CN109962246A - The loaded low platinum nucleocapsid catalyst of one kind and its preparation and application - Google Patents
The loaded low platinum nucleocapsid catalyst of one kind and its preparation and application Download PDFInfo
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- CN109962246A CN109962246A CN201711337993.1A CN201711337993A CN109962246A CN 109962246 A CN109962246 A CN 109962246A CN 201711337993 A CN201711337993 A CN 201711337993A CN 109962246 A CN109962246 A CN 109962246A
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Abstract
The present invention relates to a kind of loaded low platinum nucleocapsid catalysts and preparation method thereof, the method is obtained metal nanoparticle supports after the metal organic framework pyrolysis using transition metal (Co, Fe, Zn) doping porous carbon skeleton as carrier, being formed by the method for chemistry displacement using transition metal is core using platinum as the low platinum catalyst with core-casing structure of shell, and the component and size of core-shell structure can be realized by the metal ratio changed in multi-element metal organic backbone.Compared with prior art, the invention has the advantages that the Zn-ef ficiency in the organometallic skeletal of preparation can be used as barrier in pyrolytic process and the transition metal nanoparticles to be formed prevented to reunite, Zn-ef ficiency is more than that can evaporate with atmosphere after 900 DEG C in temperature, will not be remained in the catalyst；The platinum supported is supported on transiting metal surface in the form of shell in core-shell structure, and the carrying capacity poor efficiency of platinum is high；Transition metal nuclear energy in core-shell structure changes the Electronic Performance on platinum surface, to adjust catalytic performance；Organometallic skeletal is pyrolyzed to form the porous carbon supported of high-ratio surface, be conducive to active sites be uniformly distributed and the mass transfer of reaction process.
Description
Technical field
The present invention relates to catalyst preparation and its application fields, and in particular to a kind of system of loaded low platinum nucleocapsid catalyst
Standby and application.
Background technique
The advantages that fuel cell is due to clean and effective helps to alleviate global energy and environmental pressure, has in future wide
Wealthy application prospect.In recent years, fuel cell technology achieves biggish breakthrough in material, equipment and technical aspect, however,
Largely its commercialization process is hindered using cost is excessively high caused by noble metal catalyst.Due to being only exposed to the atom on surface
Could participate in catalysis reaction, the utilization efficiency of platinum is usually lower in traditional elctro-catalyst, people by design catalyst structure or
Person is that the mode of doping improves the utilization efficiency of platinum, forms a series of new low-platinum catalyst, for example, platinum alloy, core-shell structure,
Hollow nano skeleton, nano thin-film etc..
The low-platinum catalyst of core-shell structure generallys use cheaper and resourceful metal nanoparticle makees core, then
In the platinum (or platinum alloy) of its surface covering a thin layer (even monoatomic layer), noble metal platinum is increased substantially to realize
Utilization rate, and core metal and surface crust can further promote platinum by interactions such as geometry, electronics and stress
Catalytic activity finds a kind of simple and effective means and carrys out the volume composition of modulation core metal to change these interactions,
It has a very important significance.
Summary of the invention
The present invention is directed to the problem that pt utilization is low in traditional platinum catalyst, proposes a kind of low platinum catalyst with core-casing structure
Preparation method, the present invention realized using scheme in detail below:
A kind of loaded low platinum nucleocapsid catalyst, it is characterised in that: the low platinum nucleocapsid catalyst is with transition metal nanometer
Particle is core, and monoatomic layer platinum is shell, is supported on the porous carbon materials of N doping.The core-shell structure diameter is 2-10nm；
The molar ratio of transition metal core and platinum shell is 1:10-1:100.Transition metal core be formed in situ during heat treatment and support in
On carrier, consisting of one or more of Co, Fe, Ni, loading is mass fraction 5%-20%.Monoatomic layer platinum
Shell passes through chemical Substitutive Coating on transition metal nanometer core surface.The porous carbon support of the N doping is by metal organic framework
Organic component formed during heat treatment, and keep original space structure, diameter is 50nm-1 μm, specific surface 500-
1500cm2g-1；Nitrogen element content is 2%-8% in carrier, and form existing for N element is pyridine N, pyrroles N, is graphitized N and oxygen
Change one or more of N.
