CN109065901B - Transition metal phosphide-noble metal phosphide composite fuel cell catalyst and preparation method and application thereof - Google Patents

Transition metal phosphide-noble metal phosphide composite fuel cell catalyst and preparation method and application thereof Download PDF

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CN109065901B
CN109065901B CN201810765270.XA CN201810765270A CN109065901B CN 109065901 B CN109065901 B CN 109065901B CN 201810765270 A CN201810765270 A CN 201810765270A CN 109065901 B CN109065901 B CN 109065901B
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transition metal
noble metal
oxide
metal phosphide
hydroxide
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CN109065901A (en
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冯立纲
王复龙
郁旭
方波
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Yangzhou University
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Yangzhou University
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/923—Compounds thereof with non-metallic elements
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M4/00—Electrodes
    • H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
    • H01M4/90—Selection of catalytic material
    • H01M4/92—Metals of platinum group
    • H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/50—Fuel cells

Abstract

The invention discloses a transition metal phosphide-noble metal phosphide composite fuel cell catalyst and a preparation method and application thereof. The method takes transition metal hydroxide or oxide and noble metal as raw materials, firstly deposits the noble metal on the transition metal hydroxide or oxide to prepare a complex, and then phosphorizes the complex at low temperature to obtain the transition metal phosphide-noble metal phosphide composite catalyst. The invention directly loads the noble metal on the transition metal hydroxide or oxide, and then carries out low-temperature phosphorization, thereby effectively improving the contact between the noble metal and the carrier, enhancing the interaction force between the noble metal and the carrier, improving the stability of the catalyst and reducing the cost of the catalyst. The composite fuel cell catalyst has wide application prospect in fuel cell anode alcohol fuel oxidation and cathode oxygen reduction.

