CN101306366A - Preparation method of carbon supported platinum modified type cerium oxide composite anode catalyst - Google Patents

Preparation method of carbon supported platinum modified type cerium oxide composite anode catalyst Download PDF

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CN101306366A
CN101306366A CNA2008100401497A CN200810040149A CN101306366A CN 101306366 A CN101306366 A CN 101306366A CN A2008100401497 A CNA2008100401497 A CN A2008100401497A CN 200810040149 A CN200810040149 A CN 200810040149A CN 101306366 A CN101306366 A CN 101306366A
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cerium oxide
preparation
composite anode
type cerium
supported platinum
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林茂财
余晴春
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Shanghai Jiaotong University
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    • Y02E60/50—Fuel cells

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Abstract

The invention discloses a preparation method of a carbon carrying platinum improved cerium oxide composite anode catalyst, and belongs to the fuel cell technology field. The invention firstly prepares doped cerium oxide powder Ce1-XMXO2, wherein M is transition metal or alkaline-earth metal, and then prepares an active carbon cerium oxide carrier, wherein the weight ratio of the doped cerium oxide powder to the active carbon powder is 1:0.756-3.626. Then glycol chloroplatinate solution is added under ultrasonic dispersion and nitrogen atmosphere protection, the temperature is raised for heat preservation, the ventilation is stopped after the solution is cooled to the room temperature, filtering and washing are carried out until the filtrate is detected not to contain chloride ions, and then the catalyst is obtained through vacuum drying. Through doping other metal ions in cerium oxide, the invention optimizes the crystal structure of the cerium oxide, thereby generating more oxygen defects in the cerium oxide crystal lattice, enhancing the electrocatalysis of the platinum metal and the phoronomics of the methanol, reducing the anodic polarization, and improving the methanol electrooxidation performance of the catalyst, and the current density of the methanol electrooxidation is high.

