CN102824910A - Ternary composite catalyst containing platinum, transition metal oxide and graphene and preparation method thereof - Google Patents
Ternary composite catalyst containing platinum, transition metal oxide and graphene and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a ternary composite catalyst containing platinum, transition metal oxide and graphene and a preparation method thereof. The method comprises putting graphite oxide into water for ultrasonic dispersion, adding salt solution of the transition metal with continuous stirring so as to fully mix the system, heating to a certain temperature to react, centrifuging to get solid products after the reaction finishes, putting the solid products into a mixed solution of water and glycol for ultrasonic dispersion, adding a platinum nitrate solution and uniformly mixing, and then transferring the mixed system to a hydrothermal reactor to react and obtain the ternary composite catalyst containing the platinum, the transition metal oxide and the grapheme. The catalyst provided by the invention has a relatively good application prospect and economic benefit in fields of organic reaction catalyzing and fuel cells.
Description
Technical field
The present invention relates to a kind of combination electrode Catalysts and its preparation method, specifically is a kind of platinum-transition metal oxide-Graphene ternary complex and preparation method thereof.
Technical background
In the face of the energy crisis and the environmental pollution that increasingly sharpen, environmental protection and energy-saving and emission-reduction have become the important topic that current society faces.Development and use are efficient, the energy conversion system of cleaning (like fuel cell etc.), and the sustainable development of society is had great importance.
DMFC has broad application prospects in field of portable electronic apparatus because of its energy conversion efficiency is high, operating temperature is low, environmental pollution is little and advantage such as simple structure.The experimental results shows that reaction has very high catalytic activity to metal platinum to methanol oxidation, thereby is widely used as the electrode catalyst agent material of DMFC.Yet in the process of catalytic reaction, metal platinum surface is prone to reaction intermediate such as absorption carbon monoxide and causes catalyst poisoning, influences the original activity of catalyst.In addition, the price that metal platinum is expensive also to a great extent limit the business-like process of DMFC.
With transition metal oxide metal platinum being mixed to significantly improve the service efficiency of metal platinum, reduces cost.Yet the specific area of transition metal oxide is less and electric conductivity is relatively poor; Therefore be necessary to introduce the matrix material of material with carbon element as composite catalyst; Thereby promote the dispersion of nano platinum particle and the charge transfer resistance of reduction composite catalyst, further promote electro catalytic activity.
Activated carbon, CNT etc. all are the catalyst carriers of using always, in the nearest research, obtain ternary complex catalyst through metal platinum and transition metal oxide are loaded on the material with carbon elements such as activated carbon, CNT, can obtain better platinum catalytic effect.（Application?of?Pt+RuO
2?catalysts?prepared?by?thermal?decomposition?of?polymeric?precursors?to?DMFC.Journal?of?Power?Sources?2006,158,1195-1201;MnO
2/CNT?supported?Pt?and?PtRu?nanocatalysts?for?direct?methanol?fuel?cells.Langmuir?2009,25,7711-7717）。Graphene has advantages such as bigger serface, high conductivity, high mechanical properties, electrochemical stability as a kind of new carbon.Therefore compare the Graphene carrier as catalyst preferably with the conventional carbon material.CN101966453 discloses the method that platinum is loaded to Graphene through ultrasonic.CN101733094 discloses a kind of Pt-CeO2/ Graphene eelctro-catalyst, is dispersed in the ethylene glycol the graphite oxide nanometer sheet is ultrasonic, adds platinum acid chloride solution then; Cerous nitrate; Aqueous ammonium and sodium acetate aqueous solution, and fully mix, mixture is carried out the heating using microwave preparation.But, the platinum how load height is disperseed on Graphene, especially preparing platinum-transition metal oxide-Graphene ternary complex still is a challenging job.
