CN108110260B - A kind of fuel-cell catalyst and preparation method of metal-organic framework modification - Google Patents
A kind of fuel-cell catalyst and preparation method of metal-organic framework modification Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 71
- 230000004048 modification Effects 0.000 title claims abstract description 27
- 238000012986 modification Methods 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 239000012621 metal-organic framework Substances 0.000 title claims description 82
- 239000000843 powder Substances 0.000 claims abstract description 64
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims abstract description 41
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 40
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims abstract description 22
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 238000001179 sorption measurement Methods 0.000 claims abstract description 17
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 16
- 238000007731 hot pressing Methods 0.000 claims abstract description 16
- 239000000835 fiber Substances 0.000 claims abstract description 14
- 229910052742 iron Inorganic materials 0.000 claims abstract description 13
- 239000011159 matrix material Substances 0.000 claims abstract description 13
- 239000005711 Benzoic acid Substances 0.000 claims abstract description 11
- 235000010233 benzoic acid Nutrition 0.000 claims abstract description 11
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000000498 ball milling Methods 0.000 claims abstract description 9
- 150000001875 compounds Chemical class 0.000 claims abstract description 9
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 9
- 229920000049 Carbon (fiber) Polymers 0.000 claims description 29
- 239000004917 carbon fiber Substances 0.000 claims description 29
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 29
- 239000002178 crystalline material Substances 0.000 claims description 14
- 238000000034 method Methods 0.000 claims description 14
- 239000011858 nanopowder Substances 0.000 claims description 14
- 238000001556 precipitation Methods 0.000 claims description 14
- 238000004108 freeze drying Methods 0.000 claims description 9
- 229910052593 corundum Inorganic materials 0.000 claims description 7
- 239000010431 corundum Substances 0.000 claims description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 7
- 238000005119 centrifugation Methods 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000000227 grinding Methods 0.000 claims description 4
- XNGIFLGASWRNHJ-UHFFFAOYSA-N phthalic acid Chemical compound OC(=O)C1=CC=CC=C1C(O)=O XNGIFLGASWRNHJ-UHFFFAOYSA-N 0.000 claims description 4
- XMIIGOLPHOKFCH-UHFFFAOYSA-N 3-phenylpropionic acid Chemical compound OC(=O)CCC1=CC=CC=C1 XMIIGOLPHOKFCH-UHFFFAOYSA-N 0.000 claims description 3
- 239000005416 organic matter Substances 0.000 claims description 3
- WLJVXDMOQOGPHL-PPJXEINESA-N 2-phenylacetic acid Chemical compound O[14C](=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-PPJXEINESA-N 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000002245 particle Substances 0.000 claims description 2
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000013339 cereals Nutrition 0.000 claims 1
- 235000013312 flour Nutrition 0.000 claims 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims 1
- 239000010931 gold Substances 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 22
- 238000006555 catalytic reaction Methods 0.000 abstract description 11
- 238000009792 diffusion process Methods 0.000 abstract description 10
- 231100000572 poisoning Toxicity 0.000 abstract description 9
- 230000000607 poisoning effect Effects 0.000 abstract description 9
- 229910052751 metal Inorganic materials 0.000 abstract description 8
- 239000002184 metal Substances 0.000 abstract description 8
- 238000012545 processing Methods 0.000 abstract description 8
- 239000013078 crystal Substances 0.000 abstract description 5
- 239000002156 adsorbate Substances 0.000 abstract description 4
- 230000009257 reactivity Effects 0.000 abstract description 3
- 239000000126 substance Substances 0.000 abstract description 3
- 238000001035 drying Methods 0.000 abstract description 2
- 238000001914 filtration Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 150000001559 benzoic acids Chemical class 0.000 abstract 1
- 239000000446 fuel Substances 0.000 description 26
- 239000012528 membrane Substances 0.000 description 13
- 230000003197 catalytic effect Effects 0.000 description 12
- 239000011248 coating agent Substances 0.000 description 10
- 238000000576 coating method Methods 0.000 description 10
- 239000007789 gas Substances 0.000 description 9
- 208000005374 Poisoning Diseases 0.000 description 8
- 239000002737 fuel gas Substances 0.000 description 7
- 230000008859 change Effects 0.000 description 6
- 239000002105 nanoparticle Substances 0.000 description 6
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 5
