CN104549365B - A kind of ternary alloy three-partalloy reduced graphene composite catalyst and its preparation - Google Patents
A kind of ternary alloy three-partalloy reduced graphene composite catalyst and its preparation Download PDFInfo
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- CN104549365B CN104549365B CN201510014290.XA CN201510014290A CN104549365B CN 104549365 B CN104549365 B CN 104549365B CN 201510014290 A CN201510014290 A CN 201510014290A CN 104549365 B CN104549365 B CN 104549365B
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Abstract
The invention provides a kind of ternary alloy three-partalloy reduced graphene composite catalyst and preparation method thereof.Described ternary alloy three-partalloy reduced graphene composite catalyst, it is characterised in that including graphene oxide and the CuFePt ternary alloy three-partalloys being supported on graphene oxide.Its preparation method includes：Step 1：Prepare graphene oxide solid；Step 2：The aqueous solution containing graphene oxide, copper sulphate and ferrous sulfate is prepared at room temperature；Excessive reducing agent is added in the aqueous solution containing graphene oxide, copper sulphate and ferrous sulfate, and chloroplatinic acid aqueous solution is added dropwise and is reacted, by the washing of precipitate of gained, drying, ternary alloy three-partalloy reduced graphene composite catalyst (CuFePt/RGO) is produced.Catalytic performance, anti-poisoning capability and the stability of the more corresponding bianry alloy of the present invention and the pure platinum catalyst of unitary are significantly increased, and have potential application foreground in methanol fuel cell.
Description
Technical field
The invention belongs to the preparation field of catalyst composite, and in particular to a kind of alloy-reduced graphene composite wood
Expect catalyst and preparation method thereof.
Background technology
Fuel cell is a kind of sustainable and cleaning novel energy, has substitution in the near future is a large amount of at present to use
Fossil energy potential prospect, therefore obtain the extensive concern of people in recent years.Wherein DMFC (DMFC)
The methanol fuel cost that is related to by it is cheap to be easy to get, and is one of important directions of current fuel cell development.But noble metal platinum
(Pt) it is still the main catalyst used in fuel cell, causes its cost to remain high, therefore by reducing catalyst
It is still urgent problem to be solved that middle Pt contents, which reduce cost and development high performance catalyst,.By adulterating other cheap metals,
Such as Fe, Co, 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 may be used
Pt contents are reduced so as to reduce catalyst cost, can also improve catalytic activity.Graphene is combined by the present invention with alloying, is opened
Send out a kind of graphene-supported ternary alloy catalyst CuFePt/RGO environment-friendly preparation method thereof, prepared ternary alloy three-partalloy-
The catalytic performance and stability of the more corresponding bianry alloy of reduced graphene composite catalyst and the pure platinum catalyst of unitary
It is significantly increased, there is the application prospect as anode catalysts for direct methanol fuel cell.
The content of the invention
The technical problems to be solved by the invention are to provide that a kind of cost is low, anti-poisoning capability is strong, stability is high and catalysis
The preparation method of the good fuel battery anode catalyst of performance.This method adulterates cheap metal Cu and Fe in Pt and carries out alloy
Change, and be supported on graphene film, both having reduced Pt dosage reduces cost, also improves catalytic performance.Preparation process is simple
Environmental protection, there is potential application foreground in fuel battery anode catalyst.
In order to solve the above-mentioned technical problem, the invention provides a kind of ternary alloy three-partalloy-reduced graphene composite catalysis
Agent, it is characterised in that including graphene oxide and the CuFePt ternary alloy three-partalloys being supported on graphene oxide.
Present invention also offers the preparation method of above-mentioned ternary alloy three-partalloy-reduced graphene composite catalyst, and it is special
Sign is, including：
Step 1：Prepare graphene oxide solid；
Step 2：The aqueous solution containing graphene oxide, copper sulphate and ferrous sulfate is prepared at room temperature；Containing oxidation stone
Excessive reducing agent is added in the aqueous solution of black alkene, copper sulphate and ferrous sulfate, and chloroplatinic acid aqueous solution is added dropwise and is reacted, will
Washing of precipitate, the drying of gained, produce ternary alloy three-partalloy-reduced graphene composite catalyst (CuFePt/RGO).
