CN101733094B - Pt-CeO2/graphene electro-catalyst and preparation method thereof - Google Patents
Pt-CeO2/graphene electro-catalyst and preparation method thereof Download PDFInfo
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Abstract
The invention discloses a Pt-CeO2/graphene electro-catalyst which uses graphene as a carrier, platinum as an active component and CeO2 as an auxiliary component, wherein the mass fraction of the platinum contained in the Pt-CeO2/graphene electro-catalyst is 20 percent; and the mole ratio of the platinum and cerium is 1:1-2.5:1. A preparation method of the Pt-CeO2/graphene electro-catalyst comprises the following steps of: ultrasonically dispersing oxidized nano graphite sheets into glycol; then adding a chloroplatinic acid solution, an aqueous ammonium ceric nitrate solution and an aqueous sodium acetate solution, and sufficiently mixing; transferring a mixture to a microwave hydro-thermal reaction kettle; and after microwave hydro-thermal reaction, filtering, washing and drying to obtain the Pt-CeO2/graphene electro-catalyst. The preparation method has energy saving, fastness, simple process, and the like; and in addition, the prepared Pt-CeO2/graphene electro-catalyst has high electrocatalysis activity for the electrochemical oxidation of methanol and is widely used for direct methanol fuel cells.
Description
Technical field
The present invention relates to Pt-CeO
2/ Graphene eelctro-catalyst and the preparation method, belong to catalyst preparation technical field and electrochemical energy technical field.
Background technology
Advantage such as the DMFC that with methyl alcohol is fuel has energy density height, environmental friendliness, fuel is portable, operating temperature is low is with a wide range of applications.Platinum/the material with carbon element of the platinum nanoparticles of carbon load is with its excellent catalytic performance, and the eelctro-catalyst in the battery that acts as a fuel has obtained using widely.But simple Pt/C catalyst easy intermediate product of absorption methanol oxidation (like CO etc.) in to the catalytic oxidation process of methyl alcohol is poisoned its catalyst performance.Therefore, synthesis catalytic is active high and have a significant and actual application value of fuel-cell catalyst of anti-CO poisoning performance.Synthetic thisly have anti-CO fouled catalyst and mainly contain two class methods: the first is with Pt and other metals formation alloy catalyst, like PtRu/C, PtSn/C and PtNi/C etc.; It two is in precious metals pt/C catalyst, to add some transition metal oxides, like RuO
2, SnO
2And WO
3Deng.These measures have good action for the anti-CO poisoning performance that improves platinum based catalyst.Recently relevant literature research report shows CeO
2Can significantly strengthen the electrocatalysis characteristic of Pt/C catalyst and the performance that anti-CO poisons.Yu etc. have synthesized CeO
2Commercial Pt/C (E-TEK) catalyst (Yu H-B, Kim J-H, Lee H-I, Scibioh M-A, Lee J-Y, Han J-H, Yoon S-P, the HaH-Y.Development of Nanophase CeO that mix
2-Pt/C Cathode Catalyst for Direct MethanolFuel Cell, Journal of Power Sources, 2005,140 (1): 59-65), its method is at Ce (NO
3)
3Dipping commercial Pt/C (E-TEK) catalyst forms at 300 ℃ of following sintering, then with the CeO that makes then in the solution
2Doped P t/C composite catalyst carries out the oxygen electric reduction performance test as cathod catalyst, and the result shows the CeO that mixed
2Catalyst is better than unadulterated Pt/C catalyst on methyl alcohol hydrogen reduction performance.Xu etc. have synthesized Pt-CeO through two-step reaction method
2/ C catalyst (Xu C W, Shen P K.ElectrochemicalOxidation of Ethanol on Pt-CeO
2/ C Catalysts, Journal of Power Sources, 2005,142 (1-2) 27-29.; Xu C W, Shen P K.Novel Pt-CeO
2/ C catalysts for electrooxidation ofalcohols in alkaline Media.Chem.Commun., 2004, (20): 2238-2239), its method mainly is to use the microwave solid phase method to synthesize support C eO earlier
2/ C compound, and then Pt loaded on the carrier, then catalyst having been carried out the electrocatalytic oxidation property test of ethanol in the alkaline solution, its result shows CeO
2Significantly improved the electrocatalysis characteristic of Pt to ethanol.Existing these synthetic Pt-CeO
2/ C catalyst method is all accomplished through two-step method is synthetic.