Summary of the invention
The object of the present invention is to provide the platinum-transition metal oxide-Graphene ternary complex catalyst of a kind of high catalytic activity, high mithridatism and high stability; It is characterized in that this composite catalyst is through transition metal oxide-graphene oxide is prepared into binary complex; Again platinum salt and transition metal oxide-graphene oxide binary complex reaction and reduction are prepared; Wherein, The mass ratio of described platinum and transition metal oxide-graphene oxide binary complex is 1:40-40:1, is preferably 1:20-2:1, more preferably 1:10-1:1; In described transition metal oxide-graphene oxide binary complex, the mass ratio of transition metal oxide and graphene oxide is 1:10-10:1, is preferably 1:5-1:1.
Above-mentioned transition metal oxide includes but not limited to: manganese dioxide, zinc oxide, titanium dioxide, cobaltosic oxide, cupric oxide, tri-iron tetroxide etc.; Preferred manganese dioxide, zinc oxide, cobaltosic oxide, cupric oxide.
Further the invention provides a kind of method for preparing platinum-transition metal oxide-Graphene ternary complex catalyst, may further comprise the steps:
(1) graphite oxide is placed the ultrasonic dispersion of water;
(2) salting liquid of adding transition metal in the dispersion of step (1), stirring reaction is to complete;
(3) reactant of step (2) is centrifugal, isolate solid product, spend deionised water, drying obtains transition metal oxide-graphene oxide compound;
(4) product in the step (3) is placed the ultrasonic dispersion of mixed solution of water and ethylene glycol;
(5) in the dispersion of step (4), add platinum nitrate solution, mix, place water heating kettle to react completely;
(6) reactant of step (5) is centrifugal, isolate solid product, spend deionised water, drying obtains platinum-transition metal oxide-Graphene ternary complex catalyst.
In the above-mentioned steps (1), described ultrasonic time is 1-3 hour, and ultrasonic temperature is 20-40 ℃, and the concentration of the graphite oxide dispersion liquid of said acquisition is 0.1g/L-10g/L, is preferably 0.2g/L-1g/L.
In the step (2), the salt of described transition metal and the mass ratio of graphite oxide are 1:10-10:1, preferred 1:5-1:1.The described reaction time is 1h-72h, is preferably 6-24h; Reaction temperature is 20-200 ℃, is preferably 60-140 ℃.Above-mentioned transition metal oxide includes but not limited to: manganese dioxide, zinc oxide, titanium dioxide, cobaltosic oxide, cupric oxide, tri-iron tetroxide etc.; Preferred manganese oxide, zinc oxide, cobaltosic oxide, cupric oxide.The salt of described transition metal is meant the inorganic salts of transition metal, for example potassium permanganate, cobalt nitrate, copper nitrate, zinc acetate etc.
Centrifugal, washing described in the step (3), dry process are ordinary skill in the art means, and described dry run temperature is 40-80 ℃; Preferred temperature is 60 ℃.
In the step (4), the volume ratio of described water and ethylene glycol is 1:7-7:1, is preferably 1:3-3:1.Described ultrasonic time is 1-3 hour, and temperature is 20-40 ℃, and the concentration of the transition metal oxide of said acquisition-graphene oxide compound disperse object is 0.1g/L-10g/L, and preferred concentrations is 0.2g/L-1g/L.
In the step (5), the mass ratio of described metal platinum and transition metal oxide-graphene oxide compound is 1:40-40:1, is preferably 1:20-2:1, more preferably 1:10-1:1.
The present invention calculates rate of charge, is the quality that the quality of platinum salt is converted into the platinum of equimolar amounts, and then mass ratio definite and another reactant.
The described reaction time is 1h-36h, is preferably 6-24h.Reaction temperature is 60-200 ℃, is preferably 100-160 ℃.
Centrifugal, washing described in the step (6), dry process are ordinary skill in the art means, and described dry run temperature is 40-80 ℃, and preferred temperature is 60 ℃.
Further, the invention provides a kind of platinum-transition metal oxide-Graphene ternary complex catalyst that obtains by method for preparing.