Description

The preparation method of carbon supported platinum modified type cerium oxide composite anode catalyst
Technical field
What the present invention relates to is Preparation of catalysts method in a kind of fuel cell technology field, specifically is a kind of preparation method of carbon supported platinum modified type cerium oxide composite anode catalyst.
Background technology
That DMFC has is simple in structure, energy density is high, start-up time is short, advantage such as reliable.Most critical be, fuel used to generate electricity-methyl alcohol that it is used, the source is abundant, low price, it is convenient to store, and adds easily, is suitable as portable removable power supply.At present, the direct methanol fuel anode catalyst adopts platinum based catalyst more.But, because methyl alcohol oxidation on the platinum surface can produce the intermediate product that is difficult for desorption at last, as CO AdsThereby the active sites that these intermediate products can occupy platinum reduces its performance, even makes catalysqt deactivation.Because of a little, the anti-anode catalyst of poisoning of exploitation remains the emphasis of research.At present, generally the method for Cai Yonging is to add catalyst aid in platinum based catalyst, forms the desorption that synergy promotes intermediate product with platinum, and co-catalyst commonly used comprises metal and various metal oxides etc.
Find that through literature search Chinese invention patent publication number CN101185891 discloses " porous carbon supported platinum-cerium oxide catalyst for fuel cell and preparation thereof " to prior art.This technology describes a kind of preparation method of porous carbon supported platinum-cerium oxide catalyst in detail.Porous carbon dust suspension is mixed with ceric ammonium nitrate solution, and behind the adding sodium hydroxide solution, after dipping, suction filtration, washing, the drying, 200-400 ℃ of heat treatment under the protection of nitrogen atmosphere obtains the porous carbon cerium oxide powder.At last, the porous carbon cerium oxide powder is mixed with the platinum acid chloride solution of 10-25mmol/L, ultrasonic, after the adjusting pH value, under the protection of nitrogen atmosphere, drip formaldehyde, ultrasonic, to filter, washing obtains catalyst after the drying.But this technology is not investigated the influence of crystalline ceric oxide body structure to catalyst, and used co-catalyst cerium oxide can also be optimized improvement.And preparation process is more loaded down with trivial details, with the formaldehyde reduction, certain toxicity is arranged.
Summary of the invention
The present invention is directed to the deficiencies in the prior art, a kind of preparation method of carbon supported platinum modified type cerium oxide composite anode catalyst is provided, promptly improved DMFC composite anode catalyst Pt-Ce 1-XM XO 2The preparation method of/C.Auxiliary agent in the catalyst is improved doping type cerium oxide powder Ce 1-XM XO 2, wherein M is transition metal or alkaline-earth metal.This doping type cerium oxide powder has the lattice structure of optimization, and the oxygen defect in the crystal increases, and has the promoting catalysis stronger than unadulterated cerium oxide.The catalyst of the present invention's preparation, methanol oxidation current ratio carbon commonly used carries platinum or carbon supported platinum-cerium oxide catalyst height, has improved the efficient of anode catalyst, and preparation process is fit to amplify and produces than simple.
The present invention is achieved by the following technical solutions:
The present invention includes following steps:
The first step is according to doping type cerium oxide powder Ce 1-XM XO 2In x=0.02-0.08, wherein x is a mol ratio, takes by weighing cerous nitrate, doped chemical nitrate or chlorate are dissolved in the deionized water, stir.Mol ratio according to total metal ion and citric acid is 1: (1-4), take by weighing citric acid be dissolved in dried up in, be 1 according to the mol ratio of citric acid and ethylene glycol: (2-4), add ethylene glycol, stir.Afterwards, two kinds of solution are mixed, esterification, solvent evaporated obtains yellow gel.The gel of yellow in air atmosphere, is obtained flaxen doping type cerium oxide powder Ce behind the constant temperature roast 1-XM XO 2, wherein M is transition metal or alkaline-earth metal.
Described stirring, its time is 1-2 hour.
Described esterification, its time is 2-4 hour.
Described constant temperature roast, its temperature are 500 ℃-700 ℃, and the time is 3-4 hour.
Described constant temperature roast, its temperature is warmed up to 500 ℃-700 ℃ with the 5-10 ℃/min rate of heat addition.
Second step, activated carbon powder is refluxed in hydrochloric acid and nitric acid respectively, filter washing, drying.
Described backflow, its time is 2-4 hour.
The described filtrate pH=7 that washs.
Described drying, its temperature are 70 ℃-90 ℃.
The 3rd step with after the activated carbon powder of the second step gained mixes, added deionized water with the doping type cerium oxide powder of first step gained, stirred, and filtration gets improved activated carbon cerium oxide carrier after the drying.Wherein the mass ratio of doping type cerium oxide powder and activated carbon powder is: 1: (0.756-3.626).
Described stirring, its time is 24-48 hour.
The 4th goes on foot, and takes by weighing activated carbon cerium oxide carrier ultrasonic dispersion in ethylene glycol of the 3rd step gained, then under nitrogen atmosphere protection; add the chloroplatinic acid ethylene glycol solution, regulate the pH value to 9-13, after the stirring with the NaOH ethylene glycol solution; be warming up to 120 ℃-160 ℃, insulation.After being cooled to room temperature, stop ventilation, filter, wash to filtrate and can not detect chlorion, vacuum drying gets catalyst then.
