CN108736031A - A kind of self-supporting PtCo alloy nanoparticle catalyst and the preparation method and application thereof - Google Patents
A kind of self-supporting PtCo alloy nanoparticle catalyst and the preparation method and application thereof Download PDFInfo
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Abstract
The present invention relates to a kind of self-supporting PtCo alloy nanoparticle catalyst and the preparation method and application thereof, specific method is to synthesize three-dimensional self-supporting cobalt-based metal organic frame (Co-MOFs) nanometer stick array structure on carbon cloth by liquid phase means, a kind of three-dimensional porous nitrogen-doped carbon cladding metal cobalt nano-particle (Co N-C) nanorod structure is obtained by high temperature carbon thermal reduction technology, and in this, as template, utilize the difference of Pt metal and Co redox potentials, nitrogen-doped carbon/PtCo (PtCo@N-C) porous catalyst is finally obtained using easy potential replacement reaction method.Compared with prior art, composite catalyst of the invention is not necessarily to binder and conductive additive, has excellent methanol oxidation susceptibility and CO mithridatisms, flexible carbon cloth substrate is used as collector, flexible foldable, with extraordinary mechanical performance.
Description
Technical field
The present invention relates to field of fuel cell technology, and in particular to a kind of self-supporting PtCo alloy nanoparticles catalyst and
Preparation method and application.
Background technology
Fuel cell has low cost and the potentiality of zero-emission as a kind of efficient energy conversion device, it is considered to be
Solve the important channel of the growing energy crisis and problem of environmental pollution of the mankind.And methanol has degree of commercialization height, than
Energy is high, the advantages such as good portability, and therefore, direct methanol fuel cell has very promising application prospect and causes people
Extensive concern.In numerous elctro-catalysts, platinum and platinum base alloy are still most effective and most stable in methanol oxidation
Catalyst, it is expensive however, platinum reserves are limited, greatly limit its large-scale commercial applications application.In addition, the catalysis of platinum
Performance is also limited to its slower methanol oxidation kinetics and CO poisonings.
Invention content
It is good, anti-that it is an object of the present invention to overcome the above-mentioned drawbacks of the prior art and provide a kind of catalytic activity
Malicious ability is strong and the self-supporting PtCo alloy nanoparticle catalyst and the preparation method and application thereof of good mechanical property.
The purpose of the present invention can be achieved through the following technical solutions：A kind of self-supporting PtCo alloy nanoparticles catalysis
Agent, the catalyst include three-dimensional porous nitrogen-doped carbon and the Pt and Co that are coated on inside three-dimensional porous nitrogen-doped carbon, wherein institute
The mass ratio for stating Pt and Co is (0.5~0.6)：The 1 Pt and Co gross masses account for the 43%~48% of catalyst quality, described
Three-dimensional porous nitrogen-doped carbon is in array structure.The present invention using Pt and Co collectively as the active ingredient of catalyst, Pt and Co's
In conjunction with the electron binding energy reduced in Pt, the C-H cracking reactions under low potential are promoted, to improve the activity of catalyst
And mithridatism.Simultaneously as cobalt-based metal-organic framework material presoma is three-dimensional matrix structure, so porous nitrogen is mixed after calcining
Miscellaneous carbon is also array structure.The porous nitrogen-doped carbon nanometer stick array of high graphitization has bigger serface and high conductivity, is
The dispersion of PtCO nano-particles provides ideal support, may advantageously facilitate the migration of ion/proton；The nitrogen of doping can increase
Interaction between alloying pellet and carbon by force, improves the stability of catalyst；And the intrinsic catalysis energy of porous nitrogen-doped carbon
Power also makes certain contribution to the catalytic activity of raising.
