CN109065893B - Composite electro-catalytic material and preparation method and application thereof - Google Patents
Composite electro-catalytic material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 68
- 238000002360 preparation method Methods 0.000 title claims abstract description 28
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 69
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims abstract description 68
- 239000006260 foam Substances 0.000 claims abstract description 66
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 46
- 238000005406 washing Methods 0.000 claims abstract description 32
- 239000008103 glucose Substances 0.000 claims abstract description 26
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims abstract description 25
- 238000009713 electroplating Methods 0.000 claims abstract description 21
- 239000000446 fuel Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 18
- 239000000243 solution Substances 0.000 claims abstract description 18
- 229910052763 palladium Inorganic materials 0.000 claims abstract description 16
- 229910052697 platinum Inorganic materials 0.000 claims abstract description 15
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 14
- 238000007747 plating Methods 0.000 claims abstract description 14
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 239000007864 aqueous solution Substances 0.000 claims abstract description 11
- 239000012876 carrier material Substances 0.000 claims abstract description 11
- 229910052751 metal Inorganic materials 0.000 claims abstract description 11
- 239000002184 metal Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 7
- 229910000000 metal hydroxide Inorganic materials 0.000 claims abstract description 6
- 150000004692 metal hydroxides Chemical class 0.000 claims abstract description 6
- 229910002056 binary alloy Inorganic materials 0.000 claims abstract description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 216
- 229910052759 nickel Inorganic materials 0.000 claims description 69
- 239000010949 copper Substances 0.000 claims description 36
- 229910052802 copper Inorganic materials 0.000 claims description 23
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 22
- 238000000034 method Methods 0.000 claims description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 7
- 229910002621 H2PtCl6 Inorganic materials 0.000 claims description 3
- 229910002666 PdCl2 Inorganic materials 0.000 claims description 3
- 229910052737 gold Inorganic materials 0.000 claims description 3
- 239000010931 gold Substances 0.000 claims description 3
- 229910052709 silver Inorganic materials 0.000 claims description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910017052 cobalt Inorganic materials 0.000 claims description 2
- 239000010941 cobalt Substances 0.000 claims description 2
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 2
- 150000001875 compounds Chemical class 0.000 claims description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 239000004332 silver Substances 0.000 claims description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 abstract description 20
- 230000000694 effects Effects 0.000 abstract description 15
- 229910052799 carbon Inorganic materials 0.000 abstract description 12
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 abstract description 11
- 238000007254 oxidation reaction Methods 0.000 abstract description 10
- 229910000510 noble metal Inorganic materials 0.000 abstract description 9
- 230000003647 oxidation Effects 0.000 abstract description 9
- 238000003763 carbonization Methods 0.000 abstract description 5
- 208000012868 Overgrowth Diseases 0.000 abstract description 4
- 229910045601 alloy Inorganic materials 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract description 4
- 239000010411 electrocatalyst Substances 0.000 description 30
- 239000003054 catalyst Substances 0.000 description 26
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 15
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 15
- 238000006243 chemical reaction Methods 0.000 description 14
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 9
- 238000011056 performance test Methods 0.000 description 8
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 239000011162 core material Substances 0.000 description 6
- 239000013067 intermediate product Substances 0.000 description 6
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 5
- 230000000977 initiatory effect Effects 0.000 description 5
- 230000001590 oxidative effect Effects 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 101150003085 Pdcl gene Proteins 0.000 description 4
- 238000000970 chrono-amperometry Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 3
- 230000005540 biological transmission Effects 0.000 description 3
- 238000010000 carbonizing Methods 0.000 description 3
- 230000018044 dehydration Effects 0.000 description 3
- 238000006297 dehydration reaction Methods 0.000 description 3
- 238000009826 distribution Methods 0.000 description 3
- 238000002474 experimental method Methods 0.000 description 3
- 238000005187 foaming Methods 0.000 description 3
- 238000011065 in-situ storage Methods 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 231100000572 poisoning Toxicity 0.000 description 3
- 230000000607 poisoning effect Effects 0.000 description 3
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- 239000000047 product Substances 0.000 description 3
- 230000002441 reversible effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- LKDRXBCSQODPBY-VRPWFDPXSA-N D-fructopyranose Chemical compound OCC1(O)OC[C@@H](O)[C@@H](O)[C@@H]1O LKDRXBCSQODPBY-VRPWFDPXSA-N 0.000 description 2