As everyone knows, catalyst carrier has very big influence to the performance of catalyst.Activated carbon, XC-72 nano-sized carbon, CNT etc. all are some material with carbon elements multi-form or pattern, also are the catalyst carriers of using always.These different material with carbon elements have very big influence as carrier-supported precious metal platinum or platinum alloy nano particle to the electrocatalysis characteristic of catalyst.The XC-72 nano-sized carbon is a kind of business-like nano-carbon material, and the cell catalyst carrier that acts as a fuel is used widely.CNT has also obtained extensive studies as catalyst carrier.People have carried out more research to the preparation of XC-72 nano-sized carbon and carbon nanotube loaded PtRu nano-particle catalyst and to the electrocatalysis characteristic of methanol oxidation.
For electrocatalysis characteristic that further strengthens catalyst and the utilization rate that improves noble metal catalyst, research and develop a kind of new material with carbon element carrier, make nano-particle catalyst can high degree of dispersion in the above.The research of graphene nanometer sheet (a kind of cancellated individual layer nanometer sheet of bi-dimensional cellular that is made up of the mono-layer graphite carbon atom) has recently caused people's very big interest.Graphene nanometer sheet has high thermal conductivity, superpower mechanical property and distinguished electric property, and graphene nanometer sheet also has high chemical stability simultaneously, (theoretical specific area is 2620m to big specific area
2/ g) with wide electrochemical window.Therefore, graphite nano plate should have good electrocatalysis characteristic as the eelctro-catalyst of catalyst carrier preparation.
But how noble metal or the alloy nano particle in graphene nanometer sheet area load high degree of dispersion still is a challenging job.Generally mainly be based on dipping-reduction technique in carbon material surface platinum or platinum alloy nano-particle catalyst traditional preparation method; Just at first the material with carbon element carrier impregnation in containing the solution of slaine; Make slaine be adsorbed on the material with carbon element carrier surface, make its high temperature reduction under reducing atmosphere then.But thisly be difficult to the size of control load noble metal granule on carbon carrier, and the dispersion of noble metal granule on carbon carrier neither be very even based on traditional dipping-method of reducing.Document [Xue B, Chen P, Hong Q for example; Deng, Growth of Pd, Pt; Ag and Au nanoparticles on carbonnanotubes, Journal of Materials Chemistry, 2001; 11 (19): 2378-2381] report employing immersion-reduction technique is 8nm in the average grain diameter of the platinum nanoparticles of carbon nano tube surface load, and particle size distribution is between 2-12nm.Also can the material with carbon element (as: activated carbon, XC-72 nano-sized carbon, CNT etc.) as carrier be dispersed in the solution that contains slaine in addition, slowly add reductant solution (as: KBH
4Solution, formalin etc.), make metal ion be reduced into metal nanoparticle and be adsorbed on the carbon carrier surface.Because reducing agent is to add in addition, the concentration that is very easy to produce local reducing agent is greater than other place, and therefore this method is difficult to control the size and the dispersed uniform property of metal nanoparticle.
The polyalcohol method is proved to be to prepare a kind of effective ways of metal nanoparticle.In this method, polyalcohol is as the solvent and the reducing agent of slaine.At high temperature polyalcohol makes the solution metal ion be reduced into metal nanoparticle as reducing agent.Can prepare the metal nanoparticle of particle diameter with polymer as protectant polyalcohol method at 1～2nm.Heating using microwave has fast, evenly, and energy-conservation and high efficiency advantage.Microwave heating technique organic chemistry synthetic with nano material synthetic in be used widely, it can make reaction speed improve about 10～100 times.In recent years, the polyalcohol method of microwave assistant heating also is used for synthesizing noble metal nano particles (Tu WX, Liu HF, Journal of Materials Chemistry, 2000,10 (9): 2207-2211; Yu WX, Tu WX, Liu HF, Langmuir, 1999,15 (1): 6-9).Though in above these methods, use polymer as protective agent, can obtain the noble metal nano particles of tiny particle diameter.But do two shortcomings like this: the first is difficult to directly load on the material with carbon element carrier by the metal nanoparticle of polymer protection; It two is to use as eelctro-catalyst, and the polymer protective agent must at high temperature be removed, and metal nanoparticle can be reunited or grow up once more in the high-temperature process, influences the electrocatalysis characteristic of catalyst.