The present invention compared with prior art, its advantage is: the catalytic activity of (1) platinum-transition metal oxide-Graphene ternary combination electrode catalyst is high, anti-poisoning capability is strong, have extended cycle life; (2) synthetic method is comparatively simple, and the process gentleness is controlled; (3) the platinum-transition metal oxide-Graphene ternary combination electrode catalyst of application the present invention preparation has application promise in clinical practice and economic benefit in fields such as DMFCs; (4) the present invention selects for use the hybrid reaction system of ethylene glycol and water under the prerequisite that does not influence transition metal oxide, platinum salt and graphene oxide to be reduced effectively.
Description of drawings
Fig. 1 is the complex method schematic flow sheet of platinum-transition metal oxide of the present invention-Graphene ternary combination electrode catalyst.
Fig. 2 is the XRD figure of platinum-manganese dioxide-Graphene ternary complex catalyst of preparing of the embodiment of the invention 1
Fig. 3 is that (curve a), platinum-graphen catalyst (curve b) and platinum-activated-carbon catalyst (curve c) be respectively to the cyclic voltammogram of methanol catalytic oxidation for platinum-manganese dioxide-Graphene ternary combination electrode catalyst of preparing of the embodiment of the invention 1.
The specific embodiment
Following embodiment is to further specify of the present invention, rather than limits scope of the present invention.
The embodiment of the invention such as non-special instruction, said solvent, reagent, raw material and device all obtain through commercially available purchase.Graphene oxide described in the embodiment can obtain through commercially available purchase, or obtain through this area routine techniques means, the method that for example provides with reference to people such as Lei Yun (nonmetallic ore, 2011,34 (1): 4-5) preparation.
Embodiment 1: (manganese dioxide: the graphene oxide mass ratio is 1:4.6 to platinum-manganese dioxide-Graphene ternary combination electrode catalyst; Platinum: the mass ratio of manganese dioxide-graphene oxide binary complex is 1:4)
(1) the 400mg graphite oxide is joined in the 600mL deionized water, descended ultrasonic 2 hours, obtain the dispersion soln of graphene oxide at 30 ℃;
(2) in the system of the first step, add the liquor potassic permanganate of the 0.50mol/L of 20mL, 120 ℃ of stirring reactions 12 hours;
(3) system with second step centrifugalizes out solid product, spends deionised water, and 60 ℃ of down dry backs obtain manganese dioxide-graphene oxide compound;
(4) take by weighing the manganese dioxide-graphene oxide compound 20mg that obtains in the 3rd step and place 30mL deionized water and 50mL ethylene glycol mixtures, descended ultrasonic 2 hours, obtain the dispersion soln of manganese dioxide-graphene oxide compound at 30 ℃;
(5) platinum nitrate solution of the 0.73mol/L of adding 0.035mL in the system in the 4th step stirs, and is transferred in the water heating kettle and reacts, 120 ℃ of reactions 12 hours;
(6) system with the 5th step centrifugalizes out solid product, spends deionised water, and 60 ℃ of down dry backs obtain platinum-manganese dioxide-Graphene ternary combination electrode catalyst.
Fig. 2 is the XRD figure of platinum-manganese dioxide-Graphene ternary complex catalyst of adopting embodiment 1 and preparing.As shown in the figure, the characteristic peak of metal platinum and manganese dioxide is all comparatively clear in platinum-manganese dioxide-Graphene three-way catalyst, explains to contain this two kinds of components in the combination product really.In addition, do not observe the characteristic peak of graphite oxide in this XRD figure, only about 25 degree, have a Bao Feng, explain that graphite oxide has been reduced to Graphene.