- 229910000863 Ferronickel Inorganic materials 0.000 description 2
- 238000001069 Raman spectroscopy Methods 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 238000005275 alloying Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
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- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- BFDHFSHZJLFAMC-UHFFFAOYSA-L nickel(ii) hydroxide Chemical compound [OH-].[OH-].[Ni+2] BFDHFSHZJLFAMC-UHFFFAOYSA-L 0.000 description 2
- 150000007524 organic acids Chemical group 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(I) nitrate Inorganic materials [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 2
- 238000006467 substitution reaction Methods 0.000 description 2
- JJLJMEJHUUYSSY-UHFFFAOYSA-L Copper hydroxide Chemical compound [OH-].[OH-].[Cu+2] JJLJMEJHUUYSSY-UHFFFAOYSA-L 0.000 description 1
- 239000005750 Copper hydroxide Substances 0.000 description 1
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- GZCGUPFRVQAUEE-SLPGGIOYSA-N aldehydo-D-glucose Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C=O GZCGUPFRVQAUEE-SLPGGIOYSA-N 0.000 description 1
- 229910003481 amorphous carbon Inorganic materials 0.000 description 1
- 238000003556 assay Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 229910001956 copper hydroxide Inorganic materials 0.000 description 1
- 239000011258 core-shell material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 229960004887 ferric hydroxide Drugs 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 239000006262 metallic foam Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 229910021508 nickel(II) hydroxide Inorganic materials 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
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- 229910052703 rhodium Inorganic materials 0.000 description 1
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000004626 scanning electron microscopy Methods 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 229910052718 tin Inorganic materials 0.000 description 1
- 238000004627 transmission electron microscopy Methods 0.000 description 1
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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
- H01M4/8647—Inert electrodes with catalytic activity, e.g. for fuel cells consisting of more than one material, e.g. consisting of composites
-
- 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
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M8/00—Fuel cells; Manufacture thereof
- H01M8/10—Fuel cells with solid electrolytes
- H01M8/1009—Fuel cells with solid electrolytes with one of the reactants being liquid, solid or liquid-charged
- H01M8/1011—Direct alcohol fuel cells [DAFC], e.g. direct methanol fuel cells [DMFC]
- H01M8/1013—Other direct alcohol fuel cells [DAFC]
-
- 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
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- Chemical & Material Sciences (AREA)
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- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Manufacturing & Machinery (AREA)
- Sustainable Development (AREA)
- Sustainable Energy (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of fuel cells, and discloses a composite electro-catalytic material, and a preparation method and application thereof. Adding foam metal into a glucose aqueous solution, carrying out hydrothermal reaction at 130-180 ℃, washing and drying a product to obtain a carrier material taking metal hydroxide as a core and a carbon material as a shell; and (2) placing the obtained carrier material in a palladium or platinum plating solution or a binary alloy plating solution containing palladium or platinum for electroplating, washing and drying under the conditions of room temperature and stirring to obtain the composite electro-catalytic material. According to the invention, the carbon-containing hydroxide is used as a carrier to load the noble metal or alloy composite electrocatalytic material, the glucose hydrothermal carbonization can inhibit the overgrowth of the hydroxide, the morphology of the hydroxide is controlled, and the conductivity of the hydroxide is improved, so that the performance of the composite electrocatalytic material is obviously improved, and the composite electrocatalytic material has high activity and good durability on ethanol electrocatalytic oxidation.
Description
Technical Field
The invention belongs to the technical field of fuel cells, and particularly relates to a composite electro-catalytic material, and a preparation method and application thereof.
Background
The fuel cell is a chemical device for directly converting chemical energy of fuel into electric energy, and the research and development of a high-efficiency and safe fuel cell technology has great significance for solving global problems of energy, environment and the like and realizing sustainable development. Compared with the traditional hydrogen fuel cell, the direct ethanol fuel cell has the technical advantages that: the ethanol fuel has high theoretical energy density (8.0kWh kg)-1) And the ethanol is low in price and can be prepared in batches by fermenting agricultural products. In addition, the ethanol is liquid at normal temperature and normal pressure, is convenient to store and transport, and has use compatibility on the existing liquid fuel (gasoline) transport/filling infrastructure. The research on anode electrocatalytic materials with high activity, high selectivity and good stability is the key for developing ethanol fuel cell technology.
