CN104549365A - Ternary alloy-reduced graphene composite material catalyst and preparation method thereof - Google Patents

Ternary alloy-reduced graphene composite material catalyst and preparation method thereof Download PDF

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CN104549365A
CN104549365A CN201510014290.XA CN201510014290A CN104549365A CN 104549365 A CN104549365 A CN 104549365A CN 201510014290 A CN201510014290 A CN 201510014290A CN 104549365 A CN104549365 A CN 104549365A
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ternary alloy
preparation
partalloy
graphene composite
reduced graphene
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CN104549365B (en
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张煊
张蓓
刘东岳
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Donghua University
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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 invention provides a ternary alloy-reduced graphene composite material catalyst and a preparation method thereof. The ternary alloy-reduced graphene composite material catalyst is characterized by comprising graphene oxide and a CuFePt ternary alloy loaded on graphene oxide. The preparation method of the ternary alloy-reduced graphene composite material catalyst comprises the following steps: step 1, preparing a graphene oxide solid; and step 2, preparing an aqueous solution containing graphene oxide, copper sulfate and ferrous sulfate at room temperature, and adding excessive reducing agents into the aqueous solution containing graphene oxide, copper sulfate and ferrous sulfate, and dropwise adding chloroplatinic acid aqueous solution to perform reaction, and washing and drying obtained precipitates to obtain the ternary alloy-reduced graphene composite material catalyst (CuFePt/RGO). Compared with corresponding binary alloy and unary pure platinum catalysts, the ternary alloy-reduced graphene composite material catalyst provided by the invention is significantly improved in the catalytic performance, anti-poisoning capacity and stability, and has potential application prospects in methanol fuel cells.

