CN106910906A - A kind of Pd Cu Co/C ternary fuel cell anode catalysts and preparation method and application - Google Patents
A kind of Pd Cu Co/C ternary fuel cell anode catalysts and preparation method and application Download PDFInfo
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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
- H01M4/90—Selection of catalytic material
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- H—ELECTRICITY
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- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
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Abstract
The present invention relates to a kind of Pd Cu Co/C ternary fuel cell anode catalysts and preparation method and application, in catalyst, the weight/mass percentage composition of Pd is 18 23%, and the mol ratio of Pd, Cu, Co is 1.8 2.2:1.8‑2.2:1；During preparation, respectively by (NH4)2PdCl4、CuCl2·2H2O、Co(NO3)2·6H2O and trisodium citrate are added into ethylene glycol, and carbon dust is added after being well mixed, and are reacted in nitrogen atmosphere afterwards, after scrubbed, drying；The catalyst is used to carry out catalysis oxidation to formic acid.Compared with prior art, the present invention uses cheap raw material, a kind of new Pd based three-way catalysts have been synthesized by one pot of solution phase chemical reduction, not only significantly reduce cost, and the catalyst has catalysis activity and stability higher, it is applied in the catalytic oxidation process of formic acid, oxidation susceptibility of the catalyst to formic acid can be greatly improved.
Description
Technical field
The invention belongs to field of fuel cell technology, be related to a kind of Pd-Cu-Co/C ternary fuel cells anode catalyst and
Its preparation method and application.
Background technology
Fuel cell is the TRT that a kind of chemical energy that will be present in fuel and oxidant is converted into electric energy,
Both military affairs, space, power plant field had been can be applied to, the fields such as motor vehicle, mobile device, residential households had been can also be applied to.Formic acid
As a kind of ideal fuels stablized nontoxic liquid, be direct liquid fuel battery, by widely studied.Direct formic acid combustion
Material battery has energy density and OCP higher, can be used for the energy source device of portable set.Wherein, catalyst is this
The core substance of types of fuel cells.Direct methanoic acid fuel cell anode catalyst mainly has the class catalyst system of Pd, Pt two, with Pt
Compare, the Oxidation of Formic Acid process on Pd surfaces can be carried out by direct oxidation pathway, it is to avoid poisoning for intermediate product CO, have Pd
There is catalysis oxidation formic acid activity higher.Additionally, the price of Pd is relatively low, and reserves relatively enrich, thus Pd base catalyst exists
Fuel cell field has bigger potentiality.But due to the less stable of Pd base catalyst, therefore, how to be urged in guarantee Pd bases
On the premise of the excellent catalytic performance of agent, the stability of Pd base catalyst is improved as far as possible, as one of problem demanding prompt solution.
Application publication number discloses a kind of ultralow palladium carrying capacity of high-performance for the Chinese invention patent of the A of CN 104409745
The direct formic acid preparation method of anode of fuel cell elctro-catalyst Pd-CoP/C.Including：Carrier is scattered in cobalt chloride hexahydrate
In water, it is evaporated after ultrasonic disperse, stirring and obtains the first complex carrier；First complex carrier is mixed with hydration sodium hypophosphite and is ground
Mill reaction one hour, washs, is dried to obtain the second complex carrier；Second complex carrier is scattered in ethylene glycol, chlorine palladium is added
Acid, ultrasonic disperse stirring, obtains the first suspension；First suspension is stirred at room temperature down pH value is adjusted with NaOH, obtained
Second suspension；By the second suspension microwave, load type palladium catalyst is obtained after washing, drying.Above-mentioned patent disclosure
In technical scheme, it is used as altogether/co-catalyst by adding CoP, to improve catalysis activity of the palladium-based catalyst to formic acid electroxidation
And stability, while the carrying capacity of precious metal palladium can also be reduced.But, the preparation method is excessively cumbersome, and preparation process is more complicated,
Needing repeatedly charging in batches, operation inconvenience, and the Pd-CoP/C catalyst is improved by the promoting catalysis of metal-non-metal
The catalytic performance of catalyst, the synergy between catalyst components is poor, and the lifting effect of catalytic performance is undesirable.