Summary of the invention
The purpose of this invention is to provide a kind of Pt-CeO
2/ graphen catalyst and preparation method thereof.
Pt-CeO of the present invention
2/ graphen catalyst is to be carrier with the Graphene, is active component with platinum, CeO
2Be helper component, the mass fraction of platinum is 20% in the catalyst, and the mol ratio of platinum and cerium is 1: 1～2.5: 1.
Pt-CeO
2The preparation method of/graphene nano electro-catalyst, its step is following:
1) is dispersed in the ethylene glycol the graphite oxide nanometer sheet is ultrasonic; Add platinum acid chloride solution then, the ammonium ceric nitrate aqueous solution and sodium acetate aqueous solution, and fully mix; Graphite oxide nanometer sheet content is 0.6～1.1g/L in the mixture; The concentration of chloroplatinic acid is 0.0008～0.0015mol/L, and the mol ratio of chloroplatinic acid and ammonium ceric nitrate is 1: 1～2.5: 1, and the concentration of sodium acetate is 0.01～0.025mol/L;
2) mixture is transferred in the microwave hydrothermal reaction kettle, the heating using microwave reaction through filtering, wash, drying, obtained Pt-CeO after 5～10 minutes
2/ Graphene eelctro-catalyst.
Have following outstanding advantage with prior art comparison the present invention:
(1) graphene nanometer sheet is the cancellated individual layer nanometer sheet of bi-dimensional cellular that is made up of the mono-layer graphite carbon atom.Use as electro-catalyst carrier, graphene nanometer sheet has high chemical stability and big specific area.General material with carbon element can only utilize the surface of surface carbon, and the carbon of material internal can not be utilized.It is metal nanoparticles loaded mainly to be like CNT that outermost carbon surface can be used for, between graphite linings be difficult to utilize, and the pipe interior metal nano particle of CNT also is difficult to get into.The two sides of graphene nanometer sheet is supported precious metal nano-particle easily, therefore has more metal nanoparticles loaded specific area than general material with carbon element.
(2) the inventive method at first is dispersed in the graphite oxide nanometer sheet in the liquid polyol, and fully mixes with platinum acid chloride solution, ammonium ceric nitrate and SAS.Do like this and have following advantage: abundant functional group (as: hydroxyl, carbonyl and the carboxyl etc. of containing are contained on graphite oxide nanometer sheet surface; Sketch map is seen Fig. 1); Therefore in liquid polyol, reunited again no longer easily later on or be deposited in together by ultrasonic dispersion; And the functional group on graphite oxide surface can be adsorbed on precious metal ion in the polyhydric alcohol solutions surface of graphite oxide nanometer sheet through complexing, reaches the high mixed (the graphite oxide nanometer sheet can be regarded a big molecule as) of molecule and ion aspect.Under the microwave radiation, mixed system is by Fast Heating, and at high temperature, polyalcohol has reproducibility, with the graphite oxide nanometer sheet and be adsorbed on the reduction of its surperficial precious metal ion.In the solvent thermal process of heating using microwave, the solution that contains ammonium ceric nitrate generates CeO simultaneously
2Nano particle obtains high degree of dispersion and uniform Pt-CeO at last
2/ graphene nano electro-catalyst.
The present invention adds a spot of SAS as stabilizing agent in synthetic solvent, the Pt-CeO that is synthesized
2Nano platinum particle has tiny and uniform particle diameter in/the graphene nano electro-catalyst, and average grain diameter can be regulated and control about 3.0nm, and nano platinum particle is uniformly dispersed at the nano-sized carbon carrier.
The present invention has adopted microwave heating technique, has fast, evenly, the energy-conservation and high advantage of efficient.
The Pt-CeO that the present invention synthesizes
2/ graphen catalyst has higher electro catalytic activity than Pt/ graphen catalyst to the electroxidation of methyl alcohol, and has the anti-CO poisoning performance of improvement, has widely as the eelctro-catalyst of direct alcohol fuel battery and uses.
