CN109950566A - A kind of high-performance oxygen reduction catalyst and its preparation method based on function of surface enhancing - Google Patents
A kind of high-performance oxygen reduction catalyst and its preparation method based on function of surface enhancing Download PDFInfo
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- CN109950566A CN109950566A CN201910299525.2A CN201910299525A CN109950566A CN 109950566 A CN109950566 A CN 109950566A CN 201910299525 A CN201910299525 A CN 201910299525A CN 109950566 A CN109950566 A CN 109950566A
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- catalyst
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- hcm
- oxygen
- platinum
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 239000001301 oxygen Substances 0.000 title claims abstract description 51
- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 230000009467 reduction Effects 0.000 title claims abstract description 13
- 230000002708 enhancing effect Effects 0.000 title claims abstract description 8
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 140
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 31
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 24
- 125000005842 heteroatom Chemical group 0.000 claims abstract description 21
- 239000011258 core-shell material Substances 0.000 claims abstract description 12
- 239000002245 particle Substances 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims description 27
- 229910052697 platinum Inorganic materials 0.000 claims description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 21
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 15
- 239000000243 solution Substances 0.000 claims description 15
- 239000007789 gas Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 13
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000008246 gaseous mixture Substances 0.000 claims description 12
- 238000010438 heat treatment Methods 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 229910052751 metal Chemical class 0.000 claims description 11
- 239000002184 metal Chemical class 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 239000007787 solid Substances 0.000 claims description 10
- 239000002904 solvent Substances 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 10
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 9
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- 238000003756 stirring Methods 0.000 claims description 9
- PAYRUJLWNCNPSJ-UHFFFAOYSA-N Aniline Chemical compound NC1=CC=CC=C1 PAYRUJLWNCNPSJ-UHFFFAOYSA-N 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 229910052786 argon Inorganic materials 0.000 claims description 8
- 238000001914 filtration Methods 0.000 claims description 8
- 150000003057 platinum Chemical class 0.000 claims description 8
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 7
- 239000011268 mixed slurry Substances 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 7
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 6
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 150000002431 hydrogen Chemical class 0.000 claims description 6
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 claims description 6
- 238000002156 mixing Methods 0.000 claims description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 6
- 239000005416 organic matter Substances 0.000 claims description 6
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 6
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 5
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 5
- 229910017604 nitric acid Inorganic materials 0.000 claims description 5
- VYFYYTLLBUKUHU-UHFFFAOYSA-N dopamine Chemical compound NCCC1=CC=C(O)C(O)=C1 VYFYYTLLBUKUHU-UHFFFAOYSA-N 0.000 claims description 4
- 238000000227 grinding Methods 0.000 claims description 4
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 4
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims description 3
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 3
- YNPNZTXNASCQKK-UHFFFAOYSA-N Phenanthrene Natural products C1=CC=C2C3=CC=CC=C3C=CC2=C1 YNPNZTXNASCQKK-UHFFFAOYSA-N 0.000 claims description 3
- DGEZNRSVGBDHLK-UHFFFAOYSA-N [1,10]phenanthroline Chemical compound C1=CN=C2C3=NC=CC=C3C=CC2=C1 DGEZNRSVGBDHLK-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
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- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- MPMSMUBQXQALQI-UHFFFAOYSA-N cobalt phthalocyanine Chemical compound [Co+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 MPMSMUBQXQALQI-UHFFFAOYSA-N 0.000 claims description 3
- MGNCLNQXLYJVJD-UHFFFAOYSA-N cyanuric chloride Chemical compound ClC1=NC(Cl)=NC(Cl)=N1 MGNCLNQXLYJVJD-UHFFFAOYSA-N 0.000 claims description 3
- KTWOOEGAPBSYNW-UHFFFAOYSA-N ferrocene Chemical compound [Fe+2].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 KTWOOEGAPBSYNW-UHFFFAOYSA-N 0.000 claims description 3
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 3
- 239000011261 inert gas Substances 0.000 claims description 3
- 229910052742 iron Inorganic materials 0.000 claims description 3
- FBAFATDZDUQKNH-UHFFFAOYSA-M iron chloride Chemical compound [Cl-].[Fe] FBAFATDZDUQKNH-UHFFFAOYSA-M 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 239000003273 ketjen black Substances 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 3
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims description 3
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims description 3
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 claims description 3
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims description 2
- -1 acyl acetone platinum Chemical compound 0.000 claims description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 239000006185 dispersion Substances 0.000 claims description 2