Description

Transition metal phosphide-noble metal phosphide composite fuel cell catalyst and preparation method and application thereof
Technical Field
The invention belongs to the technical field of electrochemical fuel cells, and particularly relates to a transition metal phosphide-noble metal phosphide composite fuel cell catalyst, and a preparation method and application thereof.
Background
The direct alcohol fuel cell is a reaction device which directly adopts liquid (such as methanol, ethanol and other liquid) as fuel to convert chemical energy into electric energy, and has the advantages of high energy density, easy transportation and storage of the fuel, low operation temperature, environmental friendliness and the like, so the direct alcohol fuel cell has wide application prospect in the fields of portable electronic equipment, electric automobiles and the like, but some key technical problems are still solved before the large-scale commercial application of the direct alcohol fuel cell. One of the difficulties is electrode catalyst, and the catalyst used in the current direct alcohol fuel cell is mainly Pt/C or Pd/C catalyst. However, these catalysts have serious disadvantages such as poor stability and durability of the catalyst, high noble metal loading and low utilization rate, and also have problems of lowering the activity of the catalyst due to the poisoning phenomenon of the Pt or Pd catalyst which is easily generated during the use thereof, which seriously hinders the commercialization process. Therefore, researchers have conducted studies from various viewpoints of the composition, structure, and preparation method of the catalyst. For example, binary or multicomponent alloys of Pt or Pd and other metals are prepared, and more suitable catalyst supports such as carbides, borides and nitrides are sought to improve their activity, etc. The use of highly efficient catalyst promoters is considered to be the most effective measure among the numerous measures.
Chinese patents 201410669156.9 and 201410669128.7 disclose a method for synthesizing a noble metal-transition metal phosphide anode electrocatalyst, which greatly improves the activity of the catalyst, but the preparation of the catalyst by using carbon as a composite carrier to support noble metal nanoparticles can cause some serious problems, such as instability, particle migration, weak interaction and the like of the catalyst. Therefore, there is a need to develop a platinum-based catalyst having improved stability and activity.
Disclosure of Invention
The invention aims to provide a transition metal phosphide-noble metal phosphide composite fuel cell catalyst, and a preparation method and application thereof. According to the method, precious metal is deposited on transition metal hydroxide or oxide, and then low-temperature phosphorization is carried out to obtain the transition metal phosphide-precious metal phosphide composite fuel cell catalyst.
The technical scheme for realizing the purpose of the invention is as follows:
the preparation method of the transition metal phosphide-noble metal phosphide composite fuel cell catalyst comprises the following specific steps:
step 1, dispersing a transition metal hydroxide or oxide in ethylene glycol, stirring, performing ultrasonic dispersion uniformly to obtain a first suspension, adding chloropalladite or chloroplatinic acid under the stirring condition, adjusting the pH value to 10-12, and stirring and dispersing uniformly to obtain a second suspension;
step 2, performing microwave radiation on the second suspension, washing and vacuum drying to obtain a complex of the noble metal and the transition metal hydroxide or oxide;
and 3, mixing the complex of the noble metal and the transition metal hydroxide or oxide with sodium hypophosphite, and carrying out low-temperature phosphorization at the temperature of 300-400 ℃ under the protection of nitrogen to obtain the transition metal phosphide-noble metal phosphide composite fuel cell catalyst.
In step 1, the transition metal hydroxide or oxide is selected from nickel hydroxide, cobalt hydroxide, ferric hydroxide, cobalt oxide, ferroferric oxide or nickel oxide, and the like.
Preferably, in the step 1, the mass volume ratio of the transition metal hydroxide or oxide to the ethylene glycol is 20-200: 50-150 mg/mL.
Preferably, in the step 1, the stirring time is 20min to 40min, and the ultrasonic time is 10min to 30 min.
Preferably, in the step 1, the mass ratio of the transition metal hydroxide or oxide to the chloropalladate or chloroplatinic acid is 20-200: 5 to 40.
Preferably, in step 1, 1mol L is used-1The pH is adjusted with sodium hydroxide solution.
Preferably, in the step 2, the microwave radiation power is 600-900W.
Preferably, in step 2, in the microwave radiation process, the microwave radiation time is 60s to 120s each time, 30s is stopped in the middle, and the microwave radiation is performed for 3 times.
Preferably, in the step 2, the vacuum drying temperature is 60-80 ℃.
Preferably, in the step 3, the mass ratio of the noble metal-transition metal hydroxide or oxide to the sodium hypophosphite is 1: 5-1: 20.
Preferably, in the step 3, the low-temperature phosphating time is 1-3 h, and the heating rate is 3 ℃ for min-1。
The invention also provides the transition metal phosphide-noble metal phosphide composite fuel cell catalyst prepared by the preparation method.
Furthermore, the invention provides an application of the transition metal phosphide-noble metal phosphide composite fuel cell catalyst in preparation of a direct alcohol fuel cell.
Compared with the prior art, the invention has the following advantages:
(1) according to the invention, the noble metal is directly loaded on the transition metal hydroxide or oxide, and then low-temperature phosphorization is carried out, so that the contact between the noble metal and the carrier is effectively improved, the interaction force between the noble metal and the carrier is enhanced, the stability of the catalyst is improved, and the cost of the catalyst is reduced;
(2) the method has the advantages of simple and convenient operation, mild conditions and short cycle time, and can realize large-scale production.
Drawings
FIG. 1 shows a PtP obtained in example 12-Ni2XRD pattern of P catalyst.
FIG. 2 shows PtP obtained in example 12-Ni2Cyclic voltammogram of electrocatalytic oxidation of methanol by P catalyst.
FIG. 3 shows PtP obtained in example 12-Ni2Linear sweep voltammogram of P catalyst.