A kind of preparation method of self-supporting PtCo alloy nanoparticle catalyst as described above, includes the following steps：
(1) carbon cloth is put into the aqueous solution of acetone and is ultrasonically treated, washed drying, be subsequently placed in precursor solution
In, form cobalt-based metal organic frame compound, wherein the precursor solution is water-soluble for the mixing of cobalt nitrate and methylimidazole
Liquid；
(2) cobalt-based metal organic frame compound is calcined, obtains the three-dimensional porous nitrogen-doped carbon of cladding Co nano particles；
(3) the three-dimensional porous nitrogen-doped carbon of obtained cladding Co nano particles is immersed in H2PtCl4In Pt solution to get
The self-supporting PtCo alloy nanoparticle catalyst.
Since the carbon cloth that carbon fiber is compiled into is a kind of good three-dimensional conductive substrate material, its effect on the one hand can be with
The electric conductivity specific surface area for increasing material prepared is conducive to increase active site；On the other hand the activity being grown on carbon cloth
Material can save the step of electrode is made as other fine catalysts directly as catalysis electrode.In whole preparation process
Middle Co ecto-entads are gradually replaced by Pt, form alloying pellet.
The time that the carbon cloth is ultrasonically treated in the aqueous solution of acetone is 20~30min, and ultrasound is for cleaning carbon
Cloth.
It is 60~80 DEG C that the washing, which uses deionized water, drying temperature,.
In the precursor solution, the molar ratio of cobalt nitrate and methylimidazole is 1:(15~20).
The calcining is in Ar and H2Mixing atmosphere in carry out, wherein wherein, Ar accounts for Ar and H2The 90% of total volume~
95%.H2Addition the catalytic action of Co, array structure surface can be promoted to grow some carbon nanotubes in calcination process, increase
The specific surface area of structure.
700~900 DEG C are warming up to be less than 5 DEG C/min, and after 2~4h of heat preservation, naturally rings to room temperature.700~900 DEG C can
So that cobalt-based metal organic frame array heights are graphitized, increase electric conductivity.
The H2PtCl4A concentration of 0.5~2mmol/L of Pt solution coats the three-dimensional porous nitrogen-doped carbon of Co nano particles
In H2PtCl4Soaking time is 2~4min in Pt solution.
A kind of application of self-supporting PtCo alloy nanoparticle catalyst as described above, the catalyst is for methanol fuel electricity
The anode in pond.Methanol oxidation occurs for methanol fuel cell positive pole, and oxygen reduction reaction occurs for cathode.Material prepared by the present invention
Methanol oxidation catalyst, for methanol fuel cell anode.
Compared with prior art, beneficial effects of the present invention are embodied in following several respects：
(1) when the catalyst is used for the anode of methanol fuel cell, methanol aoxidizes initial potential height, anodic current density
Greatly；
(2) when the catalyst is used for the anode of methanol fuel cell, CO mithridatisms and excellent durability.
Description of the drawings
Fig. 1 is three-dimensional porous Co@N-C scanning electron microscopic picture；
Fig. 2 is three-dimensional PtCo@N-C catalyst flat scanning electron microscopic pictures；
Fig. 3 is PtCo@N-C and Pt/C in 0.5M H2SO4Electrolyte in 50mV/s sweep speed test CV curves.
Fig. 4 is PtCo@N-C and Pt/C in 0.5M CH3OH+0.5M H2SO4Electrolyte in fast test swept with 50mV/s
CV curves.
Fig. 5 is PtCo@N-C and Pt/C in 0.5M CH3OH+0.5M H2SO4Electrolyte in the increased peak of cycle-index
Current density compares.
Fig. 6 is PtCo@N-C and Pt/C in 0.5M H2SO4Electrolyte in the CO mithridatism CV curves tested.
Specific implementation mode
It elaborates below to the embodiment of the present invention, the present embodiment is carried out lower based on the technical solution of the present invention
Implement, gives detailed embodiment and specific operating process, but protection scope of the present invention is not limited to following implementation
Example.