- 238000010521 absorption reaction Methods 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 239000002253 acid Substances 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 150000001558 benzoic acid derivatives Chemical class 0.000 description 2
- 239000003426 co-catalyst Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 239000000306 component Substances 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 150000003022 phthalic acids Chemical class 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 239000002574 poison Substances 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 1
- 229910019026 PtCr Inorganic materials 0.000 description 1
- 229910019041 PtMn Inorganic materials 0.000 description 1
- 229910019017 PtRh Inorganic materials 0.000 description 1
- 229910002849 PtRu Inorganic materials 0.000 description 1
- 229910002847 PtSn Inorganic materials 0.000 description 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 230000001147 anti-toxic effect Effects 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000000536 complexating effect Effects 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 235000013399 edible fruits Nutrition 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010406 interfacial reaction Methods 0.000 description 1
- 239000010416 ion conductor Substances 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- WLJVXDMOQOGPHL-UHFFFAOYSA-N phenylacetic acid Chemical class OC(=O)CC1=CC=CC=C1 WLJVXDMOQOGPHL-UHFFFAOYSA-N 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000007784 solid electrolyte Substances 0.000 description 1
Classifications
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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
- H01M4/8663—Selection of inactive substances as ingredients for catalytic active masses, e.g. binders, fillers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
- H01M4/8828—Coating with slurry or ink
- H01M4/8839—Painting
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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
- H01M4/88—Processes of manufacture
- H01M4/8875—Methods for shaping the electrode into free-standing bodies, like sheets, films or grids, e.g. moulding, hot-pressing, casting without support, extrusion without support
-
- 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
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Nanotechnology (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Crystallography & Structural Chemistry (AREA)
- Composite Materials (AREA)
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
The present invention proposes a kind of fuel-cell catalyst and preparation method of metal organic frame modification, low-temperature hydrothermal processing is carried out after evenly mixing using iron powder, benzoic acid class, hydrofluoric acid, nitric acid, granular crystals substance is obtained after filtration drying, dry ball milling crushing is carried out later, crystal is crushed to micron-sized powder, it is compound with the progress hot pressing of Pt/C catalyst, so that powder is uniformly embedded in the carbon fibre carrier back side, forms dot matrix adsorption layer.The present invention with carbon fibre carrier is compounded to form dot matrix adsorption layer after being reacted with benzoic acid type organic using metallic iron, passes through Fe in skeleton structure3+It is reduced to Fe2+There is selective catalysis and adsorption effect to the CO adsorbates containing pi bond, the catalysis of CO and adsorbance in gas diffusion layers can be effectively improved, reduce the danger of catalyst poisoning, improve reactivity.
Description
Technical field
The present invention relates to fuel cell material fields, and in particular to a kind of fuel cell of metal-organic framework modification is urged
Agent and preparation method.
Background technology
Due to non-renewable for traditional fossil fuel, and environmental pollution caused by during use is serious, seeks ring
The renewable sources of energy of guarantor's type are the severe tasks of 21 century facing mankind.Fuel cell (Fuel cell) is a kind of novel energy
Source technology directly converts the chemical energy of fuel to electric energy by electrochemical reaction, and fuel used is hydrogen, methanol and hydrocarbon
The hydrogen-rich materials such as class, there are no pollution to the environment and with high energy efficiency and high power density, therefore, fuel cell has
Have broad application prospects.
Proton Exchange Membrane Fuel Cells (Proton Exchange Membrane Fuel Cell, PEMFC)) it is after alkali
Property fuel cell (AFC), phosphoric acid fuel cell (PAFC), molten carbonate fuel cell (MCFC) and solid oxide fuel electricity
Pond (SOFC) and the 5th Replacing fuel battery to grow up have energy conversion rate using polymeric membrane as solid electrolyte
The features such as high and low temperature starts, electroless matter is revealed, is widely used in light-duty vehicle, portable power and small drive device.