Description

A kind of ternary alloy three-partalloy-reduced graphene composite catalyst and preparation thereof
Technical field
The invention belongs to the preparation field of catalyst composite, be specifically related to a kind of alloy-reduced graphene composite catalyst and preparation method thereof.
Background technology
Fuel cell is a kind of sustainable and clean novel energy, has the potential prospect replacing a large amount of fossil energy used at present in the near future, therefore obtains the extensive concern of people in recent years.Wherein the methanol fuel related to is with low cost is easy to get because of it for direct methanol fuel cell (DMFC), is one of important directions of current fuel cell development.But noble metal platinum (Pt) remains the catalyst of main use in fuel cell, cause its cost to remain high, therefore reduce costs and develop high performance catalyst remain problem demanding prompt solution by Pt content in reduction catalyst.By other cheap metal, such as Fe, the Co of adulterating, Ni, Cu etc., synthesis bianry alloy catalyst Pt-M (D.Chen, et al, Carbon, 2014,68,755-762) or ternary alloy catalyst Pt-M1-M2 (X.Sun, et al, JAm Chem Soc, 2014,136,5745-5749), not only can reduce Pt content thus reduce catalyst cost, also can improve catalytic activity.Graphene combines with alloying by the present invention, develop the environment-friendly preparation method thereof of a kind of graphene-supported ternary alloy catalyst CuFePt/RGO, prepared ternary alloy three-partalloy-more corresponding bianry alloy of reduced graphene composite catalyst and the catalytic performance of the pure platinum catalyst of unitary and stability are all significantly increased, and have the application prospect as anode catalysts for direct methanol fuel cell.
Summary of the invention
Technical problem to be solved by this invention is to provide the preparation method of the fuel battery anode catalyst that low, the anti-poisoning capability of a kind of cost is strong, stability is high and catalytic performance is good.The method cheap metal Cu and Fe that adulterate in Pt carries out alloying, and load is on graphene film, and the consumption both having reduced Pt reduces cost, also improves catalytic performance.The simple environmental protection of preparation process, has potential application foreground in fuel battery anode catalyst.
In order to solve the problems of the technologies described above, the invention provides a kind of ternary alloy three-partalloy-reduced graphene composite catalyst, it is characterized in that, comprise graphene oxide and the CuFePt ternary alloy three-partalloy of load on graphene oxide.
Present invention also offers the preparation method of above-mentioned ternary alloy three-partalloy-reduced graphene composite catalyst, it is characterized in that, comprising:
Step 1: prepare graphene oxide solid;
Step 2: the aqueous solution of preparation containing graphene oxide, copper sulphate and ferrous sulfate under room temperature; Excessive reducing agent is added in the aqueous solution containing graphene oxide, copper sulphate and ferrous sulfate, and drip chloroplatinic acid aqueous solution and react, by the washing of precipitate of gained, drying, obtain ternary alloy three-partalloy-reduced graphene composite catalyst (CuFePt/RGO).
Preferably, the preparation method of the graphene oxide solid in described step 1 comprises: by graphite powder and concentration be more than 60% nitric acid and concentration be more than 90% sulfuric acid mix in ice-water bath, add potassium permanganate under stirring, add H 2o 2solution, hold over night; By washing of precipitate, be drying to obtain graphene oxide solid.
More preferably, the ratio of described graphite powder, potassium permanganate, nitric acid and sulfuric acid is 1g: 3-5g: 2-4ml: 25-35ml.
More preferably, described H 2o 2the concentration of solution is 20-30%, H 2o 2the ratio of the consumption of solution and the consumption of graphite powder is 1-3ml: 1g.
More preferably, after adding potassium permanganate, be warming up to 45 ~ 50 DEG C, magnetic agitation 0.5-1.5h, add deionized water, the ratio of the consumption of deionized water and the consumption of graphite powder is 50-70ml: 1g, is cooled to room temperature, then adds H 2o 2solution.
Preferably, the sodium borohydride aqueous solution of to be concentration the be 0.1-0.2M of the reducing agent in described step 2.
Preferably, the mass ratio of the graphene oxide in described step 2, copper sulphate, ferrous sulfate and chloroplatinic acid is 20-25: 6-8: 7-9: 13-17.
Preferably, in described ternary alloy three-partalloy-reduced graphene composite catalyst, the atomicity ratio of copper iron platinum is 1: 1: 1.
Preferably, the reaction temperature in described step 2 is 25 ~ 30 DEG C, and the reaction time is 6-8h.