- 229960003638 dopamine Drugs 0.000 claims description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical class C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 2
- SVMCDCBHSKARBQ-UHFFFAOYSA-N acetic acid;cobalt Chemical compound [Co].CC(O)=O SVMCDCBHSKARBQ-UHFFFAOYSA-N 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
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- 239000012495 reaction gas Substances 0.000 abstract description 3
- 238000003795 desorption Methods 0.000 abstract description 2
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 25
- 239000000446 fuel Substances 0.000 description 12
- 238000000034 method Methods 0.000 description 10
- 239000000543 intermediate Substances 0.000 description 9
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 8
- 238000010586 diagram Methods 0.000 description 8
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000012360 testing method Methods 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- 238000009826 distribution Methods 0.000 description 5
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 5
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- 230000005540 biological transmission Effects 0.000 description 4
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- 238000011068 loading method Methods 0.000 description 4
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 4
- 206010013786 Dry skin Diseases 0.000 description 3
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
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- 240000000146 Agaricus augustus Species 0.000 description 2
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 2
- 241000282320 Panthera leo Species 0.000 description 2
- 229910002844 PtNi Inorganic materials 0.000 description 2
- QYSYEILYXGRUOM-UHFFFAOYSA-N [Cl].[Pt] Chemical compound [Cl].[Pt] QYSYEILYXGRUOM-UHFFFAOYSA-N 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
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- 125000001309 chloro group Chemical group Cl* 0.000 description 2
- 229940011182 cobalt acetate Drugs 0.000 description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 description 2
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- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OEBXWWBYZJNKRK-UHFFFAOYSA-N 1-methyl-2,3,4,6,7,8-hexahydropyrimido[1,2-a]pyrimidine Chemical compound C1CCN=C2N(C)CCCN21 OEBXWWBYZJNKRK-UHFFFAOYSA-N 0.000 description 1
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- 229910017052 cobalt Inorganic materials 0.000 description 1
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Classifications
-
- 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
Landscapes
- Catalysts (AREA)
Abstract
The invention discloses a kind of high-performance oxygen reduction catalysts based on function of surface enhancing, and provide the preparation method of above-mentioned catalyst.Catalyst is the HCM/Pt/C catalyst with core-shell structure, and wherein shell material is a kind of porous Heteroatom doping carbon material, is coated on the activated centre Pt surface.Since this Heteroatom doping carbon material has a kind of special absorption-enrichment effect to oxygen, it can provide a kind of oxygen-enriched environment for active site, the collision frequency of raising reaction gas oxygen and active site, significantly the kinetic reaction rate of raising oxygen reduction reaction.The electronic effect in the interface HCM/Pt can optimize the electronic structure of Pt simultaneously, so that Pt is died down the absorption of oxygen reduction reaction intermediate product, improve its desorption rate, provide site for subsequent Oxygen Adsorption.On the other hand, the carbon shell of Pt particle periphery can prevent its migration, reunite, and substantially increase the overall stability of catalyst.
Description
Technical field
The invention belongs to electrochemical field, in particular to a kind of high-performance oxygen reduction catalyst based on function of surface enhancing
And preparation method thereof.
Background technique
The severe challenge and environmental degradation increasingly exhausted in face of fossil fuel resource is huge to health of people life bring
Pressure, society are higher and higher to the cry of Looking For Substitutions Of Oil.Fuel cell is one kind with high energy such as reproducible hydrogen, alcohols
Substance is fuel, directly converts the chemical energy in fuel to the energy conversion device of electric energy, has energy conversion efficiency height, row
It lowers, pollute the advantages that small.Based on these advantages, fuel cell is in electrical source of power, backup power source and small-sized fixed power supply system
The fields such as system are with a wide range of applications, and are expected to solve the energy got worse that the whole world faces in the following help and environment is asked
Topic.Currently, cost, activity, stability and the mithridatism of fuel battery negative pole side oxygen reduction reaction catalyst are the productions for restricting it
The principal element of industry, is mainly shown as:
1. fuel battery negative pole side oxygen reduction reaction is a kind of heterogeneous reaction of complexity, it is related to a series of suction/be desorbed
Journey and polyelectron reaction, cause its kinetic reaction slowly and biggish overpotential, seriously reduce the efficiency of battery.
2.Pt base catalyst is the widely applied catalyst of current fuel cell, has higher catalysis to live oxygen reduction reaction
Property.However, Pt resource is limited, expensive, keep catalyst cost high；In addition, the activity of existing Pt base catalyst is also
The requirement of commercial applications cannot be fully met.
