CN106410224B - A kind of cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst and its preparation method and application - Google Patents
A kind of cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst and its preparation method and application Download PDFInfo
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Abstract
A kind of cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst and its preparation method and application based on metal organic framework compound.The present invention is with metal organic framework compound [Co (O-BDC) (bbp)] for presoma, cobalt carbon pores shape oxygen reduction electro-catalyst is prepared for through high-temperature calcination, wherein carbon material inherits its porous structure, and cobalt simple substance uniform load is on the carbon material.Oxygen reduction electro-catalyst of the present invention has high electric conductivity and specific surface area, effectively reduces the overpotential of hydrogen reduction, shows that its hydrogen reduction process is 4 ideal electronics hydrogen reduction catalytic process by rotating disk electrode (r.d.e) and rotating ring disk electrode (r.r.d.e).The elctro-catalyst has given full play to the synergistic effect of metallic cobalt and carbon material in terms of electro-catalysis, has important theoretical and practical significance to exploitation novel electrochemical catalyst and energy conversion and memory device.
Description
Technical field:
The invention belongs to novel energy resource material technology and electrochemical catalysis fields, and in particular to cobalt carbon pores shape nano-complex
Material catalyst；The preparation method for further relating to the catalyst and its electro-catalysis in the Cathodic oxygen reduction of fuel cell
Using.
Background technique:
As the mankind are continuously increased cleaning and sustainable energy demand, great effort has been put into height by scientists
In terms of the research and development of effect, low cost and environmentally friendly energy conversion and stocking system.Wherein oxygen reduction reaction (ORR) is
The generally existing cathode reaction in fuel cell and metal-air battery, it is contemplated that the activity and stability of catalyst are used for
The catalyst of ORR reaction mainly has Pt and its alloy, but these noble metals are very rare in nature, and price is high
Expensive, fuel cell popularization receives great obstruction.Exploitation high-performance, inexpensive oxygen reduction cathode electrocatalyst material are to push
Fuel cell and its technology develop critical issue urgently to be resolved, and therefore, research and development non noble metal oxygen reduction catalyst becomes this
Hot subject concerned by people in field.Although the carbon material reported at present/transition metal composite catalyst is in ORR catalytic performance
With there are certain potentiality in stability, but there are still be unevenly distributed, compare table for carbon material and metal oxide in composite catalyst
The problems such as face is small and catalytic performance is low.
Metal-organic framework materials (Metal-organic framework, MOF) are one kind by transition metal atoms cluster
It is coordinated with containing covalent bond between multiple tooth carboxylic acid organic ligand (based on organic anionic ligands containing carboxylic acid) or ionic-covalent bonds
The porous crystalline material for acting on self assembly and being formed is widely used in the fields such as catalysis, gas storage and separation.Since its is porous
Skeleton structure, MOF is typically used as the conductive porous carbon nanomaterial of foraminous die plate preparation, and as catalyst for clear
In clean energy conversion and stocking system.As researcher is corresponding more by precursor preparation of different MOF compounds
Hole carbon nanomaterial, and in hydrogen storage and methanol fuel cell.Although at present using MOF as precursor preparation porous carbon nanometer material
Material achieves certain achievement, but yet there are no with MOF compound [Co (O-BDC) (bbp)] as precursor preparation cobalt carbon pores shape
Nano-complex (Co/NPCC) and the report for studying its ORR electrocatalysis characteristic.
The present invention uses hydro-thermal method to synthesize MOF compound [Co (O-BDC) (bbp)] first, before being with this MOF compound
Driving body, high-temperature calcination prepares Co/NPCC under an inert atmosphere, and due to the porous skeleton structure of MOF, carbon material is inherited after calcining
Its porous structure, and metal has then been reduced into simple substance, and equably loads on the carbon material, gained Co/NPCC catalyst
With high electric conductivity and specific surface area, the overpotential of ORR is effectively reduced as oxygen reduction catalyst, passes through rotating circular disk electricity
Pole (RDE) and rotating ring disk electrode (r.r.d.e) (RRDE) show that its ORR process is 4 electronic catalytic mechanism, are ideal ORR reactions
Process.The elctro-catalyst has given full play to the synergistic effect of metal Co and carbon material in terms of electro-catalysis, to exploitation novel electrochemical
Chemical catalyst and energy conversion and memory device have important theoretical and practical significance.
