CN1719647A - Carbon carried Pd/oxide composite electric catalyst and preparing process thereof - Google Patents

Carbon carried Pd/oxide composite electric catalyst and preparing process thereof Download PDF

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CN1719647A
CN1719647A CNA2005100346212A CN200510034621A CN1719647A CN 1719647 A CN1719647 A CN 1719647A CN A2005100346212 A CNA2005100346212 A CN A2005100346212A CN 200510034621 A CN200510034621 A CN 200510034621A CN 1719647 A CN1719647 A CN 1719647A
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carbon
oxide
palladium
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CN100353599C (en
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沈培康
徐常威
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Sun Yat Sen University
National Sun Yat Sen University
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    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

This invention relates to a carbon carried Pd/oxide compound electro catalyst and its preparation method, which adheres nm particles of Pd and an oxide on the powdered carbon surface to process the catalyst of carbon carried Pd/oxide compound, heats carbon and nitrate alternately to quickly process the oxide and reduces PdCl3 by NaBH4 to deposit Pd on the carbon carried oxide to get the catalyst.

Description

Carbon carries palladium/Pd/oxide composite electric catalyst and preparation method thereof
Technical field
The present invention relates to a kind of oxide that is used for direct alkaline alcohol types of fuel cells and strengthen non-platinum carbon and carry palladium/oxide catalyst and preparation method thereof, belong to field of energy source materials.
Background technology
Fuel cell is a kind of green energy resource technology.Significant to solving " energy shortage " and " environmental pollution " this two hang-up that the present world faces.Directly alcohol fuel battery not be because fuel need be directly used in generating through reformation, has advantages such as energy density height, low price, volume are little, in light weight, easy to carry, and application prospect is very extensive.
At present, being used for direct alcohol fuel battery (DAFC) anode electrocatalyst mainly is noble metal platinum and platinum alloy.Wherein, PtRu is the maximum catalyst of research, also is to use the most maturation resisting CO poison catalyst the most widely
Figure A20051003462100031
S.L., et al.Electrochim.Acta, 2003,48,3607], and realized commercialization.Platinum is directly being used the problem that still has in the alcohol fuel battery because it is rare, cost an arm and a leg and easily poisoned by carbon monoxide.Therefore, people pay attention to by platinum metal catalyst is modified, and to improve its catalytic activity, reach the purpose that reduces noble metal dosage in the catalyst, reduces the catalyst cost.Simultaneously, the research of exploitation non-platinum catalyst is also extensively carried out.One of them reasonable approach is to replace acidic electrolyte bath commonly used now with alkaline electrolyte.Acidic electrolyte bath has limited the catalyst use widely, has only corrosion resistant noble metal can supply to select the electro catalytic activity that the platinum performance is higher for use.Catalytic activity is very little in a lot of acid mediums, even does not have active metal (as palladium), and activity of such catalysts can significantly promote in alkaline medium, and selection of catalysts is not subjected to the restriction of noble metal yet.
Traditional liquid basified fuel cell (AFC) is easy to carbonating, and the carbonate deposition of formation is at catalyst surface, thereby lowers efficiency greatly and useful life, and industrialization is restricted.If our imagination in conjunction with the overall merit of AFC and DAFC, adopts the anionic electroconductive film to replace the liquid hydrogen oxide electrolyte, just can not produce problem such as carbonating.