3. Pt is more soluble under the conditions of the strong corrosive of fuel cell operation, high oxidative；Meanwhile carbon carrier also holds
It is easily corroded, causes the migration of Pt particle, reunites and fall off, reduce the stability of catalyst.
4. the methanol of anode of fuel cell side can penetrate into cathode by proton exchange membrane, in Pt catalyst surface methanol oxygen
The intermediate CO for changing reaction can be adsorbed on by force the surface Pt, occupy the active site of Pt, and it is living to the catalysis of oxygen reduction reaction to reduce it
Property.
Therefore, it is electric to fuel come latent active, stability and the mithridatism for improving platinum catalyst to design a kind of resulting structure
The industrialized development in pond is of great significance.
Recent domestic has been done largely for activity, stability and the mithridatism of the reaction of platinum base agent catalytic oxidation-reduction
Research: " Ultrafine jagged platinum nanowires enable ultrahigh mass activity for
The oxygen reduction reaction " PtNi nano wire oxygen reduction catalyst is reported, wherein the electrons of Ni exist
The interface Ni/Pt adjusts the electronic structure of Pt to Pt transfer, to weaken its absorption to reaction intermediate；Due to Ni and Pt
Geometric size difference, lattice mismatch existing for the interface Ni/Pt can shorten Pt-Pt atomic distance, change in the d band energy level of Pt
The heart weakens the absorption to reaction intermediate.Meanwhile laciniation is as much as possible exposes Pt, provides work for reaction
Property site.But the precipitation of Ni is a big drawback of the catalyst under the conditions of strong corrosive, high oxidative.For resolved vector corruption
Erosion and catalyst cost problem, Liao et al. is using the method for pulsed deposition on the surface corrosion resistance stronger material TiNiN
One layer of platinum is plated, this method substantially increases the utilization rate of Pt on the basis of low Pt carrying capacity, with " Transition Metal
Nitride Coated with Atomic Layers of Pt as a Low-Cost,Highly Stable
Electrocatalyst for the Oxygen Reduction Reaction " it is that topic is delivered.But since TiNiN is poor
Electric conductivity greatly limits the catalytic activity of the catalyst, while interaction weaker between carrier and Pt also could not be from root
The dissolution of Pt is solved the problems, such as in sheet, migration, is reunited and is fallen off.Other than in addition to constructing function carrier and changing catalyst composition, name
Referred to as " Oxygen reduction in nanoporous metal-ionic liquid composite
Electrocatalysts " document report coat one layer of ionic liquid [MTBD] [beti] in PtNi particle surface, due to
Reaction gas oxygen is higher in solubility wherein, which improves the collision frequency of oxygen Yu Pt reaction site.But
Oxygen lower migration rate in the ionic liquid greatly limits the performance of catalyst, while the loss of ionic liquid is also
Urgent problem to be solved.In terms of mithridatism, entitled " Ultrathin Carbon-Coated Pt/Carbon
Nanotubes:A Highly Durable Electrocatalyst for Oxygen Reduction " document report
One layer of carbon shell is coated to prevent methanol from contacting with Pt active site in Pt nanoparticle surface, but the carbon shell is to a certain extent
Diffusion of the oxygen to active site is prevented, so that its oxygen reduction activity substantially reduces.
Summary of the invention
The purpose of the present invention is to solve existing oxygen reduction reaction poor catalyst activities, and because of the migration of Pt, reuniting causes
Stability bad and poor mithridatism the problem of, a kind of high activity based on mesoscopic structure, high stability, height are provided
The fuel-cell catalyst of mithridatism, and the preparation method of above-mentioned catalyst is provided.
To achieve the goals above, the invention adopts the following technical scheme: a kind of high-performance based on function of surface enhancing
Oxygen reduction catalyst, the catalyst are the HCM/Pt/C catalyst with core-shell structure, and wherein C is Pt catalyst in the bottom
Carrier, HCM be Heteroatom doping porous carbon materials, be coated on the surface of catalyst active center Pt.
A kind of preparation method of the high-performance oxygen reduction reaction catalyst based on function surface active region, including following step
It is rapid:
Step 1: after nano carbon particle and solvent are mixed, filtering drying is handled with acid solution later, after diafiltration
It washs to neutrality, drying, grinding obtain pretreated carbon carrier；
Step 2: pretreated carbon carrier is added in the aqueous solution of platinum salt and is mixed, mixture ultrasonic disperse machine again
Tool stirs to get mixed slurry；Mixed slurry is dry, and obtained solid powder is placed in tube furnace, heats under reducing atmosphere
Obtain supporting the catalyst intermediate of platinum；
Step 3: in a solvent by the catalyst intermediate dispersion for supporting platinum, the stirring of organic matter containing hetero atom is added；It will mix
Object drying is closed, obtained solid powder is placed in tube furnace, and heating obtains the HCM/ with core-shell structure under the conditions of gas shield
Pt/C catalyst.