Palladium (Pd) or platinum (Pt) has a good performance for the electrocatalytic oxidation of ethanol, but at a mild temperature, strong adsorption of a carbon-containing intermediate product generated by the ethanol oxidation reaction on the surface of the catalyst easily causes catalyst poisoning, so that the monometallic Pd or Pt is not an anode catalyst for the effective electrocatalytic oxidation of ethanol. In response to this problem, improvements have generally been made by both methods of catalyst alloying and the introduction of oxide or hydroxide supports. Precious metal (such as Au, Ag, Rh and the like) or non-precious metal (such as Ni, Co, Cu, Sn and the like) is introduced for alloying so as to modulate the electronic structure of Pd or Pt, thereby regulating the acting force of the surface of the catalyst and ethanol or an intermediate product thereof to improve the intrinsic activity and the reaction selectivity of the catalyst; and the oxide or hydroxide is introduced in order to construct a composite catalyst composed of Pd or Pt noble metals. The noble metal in the composite catalyst electrically catalyzes ethanol, and the oxide or hydroxide carrier is not only favorable for the dispersion and the prevention of agglomeration of the metal catalyst, but also can provide hydroxyl (-OH) to assist in further oxidizing and eliminating carbon-containing intermediate products which are adsorbed on the surface of the noble metal and cause catalyst poisoning. The two methods improve the performance of the single metal Pd or Pt for the electrocatalytic oxidation of ethanol, and particularly, the composite catalyst prepared by adopting an oxide or hydroxide carrier has excellent electrocatalytic performance. However, the oxide or hydroxide supports that typically provide hydroxyl groups have poor electrical conductivity, limiting further improvements in electrocatalyst performance.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a preparation method of a composite electro-catalytic material.
Another object of the present invention is to provide a composite electrocatalytic material prepared by the above method.
The invention further aims to provide application of the composite electro-catalytic material in an ethanol fuel cell.
A preparation method of a composite electro-catalytic material comprises the following preparation steps:
(1) adding foam metal into a glucose aqueous solution, carrying out hydrothermal reaction at 130-180 ℃, washing and drying a product to obtain a carrier material taking metal hydroxide as a core and a carbon material as a shell;
(2) and (2) placing the carrier material obtained in the step (1) in a palladium or platinum plating solution or a binary alloy plating solution containing palladium or platinum at room temperature under the stirring condition for electroplating, washing and drying to obtain the composite electro-catalytic material.
Preferably, the metal foam in step (1) is subjected to acid washing and alcohol washing before use.
Preferably, the foamed metal in step (1) is foamed nickel, foamed copper or foamed nickel-iron alloy.
Preferably, the concentration of the glucose aqueous solution in the step (1) is 0.02-0.08M.
Preferably, the hydrothermal reaction time in the step (1) is 12-24 h.
Preferably, the washing in the step (1) refers to washing with water and washing with alcohol, and the drying refers to drying at 40-80 ℃ for 4-8 h.
Preferably, the palladium or platinum plating solution in step (2) is palladium chloride (PdCl)2) Or chloroplatinic acid (H)2PtCl6) An aqueous solution of (a); the binary alloy plating solution containing palladium or platinum is PdCl2Or H2PtCl6And a compound of any one element of gold, silver, copper, nickel and cobalt.
Preferably, the conditions of the electroplating in the step (2) are as follows: the current density is 0.20-30 mA/cm2The electroplating time is 60-300 s.
A composite electrocatalytic material is prepared by the method.
The composite electrocatalytic material consists of noble metal or its alloy and carbon-containing hydroxide carrier.
The hydroxide in the carbon-containing hydroxide carrier is in a lamellar shape, the thickness of the hydroxide is 1-5 nm, and carbon has an amorphous structure or graphitized carbon.
The application of the composite electro-catalytic material in the ethanol fuel cell comprises the following steps: the composite electro-catalytic material is used as an anode in the ethanol fuel cell, under the catalytic action of the composite electro-catalytic material, ethanol is subjected to electro-catalytic oxidation to obtain acetic acid, four electrons are released and provided for a cathode, and oxygen adsorbed to the cathode is converted into water, so that chemical energy is converted into electric energy.