Directly the used fuel of alcohol fuel battery mainly is methyl alcohol now, methyl alcohol has only a carbon atom, it is the simplest pure molecule, in direct alcohol fuel battery is most widely used alcohol, but methyl alcohol is toxic, be to the disagreeableness fuel of environment, want to realize that alcohol fuel battery is movably using in the field of power supplies such as mobile phone, notebook computer and electric motor car etc., other alcohol of necessary exploration or liquid fuel replace methyl alcohol.Wherein, what people were most interested in is ethanol, and it is the simplest chain alcohol molecule, wide material sources, and toxicity is less, is renewable, the environment-friendly type energy.Ethanol can corn, wheat, potato class etc. be raw material with fermentation method production, its raw materials for production are biogenic, are a kind of regenerative resources.The CO that the ethanol complete oxidation is discharged 2With the CO that biogenic growth consumed as raw material 2Quantity maintain an equal level in theory, this can reduce CO2 emission, makes contributions for reducing the whole world " greenhouse effect " gas.In the fuel that can replace methyl alcohol as direct alcohol fuel battery, polyhydroxy alcohols such as ethylene glycol, glycerine also are up-and-coming fuel.They have high boiling point, not volatile, and they are easy to electrochemical oxidation simultaneously.Replace methyl alcohol with the polyhydroxy alcohols, the theoretical current density of fuel cell is bigger.
The catalytic activity that we have attempted using oxide to improve platinum based catalyst is used for direct alkaline alcohol types of fuel cells [Xu and Shen, Chem Commun, 2004,2238], obtain reasonable result, the present invention proposes the anode catalyst that palladium-based catalyst that a kind of new oxide improves catalytic activity is used for direct alkaline alcohol types of fuel cells.Because Pd reserves on earth are Pt 50 times [Savadogo O, et al.Electrochem Commun, 2004,6,105], resource is abundanter.CO at the adsorption strength on the palladium electrode less than its adsorption strength [Ha S on platinum electrode, et al.Fuel Cells, 2004,4,337], so CO does not have the strong of platinum to poisoning of palladium, improves the electro catalytic activity to the alkanol molecule oxidation to a certain extent, thereby is expected to palladium is applied on the fuel cell.
Summary of the invention
The object of the present invention is to provide a kind of novel carbon to carry palladium/oxide composite anode Catalysts and its preparation method, this preparation method is easy, the catalyst that makes can be with methyl alcohol, ethanol, ethylene glycol, glycerine direct catalytic oxidation and chemical energy is converted into electric energy, cheap, excellent performance in alkaline environment.
It is that the nano particle of Metal Palladium and oxide forms equally distributed composite carbon attached to carbon dust surface and carries palladium/complex oxide that carbon of the present invention carries palladium/Pd/oxide composite electric catalyst, and oxide is CeO 2, NiO, Co 3O 4, Mn 3O 4In one or more mixture, the weight ratio of palladium/oxide is 0.5-6: 1.Wherein carbon dust can be activated carbon, graphite powder, carbon fiber, carbosphere.The reasonable weight ratio of the Metal Palladium/oxide in the catalyst is 1-3: 1.
The step of the inventive method is:
(1) prepare the carbon-supported metal oxide earlier, carbon carries oxide and obtains fast with one step of mixture that microwave alternately heats carbon and nitrate;
(2) carry oxide with the isopropanol water solution dispersed carbon, make suspension;
(3) dissolve PdCl with aqueous hydrochloric acid solution 3Add in the described suspension of step (2) ultrasonic agitation;
(4) at the ultrasonic reducing agent aqueous solution that slowly drips down, the sediment that obtains cleans with distilled water, the sediment that obtains after cleaning is dried in 80 ℃ of baking ovens obtain sample.
The preparation method that carbon of the present invention carries oxide is:
(1) a certain proportion of carbon black and metal nitrate are joined in the container, add an amount of solvent, under the ultrasonic wave effect, fully mix, be placed on 80 ℃ of dryings in the baking oven.After the drying above-mentioned sample carried out following microwave heating program: heated 20 seconds, and stopped carrying out repeatedly six times in 60 seconds, obtain corresponding carbon after the reaction system cooling and carry oxide.Solvent is an isopropanol water solution, and alcohol is 1: 20 with the ratio of water, is preferably 1: 8, is generally 1: 3.