PEMFC is mainly made of components such as end plate, bipolar plates and membrane electrodes.Membrane electrode is the core component of PEMFC, main
It to be made of gas diffusion layers, Catalytic Layer and proton exchange membrane.Wherein, the Catalytic Layer positioned at proton exchange membrane both sides is substantially carried out
The transmission of reactant, reactant conduct and the discharge of reaction product in the interfacial reaction of electrochemical site, proton and electronics
Etc. significant process, be the important place that PEMFC is electrochemically reacted.And ion conductor and catalyst are PEMFC catalysis
The necessary component of layer.Currently, catalyst used in fuel cell is carbon supported platinum catalyst, it is main provide electrochemical site and
Electron channel.
Pt/C Catalytic Layers are for trace amounts of CO ratio O in fuel in Proton Exchange Membrane Fuel Cells2Sensitivity, a small amount of CO absorption
Compare O2Absorption is preferential, therefore is easy to cause catalyst poisoning, seriously affects its catalytic efficiency and service life.Inhibit Pt catalyst
Poisoning generally use adulterates scheme of another metal as co-catalyst into Pt/C catalyst, by electronic effect or matches
Position effect weakens CO in the adsorption strength of metal surface, or reduces the electroxidation potential of CO to reach the effect of anti-CO poisoning
Fruit.Pt Ru/C are the elctro-catalyst of most common CO tolerance catalysts, and the widest one kind studied now, except PtRu is urged
Outside agent, the research of binary or multicomponent catalyst is also relatively broad, such as：PtIr、PtRh、PtPd、PtMn、PtCr、PtW、PtSn、
PtMo, PdAu etc., but the electronic configuration and orbital energy level due to each element are different, to the antitoxin performances of CO after alloy
Influence also differ, some even than be free of any auxiliary agent Pt it is also poor.
Other than improving catalyst activity itself, researcher also attempts to set about research raising catalyst performance from gas diffusion layers
The method of energy, Chinese invention patent application number 200710012714.4 disclose a kind of anti-CO of raising Proton Exchange Membrane Fuel Cells
The method of performance, supported in anode of proton exchange membrane fuel cell diffusion layer has the Pt that gating catalytic oxidation acts on to CO gases
Or Au catalyst can cause the CO gases that proton exchange film fuel battery performance is decayed miscellaneous under conditions of injecting a small amount of oxygen
Matter will generate the CO that very little is influenced on battery performance when passing through diffusion layer by catalysis oxidation, reaction2, to improve proton exchange
The CO resistance performance of membrane cell has pushed the development and application of fuel cell.But Pt or Au catalyst still faces reserves
Less, problem expensive, poison resistance is poor.
It is difficult to effectively solve the problems, such as that CO is poisoned in face of traditional catalyst, how to develop height and effectively improve gas diffusion layers
The catalysis of middle CO and the catalyst of adsorbance reduce the cost of fuel cell to reduce the dependence to Pt, are urged for Pt is inhibited
The research of agent poisoning has highly important practical significance.
Invention content
After using metallic iron to be complexed with benzoic acid type organic, pass through Fe in skeleton structure3+It is reduced to Fe2+To containing π
The CO adsorbates of key have selective catalysis and adsorption effect, can be with by being compounded to form dot matrix adsorption layer with carbon fibre carrier
The catalysis of CO and adsorbance in gas diffusion layers are effectively improved, the danger of catalyst poisoning is reduced, improves reactivity.
To solve the above problems, the present invention uses following technical scheme：
A kind of fuel-cell catalyst of metal-organic framework modification, the catalyst structure includes that Pt nano powders are uniform
The Pt/C catalyst layers for loading to the formation of the first face of carbon fiber layered vector are different from the carbon fibre carrier is uniformly embedded in
Metal-organic framework powder layer on second face in first face；
Wherein, the metal-organic framework powder is the skeleton knot that metallic iron is generated with benzoic acid type organic complex reaction
Structure.
Preferably, the grain size of the metal-organic framework powder is 10-300 μm, and the Pt particle diameter of nanometer powder is 50-
200nm, the carbon fiber draw ratio be 5-50, a diameter of 10-100 μm.
Preferably, the metal-organic framework powder and the Pt nano powders mass ratio are 0.8-1.5：1.