Preferably, the preparation method of the graphene oxide solid in described step 1 includes：It is by graphite powder and concentration
The sulfuric acid that more than 60% nitric acid and concentration is more than 90% mixes in ice-water bath, stirs lower addition potassium permanganate, adds H2O2
Solution, stand overnight；By washing of precipitate, graphene oxide solid is drying to obtain.
It is highly preferred that described graphite powder, potassium permanganate, the ratio of nitric acid and sulfuric acid are 1g: 3-5g: 2-4ml: 25-
35ml。
It is highly preferred that described H2O2The concentration of solution is 20-30%, H2O2The dosage of solution and the dosage of graphite powder
Ratio is 1-3ml: 1g.
It is highly preferred that after potassium permanganate is added, 45~50 DEG C, magnetic agitation 0.5-1.5h are warming up to, adds deionization
The ratio of water, the dosage of deionized water and the dosage of graphite powder is 50-70ml: 1g, is cooled to room temperature, adds H2O2Solution.
Preferably, the reducing agent in described step 2 is the sodium borohydride aqueous solution that concentration is 0.1-0.2M.
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, the atomicity ratio of copper and iron platinum is 1: 1 in described ternary alloy three-partalloy-reduced graphene composite catalyst
∶1。
Preferably, the reaction temperature in described step 2 is 25~30 DEG C, reaction time 6-8h.
Preferably, in described step 2, described excessive reducing agent adds in three times, is containing graphene oxide, sulphur
After adding reductant solution for the first time in the aqueous solution of sour copper and ferrous sulfate, chloroplatinic acid aqueous solution is added dropwise, then adds for the second time
Enter reductant solution, after 2-4h is stirred at room temperature, third time adds reductant solution, and 2-4h is stirred at room temperature, and what is added for the first time goes back
The volume ratio for the reductant solution that former agent solution, second of reductant solution added and third time add is: 9-11: 2-4:
6-8。
Preferably, the usage ratio of graphene oxide and reductant solution is 20mg in described step 2：17-23ml.
Preferably, the washing in described step 2 is first to use distilled water sonic oscillation centrifuge washing 3 times, then EtOH Sonicate
Vibrate centrifuge washing 3 times.
Preferably, described drying means is to dry 16~24h at 40~50 DEG C in vacuum drying chamber.
Preferably, mixed in described course of reaction using mechanical agitator.
Compared with prior art, the beneficial effects of the invention are as follows：
(1) present invention incorporates the advantages that alloy poisoning capability is high, stability is good, cost is low, graphene specific surface area is big,
Be prepared for graphene-supported ternary alloy catalyst, by introduce cheap transition metal Cu and Fe be prepared for it is graphene-supported
Ternary alloy catalyst CuFePt/RGO, both reduced Pt dosage, and improved catalytic performance and stability again, more accordingly
The catalytic performance of bianry alloy and the pure platinum catalyst of unitary, anti-poisoning capability and stability are significantly increased, and are fired in methanol
There is potential application foreground in material battery.
(2) instant invention overcomes general catalyst synthesis processes are complicated and use organic solvent not environmentally, made catalysis
The shortcomings of anti-poisoning capability of agent is low, catalytic performance is poor, cost is high；
(3) preparation method of the present invention is completed in the room temperature aqueous solution, and catalyst performance that is simple and environmentally-friendly, preparing is good；
Brief description of the drawings
Fig. 1 is made ternary alloy three-partalloy-reduced graphene composite catalyst CuFePt/RGO TEM figures.
Fig. 2 be made graphene-supported ternary alloy catalyst CuFePt/RGO, bianry alloy catalyst CuPt/RGO,
The FePt/RGO and pure platinum catalyst Pt/RGO of unitary is 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 catalyst CuPt/RGO,
The FePt/RGO and pure platinum catalyst Pt/RGO of unitary is in sulfuric acid medium to the chronoa mperometric plot of anodic oxidation of methanol.