Description of drawings
Fig. 1 is a graphite oxide nanometer sheet structural representation.
The specific embodiment
Embodiment 1:
With ultrasonic Treatment 148 milligrams of graphite oxide nanometer sheet are dispersed in the ethylene glycol with 150mL; Add the platinum acid chloride solution of 4mL 0.05M and the 10mM ammonium ceric nitrate aqueous solution of 20mL then; The mol ratio of platinum and cerium was at 1: 1; The sodium acetate aqueous solution that adds 1.5 milliliters of 1mol/L again, sodium acetate concentration in synthetic solvent is 0.01mol/L, fully mixes.Should transfer in the microwave hydrothermal reaction kettle by uniform mixture carry out microwave radiation heating reaction 8min.After the cooling, through filter, with acetone and deionized water fully wash, 80 ℃ of oven dry, obtain Pt-CeO
2/ graphen catalyst.Nano platinum particle has uniform particle diameter in the transmission electron microscope observing catalyst, and average grain diameter is 2.8 nanometers.It is 19.3% (theoretical value near 20%) that EDX analyzes the mass fraction that shows platinum in the catalyst, the mol ratio of Pt: Ce=1: 1.
As relatively, respectively as carrier, press above-mentioned same method and synthesize Pt-CeO with XC-72 nano-sized carbon and CNT (CNT diameter 30-40nm is with red fuming nitric acid (RFNA) and the preliminary treatment of sulfuric acid mixed acid)
21) and Pt-CeO (mass fraction of platinum is 20% to/XC-72 nanometer electrical catalyst, mol ratio Pt: Ce=1:
2(mass fraction of platinum is 20% to/CNTs nanometer electrical catalyst, mol ratio Pt: Ce=1: 1).
To methanol oxidation electrocatalysis characteristic test relatively: the Nafion solution and the deionized water of a spot of catalyst and an amount of 5% are mixed under the ultrasonic wave effect; Should be coated on the glassy carbon electrode by uniform mixture, dry the back down as measuring working electrode at 80 ℃.Reference electrode is saturated calomel electrode (SCE) during measurement, and electrolyte is 2M CH
3OH+1M H
2SO
4, platinized platinum is to electrode.With the electro catalytic activity of cyclic voltammetry experiment (sweep speed 20mV/s, 30 ℃) evaluate catalysts to methanol electrooxidation.Test result shows: methyl alcohol is at Pt-CeO
2/ Graphene, Pt-CeO
2/ XC-72 nano-sized carbon and Pt-CeO
2The peak current of catalytic oxidation is respectively to be 16.2mA on the/CNTs catalyst, and 11.3mA and 10.5mA, take-off potential are respectively 0.30V, 0.30V and 0.31V.(this is because CeO though the take-off potential of methyl alcohol oxidation on three kinds of catalyst is basic identical
2The effect of nano particle), but methyl alcohol is at Pt-CeO
2The current peak of oxidation is obviously greater than at Pt-CeO on the/graphen catalyst
2/ XC-72 nano-sized carbon and Pt-CeO
2On/CNTs the catalyst, the Pt-CeO that the present invention synthesizes is described
2/ graphen catalyst compares Pt-CeO
2/ XC-72 nano-sized carbon and Pt-CeO
2/ CNTs catalyst has better electro catalytic activity to methanol oxidation.
Embodiment 2:
With ultrasonic Treatment 336 milligrams of graphite oxide nanometer sheet are dispersed in the ethylene glycol with 300mL; Add the platinum acid chloride solution of 8mL 0.05M and the 10mM ammonium ceric nitrate aqueous solution of 20mL then; The mol ratio of platinum and cerium was at 2: 1 in the solution; The sodium acetate aqueous solution that adds 4 milliliters of 1mol/L again, sodium acetate concentration in synthetic solvent is 0.013mol/L, fully mixes.Should transfer in the microwave hydrothermal reaction kettle by uniform mixture carry out microwave radiation heating reaction 10min.After the cooling, through filter, with acetone and deionized water fully wash, 80 ℃ of oven dry, obtain Pt-CeO
2/ graphen catalyst.Nano platinum particle has uniform particle diameter in the transmission electron microscope observing catalyst, and average grain diameter is 3.0 nanometers.It is 20.2% (theoretical value near 20%) that EDX analyzes the mass fraction that shows platinum in the catalyst, mol ratio Pt: Ce=2: 1.