Further, the nano carbon particle in step 1 is XC-72 (CARBOT company, the U.S.), XC-72R (U.S. CARBOT
Company), Black Pearls 2000 (CARBOT company, the U.S.), acetylene black, Ketjen Black series of conductive carbon black (Japan
Lion princes and dukes department) one or more kinds of mixtures.
Further, the solvent in step 1 is deionized water, ethyl alcohol, isopropanol, n-butanol, n-hexane, hexamethylene, third
One or more of ketone, n,N-Dimethylformamide plant mixture；Acid solution is one of sulfuric acid, nitric acid, acetic acid
Or two or more mixtures.
Further, the platinum salt in step 2 is chloroplatinic acid, acetylacetone,2,4-pentanedione platinum, in ammonium chloroplatinate or chloroplatinate
One or more kinds of mixtures.
Further, heating temperature is 200~600 DEG C in tube furnace in step 2, and heating time is 0.5~6h, reduction
Property atmosphere be the mixed of high-purity hydrogen, the gaseous mixture of nitrogen and hydrogen, the gaseous mixture of argon gas and hydrogen or above two gaseous mixture
It closes.
Further, the organic matter containing hetero atom in step 3 is Dopamine hydrochloride, aniline, urea, thiocarbamide, ethylenediamine, cyanogen
One or more mixtures of amine, dicyandiamide, melamine, cyanuric trichloride, ferrocene, Phen iron, cobalt phthalocyanine.
Further, the metal salt in step 3 be nickel acetate, cobalt acetate, ferric acetate, nickel chloride, cobalt chloride, iron chloride,
One or more mixtures of cobalt nitrate, nickel nitrate, ferric nitrate, nickel sulfate, cobaltous sulfate, ferric sulfate.
Further, in step 3 in tube furnace heating temperature be 400~1000 DEG C, heating time be 0.5~for 24 hours, it is lazy
Property gas be high pure nitrogen, high-purity argon gas or above two gaseous mixture mixing.
The catalyst of the application uses the whole design based on mesoscopic structure, is a kind of HCM/Pt/C with core-shell structure
Catalyst, in the core-shell structure, shell material is a kind of porous Heteroatom doping carbon material, is coated on the activated centre Pt surface.
Since this Heteroatom doping carbon material has a kind of special absorption-enrichment effect to oxygen, one kind can be provided for active site
Oxygen-enriched environment improves the collision frequency of reaction gas oxygen and active site, greatly improves the kinetic reaction of oxygen reduction reaction
Rate.The electronic effect at HCM/Pt heterojunction boundary can optimize the electronic structure of Pt simultaneously, make Pt in oxygen reduction reaction
Between the absorption of product die down, improve its desorption rate, provide site for subsequent Oxygen Adsorption.On the other hand, Pt particle periphery
Carbon shell can prevent its migration, reunite, substantially increase the overall stability of catalyst.Porous carbon shell only allows small point of oxygen etc.
Son migrates wherein, does not allow the macromoleculars such as methanol close to active site, so that the mithridatism of catalyst greatly improves.
Gained catalyst of the invention and preparation method mainly have it is following the utility model has the advantages that
(1) very uniform according to the partial size of Pt in the catalyst of this method preparation and distribution is especially uniform.
(2) for porous Heteroatom doping carbon material with a thickness of 1~2.5 nanometer, aperture is 0.7 nanometer, is evenly coated at Pt and receives
Rice corpuscles surface.By porous Heteroatom doping carbon material modification catalyst than it is no by modification catalyst activity,
Stability and mithridatism all greatly improve.
(3) some oxygen-containing intermediate productions in the Pt catalyst towards oxygen reduction reaction in the interface HCM/Pt after electronic optimization
The adsorption capacity of object weakens, and substantially increases its catalytic activity.
(4) the Heteroatom doping carbon material of Pt particle periphery can prevent its migration, reunite, and substantially increase the whole of catalyst
Body stability.
(5) porous carbon shell only allows the small molecules such as oxygen to migrate wherein, does not allow the macromoleculars such as methanol close to active sites
Point, so that the mithridatism of catalyst greatly improves.
(6) present invention has many advantages, such as at low cost, easy to operate, can be mass produced.Proton Exchange Membrane Fuel Cells,
Can be obtained in direct methanol fuel cell, metal-air battery using.
