CN104607205B - Multi-wall carbon nano tube-loaded PtCu catalyst based on deep eutectic solvents and preparation method and application of multi-wall carbon nano tube-loaded PtCu catalyst - Google Patents
Multi-wall carbon nano tube-loaded PtCu catalyst based on deep eutectic solvents and preparation method and application of multi-wall carbon nano tube-loaded PtCu catalyst Download PDFInfo
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Abstract
The invention discloses a multi-wall carbon nano tube-loaded PtCu catalyst based on deep eutectic solvents and a preparation method and an application of the multi-wall carbon nano tube-loaded PtCu catalyst. The preparation method is a simple and novel method for preparing an anode electrocatalyst for a direct methanol fuel battery. The deep eutectic solvents are firstly adopted as a medium for preparing the multi-wall carbon nano tube-loaded PtCu catalyst through a chemical reduction method. The preparation method for the catalyst is simple in process, gentle in operation condition and environmentally friendly; by using the deep eutectic solvent system, the dimensions of the catalytic nano particles can be obviously reduced, the dispersion degree and the electrochemical active surface area of noble metals are improved, and the charge transfer interaction between components of the composite material catalyst is further reinforced in a facilitated manner, so that the electro-catalytic activity and the stability of the catalyst to methanol oxidization are greatly improved, and the CO-poison-resisting capacity is excellent.
Description
Technical field
The present invention relates to electro-catalysis and fuel cell field, specifically a kind of multi-walled carbon nano-tubes based on eutectic solvent
Carry PtCu catalyst and preparation method thereof, and the application in DMFC.
Background technology
Eutectic solvent（Deep eutectic solvents, DES）Have steam force down, avirulence, biodegradable,
Unique physicochemical properties such as dissolubility and excellent conductivity, electrochemical stability window width are so as to become a kind of promising
Green solvent and be widely used in function nano materials synthesis field.At present, about fuel is prepared for medium with eutectic solvent
The Research Literature report of cell catalyst aspect is few, only relates to several following document reports：(1) 2012 year《Journal
of Physical Chemistry C》Report one kind with DES for medium electrochemistry shape controlled synthesis high surface energy Pt nanometer
Brilliant new method, successfully synthesizes the recessed tetrahexahedron Pt nanocrystalline catalyst that { 910 } and neighbouring high-index surface surround first,
Find that it shows the electro catalytic activity higher than commercial Pt black and stability to oxidation of ethanol；(2) 2012 years
《Electrochimica Acta》It is equal that report is successfully prepared a kind of shape and size for medium using cyclic voltammetry with DES
One and there is the Pt nano flower of sharp monocrystalline petal and high density atomic stepses.Obtained bayonet fittings Pt nano flower is to second
Alcohol oxidation performance goes out the electro catalytic activity higher than other shapes Pt nano flower and commercial Pt black catalystwind turbine blade and stability；(3)
2013《Chemical Communications》It is high that report successfully synthesizes { 771 } for medium using electrochemical method with DES
The six decahedron Pt nanocrystalline catalysts that index bread encloses, find that it shows the electricity higher than commercial Pt black to oxidation of ethanol and urges
Change activity and stability；(4) 2015 years《Journal of Materials Chemistry A》Report with DES as medium
The Au@Pd core shell nanoparticles catalyst with high methanol electroxidation performance prepared by electrochemical method.As can be seen here,
DES has started to receive the pass of people in fuel cell electro-catalyst preparation research field as a kind of promising green solvent
Note.However, the preparation of fuel-cell catalyst is all confined to adopt electrochemical method in the DES of above-mentioned document report, this will make
The extensive preparation of catalyst and commercial applications are subject to certain restrictions.Relevant with DES for medium pass through chemical reduction method
To prepare Pt base catalyst and to be applied to the research of DMFC there is not yet document and patent report.
Content of the invention
It is an object of the invention to provide a kind of multi-walled carbon nano-tubes based on eutectic solvent carries PtCu catalyst and its system
Preparation Method and application.This preparation method process is simple, operating condition is gentle, environmental protection；The catalyst of the method preparation is to methanol oxygen
Change and show the characteristic that electro catalytic activity is good, stability is high and resisting CO poison ability is strong.
The technical scheme realizing the object of the invention is：
One kind is based on eutectic solvent（DES）Multi-walled carbon nano-tubes（MWCNTs）Carry the preparation method of PtCu catalyst,
Comprise the steps：
1）The MWCNTs, ultrasonic disperse 2 h of 10 mg acidifyings is added in 20 mL DES；
2）After ultrasonic disperse, add the anhydrous CuSO that mass ratio is PtCu/MWCNTs=1/44Solid and 19.3 mM's
H2PtCl6DES solution, continue ultrasonic to CuSO4Solid is completely dissolved, magnetic agitation 10 min；
3）After magnetic agitation, add 60 mg NaBH4Gained suspension is transferred to 30 mL after continuing to stir by solid
In reactor, at 120～200 DEG C, react 3～15 h, product, after centrifugation, washing and vacuum drying, obtains MWCNTs and carries
PtCu catalyst.
Step 1）Described in DES be choline chloride/ethylene glycol.
Step 2）The mass ratio of middle addition Pt/Cu is Pt/Cu=1/0.1～1.
The multi-walled carbon nano-tubes that above-mentioned preparation method is obtained is applied to carry PtCu catalyst.
Above-mentioned prepared multi-walled carbon nano-tubes carries PtCu catalyst and is applied to DMFC.
