 precursor Substances 0.000 abstract description 4
- 230000001360 synchronised effect Effects 0.000 abstract description 4
- 239000012691 Cu precursor Substances 0.000 abstract 1
- 239000000203 mixture Substances 0.000 abstract 1
- 238000005303 weighing Methods 0.000 abstract 1
- 238000006243 chemical reaction Methods 0.000 description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 229910001260 Pt alloy Inorganic materials 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 239000008367 deionised water Substances 0.000 description 2
- 229910021641 deionized water Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 229910021591 Copper(I) chloride Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 230000036632 reaction speed Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
Classifications
-
- 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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- Catalysts (AREA)
Abstract
The invention relates to a method for preparing a carrier loaded Pt-Cu Nanocube catalyst, belonging to the technical field of fuel cell and catalyst synthesis. The method comprises the following steps: (1) firstly reducing a Cu precursor by utilizing a stronger reducer in the presence of a surfactant, washing to obtain Cu Nanocube, and carrying out redispersion on the Cu Nanocube by utilizing an appropriate solvent; and (2) weighing a certain amount of Cu size obtained in the step (1) to be mixed with a Pt precursor, and reducing the mixture by utilizing a weaker reducer in the presence of the surfactant; and washing to obtain Pt-Cunanocubes, and then carrying out redispersion on the Pt-Cunanocubes by utilizing the appropriate solvent. The preparation method has the characteristics that reduction is carried out through substeps, different catalysts are adopted aiming at metal precursors at different reduction potentials, and compared with synchronous reduction, the synthesis efficiency of Pt-Cu double-metal nanocube and the success rate are greatly improved.
Description
Technical field
The present invention relates to a kind of preparation method of Pt-Cu Nanocube catalyst, belong to fuel cell and catalyst synthesis technology field.
Background technology
Pt catalyst is used as fuel-cell catalyst and is studied application widely.But due to the costliness of Pt catalyst cost, and its corrosion-prone attribute in fuel cell opening and closing process.Target is transferred to non-Pt or Pt alloy catalyst by increasing researcher, and the different-shape of catalyst also has deep research to the impact of its catalytic performance in addition.Pt-Cu nanocube also obtains certain research as a kind of Pt alloy catalyst of specific morphology.
For the synthesis of Pt-Cu Nanocube catalyst, mostly adopt synchronous reduction, the presoma in view of most of non-Pt metal compares and is difficult to reduction (such as Cu
2+, Fe
2+, Ni
2+), and the presoma of Pt is than being easier to reduction, again because pattern control overflow reaction speed can not be too fast, thus needs to adopt weak reductant reaction for a long time.Obviously, under identical conditions, the presoma of Pt and the reducing degree of non-Pt common metal presoma, reduction speed, the gathering of particle and the size of size etc. are inevitable different, and this governs efficiency and the success rate of Pt-Cu bimetallic nanocube synthesis.
Summary of the invention
The technical problem to be solved in the present invention is the defect overcoming existing synchronous method of reducing, provides the high-efficiency synthetic method that a kind of step-by-step reduction prepares Pt-Cu bimetallic nanocube.
In order to solve the problems of the technologies described above, the invention provides following technical scheme:
Support a preparation method for the Pt-Cu Nanocube catalyst of carrier, comprise the steps,
(1) first use comparatively strong reductant, under the existence of surfactant, reduced by the presoma of Cu, washing can obtain Cu Nanocube, then it is again disperseed with appropriate solvent;
(2) get the Cu slurry of a certain amount of step (1), the presoma with Pt mixes, and under the existence of surfactant, reduces with weak reductant; Washing can obtain Pt-Cu nanocubes, then it is again disperseed with appropriate solvent.
Further, described preparation method also comprises the steps,
(3) do functionalization with acid to carrier, by the carrier after process with the mixing of scattered Pt-Cu nanocube slurry, washing, drying, must support the Pt-Cu nanocube catalyst of carrier.
Described strong reductant is selected from N
2h
4h
2o, NaBH
4one of; Described weak reductant is selected from PVP, one of many alkylols.
The surfactant of step (1) is selected from PVP, one of TTAB, SLS, DBS; The surfactant of step (2) is selected from halogen-containing ion Br
-, I
-one of solution, many alkyl phosphate ions TTAB.
Step (1) disperses solvent for use to be selected from one of water, ethylene glycol again; Step (2) disperses solvent for use to be alcohol again.
The described carrier of step (3) is selected from XC-72, mesoporous TiO
2one of.