Another party provides a kind of preparation method of the fuel-cell catalyst of metal-organic framework modification, specific preparation side
Method is：
（1）3-7 parts of iron powders are mixed with 14-20 parts of nitric acid by weight, after iron powder is completely dissolved, 2-3 parts of benzene are added
Acids organic matter and 1-2 parts of hydrofluoric acid, carry out hydro-thermal process after stirring evenly, hydrothermal temperature is controlled at 80-98 DEG C, by from
Heart precipitation and separation filters out precipitation, then obtains metal-organic framework crystalline material by freeze-drying；
（2）The metal-organic framework crystalline material is added in dry method ball mill, ball mill grinding is obtained to 10-300 μm
To metal-organic framework powder；
（3）The first face of carbon fiber layer is coated into Pt nano-particles, not with carbon fiber layer by the metal-organic framework powder
It is compound with hot pressing is carried out with second face in first face, so that powder is uniformly embedded in the second face described in carbon fibre carrier, is formed
Dot matrix adsorption layer obtains the fuel-cell catalyst of metal-organic framework powder modification.
Preferably, the benzoic acid type organic is one kind in benzoic acid, phenylacetic acid, benzenpropanoic acid, phthalic acid.
Preferably, the rotating speed of the centrifugation is controlled in 500-2000rpm.
Preferably, the treatment temperature of the freeze-drying is -40 ~ -20 DEG C, and pressure control is in 10-700Pa.
Preferably, the medium ball of the ball milling is corundum medium, and drum's speed of rotation is controlled in 800-3000rpm.
Preferably, the hot-pressing processing is to be heated to 200-450 DEG C, and on-load pressure is 0.8-1.5 MPa.
Current Proton Exchange Membrane Fuel Cells oxygen source is mainly air, but Pt/C Catalytic Layers are for the absorption ratio O of CO2
Absorption is preferential, therefore is easy to cause catalyst poisoning, seriously affects its catalytic efficiency and service life.Traditional co-catalyst scheme
It is difficult to effectively solve the problems, such as that CO is poisoned, supporting noble metal in anode of proton exchange membrane fuel cell diffusion layer faces reserves
Less, problem expensive, poison resistance is poor.Porous material metal-organic framework (Metal-Organic Frameworks,
MOFs) have many advantages, such as the pore structure of high-sequential, the specific surface area of superelevation and adjustable aperture, and MOFs can pass through
The modification of organic ligand introduces various functional groups and makes it have special performance, can be explored by being designed research to MOFs
A method of effectively solve the above problems.In consideration of it, the present invention proposes that a kind of fuel cell of metal organic frame modification is urged
Agent and preparation method carry out low-temperature hydrothermal processing, filtration drying after evenly mixing using iron powder, benzoic acid class, hydrofluoric acid, nitric acid
Granular crystals substance is obtained afterwards, is carried out dry ball milling crushing later, crystal is crushed to micron-sized powder, with Pt/C catalyst
It is compound to carry out hot pressing, powder is made uniformly to be embedded in the carbon fibre carrier back side, forms dot matrix adsorption layer.Use metallic iron and benzoic acid class
After organic matter complexing, pass through Fe in skeleton structure3+It is reduced to Fe2+There is selective catalysis and suction to the CO adsorbates containing pi bond
Attached effect, by being compounded to form dot matrix adsorption layer with carbon fibre carrier, and then effectively improve in gas diffusion layers the catalysis of CO and
Adsorbance reduces the danger of catalyst poisoning, improves reactivity, reduces the dependence to Precious Metals Resources.
The fuel-cell catalyst of metal organic frame modification prepared by the present invention is imitated with Pt catalyst in adsoption catalysis
Rate etc. has a clear superiority, as shown in table 1.
Table 1：
The present invention provides a kind of fuel-cell catalyst and preparation method of metal organic frame modification, with prior art phase
Than the feature and excellent effect protruded is：
1, the present invention proposes a kind of fuel-cell catalyst and preparation method of metal organic frame modification, uses metallic iron
After being complexed with benzoic acid type organic, by being compounded to form dot matrix adsorption layer with carbon fibre carrier, pass through Fe in skeleton structure3+Reduction
For Fe2+There is selective catalysis and adsorption effect to the CO adsorbates containing pi bond, effectively inhibit Pt catalyst poisonings, improve
Pt/C Catalytic Layers catalytic efficiency and service life.
