CN108054392A - A kind of preparation method and application of the bionic oxygen reduction electro-catalyst based on transition metal macrocycle - Google Patents

A kind of preparation method and application of the bionic oxygen reduction electro-catalyst based on transition metal macrocycle Download PDF

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CN108054392A
CN108054392A CN201711370053.2A CN201711370053A CN108054392A CN 108054392 A CN108054392 A CN 108054392A CN 201711370053 A CN201711370053 A CN 201711370053A CN 108054392 A CN108054392 A CN 108054392A
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carbon
transition metal
fused ring
ring compound
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CN108054392B (en
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宋玉江
韩洪仨
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Dalian University of Technology
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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
    • H01M4/8825—Methods for deposition of the catalytic active composition
    • 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
    • H01M4/9008—Organic or organo-metallic compounds
    • 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
    • H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
    • H01M4/9083—Catalytic material 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 Kinetics & Catalysis (AREA)
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Abstract

The present invention provides a kind of preparation method and applications of the bionic oxygen reduction electro-catalyst based on transition metal macrocycle, belong to catalyst of fuel batter with proton exchange film technical field.Carbon material is scattered in solvent, adds aromatic fused ring compound, ultrasound, 2~48h of stirring is filtered, and washs to filtrate achromaticity and clarification, product is dried, and obtains aromatic fused ring compound absorption carbon intermediate product.Gained aromatic fused ring compound absorption carbon complex is scattered in solution, transition metal macrocycle is added under the conditions of inert nitrogen gas or argon gas, 1~48h is stirred under the conditions of 25~100 DEG C, filtration washing is colourless to filtrate, drying.Obtain transition metal macrocycle/aromatic fused ring compound/carbon elctro-catalyst.Easy to operate, easily controllable, mild condition of the invention, the transition metal macrocycle/aromatic fused ring compound/carbon elctro-catalyst being prepared has very high oxygen reduction activity, available for Proton Exchange Membrane Fuel Cells.