FIG. 4 shows PtP obtained in example 22TEM image of the CoP catalyst.
FIG. 5 shows a PtP obtained in example 12Cyclic voltammograms of the electrocatalytic oxidation of ethanol by a CoP catalyst.
Fig. 6 is an XRD pattern of the sample prepared in comparative example 1.
Fig. 7 is an XRD pattern of the sample prepared in comparative example 2.
FIG. 8 is a cyclic voltammogram of the electrocatalytic oxidation of methanol for the catalysts prepared in comparative example 2, comparative example 3 and example 1.
Detailed Description
The present invention will be described in more detail with reference to the following examples and the accompanying drawings.
Example 1: synthesis of PtP2-Ni2P
0.02mol of nickel chloride hexahydrate is weighed, dissolved in 10ml of ultrapure water, stirred for 20min at room temperature, 10ml of (6M) sodium hydroxide solution is added dropwise, stirring is continued for 30min, 0.6mmol of sodium sulfate is added into the solution, stirring is continued for 10min, then the solution is transferred to a 50ml high-pressure reaction kettle, and the temperature is kept for 24h at 170 ℃. Naturally cooling to room temperature, centrifugally washing with ultrapure water for multiple times to obtain a product, vacuum drying at 60 deg.C for 12h, wherein the product is Ni (OH)2。
Preparation of Pt-Ni (OH)2: deposition of Pt noble Metal to Ni (OH)2Weighing chloroplatinic acid by microwave-assisted alcohol-reduction methodContaining platinum 10mg) and 40mg of Ni (OH)2Uniformly dispersing in 50ml ethylene glycol, adjusting pH to 11 with 1M sodium hydroxide solution, heating in 700W microwave oven for 1min, suspending for 30s, repeating for three times, naturally cooling to room temperature, centrifuging with ultrapure water, washing for multiple times, vacuum drying at 60 deg.C for 12h to obtain Pt-Ni (OH)2。
Preparation of PtP2-Ni2P: weighing Pt-Ni (OH)2Reacting with sodium hypophosphite in the same porcelain boat at 300 ℃ under the protection of nitrogen for 2h, wherein the Pt-Ni (OH)2And sodium hypophosphite in a mass ratio of 1:5, with sodium hypophosphite placed upstream. Grinding the obtained product, washing with large amount of ultrapure water for multiple times, and vacuum drying at 60 deg.C for 12 hr to obtain PtP product2-Ni2P。
FIG. 1 shows PtP obtained in this example2-Ni2XRD pattern of P, from which PtP is clearly seen2And Ni2The diffraction peak of P corresponds to the JCPDS 03-1204 and JCPDS 03-0953 of the standard cards respectively, and the result shows that the obtained product is PtP2-Ni2P。
The electrochemical test is carried out under a three-electrode system, and a saturated calomel electrode and a platinum electrode are respectively a reference electrode and a counter electrode. 5mg of PtP obtained in this example were taken2-Ni2Dispersing the P catalyst into a mixed solution of 950 mu l of ethanol and 50 mu l of Nafion solution, carrying out ultrasonic treatment on the solution for 30min to obtain catalyst ink, taking 5 mu l of the catalyst ink, and dripping the catalyst ink on the surface of a glassy carbon electrode (the diameter is 0.3mm) to prepare a working electrode for electrocatalytic oxidation of methanol. FIG. 2 shows PtP obtained in this example2-Ni2The cyclic voltammogram of the P catalyst for the electrocatalytic oxidation of methanol can show that the prepared PtP2-Ni2The P catalyst has good catalytic performance and stability. In addition, PtP was also tested2-Ni2Catalytic performance of P catalyst for Oxygen Reduction Reaction (ORR), FIG. 3 is PtP2-Ni2Linear sweep voltammogram of P catalyst. The curve is obtained by using a three-electrode system with a rotary glassy carbon electrode as a working electrode and a reversible hydrogen electrode and a carbon rod as a reference electrode and a counter electrode respectively at the rotating speed of the rotary glassy carbon electrodeIs 1600 revolutions per minute and the electrolyte is 0.1mol L-1KOH solution of (5). PtP can be seen in FIG. 32-Ni2The P catalyst has good catalytic performance on ORR.
Example 2: synthesis of PtP2-CoP
The preparation and specific operation are the same as in example 1, wherein Ni (OH)2By changing to Co (OH)2While in the synthesis of Co (OH)2When the nickel chloride hexahydrate is replaced by cobalt chloride hexahydrate.
FIG. 4 shows PtP produced in this example2TEM image of CoP, from which PtP is evident2The nanoparticles were uniformly dispersed on the CoP. Electrochemical testing was performed in the same manner as in example 1, and PtP was shown in FIG. 52Cyclic voltammogram of CoP catalyst on electrocatalytic oxidation of ethanol, showing that the catalyst has catalytic properties on electrocatalytic oxidation of ethanol.
Comparative example 1
The preparation and specific operation are the same as in example 1, wherein Ni (OH)2And changed into Vulcan XC-72 carbon powder. XRD measurements of the resulting product are shown in FIG. 6, which shows the XRD pattern of the sample, indicating that the Pt/C sample retains well and is not capable of yielding noble metal phosphide after phosphating, indicating that noble metal phosphide synthesis requires the presence of transition metal hydroxides or oxides.
Comparative example 2
The preparation and the specific operation were the same as in example 1, except that the temperature of the phosphating solution was adjusted to 200 ℃. As shown in FIG. 7, the phosphating was carried out at 200 ℃ and the XRD pattern of the obtained product showed Pt-Ni (OH)2The sample was well retained, indicating that 200 ℃ did not yet enable sample recovery from Pt-Ni (OH)2Conversion to PtP2-Ni2P, indicating that the temperature at 200 ℃ is insufficient to react the sample with NaH2PO2And carrying out a phosphating reaction.
Comparative example 3
The preparation and the specific operation were the same as in example 1, except that the temperature for phosphating was adjusted to 500 ℃. FIG. 8 is a cyclic voltammogram of the electrocatalytic oxidation of methanol with the catalysts of comparative example 2, comparative example 3 and example 1, catalyzed at a phosphating temperature of 200 deg.CThe catalyst has the lowest catalytic performance, and the synthesized PtP has the highest phosphatizing temperature2-Ni2The performance of the P catalyst on the electrocatalytic oxidation of methanol is improved, but the catalytic performance of the catalyst is reduced when the phosphating temperature is continuously increased.