2, the metal-organic framework materials of preparation of the invention gone out have larger grain size and specific surface area, are conducive to
The Fe being distributed in structure3+Capture to CO gases, catalytic activity are excellent.
3, the present invention can reduce dependence of the catalyst to noble metal using iron powder, benzene acrylic materials as raw material, to
The catalyst resource problem that current fuel cell is faced can be solved, modified cost can be reduced, is easy to carry out industrialization hair
Exhibition.
Specific implementation mode
In the following, the present invention will be further described in detail by way of specific embodiments, but this should not be interpreted as to the present invention
Range be only limitted to example below.Without departing from the idea of the above method of the present invention, according to ordinary skill
The various replacements or change that knowledge and customary means are made, should be included in the scope of the present invention.
Embodiment 1
（1）3 parts of iron powders are mixed with 20 parts of nitric acid by weight, after iron powder is completely dissolved, 2 parts of benzoic acid and 1 are added
Part hydrofluoric acid carries out hydro-thermal process after stirring evenly, hydrothermal temperature control, by centrifuging precipitation, centrifuges and divides at 98 DEG C
From rotating speed control in 500rpm, filter out precipitation, then by being freeze-dried, the treatment temperature of freeze-drying is -40 DEG C, gas
Voltage-controlled system obtains metal-organic framework crystalline material in 700Pa；
（2）The metal-organic framework crystalline material is added in dry method ball mill, the medium ball of ball milling is situated between for corundum
Matter, drum's speed of rotation are controlled in 800rpm, and ball mill grinding obtains the metal-organic framework powder that grain size is 300 μm of skeleton structures；
（3）The Pt nano-particles for being 50nm by the first face of carbon fiber layer coating grain size, carbon fiber draw ratio in carbon fiber layer
It is 50, a diameter of 10 μm, be 0.8 according to metal-organic framework powder and Pt nano powder mass ratioes：1 takes metal-organic framework powder
Body, the back side progress hot pressing of metal-organic framework powder and coating Pt nano powder carbon fiber layers is compound, 200 DEG C are heated to, is added
Load pressure is 1.5 Mpa, carries out hot-pressing processing, metal-organic framework powder is made uniformly to be embedded in the carbon fibre carrier back side, is formed
Dot matrix adsorption layer obtains the fuel-cell catalyst of metal-organic framework powder modification.
The fuel-cell catalyst that the metal-organic framework powder prepared in the present embodiment is modified is as battery
Anode and cathode, it is 5cm to be prepared as effect area2Monocell, output power density highest of the monocell under room temperature (25 DEG C)
Up to 26.2mW/cm2, in fuel gas (100ppmCO/H2) flow be 50ml/min, air mass flow 600ml/min, behaviour
It is 0.1MPa as pressure, under the conditions of battery temperature is 60 DEG C, after being activated to battery after 5min, continuous work 100 hours
Afterwards, it measures output power density and reaches as high as 26.0mW/cm 2, battery current do not have significant change, CO tolerance catalysts effect bright
It is aobvious.
Embodiment 2
（1）7 parts of iron powders are mixed with 18 parts of nitric acid by weight, after iron powder is completely dissolved, be added 2 parts of phthalic acids and
1 part of hydrofluoric acid carries out hydro-thermal process after stirring evenly, hydrothermal temperature is controlled at 85 DEG C, by centrifuging precipitation, centrifugation point
From rotating speed control in 2000rpm, filter out precipitation, then by being freeze-dried, the treatment temperature of freeze-drying is -34 DEG C,
Pressure control obtains metal-organic framework crystalline material in 10Pa；
（2）The metal-organic framework crystalline material is added in dry method ball mill, the medium ball of ball milling is situated between for corundum
Matter, drum's speed of rotation are controlled in 800rpm, and ball mill grinding obtains the metal-organic framework powder that grain size is 120 μm of skeleton structures；
（3）The Pt nano-particles for being 100nm by the first face of carbon fiber layer coating grain size, carbon fiber draw ratio in carbon fiber layer
It is 50, a diameter of 100 μm, be 0.8 according to metal-organic framework powder and Pt nano powder mass ratioes：1 takes metal-organic framework
Powder, the back side progress hot pressing of metal-organic framework powder and coating Pt nano powder carbon fiber layers is compound, 250 DEG C are heated to,
On-load pressure is 0.9 Mpa, carries out hot-pressing processing, metal-organic framework powder is made uniformly to be embedded in the carbon fibre carrier back side, shape
At dot matrix adsorption layer, the fuel-cell catalyst of metal-organic framework powder modification is obtained.