The content of the invention
The purpose of the present invention is exactly that a kind of catalysis activity and steady is provided for the defect for overcoming above-mentioned prior art to exist
Qualitative good and low Pd-Cu-Co/C ternary fuel cell anode catalysts of cost of material and preparation method and application.
The purpose of the present invention can be achieved through the following technical solutions：
A kind of Pd-Cu-Co/C ternary fuel cells anode catalyst, in the catalyst, the weight/mass percentage composition of Pd is 18-
23%, the mol ratio of Pd, Cu, Co is 1.8-2.2:1.8-2.2:1.
Used as preferred technical scheme, in the catalyst, the weight/mass percentage composition of Pd is 19-21%, and Pd, Cu, Co's rubs
You are than being 1.9-2.1:1.9-2.1:1.
Used as further preferred technical scheme, in the catalyst, the weight/mass percentage composition of Pd is 20%, Pd, Cu, Co's
Mol ratio is 2:2:1.
A kind of preparation method of Pd-Cu-Co/C ternary fuel cells anode catalyst, the method specifically includes following step
Suddenly：
(1) respectively by (NH4)2PdCl4、CuCl2·2H2O、Co(NO3)2·6H2O and trisodium citrate are added to ethylene glycol
In, carbon dust is added after being well mixed, and stir；
(2) pH value is adjusted to 8-10, afterwards in nitrogen atmosphere, in stirring reaction 4-6h at 150-170 DEG C；
(3) 60-80 DEG C is cooled to, and adjusts pH value to 2-4, continue to be cooled to room temperature after stirring 1.5-2.5h, filtered
To solids；
(4) after solids washing, drying, that is, described Pd-Cu-Co/C ternary fuel cell anode catalysts are obtained.
In step (1), described (NH4)2PdCl4、CuCl2·2H2O、Co(NO3)2·6H2O, trisodium citrate and carbon dust
Weight portion content be respectively 25-28 parts, 15-17 parts, 12-15 parts, 340-350 parts and 30-32 parts, and per in 1mL ethylene glycol
Add 0.4-0.5mg (NH4)2PdCl4。
In step (1), described carbon dust is that, through the carbon dust after peracid treatment, acid treatment process is：Carbon dust is scattered in nitre
In acid, through ultrasound after, in condensing reflux 5-7h at 85-95 DEG C, by suction filtration, washing, drying, grinding.Carbon dust is advance
Through peracid treatment, hydrophilic treated can be carried out to carbon dust surface, increase its Surface oxygen-containing groups, be easy to the load of metal ion.
Used as preferred technical scheme, the acid treatment process of described carbon dust is：The carbon dust for weighing 0.5-1.5g is scattered in
In the nitric acid of the 4-6mol/L of 80-120mL, after ultrasonic 20-40min, the condensing reflux 5-7h in 85-95 DEG C of oil bath, while companion
With magnetic agitation, filtering and washing after room temperature is cooled to, to the last the pH value of a drop filtrate reaches 6.8-7.2.Then collect solid
Body is placed in vacuum drying chamber, in drying 5-7h at 120-140 DEG C；After drying, grinding, 200 mesh sieves point are collected storage and are treated
With.
In step (1), described carbon dust is selected from commercially available Vulcan XC-72 carbon dusts or Vulcan XC-72R carbon dusts.
In step (2), pH value, in described NaOH/EG solution, the amount of the material of NaOH are adjusted by NaOH/EG solution
Concentration is 0.8-1.2mol/L.
In step (3), by salt acid for adjusting pH value, in described hydrochloric acid, the substance withdrawl syndrome of HCl is 0.8-
1.2mol/L.Room temperature is 20-30 DEG C.