Described ultrasonic dispersion, its time is 20-80min.
Described chloroplatinic acid ethylene glycol solution, its platinum content are 3.7-11.1mg/ml.
Described NaOH ethylene glycol solution, its concentration are 1M.
Described insulation, its time is 3-6 hour.
Described stirring, its time is 2-4 hour.
Described vacuum drying is meant under 60 ℃-80 ℃ vacuum drying 10 hours.
Compared with prior art, catalyst of the present invention improves the co-catalyst in the DMFC anode catalyst.Other metal ion mixes in the co-catalyst cerium oxide, prepared doping type cerium oxide has better crystal structure, strengthened the electroxidation dynamics of platinum, strengthened the anti-poisoning capability of platinum, improved the performance of catalyst electro-catalysis methyl alcohol methyl alcohol.The current density ratio of prepared carbon supported platinum modified type cerium oxide composite anode catalyst electro-catalysis methyl alcohol carbon commonly used carries platinum and carbon carries the high 30%-150% of platinum oxidation cerium catalyst.Be applicable to DMFC, perhaps require the Proton Exchange Membrane Fuel Cells of anti-CO.
Description of drawings
Fig. 1 is the TEM collection of illustrative plates of the catalyst of embodiment 1 preparation;
Fig. 2 is the XRD figure spectrum of the catalyst of embodiment 1 preparation;
Fig. 3 is embodiment 1, and embodiment 2, the methanol electro-oxidizing cyclic voltammetry curve figure of the catalyst of embodiment 3 preparations.
The specific embodiment
Below in conjunction with accompanying drawing embodiments of the invention are elaborated: present embodiment is being to implement under the prerequisite with the technical solution of the present invention, provided detailed embodiment and concrete operating process, but protection scope of the present invention is not limited to following embodiment.
Embodiment 1:Pt-Ce 0.98Sr 0.02O 2The preparation of/C composite anode catalyst
The first step takes by weighing 4.256 gram cerous nitrates and 0.042 gram strontium nitrate, is dissolved in the deionized water, stirs 1 hour.Mol ratio according to total metal ion and citric acid is 1: 1, take by weighing citric acid be dissolved in dried up in, be 1: 2 according to the mol ratio of citric acid and ethylene glycol, add ethylene glycol, stir after 1 hour.Two kinds of solution are mixed, esterification 2 hours, solvent evaporated obtains yellow gel.The wet gel of yellow in air atmosphere, is heated up with the 5 ℃/min rate of heat addition, behind 500 ℃ of calcining at constant temperature 180min, obtain flaxen doping type cerium oxide powder Ce 0.98Sr 0.02O 2
Second step, activated carbon powder was refluxed 2 hours in hydrochloric acid and nitric acid respectively, filter, wash to filtrate pH=7,70 ℃ are dry down.
The 3rd step, according to cerium oxide powder and the mass ratio of activated carbon powder be mixes at 1: 3.570 after, adding deionized water and stirring 24 hours must carrier behind the filtration drying.
The 4th step; take by weighing the 88.8mg carrier; be scattered in the ethylene glycol solution, behind the ultrasonic 20min, move in the there-necked flask; under the protection of nitrogen atmosphere; adding platinum content is the chloroplatinic acid ethylene glycol solution of 3.7mg/ml, regulates pH value to 9 with the NaOH ethylene glycol solution of 1M, stirs after 2 hours; be warming up to 120 ℃, be incubated 3 hours.After being cooled to room temperature, stop ventilation, filter, wash to filtrate and can not detect chlorion, under 60 ℃, vacuum drying gets catalyst after 10 hours then.Wherein the carrying capacity of platinum is 20%.
The TEM test is observed on Japanese JEOL JEM-2010FX type transmission electron microscope, and accelerating potential 200kV amplifies 150,000 times.The Pt-Ce that makes 0.98Sr 0.02O 2The electric transmission electron microscope picture of/C catalyst is seen Fig. 1.As seen from Figure 1, platinum grain and cerium oxide particle are uniformly dispersed in activated carbon surface, and granular size is 2-4nm.
XRD test is being carried out on full-automatic x-ray powder diffraction instrument D/max2000 (Rigakua), and CuK alpha ray source is a radiation source, step-length 0.02, sweep speed be 4 (°)/min.The Pt-Ce that makes 0.98Sr 0.02O 2The XRD figure spectrum of/C catalyst is seen Fig. 2.In Fig. 2, the diffraction maximum about 28 °, 33 °, 48 °, 56 ° is corresponding CeO respectively 2(111), CeO 2(200), CeO 2(220), CeO 2The characteristic peak of cubic structure (311), and the unadulterated relatively CeO of each feature angle of diffraction 2Negative to some extent moving illustrates that the Sr ion doping advances CeO 2Lattice causes cell parameter to become big.Elsewhere, 39 °, the diffraction maximum that occurs about 46 ° and 68 ° is the characteristic peak of typical face-centered cubic (fcc) platinum crystal.
The methanol electro-oxidizing cyclic voltammetric method of catalyst is as follows: after the absolute ethyl alcohol of getting 5 milligrams of catalyst fineses and 50 microlitre mass content and be 5% Nafion solution and 1 milliliter mixes, ultrasonic 30 minutes catalyst slurry.The catalyst slurry of 5 microlitres is applied to makes working electrode on the glass-carbon electrode.In three-electrode system, be to electrode with the metal platinized platinum, saturated calomel electrode is a reference electrode, 0.5M H 2SO 4+ 1M CH 3OH is an electrolyte, carries out the test of cyclic voltammetric in-0.24V～1V voltage range.Prepared Pt-Ce 0.98Sr 0.02O 2The cyclic voltammetry curve of/C as shown in Figure 3, by with catalyst Pt-CeO 2/ C contrasts as can be known, and the methanol electro-oxidizing current ratio of improved catalyst is not improved high by 30%, and the performance of electroxidation methyl alcohol is higher.