Description

A kind of preparation of the bionic oxygen reduction electro-catalyst based on transition metal macrocycle Method and application
Technical field
The invention belongs to Electro Catalysts for PEMFC technical field, be related to a kind of transition metal macrocycle/ The preparation method and application of azacyclo- functionalization aromatic fused ring compound/carbon elctro-catalyst.
Background technology
Proton Exchange Membrane Fuel Cells (PEMFC) is received since power density is high, starts fast, advantages of environment protection Extensive concern.Platinum-based electrocatalyst is one of core material of PEMFC, but platinum dosage is big, expensive, limits PEMFC Extensive use.One of solution is the base metal elctro-catalyst of developing low-cost, high efficiency and high stability to replace For platinum-based electrocatalyst, to promote the commercialization process of PEMFC.
It is well known that biological enzyme has high catalytic activity and selectivity in vivo.Wherein cromoci aoxidizes The hydrogen reduction enzyme using metalloporphyrin macrocyclic compound as major catalytic site such as enzyme, cytochrome P 450 enzymes all has very excellent Catalytic oxidation-reduction reaction ability, to we provide very more bionical references, such as on metalloporphyrin introduce imidazoles, The axial ligand of the azacyclo-s such as pyridine as transition metal macrocycle etc..Wei etc. is fixed imidazole group by covalent linkage Ferriporphyrin is supported on carbon nanotubes in carbon nano tube surface, then by the axial coordination of metalloporphyrin and imidazole group On imidazole group, obtained elctro-catalyst have very high oxygen reduction activity and good durability (Angew.Chem., 2014, 126, 6777-6781).Cao etc. supports pyridine on the carbon material by covalent bond, is acted on afterwards also with axial ligand The sample that iron-phthalocyanine is complexed has higher oxygen reduction activity and preferable durability (Nature Communications,2013,4,2076-2092).However it is complicated by fixing covalent bond experimental method on the carbon nanotubes, Covalent bond substitution efficiency is low, and the derivative of covalent bond can make script SP in script carbon nanotubes2The big pi bond of hydridization becomes SP3It is miscellaneous Change, destroy the conductive capability of script carbon material.
Method made above is simplified and is optimized by the present invention, we attempt a kind of non-covalent bond functionalized carbon nanometer material The method that material fixes transition metal macrocycle using axial ligand.Numerous reports show aromatic fused ring compound (such as：Pyrene, anthracene) It can interact that Irreversible Adsorption (Nanoscience and occur by its strong π-π between carbon material Nanotechnology,2007,7,3081-3088).We are made by the azacyclo- functionalization to aromatic fused ring compound Its ability with complexing metal macrocyclic compound, so as to make Metallomacrocycle chemical combination in the case where not destroying carbon material electric conductivity The complexing that object can be stablized enhances its hydrogen reduction catalytic capability on nitrogen heterocyclic.
The content of the invention
The object of the present invention is to provide transition metal macrocycle/azacyclo- functionalization aromatic fused ring compound/carbon is bionical The preparation method and application of elctro-catalyst, this method is easy to operate, easily controllable, mild condition.The Metallomacrocycle chemical combination Object/azacyclo- functionalization aromatic fused ring compound/bionical elctro-catalyst of carbon is with the carbon materials with high-specific surface area and high conductivity Material, using the aromatic fused ring compound of nitrogen heterocyclic ring functionalization as bridged linkage, on the one hand can pass through condensed ring virtue as carrier Irreversible Adsorption occurs for fragrant structure and the strong π-π interactions of carbon material key, right on the premise of carbon material electric conductivity is not destroyed Carbon material carries out azacyclo- functionalization, and another aspect azepine ring structure, which carries out transition metal macrocycle ligand complex, becomes bionical Oxygen reduction catalytic activity center.The transition metal macrocycle being prepared/azacyclo- functionalization aromatic fused ring compound/carbon is bionical Elctro-catalyst has preferable hydrogen reduction comprehensive performance, available for Proton Exchange Membrane Fuel Cells.
Technical scheme：
A kind of preparation method of the bionic oxygen reduction electro-catalyst based on transition metal macrocycle, step are as follows：