In step (4), described drying is vacuum drying, and the vacuum drying temperature is 55-65 DEG C, and the time is 10-
14h。
A kind of application of Pd-Cu-Co/C ternary fuel cells anode catalyst, the catalyst is used to be catalyzed formic acid
Oxidation.
At present, the research of the activity and anti-poisoning ability of Pd base catalyst is further improved, is mainly considered from two broad aspects：
(1) by Pd and the alloying of other metals；(2) catalyst of special appearance structure is prepared.Wherein, alloy catalyst can be adopted
Synthesized with easy technique, and greatly reduce the consumption of noble metal, and then reduces cost.Research has shown that, three-element catalytic
Agent shows more flexible relative to two-spot catalyst in terms of component, structure, Electronic Performance regulation and control, therefore the present invention selects three
First catalyst.
The present invention overcomes traditional technical problem that Pd/C catalyst price is high, stability is poor, prepare a kind of good dispersion,
The low new Pd-Cu-Co/C three-way catalysts of noble metal dosage, while with cheap raw material (NH4)2PdCl4、
CuCl2·2H2O and Co (NO3)2·6H2O carries out the preparation of catalyst, significantly reduces the content of precious metals pd, and then reduce
Production cost and use cost, while the catalyst has excellent formic acid electrooxidation activity and stability.
In catalyst of the present invention, active component is adjusted by electro transfer effect between tri- kinds of metal components of Pd, Cu, Co
D bands center, and then improve the catalytic performance of catalyst.Its mechanism of action is：In the electro-oxidation process of formic acid, intermediate product is such as
The generation of CO can poison catalyst, so that the catalytic performance of catalyst is reduced, and the addition of the transition metal such as Cu, Co can effectively drop
The d bands center of low noble metal, and then the absorption of catalyst surface species is reduced, consequently facilitating poisoning the desorption of species, promote first
The electroxidation of acid.
Catalyst of the present invention in the preparation, using " alcohol reduction synthesis technology " this efficient, environment-friendly technical method,
Cumbersome technique in building-up process is reduced, while improve noble metal dispersiveness on the carbon carrier.Wherein, trisodium citrate
Used as stabilizer, simultaneously as solvent and reducing agent, the carbon dust after acid treatment is used as carrier material for ethylene glycol.Course of reaction is divided into
Two stages：First stage is reacted using high temperature, high ph-values condition, second stage has been arrived, in order to avoid higher pH condition
The mutually exclusive influence to alloy nano particle load effect between lower nano-particle, reaction solution is cooled down, and reduce
PH value, the load good to ensure metal nanoparticle.
Compared to other cumbersome method for preparing catalyst, the present invention uses " one pot of liquid-phase reduction simple to operation
Method ", all of will react in precursor addition reaction vessel, control rational reaction condition just can directly obtain catalyst.
Compared with being improved by way of catalyst catalytic performance the promoting catalysis of metal-non-metal, Pd-Cu-Co/C of the present invention tri-
First catalyst improves the catalytic performance of catalyst by the synergy between ternary metal, and the lifting effect of catalytic performance is bright
It is aobvious.
Compared with prior art, the invention has the characteristics that：
1) cheap raw material is used, a kind of new Pd base ternarys has been synthesized by one pot of solution phase chemical reduction and has been urged
Agent, not only significantly reduces cost of material and production cost, and the catalyst has catalysis activity and stability higher,
It is applied in the catalytic oxidation process of formic acid, oxidation susceptibility of the catalyst to formic acid can be greatly improved；
2) catalyst size is small, and alloying level is high, active component good dispersion on the carbon carrier, is urged with Pd/C
Agent is compared, with Formic Acid Catalytic Oxidation performance higher, catalyst stability and CO tolerance catalysts ability；
3) method for preparing catalyst is simple, cumbersome technique in building-up process is reduced, while can improve noble metal existing
Dispersiveness on carbon carrier.