The preparation method of the low platinum nucleocapsid catalyst includes the following steps,
(1) synthesis of metal organic framework: the mixed solution of zinc salt, transition metal salt and organic ligand is prepared；
It is reacted under the conditions of 30 DEG C -120 DEG C, metal organic framework is then separated to obtain by centrifugation or suction filtration；
(2) preparation of the porous carbon materials of loaded N doping: the metal organic framework that step (1) is obtained is in indifferent gas
The porous carbon materials that high temperature cabonization must be supported with the N doping of transition metal nanoparticles are carried out under atmosphere；
(3) preparation of loaded low platinum nucleocapsid catalyst: the porous carbon materials for the loaded N doping that step (2) are obtained
Slurries are made in Yu Shuizhong, and chloroplatinic acid aqueous solution is added dropwise in the slurries under inert gas shielding and continues stirring until slurries
Uniformly, it is filtered, washed to obtain loaded low platinum nucleocapsid catalyst.
Zinc salt described in step (1) and transition metal salt have same anion；The transition metal salt be cobalt nitrate,
The one or more of cobalt chloride, ferric nitrate, iron chloride, nickel nitrate, nickel chloride；The organic ligand is 2-methylimidazole；
The solvent is one or more of methanol, ethyl alcohol, water and DMF.
Zinc ion concentration is 0.0125-0.1mol/L, zinc ion and transition metal ions in step (1) described mixed solution
Molar ratio be 100:1-1:1；The ratio of the amount of the substance of zinc ion and organic ligand is 1:4-1:8.
High temperature cabonization treatment process described in step (2) is to be warming up to 900-1100 DEG C and keep 0.5-3h, is then cooled down
To room temperature；The heating rate of slave room temperature to carburizing temperature in the temperature-rise period is 2-5 DEG C/min；The temperature-fall period
Middle rate of temperature fall is 1-10 DEG C/min；The inert atmosphere is one or both of nitrogen, argon gas, helium, neon.
The concentration of slurries described in step (3) is 1-5g L-1；Inert gas is nitrogen, argon gas, helium, one in neon
Kind or two kinds of gaseous mixture；The concentration of chloroplatinic acid aqueous solution is 100-1000 μ g mL-1；The slurries and chloroplatinic acid aqueous solution
Volume ratio is 1:10-1:100.
The application of the low platinum nucleocapsid catalyst, the catalyst can be polymer dielectric film fuel cell and metal
Air battery cathode oxygen reduction reaction elctro-catalyst.
Compared with prior art, the present invention has the advantage that Zn-ef ficiency in organometallic skeletal can in pyrolytic process
To prevent the transition metal nanoparticles to be formed from reuniting as barrier, Zn-ef ficiency is more than in temperature can be with gas after 800 DEG C
Atmosphere evaporation, will not remain in the catalyst；The platinum supported is supported on transition in the form of shell in core-shell structure terminates surface, platinum
Carrying capacity poor efficiency is high；Transition metal nuclear energy in core-shell structure changes the Electronic Performance on platinum surface, to adjust catalytic performance；
Organometallic skeletal is pyrolyzed to form the porous carbon supported of high-ratio surface, be conducive to active sites be uniformly distributed and the biography of reaction process
Matter.Before having wide application for polymer dielectric film fuel cell and metal air battery cathodes oxygen reduction reaction elctro-catalyst
Scape.