Preferably, in described step 2, described excessive reducing agent divides three times and adds, add reductant solution for the first time in the aqueous solution containing graphene oxide, copper sulphate and ferrous sulfate after, drip chloroplatinic acid aqueous solution, second time adds reductant solution subsequently, after stirring at room temperature 2-4h, third time adds reductant solution, stirring at room temperature 2-4h, the volume ratio of the reductant solution that the reductant solution that first time adds, second time add and the reductant solution that third time adds is: 9-11: 2-4: 6-8.
Preferably, in described step 2, the usage ratio of graphene oxide and reductant solution is 20mg:17-23ml.
Preferably, the washing in described step 2 is for first to use distilled water sonic oscillation centrifuge washing 3 times, then EtOH Sonicate vibration centrifuge washing 3 times.
Preferably, described drying means is dry 16 ~ 24h at 40 ~ 50 DEG C in vacuum drying chamber.
Preferably, mechanical agitator is adopted to mix in described course of reaction.
Compared with prior art, the invention has the beneficial effects as follows:
(1) present invention incorporates the advantages such as alloy poisoning capability is high, good stability, cost are low, Graphene specific area is large, prepare graphene-supported ternary alloy catalyst, graphene-supported ternary alloy catalyst CuFePt/RGO has been prepared by introducing cheap transition metal Cu and Fe, both the consumption of Pt had been decreased, turn improve catalytic performance and stability, the catalytic performance of more corresponding bianry alloy and the pure platinum catalyst of unitary, anti-poisoning capability and stability are all significantly increased, in methanol fuel cell, have potential application foreground.
(2) instant invention overcomes general catalyst synthesis processes complicated with use organic solvent not environmentally, the anti-poisoning capability of institute's controlling catalyst is low, catalytic performance is poor, high in cost of production shortcoming;
(3) preparation method of the present invention completes in room temperature water solution, and the catalyst performance of simple environmental protection, preparation is good;
Accompanying drawing explanation
Fig. 1 is the TEM figure of made ternary alloy three-partalloy-reduced graphene composite catalyst CuFePt/RGO.
Fig. 2 be made graphene-supported ternary alloy catalyst CuFePt/RGO, bianry alloy Catalysts Cu Pt/RGO, FePt/RGO and the pure platinum catalyst Pt/RGO of unitary in sulfuric acid medium to anodic oxidation of methanol cyclic voltammetry curve.
Fig. 3 be made graphene-supported ternary alloy catalyst CuFePt/RGO, bianry alloy Catalysts Cu Pt/RGO, FePt/RGO and the pure platinum catalyst Pt/RGO of unitary in sulfuric acid medium to the chronoa mperometric plot of anodic oxidation of methanol.
Embodiment
Below in conjunction with specific embodiment, set forth the present invention further.Should be understood that these embodiments are only not used in for illustration of the present invention to limit the scope of the invention.In addition should be understood that those skilled in the art can make various changes or modifications the present invention, and these equivalent form of values fall within the application's appended claims limited range equally after the content of having read the present invention's instruction.The drying equipment that the present invention adopts is DZF-6051 vacuum drying chamber; Centrifugation apparatus is 80-2 electric centrifuge; Electro-chemical test equipment is CHI 660D electrochemical workstation.
Embodiment 1
The preparation of graphene oxide.
By 0.5g graphite powder, 1.5ml concentration is the nitric acid of 69%, 15ml concentration be 98% sulfuric acid add in the round-bottomed flask of the 250ml in ice-water bath and mix, add 2.0g potassium permanganate under slow magnetic agitation, be warming up to 45 ~ 50 DEG C subsequently, magnetic agitation 1h; Add 60ml deionized water, be cooled to room temperature, add 2.0ml H 2o 2solution (30%), spends the night solution left standstill after stirring 15min.Remove supernatant liquor, with deionized water, centrifuge washing 3 times, puts into dry 24h at vacuum drying oven 40 ~ 50 DEG C, obtains graphene oxide solid.
Embodiment 2
The preparation of ternary alloy three-partalloy-reduced graphene composite catalyst CuFePt/RGO.
Get 20mg graphene oxide under room temperature and 20ml deionized water ultrasonic vibration 30min in 250ml round-bottomed flask dissolves, under stirring, add the aqueous solution that 72ul copper sulphate and copperas solution (concentration of copper sulphate and ferrous sulfate is all 0.4M) obtain containing graphene oxide, copper sulphate and ferrous sulfate respectively;
The NaBH slowly dripping 10ml and newly prepare is contained in the aqueous solution of graphene oxide, copper sulphate and ferrous sulfate to above-mentioned 4solution (5mg/ml), and the platinum acid chloride solution (0.01M) dropwise dripping 2.9ml reacts, and adds 3ml NaBH more subsequently 4solution (5mg/ml); After stirring at room temperature 3h, then continue to add 7mlNaBH 4solution (5mg/ml), continues to stir 3h, ensures that graphene oxide is reduced sufficiently, adopt mechanical agitator to mix in described course of reaction.Mixed solution is carried out centrifugally removing supernatant liquor with 4000r/min, after distilled water washes three precipitations, is placed in dry 24h at vacuum drying chamber 40 ~ 50 DEG C, obtains ternary alloy three-partalloy-reduced graphene composite catalyst CuFePt/RGO pressed powder.Characterized by TEM, visible catalyst granules is dispersed in (Fig. 1) on graphene platelet.
