CN101667644B - High-performance low-platinum catalyst for methanol fuel cell and preparation method thereof - Google Patents
High-performance low-platinum catalyst for methanol fuel cell and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a high-performance low-platinum catalyst for the methanol fuel cell. The method adopts simple displacement reaction to coat a small amount of Pt or Pt and Ru on the surface of Pd alloy and loads the materials on carbon powder together so that the dosage of precious metal Pt is greatly reduced and the cost of the catalyst is effectively reduced. The catalyst prepared by the invention has high catalytic activity of methanol oxidation electrocatalysis, good stability and long service life, thus being a good high-performance catalyst which can be directly used for methanol fuel cells.
Description
Technical field
The invention belongs to fuel cell electrode catalytic applications technical field, relate to a kind of high-performance low-platinum catalyst preparation method who is used for fuel cell, relate in particular to a kind of high-performance low-platinum catalyst preparation method who is used for methanol fuel cell.
Background technology
Fuel cell is a kind of energy conversion device that directly in the electrochemical reaction mode chemical energy of fuel is converted to electric energy without burning, have power conversion density height, pollution is little, fuel is diversified, reliability is high, noise is low and is convenient to advantages such as maintenance, be considered to most possibly obtain the alternative energy source technology of large-scale commercial applications application.
Pt has higher electro catalytic activity to methanol oxidation, adds that Pt has higher chemical stability in acid, generally all make anode catalyst with Pt.Although also there is report to make methanol oxidation catalyst with other metals, their electro catalytic activity and chemical stability are all very different than Pt.But pure Pt is subjected to the restriction of price and resource, and is easily poisoned by CO and reduce its catalytic activity.For reducing the cost of fuel cell, be more conducive to its industrialization, the research of its catalyst mainly concentrates on the Pt carrying capacity that reduces in the catalyst and improves on the catalytic efficiency.The low-temperature fuel cell catalyst of broad research and application mainly is a catalyst of making active component or main active component with platinum at present, as: the platinum catalyst of carbon load, the platinum-ruthenium alloys catalyst of carbon load, platinum-nickel alloys catalyst, platinum alloy catalyst, and be added with other catalyst that promotes composition etc.Though adopt the method for Pt and other metal alloys can reduce the cost of catalyst to a certain extent, but because desirable catalyst is at catalyst surface methyl alcohol to be produced catalytic effect, the Pt that is formed on the alloy the inside does not play the effect of catalysis, has caused the utilance of Pt still not high.
Summary of the invention
The objective of the invention is the high and low problem of utilance, a kind of preparation method of high performance catalyst of low Pt carrying capacity is provided, noble metal is used more effectively for Pt carrying capacity in the platinum catalyst that overcomes the load of prior art carbon.
The present invention is used for the preparation method of the high-performance low-platinum catalyst of methanol fuel cell, is finished by following processing step:
(1) chloride of palladium salt and metal Ni, Zn, Fe, Cu, Sn or Se or the nitrate amount of substance with 1: 0.3～1: 3 is dissolved in the ethylene glycol, adds the natrium citricum of 2～2.5 times of the amounts of total metal ion species, ultrasonic it is dissolved fully; Regulate pH to 8～10 with the KOH/ ethylene glycol solution of mass concentration 5% again, add the sodium formate of 2～4 times of the amounts of total metal ion species, add the carbon dust of 4～8 times of the theoretical total metal qualities in reduction back, ultrasonic dispersion; Transfer to then in the autoclave, reacted 8～10 hours down,, obtain the presoma of catalyst with deionized water wash, drying in 140～200 ℃;
Described palladium salt is palladium bichloride or palladium nitrate.
In order to improve the carrying capacity of metal at carbon surface, described carbon dust need carry out preliminary treatment before use: use the acetone cyclic washing earlier, under agitation use 1～3molL then
-1Acid handle, be 20～30% H at last with mass concentration
2O
2Oxidation 1～5 hour.
(2) mix chloroplatinic acid or chloroplatinic acid back soluble in water with ruthenium trichloride, transfer PH to 8～10 with KOH solution, add above-mentioned gained catalyst precursor then, under agitation, make Pt or Pt and Ru be covered in the Pd alloy surface by displacement reaction in 80～200 ℃ of reactions 1～6 hour; 2～8h is left standstill in the cooling of reaction gains, and suction filtration is used the deionized water cyclic washing, and drying obtains high-performance low-platinum catalyst.