Summary of the invention:
In view of the deficiencies of the prior art and the demand of this field research and application, an object of the present invention are to provide one
Kind cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst；With MOF compound [Co (O-BDC) (bbp)] for presoma, through high temperature
Cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst is obtained after calcining, is denoted as Co/NPCC；
The second object of the present invention is to provide a kind of preparation method of cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst,
Specifically includes the following steps:
(a) preparation of MOF compound [Co (O-BDC) (bbp)]
By 0.120g cobalt chloride hexahydrate (0.5mmol), 0.137g 1,3- bisbenzimidazole base propane (0.5mmol),
0.092g hydroxyisophthalic acid (0.5mmol) and 0.060g sodium hydroxide (1.5mmol) are added to containing 10mL deionized water
In polytetrafluoroethylsubstrate substrate stainless steel cauldron, in 160 DEG C of hydro-thermal reaction 72h after lid is sealed, diafiltration is crossed after being cooled to room temperature
Drying is washed, the MOF compound [Co (O-BDC) (bbp) of pink colour is obtained；
(b) preparation of cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst Co/NPCC
By MOF compound obtained in step (a) [Co (O-BDC) (bbp)] grind into powder, takes and a certain amount of be placed on porcelain boat
In in tube furnace, heated under nitrogen atmosphere with the rate of 5 DEG C/min, be first increased to 250 DEG C of heating 2h, be heated to 500
~800 DEG C of calcining 4h obtain the cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst Co/NPCC.
Wherein it is more that nanometer is presented in the shape of cobalt carbon pores described in step (b) nano-complex oxygen reduction electro-catalyst Co/NPCC
Pore structure has biggish specific surface area, the main reason is that carbon source is in the MOF compound with cavernous structure；The catalysis
Metal Co in agent exists in the form of simple substance, and carbon exists in the form of carbon nanotube；Doped with a small amount of nitrogen in the catalyst.
It is negative in fuel cell that the three of the object of the invention are to provide a kind of cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst
Application in the ORR of pole.
The present invention with the MOF compound [Co (O-BDC) (bbp)] with porous structure be presoma, after high-temperature calcination
Cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst Co/NPCC is made；Wherein carbon material inherits its porous structure, Er Qiedan
Matter cobalt equably loads on the carbon material, and gained Co/NPCC catalyst has high electric conductivity and specific surface area, and effectively drops
The low overpotential of ORR, the results showed that its ORR process is largely 4 electronic catalytic mechanism, is that ideal ORR reacted
Journey.
Compared with prior art, the present invention have following major advantage and the utility model has the advantages that
1) oxygen reduction catalyst of the present invention is base metal carbon composite, raw materials used easily prepared, resource
Abundant and price is lower, and large scale preparation is at low cost；
2) methanol tolerance that oxygen reduction catalyst of the present invention has had adds in 0.1mol/L KOH electrolyte
Enter 1mol/L methanol, the catalytic activity of catalyst is almost without decaying；
3) oxygen reduction catalyst of the present invention be a kind of carbon pores shape nano-complex oxygen reduction electro-catalyst, have compared with
Good ORR catalytic activity has significant excellent compared with the one-sided ORR activity of base metal/non-metallic catalyst of current research report
Gesture；
4) compared with the Pt/C catalyst of commercialization 20wt%, stability obtains oxygen reduction catalyst of the present invention
It significantly improves, good catalytic activity can be kept in fuel cell long-time service；
6) oxygen reduction catalyst agent preparation method of the present invention is simple, easily operated, convenient for large-scale production.
Detailed description of the invention:
Fig. 1 is the Pt/C catalysis of 2 gained Co/NPCC catalyst of embodiment, comparative example 1MOF, 2 business 20wt% of comparative example
The linear volt-ampere curve figure of ORR of agent modification RDE.
Fig. 2 is the linear volt-ampere song of ORR of embodiment 1,4 gained Co/NPCC catalyst of embodiment 2, embodiment 3 and embodiment
Line chart.
Fig. 3 is the linear volt-ampere curve figure of ORR that 2 gained Co/NPCC catalyst different loads amount of embodiment modifies RDE.
Fig. 4 is the ORR kinetic curve that 2 gained Co/NPCC catalyst of embodiment modifies RDE.