Comparative example 1
The preparation of bianry alloy-reduced graphene composite catalyst CuPt/RGO.
Get 20mg graphene oxide and 20ml deionized water ultrasonic vibration 30min in 250ml round-bottomed flask dissolves, under stirring, add 72ul copper-bath (0.4M); The NaBH of 10ml is slowly dripped again in solution 4solution (5mg/ml), and the platinum acid chloride solution (0.01M) dropwise dripping 2.9ml, add 3mlNaBH subsequently again 4solution (5mg/ml); After stirring at room temperature 3h, then add 7ml NaBH 4solution (5mg/ml), continues to stir 3h, ensures that graphene oxide is reduced sufficiently.Carried out centrifugally removing supernatant liquor with 4000r/min by mixed solution, after distilled water washes three precipitations, at being placed in vacuum drying oven 40 ~ 50 DEG C, dry 16 ~ 24h, obtains graphene-supported bianry alloy Catalysts Cu Pt/RGO pressed powder.
Comparative example 2
The preparation of bianry alloy-reduced graphene composite catalyst FePt/RGO.
Get 20mg graphene oxide and 20ml deionized water ultrasonic vibration 30min in 250ml round-bottomed flask dissolves, under stirring, add 72ul copperas solution (0.4M); The NaBH of 10ml is slowly dripped again in solution 4solution (5mg/ml), and the platinum acid chloride solution (0.01M) dropwise dripping 2.9ml, add 3ml NaBH subsequently again 4solution (5mg/ml); After stirring at room temperature 3h, then add 7ml NaBH 4solution (5mg/ml), continues to stir 3h, ensures that graphene oxide is reduced sufficiently.Carried out centrifugally removing supernatant liquor with 4000r/min by mixed solution, after distilled water washes three precipitations, at being placed in vacuum drying oven 40 ~ 50 DEG C, dry 16 ~ 24h, obtains graphene-supported bianry alloy catalyst Fe Pt/RGO pressed powder.
Comparative example 3
The preparation of the pure platinum catalyst Pt/RGO of graphene-supported unitary.
Get 20mg graphene oxide and 20ml deionized water ultrasonic vibration 30min in 250ml round-bottomed flask dissolves, in solution, under stirring, slowly drip the NaBH of 10ml 4solution (5mg/ml), and the platinum acid chloride solution (0.01M) dropwise dripping 2.9ml, add 3ml NaBH subsequently again 4solution (5mg/ml); After stirring at room temperature 3h, then add 7ml NaBH 4solution (5mg/ml), continues to stir 3h, ensures that graphene oxide is reduced sufficiently.Carried out centrifugally removing supernatant liquor with 4000r/min by mixed solution, after distilled water washes three precipitations, at being placed in vacuum drying oven 40 ~ 50 DEG C, dry 16 ~ 24h, obtains graphene-supported pure platinum catalyst Pt/RGO pressed powder.
By the electrocatalysis characteristic test in sulfuric acid medium of the catalyst in embodiment 2 and comparative example 1-3:
Made ternary alloy three-partalloy-reduced graphene composite catalyst CuFePt/RGO2mg is dispersed in 1ml ethanol, after sonic oscillation 30 ~ 60min, pipetting 5ul drips on the glass-carbon electrode that polishes smooth, after natural drying, drip the Nafion solution of 5ul 0.5% again, namely work electrode is obtained, by the performance of electrochemical cyclic voltammetry detecting catalyst catalytic oxidation methyl alcohol and the stability of chronoamperometry mensuration electrode after bone dry.
In the sulfuric acid made work electrode being first placed on 0.5M and 0.5M methyl alcohol mixed solution, be to electrode with platinum electrode, with saturated calomel electrode (SCE) for reference electrode, the cyclic voltammetry curve of test anodic oxidation of methanol and chronoa mperometric plot, potential scanning speed is 0.05V/s, and electric potential scanning scope is-0.2 ~ 1.0V.Result shows that the graphene-supported ternary alloy catalyst CuFePt/RGO synthesized by the present invention has good catalytic activity (Fig. 2) and stability (Fig. 3) to methanol oxidation.The bianry alloy Catalysts Cu Pt/RGO, the FePt/RGO that synthesize in comparative example 1-3 and pure platinum catalyst Pt/RGO same method are modified at glassy carbon electrode surface preparation work electrode, carry out electro-chemical test, and with the performance comparison of above-mentioned ternary alloy catalyst CuFePt/RGO, find that the catalytic activity of the more corresponding bianry alloy of graphene-supported ternary alloy catalyst (CuPt/RGO and FePt/RGO) and the pure platinum catalyst of unitary, anti-poisoning capability and stability are all significantly increased (Fig. 2 and Fig. 3).Wherein can find out catalytic activity comparatively binary and the unitary catalyst raising about 2.5 times and 5 times respectively of ternary alloy catalyst, and continuous discharge after 600 seconds ternary alloy catalyst still have the highest current density, the ternary alloy three-partalloy therefore prepared by the present invention-graphene composite material Catalysts Cu FePt/RGO has the application prospect in direct methanol fuel cell.