The consumption of described chloroplatinic acid or chloroplatinic acid and ruthenium trichloride is: the quality of theoretical platinum in reduction back or platinum ruthenium be catalyst the presoma quality 2%～30%.
When adopting the mixture of chloroplatinic acid and ruthenium trichloride, chloroplatinic acid is 1: 0.2～1: 5 with the ratio of the amount of substance of ruthenium trichloride.
The high-performance low-platinum catalyst of the present invention's preparation, Pt or Pt and Ru individual layer are covered in the also common appendix of Pd alloy surface above carbon dust; Pt or Pt and Ru account for 2～20% of catalyst gross mass; The Pd alloy that Pt or Pt and Ru modify accounts for 10～60% of catalyst gross mass.
Described Pd alloy is the alloy of Pd and Ni, Zn, Fe, Cu, Sn, Se, and the amount of substance ratio of Pd and Ni, Zn, Fe, Cu, Sn, Se is 1: 0.3～1: 3 in the Pd alloy.
Activity order according to metal, metals such as palladium in the palldium alloy in the presoma after the reduction can cement out platinum in chloroplatinic acid and the ruthenium trichloride and ruthenium, cause platinum and ruthenium to cover the surface of palldium alloy, and just be that metal platinum and the ruthenium that covers the surface works in the process of catalysis methanol, this preparation method has reduced the carrying capacity of noble metal significantly, and does not reduce catalytic performance.
Be example below with Pt-PdFe/C, to the structure of catalyst and the analyzing of performance of the present invention preparation:
1, TEM (transmission electron microscope) analysis: Fig. 1 (A) is the TEM figure of PdFe/C catalyst, and the TEM of Pt-PdFe/C schemes Fig. 1 (B) behind the Pt for the PdFe/C catalyst carries.As can be seen from Figure 1 the particle size distribution of catalyst is comparatively even; And particle size is greatly about about 5nm; And find that year particle diameter of the catalyst of platinum front and back does not have significant change, illustrate that the precious metals pt amount of area load is fewer, but the catalysis methanol test finds that noble metal has loaded on the alloy kernel.
2, XRD analysis: Fig. 2 is the XRD figure of Pd/C, PdFe/C, Pt-PdFe/C catalyst.By among the figure we as can be seen, at 40 °, 46.5 °, 67.8 °, 82 ° of (111) of representing the catalyst of face-centred cubic structure respectively, (200), (220) and (311) crystal face.Its (111) crystal face is carried out integration, according to Scherrer formula: B
2 θ=0.94 λ/rcos θ calculates, and can get their crystallite size: Pd/C is 3.1nm, and PdFe/C is 4.8nm, and Pt-PdFe/C is 4.9nm, and this is almost consistent with the result that TEM obtains.
3, cyclic voltammetric test: with the Pt-PdFe/C catalyst of the present invention's preparation at 0.5M CH
3OH/H
2SO
4Carried out the cyclic voltammetric test in the solution, confirmed the effect of the catalysis methanol oxidation that it is good, and contrasted with Johnson Matthey 40%Pt/C catalyst.Fig. 3 is that commercial catalysts Pt/C and Pt-PdFe/C are at 0.5M CH
3OH/H
2SO
4Cyclic voltammogram in the solution.As seen from Figure 3: the I of Pt-PdFe/C catalyst
f/ I
bBe 2.2, the Pt/C catalyst height (commercial Pt/C is 1.6) than commerce illustrates that it has better anti methanol toxication ability; The Pt/C catalyst of the commerce of the current density ratio that the unit mass metal produces good (Pt-PdFe/C is 0.172A, and commercial Pt/C is 0.169A) illustrates that it still has good catalytic effect under low platinum carrying capacity; And the starting voltage of finding its methanol oxidation has reduction, and than low about about 0.07 volt of commercial Pt/C catalyst, what illustrate that it compares that commercial Pt/C catalyst can make that oxidization of methanol becomes must be easier.
4, stability test: the stability to catalyst is investigated with the timing electric current, and the result as shown in Figure 4.As seen from Figure 4, at 0.5M CH
3OH/H
2SO
4In the solution, after the testing time was 1000s, Pt-PdFe/C catalyst of the present invention also had higher current density than commercial Pt/C catalyst, calculated by the identical platinum carrying capacity, approximately was four times of commercial Pt/C catalyst.
Experimental results demonstrate, the structure of other catalyst of the present invention's preparation is similar substantially with the Pt-PdFe/C catalyst to performance, all have good anti methanol toxication ability and good catalytic activity, so fully can be as the electrode catalyst of direct methanol fuel cell.