Carbon material is dispersed in solution, wherein, the concentration of carbon material in the solution is 0.1~100 mg/ml, then Azacyclo- functionalization aromatic fused ring compound is added in, controls the concentration of azacyclo- functionalization aromatic fused ring compound to be in the solution 0.1~100mg/ml；Under the conditions of -20~30 DEG C, be ultrasonically treated 0.1-5h, stirring 2~48h filter, wash it is colourless to filtrate, Product is dried, obtains aromatic fused ring compound absorption carbon intermediate product；Gained intermediate product is scattered in solution, in inertia Under the conditions of gas nitrogen or argon gas, transition metal macrocycle is added in, 1~48h, filtration washing are stirred under the conditions of 25~100 DEG C It is colourless to filtrate, it dries to get to the bionic oxygen reduction electro-catalyst based on transition metal macrocycle；
The azacyclo- functionalization aromatic fused ring compound and the mass ratio of carbon material are more than 0.01:1；
The amount of substance ratio of the transition metal macrocycle and azacyclo- functionalization aromatic fused ring compound is more than 0.1:1.
Azacyclo- functionalization aromatic fused ring compound such as the structural formula A-F, wherein n=0~10；
Monosubstituted situation, containing position on the substituent group of imidazoles or pyridine substitution pyrenyl or anthryl 1,2,3 in structural formula Number carbon；Wherein, the on-link mode (OLM) in the imidazole group structural formula such as structural formula in structural formula A, B, D, E；Pyridine takes in C and F Subrogate that put can be ortho position compared with pyridine " N ", meta or para position；
1-10 carbon on polysubstituted situation, pyrenyl or anthryl all can be by the official containing imidazoles, pyridine or both mixture It can roll into a ball and be substituted, substituent group quantity >=2；
The transition metal macrocycle is metal tetraphenylporphyrin, tetramethoxy phenyl porphyrin, four (4- carboxyl phenyls) Mixture more than one or both of porphyrin, hemin, 2,6- difluoros tetraphenylporphyrin, metal phthalocyanine, wherein, it is described Metal is iron or cobalt.
The carbon material is more than one or both of carbon black, activated carbon, carbon nanotubes, carbon fiber, graphene Mixture.
The solution is methanol, ethyl alcohol, dichloromethane, acetonitrile, tetrahydrofuran, hexamethylene, toluene, N, N- dimethyl Mixture more than one or both of formamide.
The bionic oxygen reduction electro-catalyst based on transition metal macrocycle obtained with above-mentioned preparation method is applied to Proton Exchange Membrane Fuel Cells.
The beneficial effects of the present invention are：1) carbon is cheap and easy to get, good conductivity and is easy to aromatic fused ring compound catalyst It adsorbs, while huge specific surface area can be provided for catalyst；2) aromatic fused ring compound of azacyclo- functionalization can be Irreversible Adsorption and axial complexing metal macrocyclic compound are realized on the premise of not destroying script carbon material electric conductivity to carbon material Be conducive to improve the electronics between Metallomacrocycle structure and carbon material and conduct the 3) Metallomacrocycle with imidazoles or pyridine axial coordination Compound structure is more preferable closer to catalytic activity with planting structure in biological enzyme.
Description of the drawings
Fig. 1 is the transition metal macrocycle/azacyclo- functionalization aromatic fused ring compound/bionical catalyst series of carbon prepared Synthetic route schematic diagram.
Irreversible Adsorption product occurs on the carbon nanotubes for 1 gained compound A of Fig. 2 embodiment of the present invention under the conditions of argon gas Thermogravimetric analysis (TG) curve.
The redox reactions polarization curve of 1 gained final product of Fig. 3 embodiment of the present invention, test condition：At 25 DEG C, In the 0.1M HClO of oxygen saturation4In, speed is swept with 10mV/s, electric potential scanning is carried out under the voltage of 0-1.2V (vs RHE) Test, electrode rotating speed are 1600r/min.Polarization curve shows that 1 gained base metal elctro-catalyst of embodiment has more aerobic go back Former catalytic activity.
Specific embodiment
The present invention is further illustrated with reference to the accompanying drawings and examples, and following embodiment is in order to clearly Illustrate the present invention, but the scope of protection of present invention is not limited to the scope of following embodiment statement.
Embodiment 1：