Embodiment
With reference to specific embodiment, the present invention is expanded on further.It should be understood that these embodiments are merely to illustrate the present invention
Rather than limitation the scope of the present invention.In addition, it is to be understood that after the content of the invention lectured has been read, people in the art
Member can make various changes or modifications to the present invention, and these equivalent form of values equally fall within the application appended claims and limited
Scope.The drying equipment that the present invention uses is DZF-6051 vacuum drying chamber；Centrifugation apparatus is 80-2 electric centrifuges；Electrification
Test equipment is CHI 660D electrochemical workstations.
Embodiment 1
The preparation of graphene oxide.
By 0.5g graphite powders, 1.5ml concentration is 69% nitric acid, and the sulfuric acid that 15ml concentration is 98% is added in ice-water bath
Mixed in 250ml round-bottomed flask, 2.0g potassium permanganate is added under slow magnetic agitation, then raises temperature to 45~50 DEG C, magnetic force
Stir 1h；60ml deionized waters are added, are cooled to room temperature, add 2.0ml H2O2Solution (30%), stir solution after 15min
Stand overnight.Supernatant liquor is removed, with deionized water, centrifuge washing 3 times, is put into vacuum drying oven at 40~50 DEG C and dries
24h, produce graphene oxide solid.
Embodiment 2
Ternary alloy three-partalloy-reduced graphene composite catalyst CuFePt/RGO preparation.
20mg graphene oxides and 20ml deionized waters the ultrasonic vibration 30min in 250ml round-bottomed flasks is taken to enter at room temperature
Row dissolving, is separately added into 72ul copper sulphate and copperas solution under stirring (concentration of copper sulphate and ferrous sulfate is all 0.4M)
Obtain the aqueous solution containing graphene oxide, copper sulphate and ferrous sulfate；
Slowly it is added dropwise what 10ml was newly prepared into the above-mentioned aqueous solution containing graphene oxide, copper sulphate and ferrous sulfate
NaBH4Solution (5mg/ml), and the platinum acid chloride solution (0.01M) that 2.9ml is added dropwise dropwise is reacted, and then adds 3ml NaBH again4
Solution (5mg/ml)；3h is stirred at room temperature and then is continuously added into 7ml NaBH4Solution (5mg/ml), continue to stir 3h, ensure oxygen
Graphite alkene is reduced sufficiently, and is mixed in described course of reaction using mechanical agitator.By mixed solution with 4000r/
Min carries out centrifugation and removes supernatant liquor, after distilled water washing precipitates three times, is placed in vacuum drying chamber at 40~50 DEG C and dries
24h, produce ternary alloy three-partalloy-reduced graphene composite catalyst CuFePt/RGO solid powders.Characterized by TEM,
It can be seen that catalyst granules is dispersed on graphene platelet (Fig. 1).
Comparative example 1
Bianry alloy-reduced graphene composite catalyst CuPt/RGO preparation.
20mg graphene oxides and 20ml deionized waters the ultrasonic vibration 30min in 250ml round-bottomed flasks is taken to be dissolved,
Stirring is lower to add 72ul copper-baths (0.4M)；10ml NaBH is slowly added dropwise into solution again4Solution (5mg/ml), and by
2.9ml platinum acid chloride solution (0.01M) is added dropwise in drop, then adds 3ml NaBH again4Solution (5mg/ml)；It is stirred at room temperature after 3h,
Add 7ml NaBH4Solution (5mg/ml), continue to stir 3h, ensure that graphene oxide is reduced sufficiently.By mixed solution with
4000r/min carries out centrifugation and removes supernatant liquor, after distilled water washing precipitates three times, is placed in vacuum drying oven at 40~50 DEG C and does
Dry 16~24h, produce graphene-supported bianry alloy catalyst CuPt/RGO solid powders.
Comparative example 2
Bianry alloy-reduced graphene composite catalyst FePt/RGO preparation.
20mg graphene oxides and 20ml deionized waters the ultrasonic vibration 30min in 250ml round-bottomed flasks is taken to be dissolved,
Stirring is lower to add 72ul copperas solutions (0.4M)；10ml NaBH is slowly added dropwise into solution again4Solution (5mg/ml), and
2.9ml platinum acid chloride solution (0.01M) is added dropwise dropwise, then adds 3ml NaBH again4Solution (5mg/ml)；Be stirred at room temperature 3h it
Afterwards, 7ml NaBH are added4Solution (5mg/ml), continue to stir 3h, ensure that graphene oxide is reduced sufficiently.By mixed solution
Centrifugation is carried out with 4000r/min and removes supernatant liquor, after distilled water washing precipitates three times, is placed in vacuum drying oven at 40~50 DEG C
16~24h is dried, produces graphene-supported bianry alloy catalyst Fe Pt/RGO solid powders.