The present invention compared with prior art has the following advantages:
1, the present invention uses metals such as Ni, Zn, Fe, Cu, Sn, Se to prepare the Pd alloy, and then auxiliary covers the Pd alloy surface with a little P t or Pt and Ru, and the consumption of precious metals pt is reduced significantly, has effectively reduced the cost of catalyst.
2, the catalyst of the present invention's preparation is higher to the methanol oxidation electro catalytic activity, has good stable, and long service life, is the good high performance catalyst that is used for direct methanol fuel cell.
3, the present invention prepares the reaction condition gentleness of catalyst, and preparation technology is simple, easy control of reaction conditions, and use equipment is more commonly used, is suitable for commercialization and promotes.
Description of drawings
Fig. 1 carries the TEM figure of Pt (B) back Pt-PdFe/C for PdFe/C catalyst (A) and PdFe/C catalyst.
Fig. 2 is the XRD figure of the catalyst P dFe/C and the Pt-PdFe/C of commercial catalysts Pt/C and preparation.
Fig. 3 is that commercial catalysts Pt/C and Pt-PdFe/C are at 0.5M CH
3OH/H
2SO
4Cyclic voltammogram in the solution.
Fig. 4 is that commercial catalysts Pt/C and Pt-PdFe/C catalyst are at 0.5M CH
3OH/H
2SO
4Chronoamperogram in the solution.
Embodiment
Embodiment 1:Pt-PdFe/C Preparation of catalysts
Carbon dust is used the acetone cyclic washing earlier, under agitation use 1～3molL
-1Acid handle, be 20～30% H then with mass concentration
2O
2Oxidation 1～5 hour.
Palladium bichloride 33.3mg is joined in the 50ml round-bottomed flask, add 25ml ethylene glycol, add magneton and stir, ultrasonicly more than 0.5 hour it is dissolved fully, add 290.4mg iron chloride again, add the 742.4mg natrium citricum, be stirred to dissolving fully.PH value with 5%KOH/EG solution regulator solution is 8, adds sodium formate 375.4mg, adds carbon dust 120mg, stirs ultrasonic 0.5 hour 0.5 hour; Transfer to then in the autoclave, place baking oven, in 180 ° of following placing responses 8 hours; Gained colloidal sol suction filtration detects less than till the chloride ion to solution with three water washings, and 70 ℃ of dryings get the catalyst precursor.
The 3mg chloroplatinic acid is added round-bottomed flask, and add 20ml water, with the PH=8 of KOH aqueous solution accent solution, add the catalyst precursor 50mg of aforementioned preparation, stirred 20 minutes, ultrasonic 20 minutes, reaction 4h under 80 ℃ made its displacement fully; 2h is left standstill in cooling, and suction filtration use the deionized water cyclic washing, is dried to weight in 70 °, must the Pt-PdFe/C catalyst.
After measured, in the Pt-PdFe/C catalyst, Pt accounts for 2.6% of catalyst gross mass; Pd accounts for 15% of catalyst gross mass, and Fe accounts for 14% of catalyst gross mass.The I of Pt-PdFe/C catalyst
f/ I
bBe 2.0; The current density that the unit mass metal produces is 0.170A; The starting voltage of methanol oxidation reduces about 0.05 volt than commercial Pt/C; Behind the test 1000s, calculating by identical noble metal platinum carrying capacity, approximately is 3 times of commercial Pt/C catalyst.
Embodiment 2:Pt-PdZn/C Preparation of catalysts
Palladium bichloride 33.3mg is joined in the 50ml round-bottomed flask, add 25ml ethylene glycol, add magneton and stir, ultrasonicly more than 0.5 hour it is dissolved fully, add the 125.0mg zinc chloride again, add the 650.2mg natrium citricum, be stirred to dissolving fully.PH value with 5%KOH/EG solution regulator solution is 9, adds sodium formate 230.0mg, adds carbon dust 120mg, stirs ultrasonic 0.5 hour 0.5 hour; Transfer to then in the autoclave, place baking oven, reacted 8 hours down in 180 ℃, gained colloidal sol suction filtration detects less than till the chloride ion to solution with three water washings, in 70 ℃ of dried overnight, gets the catalyst precursor.
The 3mg chloroplatinic acid is added round-bottomed flask, and add 20ml water, with the PH=9 of KOH aqueous solution accent solution, add the catalyst precursor 50mg of aforementioned preparation, stirred 20 minutes, ultrasonic 20 minutes, reaction 4h under 80 ° made its displacement fully; 4h is left standstill in cooling, and suction filtration use the deionized water cyclic washing, is dried to weight in 70 °, must the Pt-PdZn/C catalyst.