Brief description of the drawings
Fig. 1 is the Pd-Cu-Co/C three-way catalysts that prepare and the Pd/C prepared in comparative example in embodiment 1
The transmission electron microscope collection of illustrative plates of catalyst；
Fig. 2 is the Pd-Cu-Co/C three-way catalysts that prepare and the Pd/C prepared in comparative example in embodiment 1
Catalyst is in 0.5molL-1Sulfuric acid and 0.5molL-1Cyclic voltammetry collection of illustrative plates in formic acid mixed solution；
Fig. 3 is the Pd-Cu-Co/C three-way catalysts that prepare and the Pd/C prepared in comparative example in embodiment 1
Catalyst tests collection of illustrative plates in the 3600s chrono-amperometrics of 0.1V vs SCE.
Specific embodiment
The present invention is described in detail with specific embodiment below in conjunction with the accompanying drawings.The present embodiment is with technical solution of the present invention
Premised on implemented, give detailed implementation method and specific operating process, but protection scope of the present invention is not limited to
Following embodiments.
Embodiment 1：
A kind of preparation method of Pd-Cu-Co/C ternary fuel cells anode catalyst is as follows：
(1) 26.7mg (NH are weighed4)2PdCl4、16.0mg CuCl2·2H2O、13.7mg Co(NO3)2·6H2O and
345.0mg trisodium citrates, are added in the there-necked flask for filling 60mL ethylene glycol, and wherein ethylene glycol had not only made reducing agent but also made molten
Agent.The Vulcan XC-72 activated carbon powders of 31.1mg acid treatments are added after stirring, 12h is stirred.
(2) 1molL is used-1NaOH/EG solution adjusts pH=9, and above-mentioned mixed solution is transferred on heating stirrer,
Stirring reaction 5h under the conditions of 160 DEG C in nitrogen atmosphere.After be cooled to 70 DEG C, use 1molL-1Hydrochloric acid regulation pH=3 continues to stir
2h, is subsequently cooled to room temperature.
(3) with after ultra-pure water and ethanol constantly washing repeatedly, 60 DEG C of vacuum drying 12h obtain Pd-Cu-Co/C after drying
Three-way catalyst powder.
Comparative example：
A kind of preparation method of Pd/C catalyst is as follows：
(1) 26.7mg (NH are weighed4)2PdCl4With 138.0mg trisodium citrates, it is added to and fills 60mL ethylene glycol solutions
In there-necked flask, the Vulcan XC-72 activated carbon powders of 40.0mg acid treatments are added after stirring, stir 12h.
(2) 1molL is used-1NaOH/EG solution adjusts pH=9, and above-mentioned mixed solution is transferred on heating stirrer,
Stirring reaction 5h under the conditions of 160 DEG C in nitrogen atmosphere.After be cooled to 70 DEG C, use 1molL-1Hydrochloric acid regulation pH=3 continues to stir
2h, is subsequently cooled to room temperature.
(3) with after ultra-pure water and ethanol constantly washing repeatedly, 60 DEG C of vacuum drying 12h obtain Pd/C catalyst after drying
Powder.
Pd/C to being prepared in the Pd-Cu-Co/C three-way catalysts and comparative example that are prepared in embodiment 1 respectively
Catalyst is characterized and performance test, as a result as Figure 1-3.
As seen from Figure 1, two kinds of catalyst all have preferably dispersiveness, but compared with Pd/C catalyst, Pd-
Metal nanoparticle can be loaded preferably on the carbon carrier in Cu-Co/C three-way catalysts, without obvious agglomeration, and
With smaller particle size, average grain diameter is 4.3nm, and the average grain diameter of Pd/C catalyst is 5.3nm.
As seen from Figure 2, Pd-Cu-Co/C three-way catalysts have small negative shifting in take-off potential, in showing its anti-CO
Malicious ability is improved, and peak current density dramatically increases 1.7 times, shows that Pd-Cu-Co/C three-way catalysts have higher
Catalysis oxidation formic acid activity.