Fig. 5 is the ORR kinetic curve that 2 gained Co/NPCC catalyst of embodiment modifies RRDE.
The Pt/C catalyst modification that Fig. 6 is business 20wt% described in 2 gained Co/NPCC catalyst of embodiment and comparative example 2
I-t curve graph of the RDE under 0.6V constant voltage.
Specific embodiment:
To further understand the present invention, present invention will be further explained below with reference to the attached drawings and examples, but not with
Any mode limits the present invention.
Embodiment 1:
(a) preparation of MOF compound [Co (O-BDC) (bbp)]
By 0.120g cobalt chloride hexahydrate (0.5mmol), 0.137g 1,3- bisbenzimidazole base propane (0.5mmol),
0.092g hydroxyisophthalic acid (0.5mmol) and 0.060g sodium hydroxide (1.5mmol) are added to containing 10mL deionized water
In polytetrafluoroethylsubstrate substrate stainless steel cauldron, in 160 DEG C of hydro-thermal reaction 72h after lid is sealed, diafiltration is crossed after being cooled to room temperature
Drying is washed, the MOF compound [Co (O-BDC) (bbp) of pink colour is obtained；
(b) preparation of cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst Co/NPCC
By MOF compound obtained in step (a) [Co (O-BDC) (bbp)] grind into powder, takes and a certain amount of be placed on porcelain boat
In in tube furnace, heated under nitrogen atmosphere with the rate of 5 DEG C/min, be first increased to 250 DEG C of heating 2h, be heated to 500
DEG C calcining 4h, obtains the cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst Co/NPCC, specific surface area is
147.48m2/g。
Embodiment 2:
(a) preparation of Co-MOF
According to the method and condition preparation of step (a) in embodiment 1.
(b) preparation of cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst Co/NPCC
By MOF compound obtained in step (a) [Co (O-BDC) (bbp)] grind into powder, takes and a certain amount of be placed on porcelain boat
In in tube furnace, heated under nitrogen atmosphere with the rate of 5 DEG C/min, be first increased to 250 DEG C of heating 2h, be heated to 600
DEG C calcining 4h, obtains the cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst Co/NPCC, specific surface area is
162.27m2/g。
Embodiment 3:
(a) preparation of Co-MOF
According to the method and condition preparation of step (a) in embodiment 1.
(b) preparation of cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst Co/NPCC
By MOF compound obtained in step (a) [Co (O-BDC) (bbp)] grind into powder, takes and a certain amount of be placed on porcelain boat
In in tube furnace, heated under nitrogen atmosphere with the rate of 5 DEG C/min, be first increased to 250 DEG C of heating 2h, be heated to 700
DEG C calcining 4h, obtains the cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst Co/NPCC, specific surface area is
123.63m2/g。
Embodiment 4:
(a) preparation of Co-MOF
According to the method and condition preparation of step (a) in embodiment 1.
(b) preparation of cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst Co/NPCC
By MOF compound obtained in step (a) [Co (O-BDC) (bbp)] grind into powder, takes and a certain amount of be placed on porcelain boat
In in tube furnace, heated under nitrogen atmosphere with the rate of 5 DEG C/min, be first increased to 250 DEG C of heating 2h, be heated to 800
DEG C calcining 4h, obtains the cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst Co/NPCC, specific surface area is
138.52m2/g。
Embodiment 5:
200 μ L ethyl alcohol are dispersed by the resulting oxygen reduction electro-catalyst of 10mg embodiment 2 respectively and 15 μ L Nafion are molten
In liquid, after ultrasound mixes solution, 1 μ L slurry drops is taken to be applied to rotating ring disk electrode (r.r.d.e) (RRDE, 0.1256cm2) on, it is completely dry to its
Its ORR electrocatalysis characteristic is measured after dry on CHI660D electrochemical workstation.
Above-mentioned electrocatalysis characteristic test is to be saturated Ag/AgCl electrode as reference electrode, and Pt electrode is to electrode, and sweeping speed is
10mV/s, electrolyte are 0.1M KOH, need to carry out O before ORR catalytic performance test2Saturated process.RDE test result is passed through
After Koutecky-Levich formula manipulation, electron transfer number (n) can be calculated by the K-L slope of curve (B).