Detailed description of the invention
Fig. 1 is the resulting Pt/C transmission electron microscope photo of embodiment 1.
Fig. 2 is the high power transmission electron microscope photo of the resulting HCM/Pt/C catalyst with core-shell structure of embodiment 1.
Fig. 3 is the pore size distribution$ figure of the resulting porous Heteroatom doping carbon shell HCM of embodiment 1.
Fig. 4 is that the resulting Pt/C and HCM/Pt/C oxygen of embodiment 1 flows out curve ratio relatively figure.
Fig. 5 is the XPS spectrum figure of Pt in 1 resulting Pt/C and HCM/Pt/C of embodiment.
Fig. 6 is that the resulting Pt/C and HCM/Pt/C catalyst oxygen reduction performance of embodiment 1 compares figure.
Fig. 7 is the resulting HCM/Pt/C catalyst stability test figure with core-shell structure of embodiment 1.
The resulting Pt/C catalyst stability test figure of Fig. 8 embodiment 1.
Fig. 9 applies the resulting Pt/C and HCM/Pt/C catalyst methanol oxidation of example 1 and compares figure.
Specific embodiment
In order to make those skilled in the art more fully understand application scheme, below in conjunction in the embodiment of the present application
Attached drawing, the technical scheme in the embodiment of the application is clearly and completely described, it is clear that described embodiment is only
The embodiment of the application a part, instead of all the embodiments.Based on the embodiment in the application, ordinary skill people
Member's every other embodiment obtained without making creative work, all should belong to the model of the application protection
It encloses.
A kind of preparation method of high-performance oxygen reduction catalyst based on function of surface enhancing sequentially includes the following steps:
One, carbon carrier pre-processes:
It is 1:10~100 by the mass ratio of carbon carrier and solvent, carbon carrier is mixed with solvent, it is stirred at room temperature 0.5~
It is filtered after 6h, after filtration product is dried, under 10~80 DEG C of stirring conditions, handles 0.5~6h using acid solution, filter,
Filtration product is washed till pH using deionized water to be in neutrality, pretreated carbon carrier will be obtained after product drying, grinding.
Two, platinum loads:
1. being 2~60% by platinum loading, the pretreated carbon carrier of step 1 and the platinum of corrresponding quality are weighed
Salt.It is 1:1~50 by the mass ratio of platinum salt and solvent, dissolution obtains the solution of platinum salt.
2. the solution of platinum salt is added after to pretreatment in carbon carrier, mixture is obtained.
3. said mixture ultrasonic wave is dispersed 0.1~1h, then 0.1~1h of mechanical stirring, mixed slurry is obtained.
4. slurry is dry, obtained solid powder is placed in tube furnace, heats under 200~600 DEG C and reducibility gas
0.5~6h obtains the intermediate product of loaded metal platinum.
Three, porous Heteroatom doping carbon-coating cladding:
1. the mass ratio by step 2 treated intermediate product and organic matter containing hetero atom, metal salt is 1:5~500,
After 1:5~500 is mixed, it is stirred at room temperature 0.5~it filters afterwards for 24 hours, by much filtrate in 60~200 DEG C of dryings, grinding is consolidated
Body powder.
2. solid powder is placed in tube furnace, under inert gas protection, 20~1000 DEG C of heating 0.5~for 24 hours, it is natural
It is cooled to room temperature, obtains the catalyst with core-casing structure HCM/Pt/C with porous Heteroatom doping.
Material and treatment conditions illustrate in above-mentioned technical proposal:
In above-mentioned technical proposal, carbon carrier described in step 1 can be XC-72 (CARBOT company, the U.S.), XC-72R
(CARBOT company, the U.S.), Black Pearls 2000 (CARBOT company, the U.S.), acetylene black, Ketjen Black series are led
One such or several mixtures such as electric carbon black (Japanese lion princes and dukes department).
Solvent in step 1 can be deionized water, ethyl alcohol, isopropanol, n-butanol, n-hexane, hexamethylene, acetone, N,
One or more of dinethylformamide plants mixture.
Acid solution in step 1 can be one such or several mixtures such as sulfuric acid, nitric acid, acetic acid.
Platinum salt in step 2 is chloroplatinic acid, acetylacetone,2,4-pentanedione platinum, one of ammonium chloroplatinate or chloroplatinate or two
Kind or more mixture.
Loading in step 2 is the mass percent of metal platinum and carrier.
Reducing atmosphere in step 2 is the gaseous mixture of high-purity hydrogen, the gaseous mixture of nitrogen and hydrogen, argon gas and hydrogen
Or the mixing of above two gaseous mixture.