As seen from Figure 3, Pd/C catalyst is easily influenceed by CO or some intermediates, and current density becomes after 3600s
In 1.4mAcm-2, and the attenuation process of Pd-Cu-Co/C three-way catalysts substantially relaxes, and current density is still after 3600s
Up to 6.6mAcm-2, it is 4.7 times of Pd/C catalyst, illustrate Pd-Cu-Co/C three-way catalysts in formic acid electro-oxidation process
With catalytic stability higher.
In sum, Pd-Cu-Co/C three-way catalysts be uniformly dispersed, particle it is small, and have to formic acid electroxidation excellent
Catalysis activity and stability, and effectively reduce the cost of catalyst.
Embodiment 2：
A kind of Pd-Cu-Co/C ternary fuel cells anode catalyst, in the catalyst, the weight/mass percentage composition of Pd is
18%, the mol ratio of Pd, Cu, Co is 2.2:1.8:1.
A kind of preparation method of Pd-Cu-Co/C ternary fuel cells anode catalyst, the method specifically includes following step
Suddenly：
(1) by weight respectively by 25 parts of (NH4)2PdCl4, 17 parts of CuCl2·2H2O, 12 parts of Co (NO3)2·6H2O and 350
Part trisodium citrate is added into ethylene glycol, and 30 parts of carbon dusts are added after being well mixed, and is stirred, wherein, per 1mL ethylene glycol
Middle addition 0.5mg (NH4)2PdCl4, carbon dust is that, through the carbon dust after peracid treatment, acid treatment process is：By commercially available Vulcan
XC-72R carbon dusts are scattered in nitric acid, through ultrasound after, in condensing reflux 6h at 90 DEG C, be by suction filtration, washing, drying, grinding
Can；
(2) pH value is adjusted to 8 by NaOH/EG solution, afterwards in nitrogen atmosphere, in stirring reaction 4h at 170 DEG C, its
In, in NaOH/EG solution, the substance withdrawl syndrome of NaOH is 1.2mol/L；
(3) 70 DEG C are cooled to, and by salt acid for adjusting pH value to 3, continue to be cooled to room temperature after stirring 2h, be filtrated to get solid
Body thing, wherein, in hydrochloric acid, the substance withdrawl syndrome of HCl is 1mol/L；
(4) after solids is washed, 14h is vacuum dried at 55 DEG C, that is, obtains Pd-Cu-Co/C ternary fuel cells sun
Electrode catalyst.
The Pd-Cu-Co/C ternary fuel cells anode catalyst is used to carry out catalysis oxidation to formic acid.
Embodiment 3：
A kind of Pd-Cu-Co/C ternary fuel cells anode catalyst, in the catalyst, the weight/mass percentage composition of Pd is
23%, the mol ratio of Pd, Cu, Co is 1.8:2.2:1.
A kind of preparation method of Pd-Cu-Co/C ternary fuel cells anode catalyst, the method specifically includes following step
Suddenly：
(1) by weight respectively by 28 parts of (NH4)2PdCl4, 15 parts of CuCl2·2H2O, 15 parts of Co (NO3)2·6H2O and 340
Part trisodium citrate is added into ethylene glycol, and 32 parts of carbon dusts are added after being well mixed, and is stirred, wherein, per 1mL ethylene glycol
Middle addition 0.4mg (NH4)2PdCl4, carbon dust is that, through the carbon dust after peracid treatment, acid treatment process is：By commercially available Vulcan
XC-72R carbon dusts are scattered in nitric acid, through ultrasound after, in condensing reflux 5h at 95 DEG C, be by suction filtration, washing, drying, grinding
Can；
(2) pH value is adjusted to 10 by NaOH/EG solution, afterwards in nitrogen atmosphere, in stirring reaction 6h at 150 DEG C,
Wherein, in NaOH/EG solution, the substance withdrawl syndrome of NaOH is 0.8mol/L；
(3) 80 DEG C are cooled to, and by salt acid for adjusting pH value to 2, continue to be cooled to room temperature after stirring 2.5h, be filtrated to get
Solids, wherein, in hydrochloric acid, the substance withdrawl syndrome of HCl is 0.8mol/L；
(4) after solids is washed, 10h is vacuum dried at 65 DEG C, that is, obtains Pd-Cu-Co/C ternary fuel cells sun
Electrode catalyst.