(2) carbon that above-mentioned microwave method is prepared carries oxide and places a container beaker, adds an amount of isopropanol water solution, and ultrasonic agitation is disperseed, and splashes into PdCl 3Aqueous hydrochloric acid solution, at the ultrasonic slow down quantitative reducing agent aqueous solution that drips, the sediment that obtains cleans with distilled water, is 7 until the pH of the water that cleans again.The sediment that obtains after cleaning dried in 80 ℃ of baking ovens just can obtain corresponding carbon and carry Pd-oxide composite catalyst.The reducing agent aqueous solution is NaBH 4The aqueous solution.
The weight ratio that described carbon carries the palladium/oxide of palladium/metal oxide composite electrocatalyst is 0.5-6: 1, be preferably 1-3: and 1, be generally 1.5-2.5: 1.
Carbon of the present invention carries palladium/oxide composite catalyst performance evaluation with three-electrode system separately, carries out the cyclic voltammetric test on the IM6e electrochemical workstation of German ZAHNERelektrik company, and auxiliary electrode is 3.0cm 2Platinized platinum, reference electrode are Hg/HgO.
Catalyst of the present invention can be with methyl alcohol, ethanol, ethylene glycol, glycerine direct catalytic oxidation and chemical energy is converted into electric energy, cheap, the excellent performance of this catalyst in alkaline environment.Prove through electro-chemical test, shown advantages of high catalytic activity by eelctro-catalyst provided by the invention, be suitable as direct alkaline alcohols fuel cell anode catalyst, compare with the eelctro-catalyst that U.S. E-TEK company produces, the spike potential that rises of eelctro-catalyst oxidation alcohol provided by the invention moves 200mV than E-TEK eelctro-catalyst is negative, and peak current density can be up to four times of E-TEK eelctro-catalyst.On the performance that anti-pure oxidation intermediate poisons, catalyst provided by the invention has showed superior performance [Xu and Shen, J.Power Sources, 2005,142,27].
Description of drawings
Fig. 1 is the transmission electron microscope picture (TEM) of Pd-NiO/C catalyst.
Fig. 2 is 1.0mol dm -3Methyl alcohol is at 1.0mol dm -3In the KOH aqueous solution at E-TEK PtRu (2: 1)/C and Pd-Co 3O 4Cyclic voltammetry curve on (2: 1)/C electrode.
Fig. 3 is 1.0mol dm -3Ethanol is at 1.0mol dm -3Cyclic voltammetry curve in the KOH aqueous solution on E-TEK PtRu (2: 1)/C and Pd-NiO (3: 1)/C electrode.
Embodiment
Embodiment 1:
Get the 0.20g carbon black and place the 100ml beaker, add 15ml isopropanol water solution (isopropyl alcohol: water=1: 3), splash into the 0.1mol dm of 12.35ml again -3Co (NO 3) 2The aqueous solution, ultrasonic agitation 10 minutes is placed on 80 ℃ of dryings in the baking oven.After the drying above-mentioned sample carried out following microwave heating program: heated 20 seconds, and stopped carrying out repeatedly six times in 60 seconds, obtain sample after the reaction system cooling, X-ray diffraction confirms that sample is Co 3O 4/ C.
Above-mentioned microwave method prepares Co 3O 4/ C (wt 1: 2) composite material places the 100ml beaker, and (alcohol: water=1: 3), ultrasonic agitation 10 minutes splashes into the 0.1mol dm of 9.4ml then to add the 15ml isopropanol water solution -3PdCl 3Aqueous hydrochloric acid solution is again at the ultrasonic 1.0mol dm of slow Dropwise 5 ml down -3NaBH 4The aqueous solution, the sediment that obtains cleans with distilled water, is 7 until the pH of the water that cleans.The sediment that obtains after cleaning dry in 80 ℃ of baking ovens obtain sample, X-ray diffraction confirmation sample is Pd-Co 3O 4/ C.
Embodiment 2:
Get the 0.20g carbon black and place the 100ml beaker, add 15ml isopropanol water solution (isopropyl alcohol: water=1: 3), splash into the 0.1mol dm of 13.10ml again -3Mn (NO 3) 2The aqueous solution, ultrasonic agitation 10 minutes is placed on 80 ℃ of dryings in the baking oven.After the drying above-mentioned sample carried out following microwave heating program: heated 20 seconds, and stopped carrying out repeatedly six times in 60 seconds, obtain sample after the reaction system cooling, X-ray diffraction confirms that sample is Mn 3O 4/ C