After measured, in the Pt-PdZn/C catalyst, Pt accounts for 3.0% of catalyst gross mass; Pd accounts for 17% of catalyst gross mass, and Zn accounts for 12% of catalyst gross mass.The I of Pt-PdZn/C catalyst
f/ I
bBe 2.3; The current density that the unit mass metal produces is 0.174A; The starting voltage of methanol oxidation reduces about 0.08 volt than commercial Pt/C; Behind the test 1000s, calculating by identical noble metal platinum carrying capacity, approximately is 3.5 times of commercial Pt/C catalyst.
Embodiment 3:Pt-PdSn/C Preparation of catalysts
Palladium bichloride 66.7mg is joined in the 50ml round-bottomed flask, add 25ml ethylene glycol, add magneton and stir, ultrasonicly more than 0.5 hour it is dissolved fully, add the 70.1mg stannic chloride again and add the 419.3mg natrium citricum, be stirred to dissolving fully.PH value with 5%KOH/EG solution regulator solution is an alkali 9, adds sodium formate 148.3mg, adds carbon dust 120mg, stirs ultrasonic 0.5 hour 0.5 hour; Transfer in the autoclave, be placed in the baking oven, in 180 ℃ of following placing responses 8 hours.Gained colloidal sol suction filtration detects less than till the chloride ion to solution with three water washings, in 70 ° of ℃ of dried overnight, gets the catalyst precursor.
The 3mg chloroplatinic acid is added round-bottomed flask, and add 20ml water, with the PH=9 of KOH aqueous solution accent solution, add the catalyst precursor 50mg of aforementioned preparation, stirred 20 minutes, ultrasonic 20 minutes, reaction 4h under 80 ° made its displacement fully; 2h is left standstill in cooling, and suction filtration use the deionized water cyclic washing, is dried to weight in 70 °, must the Pt-PdSn/C catalyst.
After measured, in the Pt-PdSn/C catalyst, Pt accounts for 3.7% of catalyst gross mass; Pd accounts for 18% of catalyst gross mass, and Sn accounts for 10% of catalyst gross mass.The I of Pt-PdFe/C catalyst
f/ I
bBe 1.8; The current density that the unit mass metal produces is 0.154A; The starting voltage of methanol oxidation reduces about 0.02 volt than commercial Pt/C; Behind the test 1000s, calculating by identical noble metal platinum carrying capacity, approximately is 2.8 times of commercial Pt/C catalyst.
Embodiment 4:PtRu-PdCu/C Preparation of catalysts
Palladium bichloride 100.0mg is joined in the 50ml round-bottomed flask, add 25ml ethylene glycol, add magneton and stir, ultrasonicly more than 0.5 hour it is dissolved fully, add the 53.7mg copper chloride again, add the 516.7mg natrium citricum, be stirred to dissolving fully.PH value with 5%KOH/EG solution regulator solution is 10, adds sodium formate 182.8mg, adds carbon dust 120mg, stirs ultrasonic 0.5 hour 0.5 hour; Transfer in the autoclave, place baking oven, in 180 ℃ of placing responses 8 hours; Gained colloidal sol suction filtration detects less than till the chloride ion to solution with three water washings, in 70 ° of dried overnight, gets the catalyst precursor.
2mg chloroplatinic acid and 2mg ruthenic chloride are joined in the round-bottomed flask simultaneously, and add 20ml water, transfer the PH=10 of solution with the KOH aqueous solution, the catalyst precursor 50mg that adds aforementioned preparation stirred ultrasonic 20 minutes 20 minutes, reaction 4h under 80 ℃ makes its displacement fully; 4h is left standstill in cooling, and suction filtration use the deionized water cyclic washing, is dried to weight in 70 ℃, must the PtRu-PdCu/C catalyst.
After measured, in the PtRu-PdCu/C catalyst, Pt accounts for 1.4% of catalyst gross mass; Ru accounts for 1.2% of catalyst gross mass; Pd accounts for 16% of catalyst gross mass, and Ni accounts for 11% of catalyst gross mass.The I of PtRu-PdCu/C catalyst
f/ I
bBe 2.5; The current density that the unit mass metal produces is 0.176A; The starting voltage of methanol oxidation reduces about 0.09 volt than commercial Pt/C; Behind the test 1000s, calculating by identical noble metal platinum ruthenium carrying capacity, approximately is 4.3 times of commercial Pt/C catalyst.