Comparative example 3
The pure platinum catalyst Pt/RGO of graphene-supported unitary preparation.
20mg graphene oxides and 20ml deionized waters the ultrasonic vibration 30min in 250ml round-bottomed flasks is taken to be dissolved,
10ml NaBH is slowly added dropwise under stirring into solution4Solution (5mg/ml), and 2.9ml platinum acid chloride solution is added dropwise dropwise
(0.01M), then add 3ml NaBH again4Solution (5mg/ml)；3h is stirred at room temperature and then adds 7ml NaBH4Solution (5mg/
Ml), continue to stir 3h, ensure that graphene oxide is reduced sufficiently.Mixed solution is subjected to centrifugation with 4000r/min and removes upper strata
Clear liquid, after distilled water washing precipitates three times, it is placed in vacuum drying oven at 40~50 DEG C and dries 16~24h, produce graphene-supported
Pure platinum catalyst Pt/RGO solid powders.
By the catalyst in embodiment 2 and comparative example 1-3, electrocatalysis characteristic is tested in sulfuric acid medium：
Made ternary alloy three-partalloy-reduced graphene composite catalyst CuFePt/RGO2mg is dispersed in 1ml ethanol,
After 30~60min of sonic oscillation, pipette 5ul and drip on the glass-carbon electrode polished smooth, after spontaneously drying, then 5ul is added dropwise
0.5% Nafion solution, working electrode is made after being completely dried, catalyst is tested by electrochemical cyclic voltammetry and urged
Change the performance of Oxidation of Methanol and the stability of chronoamperometry measure electrode.
Made working electrode is firstly placed in 0.5M sulfuric acid and 0.5M methanol mixed solutions, using platinum electrode as to electricity
Pole, with saturated calomel electrode (SCE) for reference electrode, cyclic voltammetry curve and the chrono-amperometric for testing anodic oxidation of methanol are bent
Line, potential scanning speed 0.05V/s, electric potential scanning scope are -0.2~1.0V.As a result the graphite synthesized by the present invention is shown
The ternary alloy catalyst CuFePt/RGO of alkene load has good catalytic activity (Fig. 2) and stability (Fig. 3) to methanol oxidation.
By bianry alloy catalyst CuPt/RGO, the FePt/RGO synthesized in comparative example 1-3 and the same sample prescriptions of pure platinum catalyst Pt/RGO
Method modification carries out electro-chemical test in glassy carbon electrode surface preparation work electrode, and with above-mentioned ternary alloy catalyst CuFePt/
RGO performance comparison, find the more corresponding bianry alloy of graphene-supported ternary alloy catalyst (CuPt/RGO and FePt/
RGO) all it is significantly increased (Fig. 2 and Fig. 3) with the catalytic activity of the pure platinum catalyst of unitary, anti-poisoning capability and stability.Wherein
It can be seen that the catalytic activity of ternary alloy catalyst improves about 2.5 times and 5 times compared with binary and unitary catalyst respectively, and holding
Continuing ternary alloy catalyst after discharging 600 seconds still has highest current density, therefore ternary alloy three-partalloy-graphite prepared by the present invention
The great application prospects in DMFC of alkene composite catalyst CuFePt/RGO.