The Mn of above-mentioned microwave method preparation 3O 4/ C (1: 2) composite material places the 100ml beaker, and (alcohol: water=1: 3), ultrasonic agitation 10 minutes splashes into the 0.1mol dm of 9.4ml then to add the 15ml isopropanol water solution -3PdCl 3Aqueous hydrochloric acid solution is again at the ultrasonic 1.0mol dm of slow Dropwise 5 ml down -3NaBH 4The aqueous solution, the sediment that obtains cleans with distilled water, is 7 until the pH of the water that cleans.The sediment that obtains after cleaning dry in 80 ℃ of baking ovens obtain sample, X-ray diffraction confirmation sample is Pd-Mn 3O 4/ C.
Embodiment 3:
Get the 0.20g carbon black and place the 100ml beaker, add 15ml isopropanol water solution (isopropyl alcohol: water=1: 3), splash into the 0.1mol dm of 4.35ml again -3Ni (NO 3) 2The aqueous solution, ultrasonic agitation 10 minutes is placed on 80 ℃ of dryings in the baking oven.After the drying above-mentioned sample carried out following microwave heating program: heated 20 seconds, and stopped carrying out repeatedly six times in 60 seconds, obtain sample after the reaction system cooling, X-ray diffraction confirms that sample is NiO/C, typical transmission electron microscope picture such as Fig. 1.
NiO/C (1: the 6) composite material of above-mentioned microwave method preparation is placed the 100ml beaker, and (alcohol: water=1: 3), ultrasonic agitation 10 minutes splashes into the 0.1mol dm of 9.4ml then to add the 15ml isopropanol water solution -3PdCl 3Aqueous hydrochloric acid solution is again at the ultrasonic 1.0mol dm of slow Dropwise 5 ml down -3NaBH 4The aqueous solution, the sediment that obtains cleans with distilled water, is 7 until the pH of the water that cleans.The sediment that obtains after cleaning dry in 80 ℃ of baking ovens obtain sample, X-ray diffraction confirmation sample is Pd-NiO/C.
Embodiment 4:
Get the 0.20g carbon black and place the 100ml beaker, add 15ml isopropanol water solution (isopropyl alcohol: water=1: 3), splash into the 0.1mol dm of 5.81ml again -3CeO 2(NO 3) 2The aqueous solution, ultrasonic agitation 10 minutes is placed on 80 ℃ of dryings in the baking oven.After the drying above-mentioned sample carried out following microwave heating program: heated 20 seconds, and stopped carrying out repeatedly six times in 60 seconds, obtain sample after the reaction system cooling, X-ray diffraction confirms that sample is CeO 2/ C.
The CeO of above-mentioned microwave method preparation 2/ C (1: 2) composite material places the 100ml beaker, and (alcohol: water=1: 3), ultrasonic agitation 10 minutes splashes into the 0.1mol dm of 9.4ml then to add the 15ml isopropanol water solution -3PdCl 3Aqueous hydrochloric acid solution is again at the ultrasonic 1.0mol dm of slow Dropwise 5 ml down -3NaBH 4The aqueous solution, the sediment that obtains cleans with distilled water, is 7 until the pH of the water that cleans.The sediment that obtains after cleaning dried in 80 ℃ of baking ovens obtain sample.X-ray diffraction confirms that sample is Pd-CeO 2/ C.
Embodiment 5
The catalyst P d-Co that embodiment 1 is made 3O 4It is 0.3mg cm that/C (2: 1) is prepared into carrying capacity -2The electrode of Pd is at 1.0mol dm -3KOH+1.0mol dm -3CH 3Carrying out electrocatalysis oxidation reaction in the OH solution, its spike potential, spike potential, peak current density is respectively-0.58V ,-0.14V, 65mA cm -2, but the spike potential of the PtRu/C catalyst of E-TEK company, spike potential, peak current density be respectively-0.58V ,-0.11V, 21mA cm -2(see figure 2).
Embodiment 6
It is 0.3mgcm that Pd-NiO (6: 1)/C Preparation of Catalyst that embodiment 3 is made becomes carrying capacity -2The electrode of Pd is at 1.0moldm -3KOH+1.0mol dm -3C 2H 5Carrying out electrocatalysis oxidation reaction in the OH solution, its spike potential, spike potential, peak current density is respectively-0.62V ,-0.08V, 95mA cm -2, but the spike potential of the PtRu/C catalyst of E-TEK company, spike potential, peak current density be respectively-0.44V ,-0.03V, 20mA cm -2Wherein the peak current density of Pd-NiO/C (6: 1) is more than 4 times of PtRu/C, plays spike potential also than the negative 200mV (see figure 3) of having moved of PtRu/C.