Embodiment 1
A kind of preparation method of self-supporting PtCo alloy nanoparticle catalyst, includes the following steps：
On carbon cloth prepared by Co-MOFs nanometer stick arrays
Select carbon cloth as substrate, model first：WOS1002.Carbon cloth is respectively put into acetone and deionized water ultrasonic
Processing 20 minutes, is finally rinsed with deionized water, is put into air dry oven and is dried.
Configure Co-MOFs precursor solutions：By the cobalt nitrate (Co (NO of 40ml 25mM3)2·6H2O it) is quickly adding into
Methylimidazole (the C of 40ml 0.4M4H6N2) in aqueous solution, then stir.
At 30 DEG C, the carbon cloth handled well is immersed in the Co-MOFs precursor solutions and is reacted 4 hours.So
It is rinsed well afterwards with deionized water.
It repeats the above steps, at identical temperature and reaction time, diauxic growth Co-MOFs.
The preparation of Co@N-C nanometer stick arrays on carbon cloth
The Co-MOFs nanometer stick arrays that will be prepared on the carbon cloth, at 800 DEG C, in Ar/H2(5%H2, 95%Ar) and ring
It is made annealing treatment 2 hours in border, wherein heating rate is 5 DEG C/min.Co@N-C nanometer stick array structures are obtained after natural cooling
(Fig. 1).
The preparation of PtCo@N-C nanometer stick arrays on carbon cloth
The PtCo@N-C nanometer stick arrays prepared on carbon cloth are put into the chloroplatinic acid for the 1mM that stirred
(H2PtCl6·6H2O it) is impregnated 3 minutes in solution, is labeled as PtCo@N-C.Reactional equation is：
Co+PtCl4 2-→Co2++Pt+4Cl-
The PtCo@N-C nanometer stick arrays that will be prepared on the carbon cloth, at 400 DEG C, in Ar/H2(5%H2, 95%Ar) and ring
It is made annealing treatment 1 hour in border, wherein heating rate is 3.5 DEG C/min.PtCo@N-C nanometer stick arrays are obtained after natural cooling
Structure (Fig. 2).
The quality of Pt and Co is 0.278mg cm in the PtCo@N-C prepared-2With 0.533mg cm-2, corresponding
Atomicity ratio is 14:86.
The present invention has synthesized the three-dimensional Co-MOFs nanorod structures with bigger serface by liquid phase means, by moving back
A kind of Co@N-C structures of fire processing acquisition are prepared for Series P t in this, as carrier using easy Pt presomas immersion process
The PtCo@N-C catalyst of load, and system testing and analysis have been carried out to the electrocatalysis characteristic of catalyst.
The electrocatalysis characteristic of the PtCo@N-C catalyst prepared is by electrochemical workstation under three-electrode system
Test.Wherein, PtCo@N-C catalyst is as working electrode, the Ag/AgCl (+0.197V vs impregnated in being saturated KCl solution
RHE reference electrode, graphite rod) is used as to be used as to electrode.
Before measuring, high-purity Ar is passed through in electrolyte 20 minutes, to remove the CO and O in solution2。
The electrochemical surface area of the PtCo@N-C catalyst prepared passes through in 0.5M H2SO4Solution in test
What volt-ampere curve (CV) obtained, wherein test voltage section is 0 to 1.0V vs RHE, and it is 50mV s to sweep speed-1。
The electrochemical surface area of PtCo@N-C and the Pt/C catalyst of the preparation is respectively 20m2/ g and 14.2m2/ g,
PtCo@N-C catalyst shows the electrochemical surface area (Fig. 3) of bigger.
The methanol oxidation susceptibility of the PtCo@N-C catalyst prepared passes through comprising 0.5M H2SO4And 0.5M
CH3Test what volt-ampere curve (CV) obtained in the mixed solution of OH, wherein test voltage section is 0~1.2V vs.RHE, is swept
Speed is 50mV s-1。
The PtCo@N-C ratio Pt/C catalyst of the preparation has more negative initial voltage (0.563V<0.642V) and bigger
Just sweep peak current density (433.5mA mg-1>140mA mg-1).Therefore, PtCo@N-C catalyst shows more preferably methanol
Oxidation activity (Fig. 4).