Embodiment 2:Pt-Ce 0.95Sr 0.05O 2The preparation of/C composite anode catalyst
The first step takes by weighing 4.125 gram cerous nitrates and 0.106 gram strontium nitrate, is dissolved in the deionized water, stirs 2 hours.Mol ratio according to total metal ion and citric acid is 1: 2, take by weighing citric acid be dissolved in dried up in, be 1: 4 according to the mol ratio of citric acid and ethylene glycol, add ethylene glycol, stir after 2 hours.Two kinds of solution are mixed, esterification 4 hours, solvent evaporated obtains yellow gel.The wet gel of yellow in air atmosphere, is heated up with the 5 ℃/min rate of heat addition, behind 700 ℃ of calcining at constant temperature 240min, obtain flaxen doping type cerium oxide powder Ce 0.95Sr 0.05O 2
Second step, activated carbon powder was refluxed 2 hours in hydrochloric acid and nitric acid respectively, filter, wash filtrate pH=7,90 ℃ are dry down.
The 3rd step, according to cerium oxide powder and the mass ratio of activated carbon powder be mixes at 1: 3.626 after, adding deionized water and stirring 48 hours must carrier behind the filtration drying.
The 4th step; take by weighing the 88.8mg carrier; be scattered in the ethylene glycol solution, behind the ultrasonic 60min, move in the there-necked flask; under the protection of nitrogen atmosphere; adding platinum content is the chloroplatinic acid ethylene glycol solution of 7.4g/ml, regulates pH value to 10 with the NaOH ethylene glycol solution of 1M, stirs after 2 hours; be warming up to 140 ℃, be incubated 6 hours.After being cooled to room temperature, stop ventilation, filter, wash to filtrate and can not detect chlorion, under 80 ℃, vacuum drying gets catalyst after 10 hours then.Wherein the carrying capacity of platinum is 20%.
The methanol electro-oxidizing cyclic voltammetric method of catalyst is as follows: after the absolute ethyl alcohol of getting 5 milligrams of catalyst fineses and 50 microlitre mass content and be 5% Nafion solution and 1 milliliter mixes, ultrasonic 30 minutes catalyst slurry.The catalyst slurry of 5 microlitres is applied to makes working electrode on the glass-carbon electrode.In three-electrode system, be to electrode with the metal platinized platinum, saturated calomel electrode is a reference electrode, 0.5M H 2SO 4+ 1M CH 3OH is an electrolyte, carries out the test of cyclic voltammetric in-0.24V～1V voltage range.Prepared Pt-Ce 0.95Sr 0.05O 2The cyclic voltammetry curve of/C as shown in Figure 3, by with catalyst Pt-CeO 2/ C contrasts as can be known, and the methanol electro-oxidizing current ratio of improved catalyst is not improved high by 150%, and the performance of electroxidation methyl alcohol is higher.
Embodiment 3:Pt-Ce 0.92Sr 0.08O 2The preparation of/C composite anode catalyst
The first step takes by weighing 3.995 gram cerous nitrates and 0.169 gram strontium nitrate, is dissolved in the deionized water, stirs 2 hours.Mol ratio according to total metal ion and citric acid is 1: 4, take by weighing citric acid be dissolved in dried up in, be 1: 4 according to the mol ratio of citric acid and ethylene glycol, add ethylene glycol, stir after 2 hours.With two kinds of solution esterifications 4 hours, solvent evaporated obtained yellow gel.The wet gel of yellow in air atmosphere, is heated up with the 10 ℃/min rate of heat addition, behind 700 ℃ of calcining at constant temperature 180min, obtain flaxen doping type cerium oxide powder Ce 0.92Sr 0.08O 2
Second step, activated carbon powder was refluxed 4 hours in hydrochloric acid and nitric acid respectively, filter, wash filtrate pH=7,70 ℃ are dry down.
The 3rd step, according to cerium oxide powder and the mass ratio of activated carbon powder be mixes at 1: 3.570 after, adding deionized water and stirring 48 hours must carrier behind the filtration drying.
The 4th step; take by weighing the 88.8mg carrier; be scattered in the ethylene glycol solution, behind the ultrasonic 80min, move in the there-necked flask; under the protection of nitrogen atmosphere; adding platinum content is the chloroplatinic acid ethylene glycol solution of 11.1mg/ml, regulates pH value to 13 with the NaOH ethylene glycol solution of 1M, stirs after 4 hours; be warming up to 160 ℃, be incubated 6 hours.After being cooled to room temperature, stop ventilation, filter, wash to filtrate and can not detect chlorion, under 60 ℃, vacuum drying gets catalyst after 10 hours then.Wherein the carrying capacity of platinum is 20%.
The methanol electro-oxidizing cyclic voltammetric method of catalyst is as follows: after the absolute ethyl alcohol of getting 5 milligrams of catalyst fineses and 50 microlitre mass content and be 5% Nafion solution and 1 milliliter mixes, ultrasonic 30 minutes catalyst slurry.The catalyst slurry of 5 microlitres is applied to makes working electrode on the glass-carbon electrode.In three-electrode system, be to electrode with the metal platinized platinum, saturated calomel electrode is a reference electrode, 0.5M H 2SO 4+ 1M CH 3OH is an electrolyte, carries out the test of cyclic voltammetric in-0.24V～1V voltage range.Prepared Pt-Ce 0.92Sr 0.08O 2The cyclic voltammetry curve of/C as shown in Figure 3, by with catalyst Pt-CeO 2/ C contrasts as can be known, and the methanol electro-oxidizing current ratio of improved catalyst is not improved high by 60%, and the performance of electroxidation methyl alcohol is higher.