Organic matter containing hetero atom in step 3 is Dopamine hydrochloride, aniline, urea, thiocarbamide, ethylenediamine, cyanamide, double cyanogen
One or more mixtures of amine, melamine, cyanuric trichloride, ferrocene, Phen iron, cobalt phthalocyanine.Metal salt
For nickel acetate, cobalt acetate, ferric acetate, nickel chloride, cobalt chloride, iron chloride, cobalt nitrate, nickel nitrate, ferric nitrate, nickel sulfate, sulfuric acid
One or more mixtures of cobalt, ferric sulfate.
Inert gas in step 3 is the mixing of high pure nitrogen, high-purity argon gas or above two gaseous mixture.
In above-mentioned technical proposal, the resistivity of deionized water is 16M Ω cm~18.25M Ω cm.
Embodiment 1
(1) carbon carrier pre-processes
The acetone for measuring the Vulcan XC-72R and 200g of 5g mass, Vulcan XC-72R is mixed with acetone, room temperature
It is filtered after lower stirring 6h, after much filtrate drying, is transferred in the nitric acid solution that mass fraction is 10%, is stirred under the conditions of 60 DEG C
Processing 5h is mixed, filtering products therefrom is washed till pH using deionized water and is in neutrality, after 70 DEG C of dryings, is obtained pretreated
Vulcan XC-72R carrier.
(2) metal platinum loads
1. being 12% by platinum element loading, weighs the pretreated Vulcan XC-72R of 2g and 0.66g six and be hydrated chlorine platinum
Acid, is 1:10 by chloroplatinic acid and the mass ratio of deionized water, and dissolution obtains the aqueous solution of chloroplatinic acid.2. chloroplatinic acid aqueous solution is complete
Portion is added in the pretreated Vulcan XC-72R of 2g, obtains mixture.3. mixture ultrasonic wave is dispersed 0.5h, then mechanical
0.5h is stirred, mixed slurry is obtained.4. slurry is dry, obtained solid powder is placed in tube furnace, at 400 DEG C and 5vol.%
H2/N2Lower heating 3h is taken out after cooling to get loaded metal platinum intermediate Pt/C is arrived.
(3) porous Heteroatom doping carbon-coating cladding
1. 1g load intermediate Pt/C is added in the aqueous dopamine solution of 200mL 1g/mL, ultrasonic 0.5h, stirring
6h, filtering, drying.2. obtained solid powder is placed in tube furnace, at 550 DEG C and heated under nitrogen 1h, had after cooling
There is the HCM/Pt/C catalyst of core-shell structure.
(4) TEM (transmission electron microscope) test of catalyst
The Pt/C catalyst intermediate being prepared uses transmission electron microscope, corresponding diagram 1.
The HCM/Pt/C catalyst being prepared uses transmissioning electric mirror test, corresponding diagram 2.
(5) pore-size distribution of porous Heteroatom doping carbon material HCM
The HCM being prepared uses nitrogen adsorption desorption curve and graph of pore diameter distribution, corresponding diagram 3 at 77K.
(6) the oxygen elution curve of catalyst Pt/C and HCM/Pt/C
100mg preparation Pt/C or HCM/Pt/C is put into U-tube, 1h is activated under 300 DEG C of argon gas, it is backward to drop to room temperature
It is passed through oxygen 1h in U-tube, oxygen is switched into argon gas purging, while recording the amount of catalyst physical adsorption of oxygen with mass spectrum,
Corresponding diagram 4.
(7) XPS (x-ray photoelectron spectroscopy) test of catalyst
The HCM/Pt/C catalyst being prepared uses X-ray photoelectron spectroscopic analysis, the 4f energy level spectrogram corresponding diagram of Pt
5。
(8) electrochemical property test of the HCM/Pt/C catalyst in three-electrode system
HCM/Pt/C catalyst obtained by 5 milligrams of (3) steps is weighed, is successively added to 970 microlitres of isopropanols thereto
Micro-sampling is used after sonic oscillation 30 minutes are uniformly dispersed with 30 microlitres of Nafion membrane solution (mass fraction 5%, Du Pont)
Device is drawn 5 microlitres and is evenly applied on glass carbon rotating ring disk electrode (r.r.d.e), and air drying 10 minutes.As working electrode, Ag/
AgCl electrode is reference electrode, and Pt are auxiliary electrode, using the high chloro acid solution of the 0.1mol/L of nitrogen saturation as electrolyte
Solution, in electrochemical workstation (CHI660d, Shanghai Chen Hua instrument company) record current density with voltage situation of change,
Cyclic voltammetry scan 60 is enclosed with activated catalyst surface.Then, it is tested in the perchloric acid solution of the 0.1mol/L of oxygen saturation
Linear scan polarization curve, the revolving speed of rotation electrode are 1600rpm, 0.1~1.0V of scanning range (relative to standard hydrogen electrode),
Scanning speed is 20mV/s, the curve of corresponding diagram 6.