The fuel-cell catalyst that the metal-organic framework powder prepared in the present embodiment is modified is as battery
Anode and cathode, it is 5cm to be prepared as effect area2Monocell, output power density highest of the monocell under room temperature (25 DEG C)
Up to 35.4mW/cm 2, in fuel gas (100ppmCO/H2) flow be 50ml/min, air mass flow 600ml/min, behaviour
It is 0.1MPa as pressure, under the conditions of battery temperature is 60 DEG C, after being activated to battery after 5min, continuous work 100 hours
Afterwards, it measures output power density and reaches as high as 35.1mW/cm 2, battery current do not have significant change, CO tolerance catalysts effect bright
It is aobvious.
Embodiment 3
（1）5 parts of iron powders are mixed with 20 parts of nitric acid by weight, after iron powder is completely dissolved, 3 parts of phenylacetic acids and 1 are added
Part hydrofluoric acid carries out hydro-thermal process after stirring evenly, hydrothermal temperature control, by centrifuging precipitation, centrifuges and divides at 88 DEG C
From rotating speed control in 1300rpm, filter out precipitation, then by being freeze-dried, the treatment temperature of freeze-drying is -20 DEG C,
Pressure control obtains metal-organic framework crystalline material in 10Pa；
（2）The metal-organic framework crystalline material is added in dry method ball mill, the medium ball of ball milling is situated between for corundum
Matter, drum's speed of rotation control obtain the metal-organic framework powder that grain size is 100 μm of skeleton structures in 2000rpm；
（3）The Pt nano-particles for being 150nm by the first face of carbon fiber layer coating grain size, carbon fiber draw ratio in carbon fiber layer
It is 25, a diameter of 80 μm, be 0.9 according to metal-organic framework powder and Pt nano powder mass ratioes：1 takes metal-organic framework powder
Body, the back side progress hot pressing of metal-organic framework powder and coating Pt nano powder carbon fiber layers is compound, 350 DEG C are heated to, is added
Load pressure is 0.9Mpa, carries out hot-pressing processing, metal-organic framework powder is made uniformly to be embedded in the carbon fibre carrier back side, is formed
Dot matrix adsorption layer obtains the fuel-cell catalyst of metal-organic framework powder modification.
The fuel-cell catalyst that the metal-organic framework powder prepared in the present embodiment is modified is as battery
Anode and cathode, it is 5cm to be prepared as effect area2Monocell, output power density highest of the monocell under room temperature (25 DEG C)
Up to 25.8mW/cm 2, in fuel gas (100ppmCO/H2) flow be 50ml/min, air mass flow 600ml/min, behaviour
It is 0.1MPa as pressure, under the conditions of battery temperature is 60 DEG C, after being activated to battery after 5min, continuous work 100 hours
Afterwards, it measures output power density and reaches as high as 25.2mW/cm 2, battery current do not have significant change, CO tolerance catalysts effect bright
It is aobvious.
Embodiment 4
（1）4 parts of iron powders are mixed with 18 parts of nitric acid by weight, after iron powder is completely dissolved, 3 parts of benzenpropanoic acids and 1 are added
Part hydrofluoric acid carries out hydro-thermal process after stirring evenly, hydrothermal temperature control, by centrifuging precipitation, centrifuges and divides at 89 DEG C
From rotating speed control in 1500rpm, filter out precipitation, then by being freeze-dried, the treatment temperature of freeze-drying is -25 DEG C,
Pressure control obtains metal-organic framework crystalline material in 600Pa；
（2）The metal-organic framework crystalline material is added in dry method ball mill, the medium ball of ball milling is situated between for corundum
Matter, drum's speed of rotation control obtain the metal-organic framework powder that grain size is 15 μm of skeleton structures in 2400rpm；
（3）The Pt nano-particles for being 120nm by the first face of carbon fiber layer coating grain size, carbon fiber draw ratio in carbon fiber layer
It is 35, a diameter of 65 μm, be 1.5 according to metal-organic framework powder and Pt nano powder mass ratioes：1 takes metal-organic framework powder
Body, the back side progress hot pressing of metal-organic framework powder and coating Pt nano powder carbon fiber layers is compound, 350 DEG C are heated to, is added
Load pressure is 0.8Mpa, carries out hot-pressing processing, metal-organic framework powder is made uniformly to be embedded in the carbon fibre carrier back side, is formed
Dot matrix adsorption layer obtains the fuel-cell catalyst of metal-organic framework powder modification.