Claims (10)

1, a kind of preparation method of carbon supported platinum modified type cerium oxide composite anode catalyst may further comprise the steps:
The first step is according to doping type cerium oxide powder Ce 1-XM XO 2In x=0.02-0.08, wherein x is a mol ratio, take by weighing cerous nitrate, doped chemical nitrate or chlorate are dissolved in the deionized water, stir, mol ratio according to total metal ion and citric acid is 1: 1-4, take by weighing citric acid be dissolved in dried up in, be 1 according to the mol ratio of citric acid and ethylene glycol: 2-4, add ethylene glycol, stir; Afterwards, two kinds of solution are mixed, esterification, solvent evaporated obtains yellow gel, and the gel of yellow in air atmosphere, is obtained flaxen doping type cerium oxide powder Ce behind the constant temperature roast 1-XM XO 2, wherein M is transition metal or alkaline-earth metal;
Second step, activated carbon powder is refluxed in hydrochloric acid and nitric acid respectively, filter washing, drying;
The 3rd step, with the doping type cerium oxide powder of first step gained with after the activated carbon powder of the second step gained mixes, the adding deionized water, stir, filter, get improved activated carbon cerium oxide carrier after the drying, wherein the mass ratio of doping type cerium oxide powder and activated carbon powder is 1: 0.756-3.626;
The 4th goes on foot, and takes by weighing activated carbon cerium oxide carrier ultrasonic dispersion in ethylene glycol of the 3rd step gained, then under nitrogen atmosphere protection; add the chloroplatinic acid ethylene glycol solution; regulate the pH value to 9-13 with the NaOH ethylene glycol solution, after the stirring, be warming up to 120 ℃-160 ℃; insulation; after being cooled to room temperature, stop ventilation, filter; wash to filtrate and can not detect chlorion, vacuum drying gets catalyst then.
2, the preparation method of carbon supported platinum modified type cerium oxide composite anode catalyst according to claim 1 is characterized in that, in the first step, and described esterification, its time is 2-4 hour.
3, the preparation method of carbon supported platinum modified type cerium oxide composite anode catalyst according to claim 1 and 2 is characterized in that, in the first step, described constant temperature roast, its temperature is 500 ℃-700 ℃, and the time is 3-4 hour, is warmed up to 500 ℃-700 ℃ with 5 ℃/min-10 ℃/min rate of heat addition.
4, the preparation method of carbon supported platinum modified type cerium oxide composite anode catalyst according to claim 1 is characterized in that, in second step, and the described filtrate pH=7 that washs.
According to the preparation method of claim 1 or 4 described carbon supported platinum modified type cerium oxide composite anode catalysts, it is characterized in that 5, in second step, described drying, its temperature are 70 ℃-90 ℃.
6, the preparation method of carbon supported platinum modified type cerium oxide composite anode catalyst according to claim 1 is characterized in that, in the 4th step, and described ultrasonic dispersion, its time is 20min-80min.
According to the preparation method of claim 1 or 6 described carbon supported platinum modified type cerium oxide composite anode catalysts, it is characterized in that 7, in the 4th step, described chloroplatinic acid ethylene glycol solution, its platinum content are 3.7mg/ml-11.1mg/ml.
8, according to the preparation method of claim 1 or 6 described carbon supported platinum modified type cerium oxide composite anode catalysts, it is characterized in that, in the 4th step, described NaOH ethylene glycol solution, its concentration is 1M.
9, according to the preparation method of claim 1 or 6 described carbon supported platinum modified type cerium oxide composite anode catalysts, it is characterized in that, in the 4th step, described insulation, its time is 3-6 hour.
According to the preparation method of claim 1 or 6 described carbon supported platinum modified type cerium oxide composite anode catalysts, it is characterized in that 10, in the 4th step, described vacuum drying is meant under 60 ℃-80 ℃ vacuum drying 10 hours.
CNA2008100401497A 2008-07-03 2008-07-03 Preparation method of carbon supported platinum modified type cerium oxide composite anode catalyst Pending CN101306366A (en)