Detailed description of the invention
Fig. 1: metal organic framework low power SEM photograph (embodiment 1)
Fig. 2: porous carbon support low power SEM photograph (embodiment 1)
Fig. 3: low platinum nucleocapsid catalyst XRD diagram piece (embodiment 1)
Fig. 4: low platinum nucleocapsid catalyst hydrogen reduction LSV curve (embodiment 1)
Specific embodiment
Comparative example 1
At 20 DEG C, the zinc nitrate hexahydrate of 1.470g is dissolved in 100ml methanol, 3.260 2-methylimidazole is dissolved in
100ml methanol, the former is added slowly with stirring in the latter, continues to stir 12min, is then allowed to stand 20h.Centrifuge separation, washing
Three times, it is dried in vacuo 8h at a temperature of 150 DEG C, obtains ZIF8.It takes 1g ZIF8 to be placed in corundum boat, is added with 2 DEG C/min heating rate
Heat is to 900 DEG C and keeps the temperature 2h, then is cooled to room temperature taking-up porous carbon support with 5 DEG C/min rate of temperature fall.100mg is porous carbon supported
Body is dispersed in 100mL deionized water, is passed through nitrogen protection, ultrasonic half an hour, then 100 μ g mL of 10ml is added dropwise-1Chlorine
Platinic acid aqueous solution, persistently stirs 8h, carries out decompression suction filtration and obtains catalyst, is washed with 1L deionized water, and carry out at 80 DEG C
Vacuum drying.
It is found by XRD characterization, due to not having addition transition metal, final Pt can not be supported on catalysis by chemistry displacement
In agent.
Comparative example 2
At 20 DEG C, the cabaltous nitrate hexahydrate of 1.470g is dissolved in 100ml methanol, 3.260 2-methylimidazole is dissolved in
100ml methanol, the former is added slowly with stirring in the latter, continues to stir 12min, is then allowed to stand 20h.Centrifuge separation, washing
Three times, it is dried in vacuo 8h at a temperature of 150 DEG C, obtains ZIF8.It takes 1g ZIF8 to be placed in corundum boat, is added with 2 DEG C/min heating rate
Heat is to 900 DEG C and keeps the temperature 2h, then is cooled to room temperature taking-up porous carbon support with 5 DEG C/min rate of temperature fall.100mg is porous carbon supported
Body is dispersed in 100mL deionized water, is passed through nitrogen protection, ultrasonic half an hour, then 100 μ g mL of 10ml is added dropwise-1Chlorine
Platinic acid aqueous solution, persistently stirs 8h, carries out decompression suction filtration and obtains catalyst, is washed with 1L deionized water, and carry out at 80 DEG C
Vacuum drying.
By observation scanning electron microscope characterization result discovery, make due to the dense of transition metals cobalt and without zinc
Cobalt metal nanoparticle size for barrier, formation reaches tens nanometer.
Embodiment 1
At 20 DEG C, the cabaltous nitrate hexahydrate of the zinc nitrate hexahydrate of 1.470g, 0.74g is dissolved in 100ml methanol, it will
3.260 2-methylimidazole is dissolved in 100ml methanol, the former is added slowly with stirring in the latter, continues to stir 12min, then
Stand 20h.Centrifuge separation, washing three times, are dried in vacuo 8h at a temperature of 150 DEG C, obtain Zn0.95Co0.05-ZIF8.Take 1g
Zn0.95Co0.05- ZIF8 is placed in corundum boat, is heated to 900 DEG C with 2 DEG C/min heating rate and keeps the temperature 2h, then with 5 DEG C/min cooling
Rate is cooled to room temperature taking-up porous carbon support.100mg porous carbon support is dispersed in 100mL deionized water, nitrogen is passed through
Protection, ultrasonic half an hour, then 10ml100 μ g mL is added dropwise-1Chloroplatinic acid aqueous solution, persistently stir 8h, carry out decompression suction filtration
Catalyst is obtained, is washed with 1L deionized water, and is dried in vacuo at 80 DEG C.