The preparation principle of the composite electro-catalytic material is as follows:
placing foam metal (such as nickel foam) in hydrothermal kettle containing glucose aqueous solution, electrochemically corroding the foam metal to generate metal hydroxide in situ on its surface [ Ni (OH)2]The reactions are shown in (1) to (3). Dehydrating and carbonizing glucose at a reaction temperature of 130-180 ℃ to form a carbon material, wherein the reaction can be represented by (4), and the formed carbon material is deposited on growing Ni (OH)2The produced carbonaceous material can inhibit Ni (OH)2The carbonaceous metal hydroxide has a core-shell structure in which the core is a hydroxide and the shell is a carbon material. In addition, in the process of dehydrating and carbonizing glucose, the intermediate product is organic acid which can inhibit the reaction (3) from going on and prevent the foam metal surface from generating Ni (OH) in situ2Overgrowth of (a). Then, the prepared carrier material is electroplated with noble metal or alloy, so as to prepare the supported composite electro-catalytic material.
Taking foamed nickel as an example, the chemical reaction generated in the preparation process is as follows:
Ni→Ni2++2e– (1)
1/2O2+H2O+2e–→2OH– (2)
Ni2++2OH–→Ni(OH)2 (3)
C6H12O6→H2O+C (4)
the preparation method and the obtained product have the following advantages and beneficial effects:
(1) according to the invention, the composite electrocatalytic material which takes the carbon-containing hydroxide as the carrier to load the noble metal or the alloy thereof is prepared, the hydroxide can assist the noble metal to oxidize and eliminate the carbon-containing intermediate product adsorbed on the surface of the noble metal to cause catalyst poisoning, the hydrothermal carbonization of glucose can inhibit the overgrowth of the hydroxide, the morphology of the hydroxide is controlled, and the conductivity of the hydroxide is improved, so that the performance of the composite electrocatalytic material is obviously improved.
(2) The composite electro-catalytic material disclosed by the invention is simple in preparation process and easy for large-scale production, and the prepared composite electro-catalyst has high activity and good durability on ethanol electro-catalytic oxidation.
Drawings
FIG. 1 shows Pd/Ni (OH) prepared in example 12Foam nickel and Pd/Ni (OH)2Comparison of morphology of @ C/foamed nickel composite electrocatalytic material and Pd/Ni (OH)2The distribution diagram of the constituent elements of the @ C/foamed nickel composite electrocatalytic material. (a, b) is Pd/Ni (OH)2Scanning and transmission electron microscopy of foamed nickel; (c, d) is Pd/Ni (OH)2@ C/foamed nickel scanning and transmission electron micrographs; (e-i) is Pd/Ni (OH)2The @ C/foamed nickel composite electro-catalytic material high-angle annular dark field-scanning transmission electron microscope image and the distribution diagram of Pd, Ni and C elements.
FIG. 2 shows Pd/Ni (OH) obtained in example 12Foam nickel and Pd/Ni (OH)2@ C/foam nickel electrocatalyst Raman Spectroscopy plot.
FIG. 3 shows Pd/nickel foam, Pd/Ni (OH) obtained in example 12Foam nickel and Pd/Ni (OH)2Comparison of the Performance of the @ C/foamed nickel electrocatalytic material for the oxidation of ethanol. (a) Three kinds of electrocatalyst cyclic voltammetry activity test charts have the scanning range of 0.12-1.16V and the scanning rate of 50mV s-1(ii) a (b) The activity of three electrocatalysts is tested by adopting cyclic voltammetry, the scanning range is 0.12-1.16V, and the scanning rate is 50mV s-1Circulating for 2000 times, and drawing a positive mass peak current density from each circulation to the circulation times; (c) the durability chart of three electrocatalysts is tested by adopting a chronoamperometry method, the initial potential is 0.70V vs. RHE (reversible hydrogen electrode), the scanning time is 5000s, and the scanning speed is 50mV s-1(ii) a All tests were carried out at room temperature, using a fuel solution of 1.0M C2H5OH+1.0M NaOH。