J-1=Jk -1+(Bω1/2)-1
B=0.62n F C0D0 2/3v1/6
Wherein F=96485C/mol, C0=1.2 × 10-3Mol/L, D0=1.9 × 10-5cm2/ s, v=0.01cm2/s。
RRDE test result can obtain electron transfer number (n) and H by following formula manipulation2O2Content:
N=4Id·(Id+Ir/N)
HO- 2%=200Id/N·(Id+Ir/ N),
Wherein N=0.43.
Comparative example 1:
According to the operating method of truth example 5, with [the Co (O-BDC) of MOF compound obtained in step (a) in embodiment 2
(bbp)] powder is elctro-catalyst, its ORR electrocatalysis characteristic is measured on CHI660D electrochemical workstation.
Comparative example 2:
According to the operating method of truth example 5, using the Pt/C of business 20wt% as elctro-catalyst, in CHI660D electrochemistry work
Its ORR electrocatalysis characteristic is measured on standing.
Fig. 1 is 2 gained Co/NPCC elctro-catalyst of embodiment, 1 gained MOF compound elctro-catalyst of comparative example, comparative example 2
The linear volt-ampere curve figure of ORR of the Pt/C elctro-catalyst modification RDE of the business 20wt%.As shown, MOF compound is through height
After temperature calcining, the Co/NPCC elctro-catalyst take-off potential of resulting nanoporous has just moved to 0.903V by 0.852V, it is slightly positive in
The 0.890V of commercial Pt/C elctro-catalyst, Limited diffusion current density is also by -1.714mA/cm2Increase to -5.499mA/cm2, with quotient
It is suitable with Pt/C elctro-catalyst, show that the ORR performance of Co/NPCC elctro-catalyst is slightly better than the Pt/C electro-catalysis of business 20wt%
Agent.The excellent ORR catalytic performance of Co/NPCC elctro-catalyst mainly due to calcining after carbon exist in the form of carbon nanotube, be in
Reveal nano-porous structure, Co is evenly dispersed on nanoporous carbon materials in the form of simple substance, significantly improves Co/NPCC
Elctro-catalyst specific surface area, electric conductivity and electronics conduction efficiency, show as in the steady-state process of ORR, take-off potential has occurred
It shuffles, current density has obtained significant increase, to realize the enhancing of ORR catalytic performance.
Fig. 2 is that embodiment 1, embodiment 2, embodiment 3 and 4 gained Co/NPCC elctro-catalyst of embodiment modify RDE's respectively
The linear volt-ampere curve figure of ORR, as shown, calcination temperature by 500-800 DEG C of take-off potential is respectively 0.839,0.903,
0.854 and 0.861V, limiting diffusion current are respectively -4.117, -5.499, -3.178 and -1.812mA/cm2, it can be seen that it is real
The ORR catalytic activity for applying 2 gained Co/NPCC elctro-catalyst of example is best, and electro catalytic activity is more stable, to show preferable
ORR catalytic activity.
2 gained Co/NPCC catalyst different loads amount (0.33,0.49 and 0.66mg/cm of Fig. 3 embodiment2) modification RDE
The linear volt-ampere curve figure of ORR.Load capacity is respectively 0.33,0.49 and 0.66mg/cm2When corresponding ORR take-off potential be respectively
0.882,0.903 and 0.890V, it can be seen that when load capacity is respectively 0.49mg/cm2When, Co/NPCC catalyst can play
Optimal ORR catalytic performance.
Fig. 4 is the ORR kinetic curve that 2 gained Co/NPCC catalyst of embodiment modifies that RDE is carried out.The results show that should
Average electron transfer number in ORR catalytic process is about 3.9, close to no HO2 -4 electronic transfer process of product, to illustrate Co/
The ORR process of NPCC elctro-catalyst is ideal 4 electron reaction mechanism.
Fig. 5 is the ORR kinetic curve that 2 gained Co/NPCC of embodiment modifies that RRDE is carried out.The results show that the ORR is catalyzed
Electron transfer number is about 3.9 in the process, consistent with RDE test result, and the HO of 2 electron reaction courses2 -Product is tieed up always
It holds 5% hereinafter, the further difficult ORR process is 4 ideal electron reaction mechanism, shows Co/NPCC elctro-catalyst
With good ORR catalytic activity.