The oxidation-stabilized performance of methanol of the PtCo N-C catalyst prepared is in 0.5M H2SO4With 0.5M CH3OH
Mixed solution in test it is continuous 100 cycle CV curves obtain, wherein test voltage section be 0~1.2V
Vs.RHE, it is 50mV s to sweep speed-1。
Anodic peak current density conservation rate after PtCo@N-C and the Pt/C catalyst of the preparation is recycled at 100 divides
Not Wei peak value 94.4% and 68.7%, illustrate the durability of PtCo@N-C catalyst due to business Pt/C (Fig. 5).
The antitoxin performances of CO of the PtCo N-C catalyst prepared are the 0.5M H being saturated in CO2SO4Solution in survey
Try what CV curves obtained, wherein test voltage section is -0.1~1.4V vs RHE, and it is 50mV s to sweep speed-1.Before measuring,
High-purity CO gas and A r gas are successively passed through in electrolyte each 15 minutes, it is enough to ensure to cover on active catalyst sites
CO, and there is no CO in solution.
The CO desorptions peak of PtCo@N-C and the Pt/C catalyst of the preparation is respectively at 0.92V and 1.03V, PtCo@
N-C more negative CO desorptions peak proves that it has superior CO cosolvencies (Fig. 6).
Therefore, the PtCo@N-C catalyst prepared by the present embodiment has remarkable methanol oxidate current, CO antitoxin
Property and durability.
Embodiment 2
Using preparation method similar to Example 1, the difference is that：
(1) time that carbon cloth is ultrasonically treated in the aqueous solution of acetone is 20min, and the drying temperature of carbon cloth is 60 DEG C；
(2) molar ratio of cobalt nitrate and methylimidazole is 1 in precursor solution：15.
(3) calcining is in Ar and H2Mixing atmosphere in carry out, wherein Ar accounts for the 90% of total gas volume；Calcination temperature is
700 DEG C, calcination time 4h；
(4) H used is impregnated2PtCl4A concentration of 0.5m mol/L, soaking time 4min of Pt solution.
The catalyst that upper the present embodiment is prepared is used in the anode of methanol fuel cell, finds to have after tested larger
Current density, and by the antitoxin performances of good CO.
Embodiment 3
Using preparation method similar to Example 1, the difference is that：
(1) time that carbon cloth is ultrasonically treated in the aqueous solution of acetone is 30min, and the drying temperature of carbon cloth is 80 DEG C；
(2) molar ratio of cobalt nitrate and methylimidazole is 1 in precursor solution：~20.
(3) calcining is in Ar and H2Mixing atmosphere in carry out, wherein Ar accounts for the 90%~95% of total gas volume；Calcining
Temperature is 900 DEG C, calcination time 2h；
(4) H used is impregnated2PtCl4A concentration of 2m mol/L, soaking time 2min of Pt solution.
The catalyst that upper the present embodiment is prepared is used in the anode of methanol fuel cell, finds to have after tested larger
Current density, and by the antitoxin performances of good CO.
Claims (9)
1. a kind of self-supporting PtCo alloy nanoparticle catalyst, which is characterized in that the catalyst includes three-dimensional porous N doping
Carbon and the Pt and Co being coated on inside three-dimensional porous nitrogen-doped carbon, wherein the mass ratio of the Pt and Co is (0.5~0.6)：
The 1 Pt and Co gross masses account for the 43%~48% of catalyst quality, and the three-dimensional porous nitrogen-doped carbon is in array structure.
2. a kind of preparation method of self-supporting PtCo alloy nanoparticle catalyst as described in claim 1, which is characterized in that packet
Include following steps：
(1) carbon cloth is put into the aqueous solution of acetone and is ultrasonically treated, washed drying, be subsequently placed in precursor solution, shape
At cobalt-based metal organic frame compound, wherein the precursor solution is the mixed aqueous solution of cobalt nitrate and methylimidazole；
(2) cobalt-based metal organic frame compound is calcined, obtains the three-dimensional porous nitrogen-doped carbon of cladding Co nano particles；
(3) the three-dimensional porous nitrogen-doped carbon of obtained cladding Co nano particles is immersed in H2PtCl4To get described in Pt solution
Self-supporting PtCo alloy nanoparticle catalyst.