The Pd-Cu-Co/C ternary fuel cells anode catalyst is used to carry out catalysis oxidation to formic acid.
Embodiment 4：
A kind of Pd-Cu-Co/C ternary fuel cells anode catalyst, in the catalyst, the weight/mass percentage composition of Pd is
19%, the mol ratio of Pd, Cu, Co is 2.1:1.9:1.
A kind of preparation method of Pd-Cu-Co/C ternary fuel cells anode catalyst, the method specifically includes following step
Suddenly：
(1) by weight respectively by 26 parts of (NH4)2PdCl4, 16 parts of CuCl2·2H2O, 14 parts of Co (NO3)2·6H2O and 345
Part trisodium citrate is added into ethylene glycol, and 31 parts of carbon dusts are added after being well mixed, and is stirred, wherein, per 1mL ethylene glycol
Middle addition 0.45mg (NH4)2PdCl4, carbon dust is that, through the carbon dust after peracid treatment, acid treatment process is：By commercially available Vulcan
XC-72 carbon dusts are scattered in nitric acid, through ultrasound after, in condensing reflux 7h at 85 DEG C, be by suction filtration, washing, drying, grinding
Can；
(2) pH value is adjusted to 9 by NaOH/EG solution, afterwards in nitrogen atmosphere, in stirring reaction 5h at 160 DEG C, its
In, in NaOH/EG solution, the substance withdrawl syndrome of NaOH is 1mol/L；
(3) 60 DEG C are cooled to, and by salt acid for adjusting pH value to 4, continue to be cooled to room temperature after stirring 1.5h, be filtrated to get
Solids, wherein, in hydrochloric acid, the substance withdrawl syndrome of HCl is 1.2mol/L；
(4) after solids is washed, 12h is vacuum dried at 60 DEG C, that is, obtains Pd-Cu-Co/C ternary fuel cells sun
Electrode catalyst.
The Pd-Cu-Co/C ternary fuel cells anode catalyst is used to carry out catalysis oxidation to formic acid.
Embodiment 5：
A kind of Pd-Cu-Co/C ternary fuel cells anode catalyst, in the catalyst, the weight/mass percentage composition of Pd is
21%, the mol ratio of Pd, Cu, Co is 1.9:2.1:1.
Embodiment 6：
A kind of Pd-Cu-Co/C ternary fuel cells anode catalyst, in the catalyst, the weight/mass percentage composition of Pd is
20%, the mol ratio of Pd, Cu, Co is 2:2:1.
The above-mentioned description to embodiment is to be understood that and use invention for ease of those skilled in the art.
Person skilled in the art obviously can easily make various modifications to these embodiments, and described herein general
Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to above-described embodiment, ability
Field technique personnel announcement of the invention, does not depart from improvement that scope made and modification all should be of the invention
Within protection domain.
Claims (10)
1. a kind of Pd-Cu-Co/C ternary fuel cells anode catalyst, it is characterised in that in the catalyst, the quality percentage of Pd
Content is 18-23%, and the mol ratio of Pd, Cu, Co is 1.8-2.2:1.8-2.2:1.
2. a kind of Pd-Cu-Co/C ternary fuel cells anode catalyst according to claim 1, it is characterised in that this is urged
In agent, the weight/mass percentage composition of Pd is 19-21%, and the mol ratio of Pd, Cu, Co is 1.9-2.1:1.9-2.1:1.