By XRD, the result shows that, Pt is successfully supported on a catalyst, is settled accounts by Scherrer formula, partial size is on 5 nanometers of left sides
It is right.(see Fig. 3)
Embodiment 2
At 20 DEG C, the cabaltous nitrate hexahydrate of the zinc nitrate hexahydrate of 1.470g, 0.147g is dissolved in 100ml methanol, it will
3.260 2-methylimidazole is dissolved in 100ml methanol, the former is added slowly with stirring in the latter, continues to stir 12min, then
Stand 20h.Centrifuge separation, washing three times, are dried in vacuo 8h at a temperature of 150 DEG C, obtain Zn0.9Co0.1-ZIF8.Take 1g
Zn0.95Co0.05- ZIF8 is placed in corundum boat, is heated to 900 DEG C with 2 DEG C/min heating rate and keeps the temperature 2h, then with 5 DEG C/min cooling
Rate is cooled to room temperature taking-up porous carbon support.100mg porous carbon support is dispersed in 100mL deionized water, nitrogen is passed through
Protection, ultrasonic half an hour, then 100 μ g mL of 10ml is added dropwise-1Chloroplatinic acid aqueous solution, persistently stir 8h, carry out decompression pumping
Filter obtains catalyst, is washed with 1L deionized water, and be dried in vacuo at 80 DEG C.
Embodiment 3
At 20 DEG C, the six nitric hydrate iron of the zinc nitrate hexahydrate of 1.470g, 0.74g are dissolved in 100ml methanol, it will
3.260 2-methylimidazole is dissolved in 100ml methanol, the former is added slowly with stirring in the latter, continues to stir 12min, then
Stand 20h.Centrifuge separation, washing three times, are dried in vacuo 8h at a temperature of 150 DEG C, obtain Zn0.95Co0.05-ZIF8.Take 1g
Zn0.95Co0.05- ZIF8 is placed in corundum boat, is heated to 900 DEG C with 2 DEG C/min heating rate and keeps the temperature 2h, then with 5 DEG C/min cooling
Rate is cooled to room temperature taking-up porous carbon support.100mg porous carbon support is dispersed in 100mL deionized water, nitrogen is passed through
Protection, ultrasonic half an hour, then 100 μ g mL of 10ml is added dropwise-1Chloroplatinic acid aqueous solution, persistently stir 8h, carry out decompression pumping
Filter obtains catalyst, is washed with 1L deionized water, and be dried in vacuo at 80 DEG C.
Compared to embodiment 1, the type of transition metal is changed, then is that core exists by the core-shell structure of shell of platinum using cobalt in example 1
Become in the example using iron being core using platinum as shell.
Embodiment 4
At 60 DEG C, the cabaltous nitrate hexahydrate of the zinc nitrate hexahydrate of 1.470g, 0.74g is dissolved in 100ml methanol, it will
3.260 2-methylimidazole is dissolved in 100ml methanol, the former is added slowly with stirring in the latter, continues to stir 12min, then
Stand 20h.Centrifuge separation, washing three times, are dried in vacuo 8h at a temperature of 150 DEG C, obtain Zn0.95Co0.05-ZIF8.Take 1g
Zn0.95Co0.05- ZIF8 is placed in corundum boat, is heated to 900 DEG C with 2 DEG C/min heating rate and keeps the temperature 2h, then with 5 DEG C/min cooling
Rate is cooled to room temperature taking-up porous carbon support.100mg porous carbon support is dispersed in 100mL deionized water, nitrogen is passed through
Protection, ultrasonic half an hour, then 100 μ g mL of 10ml is added dropwise-1Chloroplatinic acid aqueous solution, persistently stir 8h, carry out decompression pumping
Filter obtains catalyst, is washed with 1L deionized water, and be dried in vacuo at 80 DEG C.
Embodiment 5
At 20 DEG C, the cabaltous nitrate hexahydrate of the zinc nitrate hexahydrate of 1.470g, 0.74g is dissolved in 100ml methanol, it will
3.260 2-methylimidazole is dissolved in 100ml methanol, the former is added slowly with stirring in the latter, continues to stir 12min, then
Stand 20h.Centrifuge separation, washing three times, are dried in vacuo 8h at a temperature of 150 DEG C, obtain Zn0.95Co0.05-ZIF8.Take 1g
Zn0.95Co0.05- ZIF8 is placed in corundum boat, is heated to 1000 DEG C with 2 DEG C/min heating rate and keeps the temperature 2h, then with 5 DEG C/min drop
Warm rate is cooled to room temperature taking-up porous carbon support.100mg porous carbon support is dispersed in 100mL deionized water, nitrogen is passed through
Gas shielded, ultrasonic half an hour, then 100 μ g mL of 10ml is added dropwise-1Chloroplatinic acid aqueous solution, persistently stir 8h, depressurized
Suction filtration obtains catalyst, is washed with 1L deionized water, and is dried in vacuo at 80 DEG C.