Claims (6)

1. The preparation method of the transition metal phosphide-noble metal phosphide composite fuel cell catalyst is characterized by comprising the following specific steps of:
step 1, dispersing transition metal hydroxide or oxide in ethylene glycol, stirring, performing ultrasonic dispersion uniformly to obtain a first suspension, adding chloropalladic acid or chloroplatinic acid under the stirring condition, adjusting the pH to 10-12, and stirring and dispersing uniformly to obtain a second suspension, wherein the transition metal hydroxide or oxide is selected from nickel hydroxide, cobalt hydroxide, ferric hydroxide, cobalt oxide, ferroferric oxide or nickel oxide, and the mass-to-volume ratio of the transition metal hydroxide or oxide to the ethylene glycol is 20-200: 50-150 mg: mL, wherein the mass ratio of the transition metal hydroxide or oxide to the chloropalladic acid or the chloroplatinic acid is 20-200: 5-40;
step 2, performing microwave radiation on the second suspension, washing, and performing vacuum drying to obtain a complex of the noble metal and the transition metal hydroxide or oxide, wherein the microwave radiation power is 600-900W, the microwave radiation time is 60-120 s each time, the operation is stopped for 30s in the middle, and the microwave radiation is performed for 3 times;
and 3, mixing the complex of the noble metal and the transition metal hydroxide or oxide with sodium hypophosphite, and carrying out low-temperature phosphorization at the temperature of 300-400 ℃ under the protection of nitrogen to obtain the transition metal phosphide-noble metal phosphide composite fuel cell catalyst.
2. The preparation method according to claim 1, wherein in the step 1, the stirring time is 20min to 40min, the ultrasonic time is 10min to 30min, and 1mol L is used-1The pH is adjusted with sodium hydroxide solution.
3. The method of claim 1, wherein the vacuum drying temperature in step 2 is 60 ℃ to 80 ℃.
4. The preparation method according to claim 1, wherein in the step 3, the mass ratio of the noble metal-transition metal hydroxide or oxide to the sodium hypophosphite is 1: 5-1: 20, the low-temperature phosphating time is 1-3 h, and the temperature rise rate is 3 ℃ min-1。
5. The transition metal phosphide-noble metal phosphide composite fuel cell catalyst prepared by the preparation method according to any one of claims 1 to 4.
6. Use of the transition metal phosphide-noble metal phosphide composite fuel cell catalyst according to claim 5 in the electrocatalytic oxidation of an alcohol fuel.
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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000003711A (en) * 1998-06-12 2000-01-07 Mitsubishi Heavy Ind Ltd Solid electrolyte fuel cell
CN101597089A (en) * 2008-06-06 2009-12-09 比亚迪股份有限公司 The preparation method of a kind of transition metal hydroxide and oxide compound thereof and positive electrode material
CN105720278A (en) * 2016-03-31 2016-06-29 华中科技大学 High-efficiency multi-element transition metal phosphide hydrogen-evolution catalyst and preparation method thereof
CN105958085A (en) * 2016-05-09 2016-09-21 北京化工大学常州先进材料研究院 Preparation method for metal-organic-framework-loaded platinum-based catalyst

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2000003711A (en) * 1998-06-12 2000-01-07 Mitsubishi Heavy Ind Ltd Solid electrolyte fuel cell
CN101597089A (en) * 2008-06-06 2009-12-09 比亚迪股份有限公司 The preparation method of a kind of transition metal hydroxide and oxide compound thereof and positive electrode material
CN105720278A (en) * 2016-03-31 2016-06-29 华中科技大学 High-efficiency multi-element transition metal phosphide hydrogen-evolution catalyst and preparation method thereof
CN105958085A (en) * 2016-05-09 2016-09-21 北京化工大学常州先进材料研究院 Preparation method for metal-organic-framework-loaded platinum-based catalyst

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