(9) stability test of HCM/Pt/C catalyst
Prepare to obtain working electrode to be measured with (8) one step process, using Ag/AgCl electrode as reference electrode, Pt are auxiliary
Electrode, using oxygen saturation 0.1mol/L high chloro acid solution as electrolyte solution, electrochemical workstation (CHI660d, on
Hai Chenhua instrument company) on carry out cyclic voltammetry scan 50000 enclose, sweep speed 200mV/s, scanning range be 0.6~
1.0V (relative to standard hydrogen electrode), accelerated ageing test front and back, tests the linear polarisation curves of catalyst, in corresponding diagram 7,8
Curve.
(9) the antitoxinization performance test of HCM/Pt/C catalyst
Prepare to obtain working electrode to be measured with (8) one step process, using Ag/AgCl electrode as reference electrode, Pt are auxiliary
Electrode, the 0.1mol/L HClO being saturated with nitrogen4+1mol/L CH3OH mixed solution is electrolyte solution, in electrochemical operation
It stands and carries out cyclic voltammetry scan 6 in (CHI660d, Shanghai Chen Hua instrument company) and enclose, sweep speed 20mV/s, scanning range is
0.6~1.0V (relative to standard hydrogen electrode), the curve in corresponding diagram 9.
Experimental result:
The images of transmissive electron microscope of Pt/C shows that the particle of platinum is very small and is evenly distributed in carbon ball in Fig. 1.
The images of transmissive electron microscope of HCM/Pt/C shows that HCM shell is evenly coated at Pt particle surface in Fig. 2, the partial size of Pt with
It compares in Pt/C and does not change.
The graph of pore diameter distribution of HCM shows that the aperture of HCM is 0.7nm in Fig. 3.
Oxygen elution curve shows that the HCM/Pt/C catalyst with shell structure can be enriched with more oxygen compared to Pt/C in Fig. 4
Gas (physical absorption).
XPS figure in Fig. 5 shows that the presence of HCM makes the 4f combination of Pt that apparent negative shifting can have occurred, and illustrates HCM to Pt's
Electronic structure has apparent adjustment effect.
The catalyst with function surface active region that Fig. 6 is prepared according to the method for invention as the result is shown,
The catalyst of catalytic activity and stability than not being modified is significantly improved, and illustrates in HCM high oxygen concentration and HCM pairs
The electrical adjustment effect of Pt can greatly improve the catalytic activity of Pt.
Fig. 7 and Fig. 8 shows common commercial Pt/C after 50000 circle cyclic voltammetries, and catalytic activity decline is compared
Obviously, and with this core-shell structure catalyst by 50000 circle cyclic voltammetries after, activity substantially there is no
Variation, illustrates that this core-shell structure can effectively inhibit the migration and reunion of Pt particle, has actively to the stability aspect of catalyst
Meaning.
Fig. 9 shows that the catalyst after surface is modified by HCM has obviously the catalytic activity of methanol oxidation compared to Pt/C
Decline, illustrate that HCM shell can effectively inhibit methanol macromolecular to contact with the activated centre Pt so that HCM/Pt/C have it is preferably anti-
Poison performance.
Embodiment 2
(1) carbon carrier pre-processes
The acetone for measuring the Vulcan XC-72 and 50g of 2g mass, Vulcan XC-72 is mixed with acetone, is stirred at room temperature
It filters after mixing 3h, after much filtrate drying, is transferred in the nitric acid solution that mass fraction is 10%, under the conditions of 80 DEG C at stirring
6h is managed, filtering products therefrom is washed till pH using deionized water and is in neutrality, after 70 DEG C of dryings, obtains pretreated Vulcan
XC-72 carrier.
(2) metal platinum loads
1. being 20% by platinum element loading, weighs the pretreated Vulcan XC-72R of 2g and 1.19g six and be hydrated chlorine platinum
Sour ammonium, is 1:10 by ammonium chloroplatinate and the mass ratio of deionized water, and dissolution obtains the aqueous solution of ammonium chloroplatinate.2. by ammonium chloroplatinate
Aqueous solution is all added in the pretreated Vulcan XC-72R of 2g, obtains mixture.3. mixture ultrasonic wave is dispersed into 1h,
Mechanical stirring 1h again obtains mixed slurry.4. slurry is dry, obtained solid powder is placed in tube furnace, at 350 DEG C and
15vol.%H24h is heated under/Ar, is taken out after cooling to get loaded metal platinum intermediate Pt/C is arrived.