FIG. 4 shows Pt/Cu foam, Pt/Cu (OH) obtained in example 22Copper foam and Pt/Cu (OH)2Comparison of the performance of the @ C/copper foam electrocatalytic material for oxidizing ethanol. (a) The activity of three electrocatalysts is tested by adopting cyclic voltammetry, the scanning range is 0.12-1.16V, and the scanning rate is 50mV s-1Circulating for 2000 times, and drawing a positive mass peak current density from each circulation to the circulation times; (b) the durability chart of three electrocatalysts is tested by adopting a chronoamperometry method, the initial potential is 0.70V vs. RHE (reversible hydrogen electrode), the scanning time is 5000s, and the scanning speed is 50mV s-1(ii) a All tests were carried out at room temperature, using a fuel solution of 1.0M C2H5OH+1.0M NaOH。
FIG. 5 shows Pd-Ni/foam nickel iron, Pd-Ni/Ni (OH) obtained in example 32-Fe(OH)3Foam ferronickel and Pd-Ni/Ni (OH)2-Fe(OH)3Comparison of the performance of the @ C/foamed nickel ferroelectric catalytic material for oxidizing ethanol. The activity of three electrocatalysts is tested by adopting cyclic voltammetry, the scanning range is 0.12-1.16V, and the scanning rate is 50mV s-1The cycles were 2000 times, and the forward mass peak current density from each cycle was plotted against the number of cycles. All tests were carried out at room temperature, using a fuel solution of 1.0M C2H5OH+1.0M NaOH。
FIG. 6 shows Pd-Ag/nickel foam, Pd-Ag/Ni (OH) obtained in example 42Foam nickel and Pd-Ag/Ni (OH)2Comparison of the Performance of the @ C/foamed nickel electrocatalytic material for the oxidation of ethanol. The activity of three electrocatalysts is tested by adopting cyclic voltammetry, the scanning range is 0.12-1.16V, and the scanning rate is 50mV s-1The cycles were 2000 times, and the forward mass peak current density from each cycle was plotted against the number of cycles. All tests were carried out at room temperature, using a fuel solution of 1.0M C2H5OH+1.0M NaOH。
Detailed Description
The present invention will be described in further detail with reference to examples and drawings, but the present invention is not limited thereto.
Example 1
The composite electrocatalytic material Pd/Ni (OH) of the embodiment2@ C/foamed nickel, its preparation method is as follows:
(1) hydrothermal preparation of Ni (OH)2@ C/foamed nickel carrier
The foamed nickel (1X 1.45 cm) after the pretreatment of acid washing and alcohol washing is treated2) Placing in a container containing 0.06M grapeAnd (3) reacting for 24 hours at the reaction temperature of 140 ℃ in a sugar water solution hydrothermal kettle, naturally cooling to room temperature, washing the collected foamed nickel with water and alcohol, and drying for 6 hours at the temperature of 50 ℃ to obtain the carrier material taking nickel hydroxide as a core and carbon material as a shell.
(2) Pd carrier electroplating Pd preparation Pd/Ni (OH)2@ C/foamed nickel composite electrocatalytic material
Placing the carrier prepared in the step (1) in 8mM PdCl at room temperature under the condition of stirring2,0.5M H3BO31.0M NaCl plating solution at a current density of 0.25mA cm-2And under the condition, constant current electroplating is carried out for 100s, and the load type composite electro-catalytic material is obtained after washing and drying. The loading amount of Pd was determined by inductively coupled plasma atomic emission spectrometry (ICP-AES).
For performance comparison, Pd/nickel foam and Pd/Ni (OH) were prepared under similar conditions2Foam nickel electrocatalyst. The Pd/foamed nickel electrocatalyst means that Pd is directly electroplated on foamed nickel; Pd/Ni (OH)2The nickel foam electrocatalyst is prepared by carrying out hydrothermal reaction in a reaction kettle without glucose and filled with water, and firstly preparing Ni (OH)2Foaming nickel carrier, then electroplating Pd.