A special feature of preparation method of the present invention is its step-by-step reduction, for the metal precursor of different reduction potential, adopts different catalyst, and relative to synchronous reduction, the efficiency that Pt-Cu bimetallic nanocube synthesizes and success rate all have and significantly improve.
The emphasis of the present invention's innovation is the improvement of synthetic method.If synchronously reduce the presoma of Pt, Cu, take into account the power of two oxidation of precursor abilities, the final weak reductant that adopts at higher temperature (more than 200oC), reaction long period (more than 5h).Reaction process is then divided into two by the present invention, and the presoma for different oxidability adopts strong and weak different reducing agents, and significantly reduce the reaction time (about 2h), reaction temperature also can be controlled in about 150oC.Most critical part is due to step-by-step reduction, and such reaction system facilitates adjustable, not only can adopt organic phase system but also can adopt aqueous solution phase system (change of solvent).Research work due to forefathers shows that Pt-Cu nanocube can improve the electrocatalysis characteristic of fuel cell well.Thus, the present invention can be more efficient, synthesizes the Pt-Cu nanocube of required pattern more easily, and can improve the electrocatalysis characteristic of fuel cell well.
Accompanying drawing explanation
Accompanying drawing is used to provide a further understanding of the present invention, and forms a part for description, together with embodiments of the present invention for explaining the present invention, is not construed as limiting the invention.In the accompanying drawings:
Fig. 1 is the Pt-Cu nanocube not supporting carrier adopting the inventive method to prepare;
Fig. 2 is that another that adopt the inventive method to prepare does not support the Pt-Cu nanocube of carrier;
Fig. 3 is the electromicroscopic photograph of Pt-Cu nanocube/XC-72 prepared by the inventive method.
Detailed description of the invention
Below in conjunction with accompanying drawing, the preferred embodiments of the present invention are described, should be appreciated that preferred embodiment described herein is only for instruction and explanation of the present invention, is not intended to limit the present invention.
Support a preparation method for the Pt-Cu Nanocube catalyst of carrier, step is:
(1) by 0.5mmol CuCl
2be dissolved in 70ml EG, and add 5mmol SLS, stir and be heated to 120oC, logical argon shield, then dropwise drips 7.5mmol N simultaneously
2h
4h
2o, reaction 1h, after cooling with alcohol and deionized water washing and centrifugal.According to proportioning consumption by gained Cu nanocube ultrasonic disperse in a certain amount of EG, be made into the slurry of 0.1mol/L.
(2) 0.3mmol H is got
2ptCl
6eG solution, join in 50ml EG, be heated to 120 oC and logical argon shield, then dropwise drip the Cu nanocube slurry that 3ml prepares, after stirring, temperature is raised to 150 oC, and wherein EG not only be solvent but also be reducing agent, at this thermotonus 1h.After reaction terminates, alcohol and deionized water washing, obtain Pt-Cu bimetallic nanocubes.With alcohol, it is scattered again.
(3) XC-72 nitric acid is carried out the ultrasonic process of 5h, these carriers introduce oxygen-containing functional group.Then by admixed together according to different catalyst proportion consumptions (5%, 10%, 20%, 30%) with scattered Pt-Cu nanocube slurry for the carrier after process, ultrasonic 20h.Afterwards, washing is dry, obtains the required Pt-Cu nanocube catalyst supporting carrier.
Gained supports the electromicroscopic photograph of the Pt-Cu nanocube catalyst of carrier as Figure 1-3, as can be seen here, step-by-step reduction method can adopt different reducing agents, activating agent and the solvent needed for reaction for different presomas, can improve Reactive Synthesis efficiency to greatest extent, improve the quality of products.
It is noted that the foregoing is only the preferred embodiments of the present invention, be not limited to the present invention, although with reference to previous embodiment to invention has been detailed description, for a person skilled in the art, it still can be modified to the technical scheme described in foregoing embodiments, or carries out equivalent replacement to wherein portion of techniques feature.Within the spirit and principles in the present invention all, any amendment done, equivalent replacement, improvement etc., all should be included within protection scope of the present invention.