Claims (10)

1. ternary alloy three-partalloy-reduced graphene composite catalyst, is characterized in that, comprises graphene oxide and the CuFePt ternary alloy three-partalloy of load on graphene oxide.
2. the preparation method of ternary alloy three-partalloy according to claim 1-reduced graphene composite catalyst, is characterized in that, comprising:
Step 1: prepare graphene oxide solid;
Step 2: the aqueous solution of preparation containing graphene oxide, copper sulphate and ferrous sulfate under room temperature; In the aqueous solution containing graphene oxide, copper sulphate and ferrous sulfate, add excessive reducing agent, and drip chloroplatinic acid aqueous solution and react, by the washing of precipitate of gained, drying, obtain ternary alloy three-partalloy-reduced graphene composite catalyst.
3. the preparation method of ternary alloy three-partalloy-reduced graphene composite catalyst as claimed in claim 2, it is characterized in that, the preparation method of the graphene oxide solid in described step 1 comprises: by graphite powder and concentration be more than 60% nitric acid and concentration be more than 90% sulfuric acid mix in ice-water bath, add potassium permanganate under stirring, add H 2o 2solution, hold over night; By washing of precipitate, be drying to obtain graphene oxide solid.
4. the preparation method of ternary alloy three-partalloy-reduced graphene composite catalyst as claimed in claim 3, it is characterized in that, the ratio of described graphite powder, potassium permanganate, nitric acid and sulfuric acid is 1g: 3-5g: 2-4ml: 25-35ml.
5. the preparation method of ternary alloy three-partalloy-reduced graphene composite catalyst as claimed in claim 3, is characterized in that, described H 2o 2the concentration of solution is 20-30%, H 2o 2the ratio of the consumption of solution and the consumption of graphite powder is 1-3ml: 1g.
6. the preparation method of ternary alloy three-partalloy-reduced graphene composite catalyst as claimed in claim 2, is characterized in that, the sodium borohydride aqueous solution of to be concentration the be 0.1-0.2M of the reducing agent in described step 2.
7. the preparation method of ternary alloy three-partalloy-reduced graphene composite catalyst as claimed in claim 2, it is characterized in that, the mass ratio of the graphene oxide in described step 2, copper sulphate, ferrous sulfate and chloroplatinic acid is 20-25: 6-8: 7-9: 13-17.
8. the preparation method of ternary alloy three-partalloy-reduced graphene composite catalyst as claimed in claim 2, it is characterized in that, in described ternary alloy three-partalloy-reduced graphene composite catalyst, the atomicity ratio of copper iron platinum is 1: 1: 1.
9. the preparation method of ternary alloy three-partalloy-reduced graphene composite catalyst as claimed in claim 2, it is characterized in that, the reaction temperature in described step 2 is 25 ~ 30 DEG C, and the reaction time is 6h.
10. the preparation method of ternary alloy three-partalloy-reduced graphene composite catalyst as claimed in claim 2, it is characterized in that, in described step 2, described excessive reducing agent divides three times and adds, containing graphene oxide, after adding reductant solution for the first time in the aqueous solution of copper sulphate and ferrous sulfate, drip chloroplatinic acid aqueous solution, second time adds reductant solution subsequently, after stirring at room temperature 2-4h, third time adds reductant solution, stirring at room temperature 2-4h, the reductant solution that first time adds, the volume ratio of the reductant solution that second time adds and the reductant solution that third time adds is: 9-11: 2-4: 6-8.
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Cited By (4)

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CN106504905A (en) * 2016-11-18 2017-03-15 桂林电子科技大学 A kind of preparation method and application of Co Ni W alloys oxide graphene composite material
CN109065903A (en) * 2018-09-17 2018-12-21 苏州擎动动力科技有限公司 A kind of preparation method of high activity loading type octahedron ternary alloy catalyst
CN109378484A (en) * 2018-10-15 2019-02-22 北京化工大学 A kind of fuel cell nuclear shell on carbon dense form copper iron/copper-platinum catalyst preparation method
CN110075865A (en) * 2019-05-30 2019-08-02 安徽师范大学 A kind of quadrangle biconial platinum-iron/copper ternary metal Nanoalloy and its preparation method and application

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106504905A (en) * 2016-11-18 2017-03-15 桂林电子科技大学 A kind of preparation method and application of Co Ni W alloys oxide graphene composite material
CN109065903A (en) * 2018-09-17 2018-12-21 苏州擎动动力科技有限公司 A kind of preparation method of high activity loading type octahedron ternary alloy catalyst
CN109378484A (en) * 2018-10-15 2019-02-22 北京化工大学 A kind of fuel cell nuclear shell on carbon dense form copper iron/copper-platinum catalyst preparation method
CN110075865A (en) * 2019-05-30 2019-08-02 安徽师范大学 A kind of quadrangle biconial platinum-iron/copper ternary metal Nanoalloy and its preparation method and application
CN110075865B (en) * 2019-05-30 2022-03-15 安徽师范大学 Four-corner biconical platinum-iron-copper ternary metal nano alloy and preparation method and application thereof

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