The supported composite electrocatalytic material of the embodiment is prepared in ethanol (C)2H5OH) fuel cell, the specific application process is as follows:
the performance test of the prepared composite electro-catalytic material for oxidizing ethanol is carried out in a three-electrode electrochemical device, and the prepared electrode material is a working electrode (1 multiplied by 1 cm)2) One piece of Pt (1.5X 1.5 cm)2) For the counter electrode, the HgO/Hg electrode was used as a reference electrode, and the potential used was compared to the Reversible Hydrogen Electrode (RHE). The activity of the electrocatalyst is tested by adopting cyclic voltammetry, the scanning range is 0.12-1.16V, and the scanning rate is 50mV s-1. The durability of the electrocatalyst was tested using cyclic voltammetry and chronoamperometry. The performance tests of the electrocatalyst are carried out at room temperature, and the fuel liquid is 1.0M C2H5OH+1.0M NaOH。
Pd/Ni (OH) obtained in this example2Foam nickel and Pd/Ni (OH)2Form and elements of @ C/foamed nickel composite electro-catalytic materialThe distribution was studied using a scanning electron microscope and a transmission electron microscope, as shown in FIG. 1. As can be seen from fig. 1(a, b): in the absence of glucose, a layer of hexagonal nanosheet layer Ni (OH) is grown in situ on the surface of the nickel foam through a hydrothermal reaction2A thickness of about 50 nm; ni (OH) grown on the surface of nickel foam by hydrothermal reaction in the presence of glucose2Is a wrinkled nanosheet layer having a thickness of about 3 nm. The obvious change of the morphology can be caused by the correlation of the carbon material formed by dehydration and carbonization of glucose under the hydrothermal condition, and the formed carbon material is deposited on Ni (OH)2In this way, the overgrowth of hydroxide can be suppressed. In addition, in the dehydration and carbonization process of glucose, the intermediate product is organic acid which can inhibit the progress of the reaction (3) and cause the electrochemical corrosion of the foam nickel to generate Ni (OH)2Growth is inhibited. From Pd/Ni (OH)2@ C/foamed nickel composite electrocatalytic material high-angle annular dark field-scanning transmission electron microscope picture (FIG. 1(e-i)]It can be seen that: pd nanoclusters uniformly distributed in Ni (OH)2In the above, the carbon (C) element formed by dehydrating and carbonizing glucose under hydrothermal conditions is also observed. The formation of carbon material by dehydration and carbonization of glucose in the presence of glucose in hydrothermal reaction was further confirmed by raman spectroscopy. As shown in FIG. 2, the Raman spectrum of the sample prepared in the presence of glucose was at about 1360cm, compared to the Raman spectrum of the sample prepared in the absence of glucose in the hydrothermal reaction-1And 1587cm-1Two peaks appear in the time, and the two peaks can be identified as characteristic peaks of a D band and a G band of amorphous carbon or graphitized carbon.
Pd/Ni (OH) prepared in this example2The performance of the @ C/foamed nickel composite electro-catalytic material for oxidizing ethanol is tested and compared with Pd/foamed nickel and Pd/Ni (OH)2Comparative was made with nickel foam electrocatalytic materials. As shown in fig. 3(a), all three catalysts are active for the electrocatalytic oxidation of ethanol, and it can be seen from the forward mass peak current density that: Pd/Ni (OH)2The @ C/foamed nickel composite electrocatalyst has the optimal electrocatalytic performance and the forward mass peak current density (1295mA mg)-1) Respectively Pd/nickel foam (187mA mg)-1) And Pd/Ni (OH)2Foamed Nickel (457mA mg-1) 7 times and 3 times of the electrocatalyst. In addition, adoptPd/Ni (OH) prepared by the invention2The @ C/foamed nickel composite electrocatalyst also has better durability. As shown in FIG. 3(b), Pd/nickel foam and Pd/Ni (OH) after 2000 cycles 22/3 and 1/2 where the nickel foam electrocatalyst has lost its initial activity; and Pd/Ni (OH)2The @ C/nickel foam composite electrocatalyst still maintains 89.6% of its initial activity. Amperometric assay by chronoamperometry further indicates Pd/Ni (OH)2The @ C/foamed nickel composite electrocatalyst has better durability. As shown in FIG. 3(c), after 5000s, the activity of all three catalysts was reduced, but Pd/Ni (OH)2The reduced amplitude of the @ C/foamed nickel composite electro-catalytic material is minimum, which indicates that the catalyst has better anti-poisoning capability. The performance of the electrocatalytic material is mainly determined by the intrinsic activity, the number of active sites and the conductive capacity of the electrocatalytic material, and the overgrowth of the metal hydroxide can be controlled by adopting the composite electrocatalytic material prepared by the invention, so that the electrocatalytic performance of the electrocatalytic material is favorably improved.
Example 2
The composite electrocatalytic material of this example, Pt/Cu (OH)2@ C/copper foam, its preparation method is as follows:
(1) hydrothermal preparation of Cu (OH)2@ C/foam copper carrier
The copper foam (1X 1.45 cm) after the pretreatment of acid washing and alcohol washing is treated2) Placing in a hydrothermal kettle containing 0.08M glucose aqueous solution, reacting at 160 ℃ for 18h, naturally cooling to room temperature, washing the collected foamy copper with water and alcohol, and drying at 80 ℃ for 4h to obtain a carrier material with copper hydroxide as a core and a carbon material as a shell;
(2) preparation of Pt/Cu (OH) by carrier electroplating of Pt2@ C/foam copper composite electro-catalytic material
Placing the carrier prepared in the step (1) in 6mM H at room temperature under stirring2PtCl6Plating solution at a current density of 15mA cm-2Under the condition, constant current electroplating is carried out for 180s, and the load type composite electro-catalytic material is obtained after washing and drying. The Pt loading was determined by ICP-AES.