(curve a), platinum-graphen catalyst (curve b) and platinum-activated-carbon catalyst (curve c) be respectively to the cyclic voltammogram of methanol catalytic oxidation for platinum-manganese dioxide-Graphene ternary combination electrode catalyst of adopting embodiment 1 to prepare for Fig. 3.As can be seen from the figure; Platinum-manganese dioxide-Graphene ternary combination electrode catalyst not only has very high electro catalytic activity (forward peak current density 1350mA/mg) to methanol oxidation, and has anti-carbon monoxide poisoning capability (the forward peak current is 1.23 with the ratio of reverse peak current) preferably.
Embodiment 2: (zinc oxide: the graphene oxide mass ratio is 1:10 to platinum-zinc oxide-Graphene ternary combination electrode catalyst; Platinum: the mass ratio of zinc oxide-graphene oxide binary complex is 40:1)
(1) the 400mg graphite oxide is joined in the 4000mL deionized water, descended ultrasonic 1 hour, obtain the dispersion soln of graphene oxide at 20 ℃;
(2) in the system of the first step, add the zinc acetate solution of the 0.49mol/L of 1.00mL, 120 ℃ of stirring reactions 1 hour;
(3) system with second step centrifugalizes out solid product, spends deionised water, and 40 ℃ of down dry backs obtain zinc oxide-graphene oxide compound;
(4) take by weighing the zinc oxide-graphene oxide compound 8.00mg that obtains in the 3rd step and place 10mL deionized water and 70mL ethylene glycol mixtures, descended ultrasonic 1 hour, obtain the dispersion soln of zinc oxide-graphene oxide compound at 20 ℃;
(5) platinum nitrate solution of the 0.73mol/L of adding 2.25mL in the system in the 4th step stirs, and is transferred in the water heating kettle and reacts, 60 ℃ of reactions 36 hours;
(6) system with the 5th step centrifugalizes out solid product, spends deionised water, and 40 ℃ of down dry backs obtain platinum-zinc oxide-Graphene ternary combination electrode catalyst.
Embodiment 3: (cobaltosic oxide: the mass ratio of graphene oxide is 10:1 to platinum-cobaltosic oxide-Graphene ternary combination electrode catalyst; Platinum: the mass ratio of cobaltosic oxide-graphene oxide binary complex is 1:40)
(1) the 400mg graphite oxide is joined in the 40mL deionized water, descended ultrasonic 3 hours, obtain the dispersion soln of graphene oxide at 40 ℃;
(2) in the system of the first step, add the 1.0mol/L cobalt nitrate solution of 49.83mL, 200 ℃ of stirring reactions 72 hours;
(3) system with second step centrifugalizes out solid product, spends deionised water, and 80 ℃ of down dry backs obtain cobaltosic oxide-graphene oxide compound;
(4) take by weighing the cobaltosic oxide-graphene oxide compound 800mg that obtains in the 3rd step and place 70mL deionized water and 10mL ethylene glycol mixtures, descended ultrasonic 3 hours, obtain the dispersion soln of cobaltosic oxide-graphene oxide compound at 40 ℃;
(5) platinum nitrate solution of the 0.73mol/L of adding 0.14mL in the system in the 4th step stirs, and is transferred in the water heating kettle and reacts, 200 ℃ of reactions 1 hour;
(6) system with the 5th step centrifugalizes out solid product, spends deionised water, and 80 ℃ of down dry backs obtain platinum-cobaltosic oxide-Graphene ternary combination electrode catalyst.