By 10mg multi-walled carbon nanotubes, 40mg compounds A (n=1) is scattered in 5ml n,N-Dimethylformamide solution In, 25 DEG C of ultrasound 30min stand under the conditions of -10 DEG C, filter afterwards for 24 hours, and n,N-Dimethylformamide is washed to the pure nothing of filtrate Color is dried at 65 DEG C, and acquired black powder solid is scattered in 10ml methanol solutions and adds in 40mg hemins in nitrogen It is stirred under the conditions of 25 DEG C of condition for 24 hours, filtering methanol washs, drying colourless to filtrate.
Embodiment 2：
By 50mg multi-walled carbon nanotubes, 30mg compounds B (n=2) is scattered in 5ml tetrahydrofuran solutions, 25 DEG C of ultrasounds 30min, static under the conditions of -10 DEG C to filter afterwards for 24 hours, tetrahydrofuran washs pure colourless to filtrate, is dried at 65 DEG C, by institute It obtains black powder solid and is scattered in 10ml methanol solutions adding in 40mg Cobalt Phthalocyanines and stirring under the conditions of 55 DEG C of condition of nitrogen gas For 24 hours, filtering methanol washs, drying colourless to filtrate.The pattern and performance of gained catalyst are similar to 1 sample of embodiment, have Preferable hydrogen reduction comprehensive performance.
Embodiment 3：
By 20mg graphenes, 100mg compounds C (n=4) is scattered in 5ml cyclohexane solutions, 25 DEG C of ultrasound 120min, It is filtered after static 48h under the conditions of 20 DEG C, hexamethylene washs pure colourless to filtrate, is dried at 65 DEG C, by acquired black Powder solid, which is scattered in 10ml cyclohexane solutions, adds in 40mg tetramethoxy phenyl ferriporphyrins under the conditions of 80 DEG C of condition of nitrogen gas 12h is stirred, filtering hexamethylene washs, drying colourless to filtrate.The pattern and performance and 1 sample phase of embodiment of gained catalyst Seemingly, there is preferable hydrogen reduction comprehensive performance.
Embodiment 4：
By 100mg carbon blacks, 200mg compounds E (n=5) is scattered in 10ml dichloromethane solutions, 25 DEG C of ultrasound 30min, It is filtered after static 12h under the conditions of 0 DEG C, dichloromethane washs pure colourless to filtrate, is dried at 65 DEG C, by acquired black Powder solid is scattered in 10ml, and 20mg FePCs are added in dichloromethane solution and are stirred for 24 hours under the conditions of 45 DEG C of condition of nitrogen gas, mistake Filter dichloromethane washs, drying colourless to filtrate.The pattern and performance of gained catalyst are similar to 1 sample of embodiment, have compared with Good hydrogen reduction comprehensive performance.
Embodiment 5：
By 30mg carbon fibers, 2mg compounds F (n=7) is scattered in 20ml dichloromethane solutions, 25 DEG C of ultrasound 20min, It is filtered after static 6h under the conditions of -20 DEG C, dichloromethane washs pure colourless to filtrate, is dried at 65 DEG C, will be acquired black Color powder solid, which is scattered in 50ml dichloromethane solutions, adds in (4- carboxyl phenyls) Cob altporphyrins of 20mg tetra- in 45 DEG C of condition of nitrogen gas Under the conditions of stir 2h, filter, tetrahydrofuran wash it is colourless to filtrate, drying.The pattern and performance of gained catalyst and embodiment 1 Sample is similar, has preferable hydrogen reduction comprehensive performance.
Embodiment 6：
By 40mg carbon blacks, 500mg compounds H (n=9) is scattered in 10ml toluene solutions, 25 DEG C of ultrasound 10min, in 0 Static under the conditions of DEG C to filter afterwards for 24 hours, dichloromethane washs pure colourless to filtrate, is dried at 65 DEG C, by acquired black powder Last solid, which is scattered in 10ml toluene solutions, to be added in 10mg tetraphenyls ferriporphyrin and stirs 8h, mistake under the conditions of 25 DEG C of condition of nitrogen gas Filter, toluene wash, drying colourless to filtrate.The pattern and performance of gained catalyst are similar to 1 sample of embodiment, have preferable Hydrogen reduction comprehensive performance.
Embodiment 7：
By 5mg single-walled carbon nanotubes, 100mg compounds D (n=10) is scattered in 10ml toluene solutions, 25 DEG C of ultrasounds 10min, static under the conditions of 0 DEG C to filter afterwards for 24 hours, methanol washs pure colourless to filtrate, is dried at 65 DEG C, will be acquired black Color powder solid, which is scattered in 10ml toluene solutions, adds in 10 mg 2,6- difluoro tetraphenyl ferriporphyrins in 25 DEG C of items of condition of nitrogen gas It is stirred under part for 24 hours, filtering, toluene washs, drying colourless to filtrate.The pattern and performance of gained catalyst and 1 sample of embodiment It is similar, there is preferable hydrogen reduction comprehensive performance.