For performance comparison, Pt/copper foam and Pt/Cu (OH) were prepared under similar conditions2FoamA copper electrocatalyst. The Pt/foam copper electrocatalyst refers to directly electroplating Pt on foam copper; Pt/Cu (OH)2The copper foam electrocatalyst is prepared by carrying out hydrothermal reaction in a reaction kettle without glucose and filled with water and firstly preparing Cu (OH)2Foam copper support, then electroplate Pt.
Taking Pt/Cu (OH) of this example2The performance test experiment of the catalyst was carried out for the @ C/copper foam composite electrocatalytic material (performed according to the performance test method and conditions in example 1), and the results are shown in FIG. 4. As can be seen from fig. 4: preparation of Pt/Cu (OH)2The activity and the durability of the @ C/copper foam composite electrocatalytic material are superior to those of Pt/copper foam and Pt/Cu (OH) prepared under similar conditions2Copper foam electrocatalyst. At room temperature, Pt/Cu (OH)2@ C/foamed copper composite electro-catalytic material initial peak current density of 982mA mg-1The catalyst can be used for 2000 times of circulation and 5000s, and the catalyst can still maintain 82% and 35% of the initial activity.
Example 3
The composite electrocatalytic material of this example is Pd-Ni/Ni (OH)2-Fe(OH)3@ C/foamed nickel iron, the preparation method is as follows:
(1) hydrothermal preparation of Ni (OH)2-Fe(OH)3@ C/foam ferronickel
The foamed nickel iron (1 multiplied by 1.45 cm) after the pretreatment of acid washing and alcohol washing is treated2) Placing in a hydrothermal kettle containing 0.05M glucose aqueous solution, reacting at the reaction temperature of 150 ℃ for 15h, naturally cooling to room temperature, washing the collected foam nickel iron with water and alcohol, and drying at the temperature of 60 ℃ for 5h to obtain a carrier material taking nickel hydroxide-ferric hydroxide as a core and a carbon material as a shell;
(2) preparation of Pd-Ni/Ni (OH) by electroplating Pd-Ni on carrier2-Fe(OH)3@ C/foam nickel-iron composite electro-catalytic material
Placing the carrier prepared in the step (1) in 6mM PdCl at room temperature under stirring2And 6mM NiCl2Plating solution at a current density of 10mA cm-2And under the condition, constant current electroplating is carried out for 120s, and the load type composite electro-catalytic material is obtained after washing and drying. The supported amount of Pd and the Pd-Ni component (Pd content about 55 atm%) were determined by ICP-AES.
For performance comparison, Pd-Ni/nickel-iron foam and Pd-Ni/Ni (OH) were prepared under similar conditions2-Fe(OH)3Foam nickel iron electrocatalyst. The Pd-Ni/foam nickel ferroelectric catalyst is obtained by directly electroplating Pd-Ni on foam nickel iron; Pd-Ni/Ni (OH)2-Fe(OH)3The foam nickel iron electrocatalyst is prepared by hydrothermal reaction in a reaction kettle without glucose and filled with water, wherein the hydrothermal reaction is carried out firstly in a reaction kettle with Ni (OH)2-Fe(OH)3Foaming nickel-iron carrier, then electroplating Pd-Ni.
Taking Pd-Ni/Ni (OH) of this example2-Fe(OH)3The performance test experiment of the catalyst (performed according to the performance test method and conditions in example 1) was carried out on @ C/foamed nickel-iron composite electro-catalytic material, and the results are shown in FIG. 5. As can be seen from fig. 5: preparation of Pd-Ni/Ni (OH)2-Fe(OH)3The activity and the durability of the @ C/foamed nickel-iron composite electrocatalytic material are superior to those of Pd-Ni/foamed nickel-iron and Pd-Ni/Ni (OH) prepared under similar conditions2-Fe(OH)3Foam nickel iron catalyst. At room temperature, Pd-Ni/Ni (OH)2-Fe(OH)3The initial peak current density of the @ C/foam nickel-iron composite electro-catalytic material is 3450mA mg-1The catalyst can still maintain 92% of the initial activity after 2000 times of recycling.