Claims (6)
1. support a preparation method for the Pt-Cu Nanocube catalyst of carrier, it is characterized in that: comprise the steps,
(1) first use comparatively strong reductant, under the existence of surfactant, reduced by the presoma of Cu, washing can obtain Cu Nanocube, then it is again disperseed with appropriate solvent, and described comparatively strong reductant is selected from N
2h
4h
2o, NaBH
4one of;
(2) get the Cu slurry of a certain amount of step (1), the presoma with Pt mixes, and under the existence of surfactant, reduces with weak reductant; Washing can obtain Pt-Cu nanocube, then it is again disperseed with appropriate solvent, and described weak reductant is selected from PVP, one of many alkylols;
(3) do functionalization with sour to carrier, by the scattered Pt-Cu nanocube slurry mixing of rapid for the bearer synchronization after process (2) gained, washing, drying, must support the Pt-Cu nanocube catalyst of carrier.
2. the preparation method supporting the Pt-Cu Nanocube catalyst of carrier according to claim 1, is characterized in that: the surfactant of step (1) is selected from PVP, one of TTAB, SLS, DBS.
3. the preparation method supporting the Pt-Cu Nanocube catalyst of carrier according to claim 1, is characterized in that: the surfactant of step (2) is selected from halogen-containing ion Br
-, I
-one of solution, many alkyl phosphate ions TTAB.
4. the preparation method supporting the Pt-Cu Nanocube catalyst of carrier according to claim 1, is characterized in that: step (1) disperses solvent for use to be selected from one of water, ethylene glycol again.
5. the preparation method supporting the Pt-Cu Nanocube catalyst of carrier according to claim 1, is characterized in that: step (2) disperses solvent for use to be alcohol again.
6. the preparation method supporting the Pt-Cu Nanocube catalyst of carrier according to claim 1, is characterized in that: described carrier is selected from XC-72, mesoporous TiO
2one of.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110029583.7A CN102139219B (en) | 2011-01-27 | 2011-01-27 | Method for preparing carrier loaded Pt-Cu Nanocube catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201110029583.7A CN102139219B (en) | 2011-01-27 | 2011-01-27 | Method for preparing carrier loaded Pt-Cu Nanocube catalyst |
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| Publication Number | Publication Date |
|---|---|
| CN102139219A CN102139219A (en) | 2011-08-03 |
| CN102139219B true CN102139219B (en) | 2015-05-06 |
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|---|---|---|---|
| CN201110029583.7A Active CN102139219B (en) | 2011-01-27 | 2011-01-27 | Method for preparing carrier loaded Pt-Cu Nanocube catalyst |
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| CN (1) | CN102139219B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103143717A (en) * | 2011-12-06 | 2013-06-12 | 中国科学院大连化学物理研究所 | Platinoid bimetallic nanometer material and preparation method and application thereof |
| CN111054384B (en) * | 2018-10-16 | 2022-10-11 | 中国石油化工股份有限公司 | Catalyst for organic liquid hydrogen storage material dehydrogenation and preparation method thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1632975A (en) * | 2003-12-22 | 2005-06-29 | 中国科学院大连化学物理研究所 | Cathode electrical catalyst for proton exchange film fuel cell and uses thereof |
| CN101168130A (en) * | 2005-10-21 | 2008-04-30 | 三星Sdi株式会社 | Catalyst for oxidizing carbon monoxide and method of manufacturing the same |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2003331855A (en) * | 2002-05-16 | 2003-11-21 | Tokyo Inst Of Technol | Cathode catalyst for solid polymer fuel cell and solid polymer fuel cell |
| JP4676958B2 (en) * | 2003-08-18 | 2011-04-27 | サイミックス ソリューションズ， インコーポレイテッド | Platinum-copper fuel cell catalyst |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1632975A (en) * | 2003-12-22 | 2005-06-29 | 中国科学院大连化学物理研究所 | Cathode electrical catalyst for proton exchange film fuel cell and uses thereof |
| CN101168130A (en) * | 2005-10-21 | 2008-04-30 | 三星Sdi株式会社 | Catalyst for oxidizing carbon monoxide and method of manufacturing the same |
Non-Patent Citations (1)
| Title |
|---|
| Dan Xu,et al.Solution-Based Evolution and Enhanced Methanol Oxidation Activity of Monodisperse Platinum-Copper Nanocubes.《Angewandte Chemie International Edition》.2009,第48卷(第23期), * |
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| CN102139219A (en) | 2011-08-03 |
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Effective date of registration: 20160229 Address after: 211135, 300, Zhi Hui Road, Qilin science and Technology Innovation Park, Nanjing, Jiangsu, Nanjing Patentee after: Nanjing Dong Yan Hydrogen Energy Technology Co Ltd Address before: 210093, Tang Zhongying building A103, 15 West Jin Street, Beijing West Road, Jiangsu, Nanjing Patentee before: Nanjing University |