(3) porous Heteroatom doping carbon-coating cladding
1. 1g load intermediate Pt/C is added in the aniline of 200mL 1g/mL and the aqueous solution of ammonium persulfate, ultrasound
1.0h stirs 12h, filtering, drying.It is cold at 500 DEG C and heated under nitrogen 2h 2. obtained solid powder is placed in tube furnace
But the HCM/Pt/C catalyst with core-shell structure is obtained afterwards.
The foregoing is only a preferred embodiment of the present invention, is not intended to restrict the invention, for the skill of this field
For art personnel, the invention may be variously modified and varied.All within the spirits and principles of the present invention, made any to repair
Change, equivalent replacement, improvement etc., should all be included in the protection scope of the present invention.
Claims (9)
1. a kind of high-performance oxygen reduction catalyst based on function of surface enhancing, it is characterised in that: the catalyst is with core
The HCM/Pt/C catalyst of shell structure, wherein for C in the carrier that the bottom is Pt catalyst, HCM is the porous carbon of Heteroatom doping
Material is coated on the surface of catalyst active center Pt.
2. a kind of preparation method of the high-performance oxygen reduction catalyst based on function of surface enhancing, it is characterised in that including following step
It is rapid:
Step 1: after nano carbon particle and solvent are mixed, filtering drying is handled with acid solution later, extremely after filter washing
Neutrality, drying, grinding obtain pretreated carbon carrier；
Step 2: pretreated carbon carrier being added in the aqueous solution of platinum salt and mixed, machinery stirs mixture ultrasonic disperse again
It mixes to obtain mixed slurry；Mixed slurry is dry, and obtained solid powder is placed in tube furnace, heats and obtain under reducing atmosphere
Support the catalyst intermediate of platinum；
Step 3: in a solvent by the catalyst intermediate dispersion for supporting platinum, organic matter containing hetero atom and metal salt stirring is added；
Mixture is dried, obtained solid powder is placed in tube furnace, and heating obtains having core-shell structure under the conditions of gas shield
HCM/Pt/C catalyst.
3. preparation method according to claim 2, it is characterised in that: nano carbon particle in the step 1 be XC-72,
One or more of XC-72R, Black Pearls 2000, acetylene black, Ketjen Black series of conductive carbon black are mixed
Close object.
4. preparation method according to claim 2, it is characterised in that: the solvent in the step 1 is deionized water, second
The kind mixing of one or more of alcohol, isopropanol, n-butanol, n-hexane, hexamethylene, acetone, n,N-Dimethylformamide
Object；Acid solution is one or more mixtures of sulfuric acid, nitric acid, acetic acid.
5. preparation method according to claim 2, it is characterised in that: the platinum salt in the step 2 is chloroplatinic acid, second
One or more mixtures of acyl acetone platinum, ammonium chloroplatinate or chloroplatinate.
6. preparation method according to claim 2, it is characterised in that: heating temperature is in tube furnace in the step 2
200~600 DEG C, heating time is 0.5~6h, and reducing atmosphere is high-purity hydrogen, the gaseous mixture of nitrogen and hydrogen, argon gas and hydrogen
The mixing of the gaseous mixture of gas or above two gaseous mixture.
7. preparation method according to claim 2, it is characterised in that: the organic matter containing hetero atom in the step 3 is salt
Sour dopamine, aniline, urea, thiocarbamide, ethylenediamine, cyanamide, dicyandiamide, melamine, cyanuric trichloride, ferrocene, Phen
One or more mixtures of iron, cobalt phthalocyanine.
8. preparation method according to claim 2, it is characterised in that: the metal salt in the step 3 is nickel acetate, acetic acid
Cobalt, ferric acetate, nickel chloride, cobalt chloride, iron chloride, cobalt nitrate, nickel nitrate, ferric nitrate, nickel sulfate, cobaltous sulfate, in ferric sulfate
One or more kinds of mixtures.
9. preparation method as claimed in claim 2, it is characterised in that: in the step 3 in tube furnace heating temperature be 400~
1000 DEG C, heating time is 0.5~for 24 hours, inert gas be high pure nitrogen, high-purity argon gas or above two gaseous mixture it is mixed
It closes.
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