Claims (5)
1. preparation method who is used for the high-performance low-platinum catalyst of methanol fuel cell, finished by following processing step:
(1) chloride of palladium salt and metal Ni, Zn, Fe, Cu, Sn or Se or the nitrate amount of substance with 1: 0.3～1: 3 is dissolved in the ethylene glycol, adds the natrium citricum of 2～2.5 times of the amounts of total metal ion species, ultrasonic it is dissolved fully; Regulate pH to 8～10 with the KOH/ ethylene glycol solution of mass concentration 5% again, add the sodium formate of 2～4 times of the amounts of total metal ion species, add the carbon dust of 4～8 times of the theoretical total metal qualities in reduction back, ultrasonic dispersion; Transfer to then in the autoclave, reacted 8～10 hours down,, obtain the presoma of catalyst with deionized water wash, drying in 140～200 ℃;
(2) mix chloroplatinic acid or chloroplatinic acid back soluble in water with ruthenium trichloride, transfer pH to 8～10 with KOH solution, add above-mentioned gained catalyst precursor then, under agitation, make Pt or Pt and Ru be covered in the Pd alloy surface by displacement reaction in 80～200 ℃ of reactions 1～6 hour; 2～8h is left standstill in the cooling of reaction gains, and suction filtration is used the deionized water cyclic washing, and drying obtains high-performance low-platinum catalyst;
The consumption of described chloroplatinic acid or chloroplatinic acid and ruthenium trichloride is: the quality of theoretical platinum in reduction back or platinum ruthenium be catalyst the presoma quality 2%～30%;
When adopting the mixture of chloroplatinic acid and ruthenium trichloride, chloroplatinic acid is 1: 0.2～1: 5 with the ratio of the amount of substance of ruthenium trichloride.
2. be used for the preparation method of the high-performance low-platinum catalyst of methanol fuel cell according to claim 1, it is characterized in that: the described palladium salt of step (1) is palladium bichloride or palladium nitrate.
3. be used for the preparation method of the high-performance low-platinum catalyst of methanol fuel cell according to claim 1, it is characterized in that: described carbon dust need carry out preliminary treatment before use: use the acetone cyclic washing earlier, under agitation use 1～3molL then
-1Acid handle, be 20～30% H at last with mass concentration
2O
2Oxidation 1～5 hour.
4. the high-performance low-platinum catalyst of method preparation according to claim 1, it is characterized in that: Pt or Pt, Ru are covered in the Pd alloy surface, and common appendix is above carbon dust.
5. the high-performance low-platinum catalyst of method preparation according to claim 1, it is characterized in that: the quality of Pt or Pt, Ru is 2～20% of a catalyst gross mass; The Pd alloy that Pt or Pt and Ru modify accounts for 10～60% of catalyst gross mass.
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| CN103041823B (en) * | 2012-12-07 | 2015-05-13 | 大连科诺催化有限公司 | Core-shell type ultralow palladium-platinum fuel-cell catalyst and preparation method |
| CN105327700A (en) * | 2015-11-18 | 2016-02-17 | 华南理工大学 | Method for preparing electrocatalysts through liquid-phase reduction of hydrogen at room temperature |
| CN105762378B (en) * | 2016-03-14 | 2018-03-30 | 北京工业大学 | A kind of synthetic method of support type ternary platinum alloy catalysts |
| CN107876065B (en) * | 2017-09-27 | 2020-02-07 | 昆明理工大学 | Method for preparing nano nickel-palladium-methanol catalyst by displacement deposition in eutectic ionic liquid |
| CN108346808B (en) * | 2018-03-09 | 2020-07-17 | 青岛大学 | Palladium-tin nano-chain net-shaped catalyst and preparation method and application thereof |
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| CN111628178B (en) * | 2020-05-22 | 2021-05-28 | 西安交通大学 | Carbon-supported palladium copper tantalum nitride nano electro-catalyst for direct methanol and formic acid fuel cell and preparation method thereof |
| CN113839056B (en) * | 2021-08-28 | 2024-04-09 | 西安交通大学 | Carbon-supported palladium niobium nitride nano electro-catalyst for direct methanol and formic acid fuel cell and preparation method thereof |
| CN113948729A (en) * | 2021-10-20 | 2022-01-18 | 江苏大学 | Preparation method of binary metal platinum-palladium prismatic catalyst and application of catalyst in direct methanol fuel cell |
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