3. a kind of preparation method of self-supporting PtCo alloy nanoparticle catalyst according to claim 2, feature exist
In the time that the carbon cloth is ultrasonically treated in the aqueous solution of acetone is 20~30min.
4. a kind of preparation method of self-supporting PtCo alloy nanoparticle catalyst according to claim 2, feature exist
In it is 60~80 DEG C that the washing, which uses deionized water, drying temperature,.
5. a kind of preparation method of self-supporting PtCo alloy nanoparticle catalyst according to claim 2, feature exist
In in the precursor solution, cobalt nitrate and methylimidazole mole are 1:(15~20).
6. a kind of preparation method of self-supporting PtCo alloy nanoparticle catalyst according to claim 2, feature exist
In the calcining is in Ar and H2Mixing atmosphere in carry out, wherein Ar accounts for Ar and H2The 90%~95% of total volume.
7. a kind of preparation method of self-supporting PtCo alloy nanoparticle catalyst according to claim 6, feature exist
In the calcining step is：700~900 DEG C are warming up to be less than 5 DEG C/min, and after 2~4h of heat preservation, naturally rings to room temperature.
8. a kind of preparation method of self-supporting PtCo alloy nanoparticle catalyst according to claim 2, feature exist
In the H2PtCl4The three-dimensional porous nitrogen-doped carbon of a concentration of 0.5~2mmol/L of Pt solution, cladding Co nano particles exist
H2PtCl4Soaking time is 2~4min in Pt solution.
9. a kind of application of self-supporting PtCo alloy nanoparticle catalyst as described in claim 1, which is characterized in that the catalysis
Agent is used for the anode of methanol fuel cell.
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106328960A (en) * | 2016-10-08 | 2017-01-11 | 华南理工大学 | ZIF-67 template method for preparing cobalt-platinum core-shell particle/porous carbon composite material and catalytic application of composite material in cathode of fuel cell |
| CN107235472A (en) * | 2017-05-24 | 2017-10-10 | 华中科技大学 | Porous vertical graphene nano wall array of N doping and preparation method and application |
| CN107359320A (en) * | 2017-06-07 | 2017-11-17 | 同济大学 | A kind of N doping porous carbon/MoS2Anode material of lithium-ion battery and preparation method |
| CN108048866A (en) * | 2017-11-29 | 2018-05-18 | 华南理工大学 | The preparation of the porous carbon-coated cobalt iridium Core-shell Structure Nanoparticles of N doping and its catalysis water-splitting application |
-
2018
- 2018-05-21 CN CN201810489697.1A patent/CN108736031B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106328960A (en) * | 2016-10-08 | 2017-01-11 | 华南理工大学 | ZIF-67 template method for preparing cobalt-platinum core-shell particle/porous carbon composite material and catalytic application of composite material in cathode of fuel cell |
| CN107235472A (en) * | 2017-05-24 | 2017-10-10 | 华中科技大学 | Porous vertical graphene nano wall array of N doping and preparation method and application |
| CN107359320A (en) * | 2017-06-07 | 2017-11-17 | 同济大学 | A kind of N doping porous carbon/MoS2Anode material of lithium-ion battery and preparation method |
| CN108048866A (en) * | 2017-11-29 | 2018-05-18 | 华南理工大学 | The preparation of the porous carbon-coated cobalt iridium Core-shell Structure Nanoparticles of N doping and its catalysis water-splitting application |
Cited By (26)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109569609A (en) * | 2018-11-21 | 2019-04-05 | 江苏理工学院 | A kind of preparation method of novel nickel-base composite material |
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