As relatively, respectively as carrier, press above-mentioned same method and synthesize Pt-CeO with XC-72 nano-sized carbon and CNT (CNT diameter 30-40nm is with red fuming nitric acid (RFNA) and the preliminary treatment of sulfuric acid mixed acid)
21) and Pt-CeO (mass fraction of platinum is 20% to/XC-72 nanometer electrical catalyst, mol ratio Pt: Ce=2:
2(mass fraction of platinum is 20% to/CNTs nanometer electrical catalyst, mol ratio Pt: Ce=2: 1).
The test to the methanol oxidation electrocatalysis characteristic by embodiment 1 is compared: test result shows: methyl alcohol is at Pt-CeO
2/ Graphene, Pt-CeO
2/ XC-72 nano-sized carbon and Pt-CeO
2The peak current of catalytic oxidation is respectively to be 18.2mA on the/CNTs catalyst, and 13.6mA and 14.5mA, take-off potential be near 0.33V, 0.34V and 0.33V.The Pt-CeO that the present invention synthesizes is described
2/ graphen catalyst compares Pt-CeO
2/ XC-72 nano-sized carbon and Pt-CeO
2/ CNTs catalyst has better electro catalytic activity to methanol oxidation.(this is because CeO though the take-off potential of methyl alcohol oxidation on three kinds of catalyst is basic identical
2The effect of nano particle), but methyl alcohol is at Pt-CeO
2The peak current of oxidation is obviously greater than at Pt-CeO on the/graphen catalyst
2/ XC-72 nano-sized carbon and Pt-CeO
2On/CNTs the catalyst, the Pt-CeO that the present invention synthesizes is described
2/ graphen catalyst compares Pt-CeO
2/ XC-72 nano-sized carbon and Pt-CeO
2/ CNTs catalyst has better electro catalytic activity to methanol oxidation.
Embodiment 3:
With ultrasonic Treatment 430 milligrams of graphite oxide nanometer sheet are dispersed in the ethylene glycol with 400mL; Add the platinum acid chloride solution of 10mL 0.05M and the 10mM ammonium ceric nitrate aqueous solution of 20mL then; The mol ratio of platinum and cerium was at 2.5: 1 in the solution; The sodium acetate aqueous solution that adds 10 milliliters of 1mol/L again, sodium acetate concentration in synthetic solvent is 0.025mol/L, fully mixes.Should transfer in the microwave hydrothermal reaction kettle by uniform mixture carry out microwave radiation heating reaction 10min.After the cooling, through filter, with acetone and deionized water fully wash, 80 ℃ of oven dry, obtain Pt-CeO
2/ graphen catalyst.Nano platinum particle has uniform particle diameter in the transmission electron microscope observing catalyst, and average grain diameter is 3.2 nanometers.It is 19.6% (theoretical value near 20%) that EDX analyzes the mass fraction that shows platinum in the catalyst, mol ratio Pt: Ce=2.5: 1.
As relatively, respectively as carrier, press above-mentioned same method and synthesize Pt-CeO with XC-72 nano-sized carbon and CNT (CNT diameter 30-40nm is with red fuming nitric acid (RFNA) and the preliminary treatment of sulfuric acid mixed acid)
21) and Pt-CeO (mass fraction of platinum is 20% to/XC-72 nanometer electrical catalyst, mol ratio Pt: Ce=2.5:
2(mass fraction of platinum is 20% to/CNTs nanometer electrical catalyst, mol ratio Pt: Ce=2.5: 1).
The test to the methanol oxidation electrocatalysis characteristic by embodiment 1 is compared: test result shows: methyl alcohol is at Pt-CeO
2/ Graphene, Pt-CeO
2/ XC-72 nano-sized carbon and Pt-CeO
2The peak current of catalytic oxidation is respectively to be 16.2mA on the/CNTs catalyst, and 10.8mA, and 11.2mA, take-off potential be near 0.35V, 0.35V and 0.36V.(this is because CeO though the take-off potential of methyl alcohol oxidation on three kinds of catalyst is basic identical
2The effect of nano particle), but methyl alcohol is at Pt-CeO
2The peak current of oxidation is obviously greater than at Pt-CeO on the/graphen catalyst
2/ XC-72 nano-sized carbon and Pt-CeO
2Peak current on the/CNTs catalyst is explained the Pt-CeO that the present invention synthesizes
2/ graphen catalyst compares Pt-CeO
2/ XC-72 nano-sized carbon and Pt-CeO
2/ CNTs catalyst has better electro catalytic activity to methanol oxidation.