Claims (7)

1, a kind of carbon carries palladium/Pd/oxide composite electric catalyst, it is characterized in that this catalyst is that the nano particle of Metal Palladium and oxide forms equally distributed composite carbon attached to carbon dust surface and carries palladium/complex oxide, and oxide is CeO 2, NiO, Co 3O 4, Mn 3O 4In one or more mixture, the weight ratio of palladium/oxide is 0.5-6: 1.
2, carbon according to claim 1 carries palladium/Pd/oxide composite electric catalyst, it is characterized in that described carbon dust is activated carbon, graphite powder, carbon fiber or carbosphere.
3, carbon according to claim 1 carries palladium/Pd/oxide composite electric catalyst, and the weight ratio that it is characterized in that the Metal Palladium/oxide in the catalyst is 1-3: 1.
4, a kind of carbon carries the preparation method of palladium/Pd/oxide composite electric catalyst, it is characterized in that steps of the method are:
(1) prepare the carbon-supported metal oxide earlier, carbon carries oxide and obtains fast with one step of mixture that microwave alternately heats carbon and nitrate;
(2) carry oxide with the isopropanol water solution dispersed carbon, make suspension;
(3) dissolve PdCl with aqueous hydrochloric acid solution 3Add in the described suspension of step (2) ultrasonic agitation;
(4) at the ultrasonic reducing agent aqueous solution that slowly drips down, the sediment that obtains cleans with distilled water, the sediment that obtains after cleaning is dried in 80 ℃ of baking ovens obtain sample.
5, carbon according to claim 4 carries the preparation method of palladium/Pd/oxide composite electric catalyst, it is characterized in that in the described isopropanol water solution, and alcohol is 1: 20 with the weight ratio of water.
6, carbon according to claim 4 carries the preparation method of palladium/Pd/oxide composite electric catalyst, it is characterized in that in the described isopropanol water solution, and alcohol is 1: 8 with the weight ratio of water
7, carbon according to claim 4 carries the preparation method of palladium/Pd/oxide composite electric catalyst, it is characterized in that the described reducing agent aqueous solution is NaBH 4The aqueous solution.
CNB2005100346212A 2005-05-19 2005-05-19 Carbon carried Pd/oxide composite electric catalyst and preparing process thereof Expired - Fee Related CN100353599C (en)

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101269325B (en) * 2008-04-30 2011-06-22 复旦大学 Catalyst for direct methanoic acid fuel cell and method for producing the same
CN104001536A (en) * 2014-06-10 2014-08-27 西北师范大学 Method for preparing non-load palladium alloy electrocatalyst on gas-solution interface
CN104959142A (en) * 2015-05-25 2015-10-07 安徽海德石油化工有限公司 Catalyst for preparation of ethylene and propylene through naphtha cracking
CN108091891A (en) * 2016-11-22 2018-05-29 中国科学院大连化学物理研究所 Alkaline anion-exchange membrane fuel cell anodic nano-catalyst and preparation and application
CN109453790A (en) * 2018-09-17 2019-03-12 中山大学 A kind of nanosphere and preparation method thereof of the doped carbon encapsulation transient metal sulfide applied to electro-catalysis
CN115064716A (en) * 2022-06-29 2022-09-16 中国科学院过程工程研究所 Cerium oxide-palladium/carbon catalyst for formic acid electrooxidation and preparation method thereof

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* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA2064977C (en) * 1991-04-05 1998-09-22 Eiichi Shiraishi Catalyst for purifying exhaust gas
CN1583273A (en) * 2004-06-11 2005-02-23 中山大学 Preparing method for loaded metal oxide catalyst

Cited By (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101269325B (en) * 2008-04-30 2011-06-22 复旦大学 Catalyst for direct methanoic acid fuel cell and method for producing the same
CN104001536A (en) * 2014-06-10 2014-08-27 西北师范大学 Method for preparing non-load palladium alloy electrocatalyst on gas-solution interface
CN104959142A (en) * 2015-05-25 2015-10-07 安徽海德石油化工有限公司 Catalyst for preparation of ethylene and propylene through naphtha cracking
CN108091891A (en) * 2016-11-22 2018-05-29 中国科学院大连化学物理研究所 Alkaline anion-exchange membrane fuel cell anodic nano-catalyst and preparation and application
CN108091891B (en) * 2016-11-22 2020-11-03 中国科学院大连化学物理研究所 Anode nano catalyst of alkaline anion exchange membrane fuel cell and preparation and application thereof
CN109453790A (en) * 2018-09-17 2019-03-12 中山大学 A kind of nanosphere and preparation method thereof of the doped carbon encapsulation transient metal sulfide applied to electro-catalysis
CN115064716A (en) * 2022-06-29 2022-09-16 中国科学院过程工程研究所 Cerium oxide-palladium/carbon catalyst for formic acid electrooxidation and preparation method thereof

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