The fuel-cell catalyst that the metal-organic framework powder prepared in the present embodiment is modified is as battery
Anode and cathode, it is 5cm to be prepared as effect area2Monocell, output power density highest of the monocell under room temperature (25 DEG C)
Up to 32.4mW/cm 2, in fuel gas (100ppmCO/H2) flow be 50ml/min, air mass flow 600ml/min, behaviour
It is 0.1MPa as pressure, under the conditions of battery temperature is 60 DEG C, after being activated to battery after 5min, continuous work 100 hours
Afterwards, it measures output power density and reaches as high as 30.8mW/cm 2, battery current do not have significant change, CO tolerance catalysts effect bright
It is aobvious.
Embodiment 5
（1）7 parts of iron powders are mixed with 18 parts of nitric acid by weight, after iron powder is completely dissolved, be added 2 parts of phthalic acids and
1 part of hydrofluoric acid carries out hydro-thermal process after stirring evenly, hydrothermal temperature is controlled at 82 DEG C, by centrifuging precipitation, centrifugation point
From rotating speed control in 1200rpm, filter out precipitation, then by being freeze-dried, the treatment temperature of freeze-drying is -30 DEG C,
Pressure control obtains metal-organic framework crystalline material in 200Pa；
（2）The metal-organic framework crystalline material is added in dry method ball mill, the medium ball of ball milling is situated between for corundum
Matter, drum's speed of rotation control obtain the metal-organic framework powder that grain size is 250 μm of skeleton structures in 2500rpm；
（3）The Pt nano-particles for being 120nm by the first face of carbon fiber layer coating grain size, carbon fiber draw ratio in carbon fiber layer
It is 35, a diameter of 70 μm, be 0.9 according to metal-organic framework powder and Pt nano powder mass ratioes：1 takes metal-organic framework powder
Body, the back side progress hot pressing of metal-organic framework powder and coating Pt nano powder carbon fiber layers is compound, 350 DEG C are heated to, is added
Load pressure is 1.0Mpa, carries out hot-pressing processing, metal-organic framework powder is made uniformly to be embedded in the carbon fibre carrier back side, is formed
Dot matrix adsorption layer obtains the fuel-cell catalyst of metal-organic framework powder modification.
The fuel-cell catalyst that the metal-organic framework powder prepared in the present embodiment is modified is as battery
Anode and cathode, it is 5cm to be prepared as effect area2Monocell, output power density highest of the monocell under room temperature (25 DEG C)
Up to 26.7mW/cm 2, in fuel gas (100ppmCO/H2) flow be 50ml/min, air mass flow 600ml/min, behaviour
It is 0.1MPa as pressure, under the conditions of battery temperature is 60 DEG C, after being activated to battery after 5min, continuous work 100 hours
Afterwards, it measures output power density and reaches as high as 26.0mW/cm 2, battery current do not have significant change, CO tolerance catalysts effect bright
It is aobvious.
Comparative example 1
It is impregnated in chloroplatinic acid the carbon paper of anode diffusion layer, under the conditions of hydrogen reducing, by crystal reaction tube temperature
600 DEG C are increased to, and is kept for 2 hours, cathod catalyst and anode catalyst of the 20wt%Pt/C for PEMFC are obtained, it will
Its prepared effective area is 5cm2Monocell, output power density of the monocell under room temperature (25 DEG C) reach as high as
12.1mW/cm2 , in fuel gas (100ppmCO/H 2) flow be 50ml/min, air mass flow 600ml/min, operation pressure
Power is 0.1MPa, and battery temperature is 60 DEG C, and after being activated to battery after 5min, continuous work measures defeated after 100 hours
Go out power density and is up to 6.1mW/cm2, cell voltage electric current all reduced, and CO tolerance catalysts effect is bright not as good as embodiment 1
It is aobvious.