Embodiment 4: (cupric oxide: the mass ratio of graphene oxide is 1:1 to platinum-cupric oxide-Graphene ternary combination electrode catalyst; Platinum: the mass ratio of cupric oxide-graphene oxide binary complex is 1:1)
(1) the 400mg graphite oxide is joined in the 400mL deionized water, descended ultrasonic 2 hours, obtain the dispersion soln of graphene oxide at 30 ℃;
(2) in the system of the first step, add the 1.0mol/L Schweinfurt green solution of 5.03mL, 80 ℃ of stirring reactions 36 hours;
(3) system with second step centrifugalizes out solid product, spends deionised water, and 60 ℃ of down dry backs obtain cupric oxide-graphene oxide compound;
(4) take by weighing the cupric oxide-graphene oxide compound 80mg that obtains in the 3rd step and place 40mL deionized water and 40mL ethylene glycol mixtures, descended ultrasonic 2 hours, obtain the dispersion soln of cupric oxide-graphene oxide compound at 30 ℃;
(5) platinum nitrate solution of the 0.73mol/L of adding 0.56mL in the system in the 4th step stirs, and is transferred in the water heating kettle and reacts, 160 ℃ of reactions 24 hours;
(6) system with the 5th step centrifugalizes out solid product, spends deionised water, and 60 ℃ of down dry backs obtain platinum-cupric oxide-Graphene ternary combination electrode catalyst.
Embodiment 5
According to the method for embodiment 1, the ternary complex catalyst that embodiment 2-4 is prepared is used for methanol catalytic oxidation, and experimental result shows:
The ratio of forward peak current density forward peak current and reverse peak current
Embodiment 2 861mA/mg 1.09
Embodiment 3 695mA/mg 1.16
Embodiment 4 1077mA/mg 1.02
Claims (10)
1. platinum-transition metal oxide-Graphene ternary complex catalyst; It is characterized in that this composite catalyst is through transition metal oxide-graphene oxide is prepared into binary complex; Again platinum salt and transition metal oxide-graphene oxide binary complex reaction and reduction are prepared; Wherein, the mass ratio of described platinum and transition metal oxide-graphene oxide binary complex is 1:40-40:1; In described transition metal oxide-graphene oxide binary complex, the mass ratio of transition metal oxide and graphene oxide is 1:10-10:1.
2. method for preparing platinum-transition metal oxide-Graphene ternary complex catalyst may further comprise the steps:
(1) graphite oxide is placed the ultrasonic dispersion of water;
(2) salting liquid of adding transition metal in the dispersion of step (1), stirring reaction is to complete;
(3) reactant of step (2) is centrifugal, isolate solid product, spend deionised water, drying obtains transition metal oxide-graphene oxide compound;
(4) product in the step (3) is placed the ultrasonic dispersion of mixed solution of water and ethylene glycol;
(5) in the dispersion of step (4), add platinum nitrate solution, mix, place water heating kettle to react completely;
(6) reactant of step (5) is centrifugal, isolate solid product, spend deionised water, drying obtains platinum-transition metal oxide-Graphene ternary complex catalyst.
3. method according to claim 2 is characterized in that, the ultrasonic time described in the step (1) is 1-3 hour, and ultrasonic temperature is 20-40 ℃; The concentration of the graphite oxide dispersion liquid of said acquisition is 0.1g/L-10g/L.
4. method according to claim 2 is characterized in that, the reaction time described in the step (2) is 1h-72h; Reaction temperature is 20 ℃-200 ℃; The transition metal oxide of described acquisition and the mass ratio of graphite oxide are 1:10-10:1.
5. method according to claim 2 is characterized in that described transition metal oxide is selected from manganese dioxide, titanium dioxide, zinc oxide, cupric oxide.
6. method according to claim 2 is characterized in that, the volume ratio of water and ethylene glycol is 1:7-7:1 in the step (4); Ultrasonic time is 1-3 hour, and temperature is 20-40 ℃.
7. method according to claim 2 is characterized in that, the transition metal oxide-Graphene binary complex dispersion concentration that obtains in the step (4) is 0.1g/L-10g/L.
8. method according to claim 2 is characterized in that, the mass ratio of metal platinum and transition metal oxide-graphene oxide binary complex is 1:40-40:1 in the step (5).
9. method according to claim 2 is characterized in that the reaction time described in the step (5) is 1h-36h, and reaction temperature is 60 ℃-200 ℃.
10. platinum-transition metal oxide-Graphene ternary complex catalyst is characterized in that this composite catalyst prepares through any described method of claim 2-9.
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