Since heat treatment temperature rises, the degree of graphitization of carbon carrier increases, and catalyst electric conductivity gets a promotion.
Embodiment 6
At 20 DEG C, the cabaltous nitrate hexahydrate of the zinc nitrate hexahydrate of 1.470g, 0.74g is dissolved in 100ml methanol, it will
3.260 2-methylimidazole is dissolved in 100ml methanol, the former is added slowly with stirring in the latter, continues to stir 12min, then
Stand 20h.Centrifuge separation, washing three times, are dried in vacuo 8h at a temperature of 150 DEG C, obtain Zn0.95Co0.05-ZIF8.Take 1g
Zn0.95Co0.05- ZIF8 is placed in corundum boat, is heated to 900 DEG C with 5 DEG C/min heating rate and keeps the temperature 2h, then with 5 DEG C/min cooling
Rate is cooled to room temperature taking-up porous carbon support.100mg porous carbon support is dispersed in 100mL deionized water, nitrogen is passed through
Protection, ultrasonic half an hour, then 100 μ g mL of 10ml is added dropwise-1Chloroplatinic acid aqueous solution, persistently stir 8h, carry out decompression pumping
Filter obtains catalyst, is washed with 1L deionized water, and be dried in vacuo at 80 DEG C.
Embodiment 7
At 20 DEG C, the cabaltous nitrate hexahydrate of the zinc nitrate hexahydrate of 1.470g, 0.74g is dissolved in 100ml methanol, it will
3.260 2-methylimidazole is dissolved in 100ml methanol, the former is added slowly with stirring in the latter, continues to stir 12min, then
Stand 20h.Centrifuge separation, washing three times, are dried in vacuo 8h at a temperature of 150 DEG C, obtain Zn0.95Co0.05-ZIF8.Take 1g
Zn0.95Co0.05- ZIF8 is placed in corundum boat, is heated to 900 DEG C with 2 DEG C/min heating rate and keeps the temperature 2h, then with 5 DEG C/min cooling
Rate is cooled to room temperature taking-up porous carbon support.100mg porous carbon support is dispersed in 100mL deionized water, argon gas is passed through
Protection, ultrasonic half an hour, then 100 μ g mL of 10ml is added dropwise-1Chloroplatinic acid aqueous solution, persistently stir 8h, carry out decompression pumping
Filter obtains catalyst, is washed with 1L deionized water, and be dried in vacuo at 80 DEG C.
Claims (10)
1. a kind of loaded low platinum nucleocapsid catalyst, it is characterised in that: the low platinum nucleocapsid catalyst is with transition metal nanometer
Grain is core, and using platinum as shell, transition metal nanoparticles are supported on the porous carbon materials of N doping；In transition metal core metal with
The molar ratio of platinum is 1:10-1:100；Transition metal core loading is mass fraction 5%-20%.
2. loaded low platinum nucleocapsid catalyst as described in claim 1, it is characterised in that: the core-shell structure outer diameter is 2-
10nm；Platinum shell is wrapped in the outer surface of transition metal nanoparticles core in the form of monoatomic layer.
3. loaded low platinum nucleocapsid catalyst as described in claim 1, it is characterised in that: one in transition metal Co, Fe, Ni
Kind is two or more, and its in-situ impregnation is on carrier.
4. loaded low platinum nucleocapsid catalyst as described in claim 1, it is characterised in that: the porous carbon materials of the N doping are
Diameter is 50nm-1 μm of particle, specific surface 500-1500cm2g-1；Nitrogen mass content is 2%-8%, existing for N element
Form is pyridine N, pyrroles N, is graphitized one or more of N and oxidation N.