3. a kind of preparation method of Pd-Cu-Co/C ternary fuel cells anode catalyst as claimed in claim 1 or 2, it is special
Levy and be, the method specifically includes following steps：
(1) respectively by (NH4)2PdCl4、CuCl2·2H2O、Co(NO3)2·6H2O and trisodium citrate are added into ethylene glycol, are mixed
Uniform rear addition carbon dust is closed, and is stirred；
(2) pH value is adjusted to 8-10, afterwards in nitrogen atmosphere, in stirring reaction 4-6h at 150-170 DEG C；
(3) 60-80 DEG C is cooled to, and adjusts pH value to 2-4, continue to be cooled to room temperature after stirring 1.5-2.5h, be filtrated to get solid
Body thing；
(4) after solids washing, drying, that is, described Pd-Cu-Co/C ternary fuel cell anode catalysts are obtained.
4. the preparation method of a kind of Pd-Cu-Co/C ternary fuel cells anode catalyst according to claim 3, it is special
Levy and be, in step (1), described (NH4)2PdCl4、CuCl2·2H2O、Co(NO3)2·6H2O, trisodium citrate and carbon dust
Weight portion content adds in being respectively 25-28 parts, 15-17 parts, 12-15 parts, 340-350 parts and 30-32 parts, and every 1mL ethylene glycol
Enter 0.4-0.5mg (NH4)2PdCl4。
5. the preparation method of a kind of Pd-Cu-Co/C ternary fuel cells anode catalyst according to claim 3, it is special
Levy and be, in step (1), described carbon dust is that, through the carbon dust after peracid treatment, acid treatment process is：Carbon dust is scattered in nitric acid
In, through ultrasound after, in condensing reflux 5-7h at 85-95 DEG C, by suction filtration, washing, drying, grinding.
6. the preparation method of a kind of Pd-Cu-Co/C ternary fuel cells anode catalyst according to claim 3, it is special
Levy and be, in step (1), described carbon dust is selected from commercially available Vulcan XC-72 carbon dusts or Vulcan XC-72R carbon dusts.
7. the preparation method of a kind of Pd-Cu-Co/C ternary fuel cells anode catalyst according to claim 3, it is special
Levy and be, in step (2), pH value is adjusted by NaOH/EG solution, in described NaOH/EG solution, the amount of the material of NaOH is dense
It is 0.8-1.2mol/L to spend.
8. the preparation method of a kind of Pd-Cu-Co/C ternary fuel cells anode catalyst according to claim 3, it is special
Levy and be, in step (3), by salt acid for adjusting pH value, in described hydrochloric acid, the substance withdrawl syndrome of HCl is 0.8-1.2mol/
L。
9. the preparation method of a kind of Pd-Cu-Co/C ternary fuel cells anode catalyst according to claim 3, it is special
Levy and be, in step (4), described drying is vacuum drying, and the vacuum drying temperature is 55-65 DEG C, and the time is 10-14h.
10. a kind of application of Pd-Cu-Co/C ternary fuel cells anode catalyst as claimed in claim 1 or 2, its feature
It is that the catalyst is used to carry out catalysis oxidation to formic acid.
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Cited By (2)
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| CN112490451A (en) * | 2020-11-05 | 2021-03-12 | 上海电力大学 | Cu-CoNCNs catalyst derived from folic acid, preparation and application thereof |
| CN114373946A (en) * | 2021-12-17 | 2022-04-19 | 上海电力大学 | Bent porous ultrathin flaky difunctional PdCu or PdCu/C catalyst and preparation method and application thereof |
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| CN112490451A (en) * | 2020-11-05 | 2021-03-12 | 上海电力大学 | Cu-CoNCNs catalyst derived from folic acid, preparation and application thereof |
| CN114373946A (en) * | 2021-12-17 | 2022-04-19 | 上海电力大学 | Bent porous ultrathin flaky difunctional PdCu or PdCu/C catalyst and preparation method and application thereof |
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