Claims (10)

  1. A kind of 1. preparation method of the bionic oxygen reduction electro-catalyst based on transition metal macrocycle, which is characterized in that step It is rapid as follows：
    Carbon material is dispersed in solution, wherein, the concentration of carbon material in the solution is 0.1~100mg/ml, is added Azacyclo- functionalization aromatic fused ring compound, it is 0.1 to control the concentration of azacyclo- functionalization aromatic fused ring compound in the solution ~100mg/ml；Under the conditions of -20~30 DEG C, 0.1-5h is ultrasonically treated, 2~48h of stirring is filtered, and washs, general colourless to filtrate Product is dried, and obtains aromatic fused ring compound absorption carbon intermediate product；Gained intermediate product is scattered in solution, in indifferent gas Under the conditions of body nitrogen or argon gas, transition metal macrocycle is added in, 1~48h is stirred under the conditions of 25~100 DEG C, filtration washing is extremely Filtrate is colourless, dries to get to the bionic oxygen reduction electro-catalyst based on transition metal macrocycle；
    The azacyclo- functionalization aromatic fused ring compound and the mass ratio of carbon material are more than 0.01:1；
    The amount of substance ratio of the transition metal macrocycle and azacyclo- functionalization aromatic fused ring compound is more than 0.1:1.
  2. 2. preparation method according to claim 1, which is characterized in that the azacyclo- functionalization aromatic fused ring compound Such as structural formula A-F, wherein n=0~10；
    Monosubstituted situation, substituent group substitution pyrenyl or anthryl on position 1 in structural formula, 2, No. 3 carbon；Wherein, structural formula A, B, D, the on-link mode (OLM) in the imidazole group structural formula such as structural formula in E；The position of substitution of pyridine is compared with pyridine " N " in C and F Ortho position, meta or para position；
    1-10 carbon on polysubstituted situation, pyrenyl or anthryl all can be by the functional group containing imidazoles, pyridine or both mixture Substituted, substituent group quantity >=2；
  3. 3. preparation method according to claim 1 or 2, which is characterized in that the transition metal macrocycle is metal four Phenyl porphyrin, tetramethoxy phenyl porphyrin, four (4- carboxyl phenyls) porphyrins, hemin, 2,6- difluoros tetraphenylporphyrin, metal phthalein Mixtures more than one or both of cyanines, wherein, the metal is iron or cobalt.
  4. 4. preparation method according to claim 1 or 2, which is characterized in that the transition metal macrocycle and azacyclo- It is connected between functionalization aromatic fused ring compound by coordinate bond.
  5. 5. preparation method according to claim 1 or 2, which is characterized in that the carbon material is carbon black, activated carbon, carbon Mixture more than one or both of nanotube, carbon fiber, graphene.
  6. 6. preparation method according to claim 3, which is characterized in that the carbon material is carbon black, activated carbon, carbon nanometer Mixture more than one or both of pipe, carbon fiber, graphene.
  7. 7. according to the preparation method described in claim 1,2 or 5, which is characterized in that the solution is methanol, ethyl alcohol, dichloro Mixture more than one or both of methane, acetonitrile, tetrahydrofuran, hexamethylene, toluene, N,N-dimethylformamide.
  8. 8. preparation method according to claim 3, which is characterized in that the solution for methanol, ethyl alcohol, dichloromethane, Mixture more than one or both of acetonitrile, tetrahydrofuran, hexamethylene, toluene, N,N-dimethylformamide.
  9. 9. preparation method according to claim 4, which is characterized in that the solution for methanol, ethyl alcohol, dichloromethane, Mixture more than one or both of acetonitrile, tetrahydrofuran, hexamethylene, toluene, N,N-dimethylformamide.
  10. 10. the bionic oxygen reduction electro-catalyst based on transition metal macrocycle obtained with above-mentioned preparation method is applied to matter Proton exchange film fuel cell.
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CN110208323A (en) * 2019-05-30 2019-09-06 济南大学 For detecting the organic/inorganic composite material and gas sensor of nitrogen dioxide
CN111146457A (en) * 2019-12-27 2020-05-12 大连理工大学 Preparation and application of porous composite material electrocatalyst based on bimetallic macrocyclic compound
CN111146452A (en) * 2019-12-27 2020-05-12 大连理工大学 Porphyrin zeolite imidazole framework hybrid electrocatalyst and preparation method and application thereof
CN111370712A (en) * 2020-02-24 2020-07-03 中南大学 Preparation method of high-activity electrochemical oxygen reduction catalyst
CN112366325A (en) * 2020-11-10 2021-02-12 河北工业大学 Preparation method and application of carbon nanotube loaded iron phthalocyanine composite material with adjustable functional groups
CN113072547A (en) * 2021-03-31 2021-07-06 广东工业大学 Compound and triplet-triplet annihilation up-conversion system

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CN110208323A (en) * 2019-05-30 2019-09-06 济南大学 For detecting the organic/inorganic composite material and gas sensor of nitrogen dioxide
CN111146457A (en) * 2019-12-27 2020-05-12 大连理工大学 Preparation and application of porous composite material electrocatalyst based on bimetallic macrocyclic compound
CN111146452A (en) * 2019-12-27 2020-05-12 大连理工大学 Porphyrin zeolite imidazole framework hybrid electrocatalyst and preparation method and application thereof
CN111370712A (en) * 2020-02-24 2020-07-03 中南大学 Preparation method of high-activity electrochemical oxygen reduction catalyst
CN112366325A (en) * 2020-11-10 2021-02-12 河北工业大学 Preparation method and application of carbon nanotube loaded iron phthalocyanine composite material with adjustable functional groups
CN113072547A (en) * 2021-03-31 2021-07-06 广东工业大学 Compound and triplet-triplet annihilation up-conversion system
CN113072547B (en) * 2021-03-31 2022-10-21 广东工业大学 Compound and triplet-triplet annihilation up-conversion system

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