5. a kind of preparation method of any low platinum nucleocapsid catalyst of claim 1-4, it is characterised in that: including following step
It is rapid:
(1) synthesis of metal organic framework: the mixed solution of zinc salt, transition metal salt and organic ligand is prepared；In 30 DEG C -120
It is reacted under the conditions of DEG C, metal organic framework is then separated to obtain by centrifugation or suction filtration；
(2) preparation of the porous carbon materials of loaded N doping: the metal organic framework that step (1) is obtained is under inert atmosphere
The porous carbon materials of N doping of transition metal nanoparticles must be supported with by carrying out high temperature cabonization；
(3) preparation of loaded low platinum nucleocapsid catalyst: the porous carbon materials for the loaded N doping that step (2) are obtained are in water
In slurries are made, chloroplatinic acid aqueous solution is added dropwise under inert gas shielding in the slurries and to continue stirring until slurries equal
It is even, it is filtered, washed to obtain loaded low platinum nucleocapsid catalyst.
6. the preparation method of low platinum nucleocapsid catalyst as claimed in claim 5, it is characterised in that: zinc salt described in step (1) and
Transition metal salt has same anion；The transition metal salt is cobalt nitrate, cobalt chloride, ferric nitrate, iron chloride, nitric acid
The one or more of nickel, nickel chloride；The organic ligand is 2-methylimidazole；The solvent be methanol, ethyl alcohol, water and
One or more of DMF.
7. the preparation method of low platinum nucleocapsid catalyst as claimed in claim 5, it is characterised in that: step (1) described mixed solution
Middle zinc ion concentration is 0.0125-0.1mol/L, and the molar ratio of zinc ion and transition metal ions is 100:1-1:1；Zinc ion
Ratio with the amount of the substance of organic ligand is 1:4-1:8.
8. the preparation method of loaded low platinum nucleocapsid catalyst as claimed in claim 5, it is characterised in that: described in step (2)
High temperature cabonization treatment process is to be warming up to 900-1100 DEG C and keep 0.5-3h, is then cooled to room temperature；In the temperature-rise period
Slave room temperature to carburizing temperature heating rate be 2-5 DEG C/min；In the temperature-fall period rate of temperature fall be 1-10 DEG C/
min；The inert atmosphere is one or both of nitrogen, argon gas, helium, neon.
9. the preparation method of loaded low platinum nucleocapsid catalyst as claimed in claim 5, it is characterised in that: described in step (3)
The concentration of slurries is 1-5g L-1；Inert gas is the gaseous mixture of one or both of nitrogen, argon gas, helium, neon；Chlorine platinum
The concentration of aqueous acid is 100-1000 μ g mL-1；The volume ratio of the slurries and chloroplatinic acid aqueous solution is 1:10-1:100.
10. the application of low platinum nucleocapsid catalyst as described in claim 1-4 is any, it is characterised in that: the catalyst is polymerization
Object dielectric film fuel cell and metal air battery cathodes oxygen reduction reaction elctro-catalyst.
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| CN114733533A (en) * | 2022-04-06 | 2022-07-12 | 青岛科技大学 | Preparation method and application of carbon-based metal catalyst derived from isomeric MOF1@ MOF2 |
| CN114733533B (en) * | 2022-04-06 | 2023-11-21 | 青岛科技大学 | Preparation method and application of carbon-based metal catalyst derived from isomerism MOF1@MOF2 |
| CN115125579A (en) * | 2022-05-19 | 2022-09-30 | 上海理工大学 | Preparation method and application of platinum monoatomic coordination cobalt-platinum alloy in limitation of nitrogen-doped porous carbon |
| CN115125579B (en) * | 2022-05-19 | 2023-05-12 | 上海理工大学 | Preparation method and application of platinum monoatomic synergistic cobalt-platinum alloy limited in nitrogen-doped porous carbon |
| CN115064711A (en) * | 2022-07-13 | 2022-09-16 | 清科(深圳)氢能科技有限公司 | Preparation method and application of high-activity in-situ nitrogen-doped carbon carrier loaded platinum-based alloy catalyst |
| CN115064711B (en) * | 2022-07-13 | 2024-05-31 | 清科(深圳)氢能科技有限公司 | Preparation method and application of nitrogen-doped carbon carrier-supported platinum-based alloy catalyst |
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