Comparative example 2
According to 1 technological process of same embodiment, the fuel-cell catalyst of metal organic frame modification is prepared, is then used with it
In the cathod catalyst of PEMFC, anode catalyst is used for 20wt%Pt/C, it is 5cm to be prepared as effect area2Monocell, it is single
Output power density of the battery under room temperature (25 DEG C) reaches as high as 19.1mW/cm 2 , in fuel gas (100ppmCO/H2 )
Flow is 50ml/min, and air mass flow 600ml/min, operating pressure is 0.1MPa, under the conditions of battery temperature is 60 DEG C,
After being activated to battery after 5min, continuous work measures output power density and is up to 11.7mW/cm after 100 hours2, electricity
Cell voltage electric current is all reduced, and CO tolerance catalysts effect is apparent not as good as embodiment 1, further illustrates that MOFs is used as cathode simultaneously
When with anode catalyst, Pt/C Catalytic Layer better catalytic activities.
Table 2
Claims (8)
1. a kind of fuel-cell catalyst of metal-organic framework modification, which is characterized in that the catalyst structure includes that Pt receives
The Pt/C catalyst layers and be uniformly embedded in the carbon fiber that rice flour body uniform load is formed to the first face of carbon fiber layered vector
Carrier is different from the metal-organic framework powder layer on second face in first face；Wherein, the metal-organic framework powder
Body is the skeleton structure that metallic iron is generated with benzoic acid type organic complex reaction；
The preparation method of the catalyst, includes the following steps：
（1）3-7 parts of iron powders are mixed with 14-20 parts of nitric acid by weight, after iron powder is completely dissolved, 2-3 parts of benzoic acid classes are added
Organic matter and 1-2 parts of hydrofluoric acid carry out hydro-thermal process after stirring evenly, hydrothermal temperature is controlled at 80-98 DEG C, by centrifugation point
From precipitation, precipitation is filtered out, then metal-organic framework crystalline material is obtained by freeze-drying；
（2）The metal-organic framework crystalline material is added in dry method ball mill, ball mill grinding obtains gold to 10-300 μm
Category-organic frame powder；
（3）The first face of carbon fiber layer is coated into Pt nano-powders, by the metal-organic framework powder and carbon fiber layer difference with
The second face progress hot pressing in first face is compound, so that powder is uniformly embedded in the second face described in carbon fibre carrier, forms dot matrix
Adsorption layer obtains the fuel-cell catalyst of metal-organic framework powder modification.
2. a kind of fuel-cell catalyst of metal-organic framework modification as described in claim 1, which is characterized in that described
The grain size of metal-organic framework powder is 10-300 μm, and the Pt particle diameter of nanometer powder is 50-200nm, the carbon fiber major diameter
Than for 5-50, a diameter of 10-100 μm.
3. a kind of fuel-cell catalyst of metal-organic framework modification as described in claim 1, which is characterized in that described
Metal-organic framework powder is 0.8-1.5 with the Pt nano-powders mass ratio：1.
4. a kind of fuel-cell catalyst of metal-organic framework modification according to claim 1, which is characterized in that institute
It is one kind in benzoic acid, phenylacetic acid, benzenpropanoic acid, phthalic acid to state benzoic acid type organic.
5. a kind of fuel-cell catalyst of metal-organic framework modification according to claim 1, which is characterized in that institute
The rotating speed for stating centrifugation is controlled in 500-2000rpm.
6. a kind of fuel-cell catalyst of metal-organic framework modification according to claim 1, which is characterized in that institute
The treatment temperature for stating freeze-drying is -40 ~ -20 DEG C, and pressure control is in 10-700Pa.
7. a kind of fuel-cell catalyst of metal-organic framework modification according to claim 1, which is characterized in that institute
The medium ball for stating ball milling is corundum medium, and drum's speed of rotation is controlled in 800-3000rpm.
8. a kind of fuel-cell catalyst of metal-organic framework modification according to claim 1, which is characterized in that institute
It states hot pressing to be complex as being heated to 200-450 DEG C, on-load pressure is 0.8-1.5 MPa.
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