Embodiment 4:
With ultrasonic Treatment 240 milligrams of graphite oxide nanometer sheet are dispersed in the ethylene glycol with 350mL; Add the platinum acid chloride solution of 6mL 0.05M and the 10mM ammonium ceric nitrate aqueous solution of 20mL then; The mol ratio of platinum and cerium was at 1.5: 1 in the solution; The sodium acetate aqueous solution that adds 7 milliliters of 1mol/L again, sodium acetate concentration in synthetic solvent is 0.02mol/L, fully mixes.Should transfer in the microwave hydrothermal reaction kettle by uniform mixture carry out microwave radiation heating reaction 10min.After the cooling, through filter, with acetone and deionized water fully wash, 80 ℃ of oven dry, obtain Pt-CeO
2/ graphen catalyst.Nano platinum particle has uniform particle diameter in the transmission electron microscope observing catalyst, and average grain diameter is 2.9 nanometers.It is 20.3% (theoretical value near 20%) that EDX analyzes the mass fraction that shows platinum in the catalyst, mol ratio Pt: Ce=1.5: 1.
The test to the methanol oxidation electrocatalysis characteristic by embodiment 1 is compared: test result shows: methyl alcohol is at Pt-CeO
2/ Graphene, Pt-CeO
2/ XC-72 nano-sized carbon and Pt-CeO
2The peak current of catalytic oxidation is respectively to be 19.2mA on the/CNTs catalyst, and 13.3mA, and 13.6mA, take-off potential be near 0.31V, 0.30V and 0.31V.(this is because CeO though the take-off potential of methyl alcohol oxidation on three kinds of catalyst is basic identical
2The effect of nano particle), but methyl alcohol is at Pt-CeO
2The peak current of oxidation is obviously greater than at Pt-CeO on the/graphen catalyst
2/ XC-72 nano-sized carbon and Pt-CeO
2Peak current on the/CNTs catalyst is explained the Pt-CeO that the present invention synthesizes
2/ graphen catalyst compares Pt-CeO
2/ XC-72 nano-sized carbon and Pt-CeO
2/ CNTs catalyst has better electro catalytic activity to methanol oxidation.
Claims (1)
1. Pt-CeO
2The preparation method of/Graphene eelctro-catalyst, this catalyst is a carrier with the Graphene, is active component with platinum, CeO
2Be helper component, the mass fraction of platinum is 20% in the catalyst, and the mol ratio of platinum and cerium is 1: 1～2.5: 1, it is characterized in that Pt-CeO
2The preparation method's of/Graphene eelctro-catalyst step is following:
1) is dispersed in the ethylene glycol the graphite oxide nanometer sheet is ultrasonic; Add platinum acid chloride solution then, the ammonium ceric nitrate aqueous solution and sodium acetate aqueous solution, and fully mix; Graphite oxide nanometer sheet content is 0.6～1.1g/L in the mixture; The concentration of chloroplatinic acid is 0.0008～0.0015mol/L, and the mol ratio of chloroplatinic acid and ammonium ceric nitrate is 1: 1～2.5: 1, and the concentration of sodium acetate is 0.01～0.025mol/L;
2) mixture is transferred in the microwave hydrothermal reaction kettle, the heating using microwave reaction through filtering, wash, drying, obtained Pt-CeO after 5～10 minutes
2/ Graphene eelctro-catalyst.
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| CN107732203B (en) * | 2017-10-16 | 2020-11-03 | 河源广工大协同创新研究院 | Preparation method of nano cerium dioxide/graphene/sulfur composite material |
| CN110021759B (en) * | 2019-03-27 | 2023-01-10 | 内蒙古科技大学 | Preparation method of platinum-nickel alloy catalyst |
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