The size and dimension of catalytic nanoparticle and the dicyandiamide solution prepared used by catalyst in fuel cell electro-catalyst
Closely related.The invention provides a kind of simple novel method preparing DMFC anode electrocatalyst,
First with eutectic solvent as medium, multi-walled carbon nano-tubes is prepared using chemical reduction method and carries PtCu catalyst.This catalysis
The preparation method of agent, process is simple, operating condition is gentle, environmental protection, can substantially reduce catalysis using eutectic solvent system and receive
The size of rice grain, improves dispersion and the electrochemical active surface of noble metal, also helps enhancing composite simultaneously and urges
Electric charge transfer between each group is divided in agent interacts, thus drastically increasing the electro-catalysis work that catalyst aoxidizes to methanol
Property and stability, and there is the ability of excellent resisting CO poison.
Brief description
Fig. 1 is to prepare the block diagram that multi-walled carbon nano-tubes carries PtCu catalyst in embodiment DES.
Fig. 2 is that the MWCNTs of preparation in embodiment DES carries PtCu（A,D）, MWCNTs carry Pt（B,E）Prepare with aqueous systems
MWCNTs carry Pt（C,F）The TEM figure of catalyst and size distribution plot.
Specific embodiment
With reference to the accompanying drawings and examples present invention is further described, but is not limitation of the invention.
Embodiment
With reference to Fig. 1, PtCu catalyst is carried for medium preparation MWCNTs with choline chloride/ethylene glycol DES, detailed process is such as
Under：Add 10 mg through dense HNO in 20 mL choline chlorides/ethylene glycol DES3The MWCNTs of acidification, ultrasonic disperse 2 h
Afterwards, add the anhydrous CuSO that mass ratio is PtCu/MWCNTs=1/44Solid and the H of 19.3 mM2PtCl6DES solution, control
Make added Pt/Cu mass ratio be Pt/Cu=1/0.1～1, continuation ultrasonic to CuSO4Solid is completely dissolved, magnetic agitation
60 mg NaBH are added after 10 min4Gained suspension is transferred in 30 mL reactors after continuing to stir by solid, 120～
3～15 h are reacted at 200 DEG C.Product, after centrifugation, washing and vacuum drying, obtains MWCNTs and carries PtCu alloy nano
Grain catalyst.
Tem analysis show, in DES, the MWCNTs of preparation carries the chi that PtCu and MWCNTs carries Pt nano-particle in Pt catalyst
Very little significantly reduce, its average-size is respectively 2.8 nm and 3.1 nm and urges hence it is evident that carrying Pt less than the MWCNTs of preparation in aqueous systems
The size of Pt nano-particle in agent（15 nm）.The TEM figure of above-mentioned three kinds of catalyst and size distribution plot are shown in Fig. 2.
By the MWCNTs that cyclic voltammetry and chronoamperometry compare in DES preparation carry PtCu, MWCNTs carry Pt and
In aqueous systems, the MWCNTs of preparation carries electrochemical properties and the electrocatalysis characteristic to methanol oxidation of Pt catalyst.Result table
Bright, the MWCNTs load PtCu catalyst of preparation in DES has higher electrochemical active surface, and it is urged to the electricity of methanol oxidation
The MWCNTs changing preparation in the MWCNTs load Pt preparing in activity respectively same medium and aqueous systems carries 2.6 Hes of Pt catalyst
11.8 times.Additionally, the MWCNTs load PtCu catalyst of preparation also shows excellent methanol oxidizing and electrochemical stability in DES.
PtCu, MWCNTs are carried by the MWCNTs that electrochemistry CO stripping voltammetry compares preparation in DES and carries Pt and water body
In system, the MWCNTs of preparation carries the performance of the resisting CO poison of Pt catalyst.Result is pointed out, the MWCNTs that CO is prepared in DES carries
Initial oxidation current potential on PtCu catalyst carries preparation in Pt and aqueous systems than the MWCNTs of preparation in same medium respectively
MWCNTs load Pt catalyst is born and has been moved 80 and 120 mV, and it is excellent that this shows that the MWCNTs load PtCu catalyst of preparation in DES has
Resisting CO poison ability.
Claims (3)
1. a kind of multi-walled carbon nano-tubes based on eutectic solvent carries the preparation method of PtCu catalyst, it is characterized in that, including such as
Lower step：
1）The multi-walled carbon nano-tubes MWCNTs, ultrasonic disperse 2 h of 10 mg acidifyings is added in 20 mL eutectic solvent DES；
2）After ultrasonic disperse, add the anhydrous CuSO that mass ratio is PtCu/MWCNTs=1/44Solid and 19.3 mM's
H2PtCl6DES solution, continue ultrasonic to CuSO4Solid is completely dissolved, magnetic agitation 10 min；
3）After magnetic agitation, add 60 mg NaBH4Gained suspension is transferred to 30 mL reactors after continuing to stir by solid
In, react 3～15 h at 120～200 DEG C, product, after centrifugation, washing and vacuum drying, obtains MWCNTs load PtCu and urges
Agent；
Step 1）Described in DES be choline chloride/ethylene glycol；
Step 2）The mass ratio of middle addition Pt/Cu is Pt/Cu=1/0.1～1.
2. use the multi-walled carbon nano-tubes that preparation method described in claim 1 is obtained to carry PtCu catalyst.
3. multi-walled carbon nano-tubes described in claim 2 carries application in DMFC for the PtCu catalyst.
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| CN108054398B (en) * | 2017-12-14 | 2020-07-10 | 广西师范大学 | Pt open hollow sphere structure catalyst and preparation method and application thereof |
| CN108878911B (en) * | 2018-06-19 | 2021-06-08 | 广西师范大学 | Nitrogen-doped carbon nanotube Pt-supported catalyst based on eutectic solvent and preparation method and application thereof |
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