Claims (7)
1. a kind of preparation method of ternary alloy three-partalloy-reduced graphene composite catalyst, described ternary alloy three-partalloy-reduction graphite
Alkene composite catalyst includes graphene oxide and the CuFePt ternary alloy three-partalloys being supported on graphene oxide, its feature exist
In the preparation method includes：
Step 1：Prepare graphene oxide solid；
Step 2：The aqueous solution containing graphene oxide, copper sulphate and ferrous sulfate is prepared at room temperature；Containing graphene oxide,
Excessive reducing agent is added in the aqueous solution of copper sulphate and ferrous sulfate, and chloroplatinic acid aqueous solution is added dropwise and is reacted, by gained
Washing of precipitate, drying, produce ternary alloy three-partalloy-reduced graphene composite catalyst；Wherein, described reducing agent is concentration
For 0.1-0.2M sodium borohydride aqueous solution, the usage ratio of graphene oxide and reductant solution is 20mg：17-23ml, institute
The reducing agent stated adds in three times, is added for the first time also in the aqueous solution containing graphene oxide, copper sulphate and ferrous sulfate
After former agent solution, dropwise addition chloroplatinic acid aqueous solution, then second of addition reductant solution, after 2-4h is stirred at room temperature, adds for the third time
Enter reductant solution, 2-4h, the reductant solution added for the first time, second of reductant solution and the 3rd added is stirred at room temperature
The volume ratio of the reductant solution of secondary addition is:9-11：2-4：6-8.
2. the preparation method of ternary alloy three-partalloy as claimed in claim 1-reduced graphene composite catalyst, its feature exist
In the preparation method of the graphene oxide solid in described step 1 includes：By the nitric acid that graphite powder and concentration are more than 60%
Mixed with concentration for more than 90% sulfuric acid in ice-water bath, stir lower addition potassium permanganate, add H2O2Solution, stand overnight；
By washing of precipitate, graphene oxide solid is drying to obtain.
3. the preparation method of ternary alloy three-partalloy as claimed in claim 2-reduced graphene composite catalyst, its feature exist
In the ratio of, described graphite powder, potassium permanganate, nitric acid and sulfuric acid be 1g:3-5g:2-4ml:25-35ml.
4. the preparation method of ternary alloy three-partalloy as claimed in claim 2-reduced graphene composite catalyst, its feature exist
In described H2O2The concentration of solution is 20-30%, H2O2The ratio of the dosage of solution and the dosage of graphite powder is 1-3ml：1g.
5. the preparation method of ternary alloy three-partalloy as claimed in claim 1-reduced graphene composite catalyst, its feature exist
In the mass ratio of graphene oxide, copper sulphate, ferrous sulfate and chloroplatinic acid in described step 2 is 20-25:6-8:7-9:
13-17。
6. the preparation method of ternary alloy three-partalloy as claimed in claim 1-reduced graphene composite catalyst, its feature exist
In the atomicity ratio of copper and iron platinum is 1 in described ternary alloy three-partalloy-reduced graphene composite catalyst:1:1.
7. the preparation method of ternary alloy three-partalloy as claimed in claim 1-reduced graphene composite catalyst, its feature exist
In the reaction temperature in described step 2 is 25 ~ 30 DEG C, reaction time 6h.
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| CN106504905B (en) * | 2016-11-18 | 2018-09-07 | 桂林电子科技大学 | A kind of preparation method and application of Co-Ni-W alloyed oxides-graphene composite material |
| CN109065903B (en) * | 2018-09-17 | 2020-10-23 | 苏州擎动动力科技有限公司 | Preparation method of high-activity load type octahedral ternary alloy catalyst |
| CN109378484B (en) * | 2018-10-15 | 2021-07-13 | 北京化工大学 | Preparation method of carbon-supported core-shell compact copper-iron-copper-platinum catalyst for fuel cell |
| 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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| CN102000590A (en) * | 2010-10-29 | 2011-04-06 | 江苏大学 | Preparation method of graphite/FePt nano-catalyst for fuel cell |
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| CN102000590A (en) * | 2010-10-29 | 2011-04-06 | 江苏大学 | Preparation method of graphite/FePt nano-catalyst for fuel cell |
Non-Patent Citations (2)
| Title |
|---|
| Fabrication of Pt-Cu/RGO hybrids and their electrochemical performance for the oxidation of methanol and formic acid in acid media;Feihui Li et al;《Carbon》;20130605;第64卷;11-19 * |
| X-Ray absorption spectroscopic and electrochemical analyses of Pt-Cu-Fe ternary alloy electrocatalysts supported on carbon;Jihoon Cho et al;《J.Chem.Faraday Trans》;19981231;第94卷;2835-2841 * |
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