The Pt/C catalyst modification that Fig. 6 is business 20wt% described in 2 gained Co/NPCC catalyst of embodiment and comparative example 2
I-t curve graph of the RDE under 0.6V constant voltage.As shown, Co/NPCC modified electrode is without obvious work electricity in oxygen-free environment
It flows, starts logical oxygen after 20min, response current is gradually promoted, and ORR reaction has occurred in this explanation, and total overall reaction is ORR mistake
Journey, during the about ORR of 2h, electric current has almost no change, and illustrates that Co/NPCC elctro-catalyst has good stabilization
Property, good catalytic activity can be kept in the long-time service of fuel cell, (dripped in about 50mL electrolyte after instilling 1M methanol
Enter 1mL), for business 20wt%Pt/C electrode current decaying 38%, the current attenuation of Co-CNT modified electrode is not
Foot 10% shows that Co/NPCC has the methanol tolerance jamming performance better than commercialization noble metal electrocatalyst, can be used as pluralities of fuel
The decorative material of cell cathode.
Claims (3)
1. a kind of cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst, it is characterised in that the elctro-catalyst is with MOF chemical combination
Object [Co (O-BDC) (bbp)] is presoma, and cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst is obtained after high-temperature calcination,
It is denoted as Co/NPCC；
The preparation method of the cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst Co/NPCC, it is characterised in that specific steps
It is as follows:
(a) preparation of MOF compound [Co (O-BDC) (bbp)]
By 0.120g cobalt chloride hexahydrate (0.5mmol), 0.137g 1,3- bisbenzimidazole base propane (0.5mmol), 0.092g
Hydroxyisophthalic acid (0.5mmol) and 0.060g sodium hydroxide (1.5mmol) are added to the polytetrafluoro containing 10mL deionized water
In ethylene substrate stainless steel cauldron, in 160 DEG C of hydro-thermal reaction 72h after lid is sealed, it is cooled to room temperature rear filtration washing drying,
Obtain the MOF compound [Co (O-BDC) (bbp)] of pink colour；
(b) preparation of cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst Co/NPCC
By MOF compound obtained in step (a) [Co (O-BDC) (bbp)] grind into powder, take it is a certain amount of be placed in porcelain boat in
In tube furnace, is heated under nitrogen atmosphere with the rate of 5 DEG C/min, be first increased to 250 DEG C of heating 2h, be heated to 500~800
DEG C calcining 4h, obtains the cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst Co/NPCC.
2. a kind of cobalt carbon pores shape nano-complex oxygen reduction electro-catalyst according to claim 1, it is characterised in that this is urged
Nano-porous structure is presented in agent, and the metal Co in catalyst exists in the form of simple substance, and carbon exists in the form of carbon nanotube；
Doped with a small amount of nitrogen in the catalyst.
3. described in any item a kind of cobalt carbon pores shape nano-complex oxygen reduction electro-catalysts according to claim 1~2, feature
It is Cathodic oxygen reduction of the catalyst for fuel cell.
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| CN107597162B (en) * | 2017-09-05 | 2019-12-20 | 中山大学 | Nitrogen-doped carbon material with bifunctional oxygen catalysis performance and rich in CNTs and Co particles, and preparation method and application thereof |
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| CN108176364A (en) * | 2017-12-06 | 2018-06-19 | 江苏大学 | The preparation method of cobalt/carbon nano-composite material derived from a kind of metal organic framework |
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| CN109647477B (en) * | 2018-11-26 | 2021-10-22 | 大连理工大学 | Rapid preparation method and application of high-yield MOF (Metal organic framework) derivative catalyst |
| CN109728282B (en) * | 2018-12-30 | 2020-02-18 | 北京乐华锂能科技有限公司 | Preparation method of porous transition metal oxide/carbon composite material |
| CN110694578A (en) * | 2019-09-23 | 2020-01-17 | 五邑大学 | Co-C-N composite material and preparation method and application thereof |
| CN111001427B (en) * | 2019-12-24 | 2021-05-14 | 山西大学 | Cobalt-nitrogen co-doped carbon-based electrocatalyst material and preparation method thereof |
| CN113231071A (en) * | 2021-03-29 | 2021-08-10 | 同济大学 | Mesoporous Co/CoO/SnO carbon nano-cubic composite catalyst and preparation method and application thereof |
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