Example 4
The supported composite electrocatalytic material of the embodiment is Pd-Ag/Ni (OH)2@ C/foamed nickel, its preparation method is as follows:
(1) hydrothermal preparation of Ni (OH)2@ C/foamed nickel
The foamed nickel (1X 1.45 cm) after the pretreatment of acid washing and alcohol washing is treated2) Placing in a hydrothermal kettle containing 0.06M glucose aqueous solution, reacting at 140 ℃ for 12h, naturally cooling to room temperature, washing the collected foam nickel with water and alcohol, and drying at 50 ℃ for 6h to obtain the carrier material taking nickel hydroxide as a core and a carbon material as a shell.
(2) Preparation of Pd-Ag/Ni (OH) by electroplating Pd-Ag on carrier2@ C/foamed nickel composite electrocatalytic material
Placing the carrier prepared in the step (1) in 10mM PdCl at room temperature under stirring2And 10mM AgNO3Plating bath at a current density of 1.50mA cm-2Under the condition, constant current electroplating is carried out for 180s, and the load type composite electro-catalytic material is obtained after washing and drying. The loading amount of Pd and the Pd-Ag component (Pd content about 48 atm%) were determined by ICP-AES.
For performance comparison, Pd-Ag/nickel foam and Pd-Ag/Ni (OH) were prepared under similar conditions2Foam nickel electrocatalyst. The Pd-Ag/foam nickel ferroelectric catalyst means that Pd-Ag is directly electroplated on the foam nickel; Pd-Ag/Ni (OH)2The nickel foam electrocatalyst is prepared by carrying out hydrothermal reaction in a reaction kettle without glucose and filled with water, and firstly preparing Ni (OH)2Foaming nickel carrier, then electroplating Pd-Ag.
Taking the Pd-Ag/Ni (OH) of this example2The performance test experiment of the catalyst was carried out with @ C/foamed nickel composite electrocatalytic material (according to the performance test method and conditions in example 1), and the results are shown in FIG. 6. As can be seen from fig. 6: preparation of Pd-Ag/Ni (OH)2The activity and the durability of the @ C/foamed nickel composite electrocatalytic material are superior to those of Pd-Ag/foamed nickel and Pd-Ag/Ni (OH) prepared under similar conditions2Foam nickel catalyst. At room temperature, Pd-Ag/Ni (OH)2The initial peak current density of the @ C/foamed nickel composite electro-catalytic material is 4580mA mg-1The catalyst can be recycled for 2000 times, and the catalyst can still maintain 95% of the initial activity.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.
Claims (9)
1. The preparation method of the composite electro-catalytic material is characterized by comprising the following preparation steps:
(1) adding foam metal into a glucose aqueous solution, carrying out hydrothermal reaction at 130-180 ℃, washing and drying a product to obtain a carrier material taking metal hydroxide as a core and a carbon material as a shell;
(2) placing the carrier material obtained in the step (1) in a palladium or platinum plating solution or a binary alloy plating solution containing palladium or platinum at room temperature under stirring conditions for electroplating, washing and drying to obtain a composite electro-catalytic material;
the foam metal in the step (1) is foam nickel, foam copper or foam nickel-iron alloy.
2. The method of claim 1, wherein the composite electrocatalytic material is prepared by the steps of: the foam metal in the step (1) is subjected to pretreatment of acid washing and alcohol washing before use.
3. The method of claim 1, wherein the composite electrocatalytic material is prepared by the steps of: the concentration of the glucose aqueous solution in the step (1) is 0.02-0.08M.
4. The method of claim 1, wherein the composite electrocatalytic material is prepared by the steps of: the hydrothermal reaction time in the step (1) is 12-24 hours.
5. The method of claim 1, wherein the composite electrocatalytic material is prepared by the steps of: the washing in the step (1) refers to washing with water and washing with alcohol, and the drying refers to drying for 4-8 hours at 40-80 ℃.
6. The method of claim 1, wherein the composite electrocatalytic material is prepared by the steps of: the plating solution of palladium or platinum in the step (2) is PdCl2Or H2PtCl6An aqueous solution of (a); the binary alloy plating solution containing palladium or platinum is PdCl2Or H2PtCl6And a compound of any one element of gold, silver, copper, nickel and cobalt.
7. The method for preparing a composite electro-catalytic material as claimed in claim 1, wherein the electroplating in step (2) is constant current electroplating, provided that: current density of 0.20~30 mA/cm2The electroplating time is 60-300 s.
8. A composite electrocatalytic material, characterized by: prepared by the method of any one of claims 1 to 7.
9. Use of the composite electrocatalytic material of claim 8 in an ethanol fuel cell.
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