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Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103028401A (en) * 2012-12-13 2013-04-10 北京化工大学常州先进材料研究院 Direct methanol fuel cell anode catalyst and preparation method thereof
CN105080537A (en) * 2015-07-21 2015-11-25 中国科学院福建物质结构研究所 Non-precious metal catalyst for CO oxidative dehydrogenation and preparation method for non-precious metal catalyst
CN107999065A (en) * 2016-11-01 2018-05-08 中国石油化工股份有限公司 Butadiene synthesizes the catalyst of 1,4- diacetoxy butane processes
CN110783578A (en) * 2019-10-11 2020-02-11 成都新柯力化工科技有限公司 Pre-dispersion method of fuel cell catalyst slurry
CN112886032A (en) * 2021-02-18 2021-06-01 南京时拓能源科技有限公司 Preparation method of platinum-based catalyst taking heteroatom-doped metal oxide as carrier

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN103028401A (en) * 2012-12-13 2013-04-10 北京化工大学常州先进材料研究院 Direct methanol fuel cell anode catalyst and preparation method thereof
CN105080537A (en) * 2015-07-21 2015-11-25 中国科学院福建物质结构研究所 Non-precious metal catalyst for CO oxidative dehydrogenation and preparation method for non-precious metal catalyst
CN107999065A (en) * 2016-11-01 2018-05-08 中国石油化工股份有限公司 Butadiene synthesizes the catalyst of 1,4- diacetoxy butane processes
CN107999065B (en) * 2016-11-01 2019-12-10 中国石油化工股份有限公司 catalyst for synthesizing 1, 4-diacetoxybutane from butadiene
CN110783578A (en) * 2019-10-11 2020-02-11 成都新柯力化工科技有限公司 Pre-dispersion method of fuel cell catalyst slurry
CN112886032A (en) * 2021-02-18 2021-06-01 南京时拓能源科技有限公司 Preparation method of platinum-based catalyst taking heteroatom-doped metal oxide as carrier

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