CN104409745A - Preparation method of high-performance superlow-palladium-capacity anode electrocatalyst Pd-CoP/C of direct formic acid fuel cell - Google Patents
Preparation method of high-performance superlow-palladium-capacity anode electrocatalyst Pd-CoP/C of direct formic acid fuel cell 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
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- H01M4/8817—Treatment of supports before application of the catalytic active composition
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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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
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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Abstract
The invention relates to a preparation method of a high-performance superlow-palladium-capacity anode electrocatalyst Pd-CoP/C of a direct formic acid fuel cell and belongs to the technical field of fuel cells. The preparation method comprises the following steps: dispersing a carrier and cobalt chloride hexahydrate in water, drying to obtain a first compound carrier by distillation after ultrasonic dispersing and stirring; mixing and grinding the first compound carrier and hydrated sodium hypophosphite for one-hour reaction, and washing and drying the reactant to obtain a second compound carrier; dispersing the second compound carrier in glycol, adding hexachloropalladate, and performing ultrasonic dispersing and stirring to obtain a first turbid liquid; stirring the first turbid liquid at the room temperature, and regulating the pH value with sodium hydroxide to obtain a second turbid liquid; performing microwave radiation on the second turbid liquid, and obtaining a supported palladium catalyst. The palladium-based catalyst prepared by the method has extremely high catalytic activity and relatively high stability to formic acid electro-oxidation. Meanwhile, the capacity of the precious metal palladium can be reduced, and the method is simple to operate, short in preparation period and suitable for mass production.
Description
Technical field
The present invention relates to field of fuel cell technology, be specifically related to the method for making of the direct formic acid anode of fuel cell eelctro-catalyst Pd-CoP/C of a kind of high-performance ultralow palladium carrying capacity.
Background technology
As the alternative fuel of methyl alcohol, in recent years, direct formic acid fuel (DFAFC) battery obtains a large amount of concerns of people.The same with methyl alcohol, formic acid, only containing a carbon atom, not containing C-C key, is easy to oxidation, low price, abundance.Moreover, the advantage that formic acid also has a lot of methyl alcohol incomparable: more nontoxic than formic acid with methanol phase, is permitted as food additives by U.S. food and Drug Administration; It is nonflammable, and storage and transportation safety are conveniently; The theoretical electromotive force of DFAFC is 1.48V 25 DEG C time, at several pem fuel (CH
3oH, HCHO, H
2) in battery, DFAFC has the highest theoretical open circuit voltage; When doing fuel with formic acid, the concentration of formic acid can be very high, even if concentration is up to 20mol L
-1, still have good performance, its freezing point also reduces greatly simultaneously; Formic acid has the oxidation kinetics speed of an order of magnitude higher than methyl alcohol, makes DFAFC have higher specific power and suitable low-temperature working; Formic acid itself is a kind of electrolyte, is conducive to the proton conductivity increasing solution in anode chamber; The low transmission of formic acid and corresponding high fuel availability compensate for formic acid and methyl alcohol (4900Wh L
-1) and ethanol (6280Wh L
-1) low specific energy density (the 2104Wh L that compares
-1).The advantage of these uniquenesses of formic acid makes it become a kind of rising methyl alcohol alternative fuel, thus greatly facilitates the research and development of DFAFC.
Current direct methanoic acid fuel cell catalyst mainly comprises palladium black and load type palladium catalyst.But existing direct methanoic acid fuel cell still exists following shortcoming, as stability and durability are still poor, noble-metal-supported amount still higher, noble metal utilisation is still lower etc. and do not reach business-like technical requirement.
Prior art discloses the preparation method of multiple direct methanoic acid fuel cell catalyst, activity and the stability of palladium-based catalyst is improved by preparing alloy or nonmetal doping, if Qin is by the activity (Y.-H.Qin of preparation PdAu alloy raising catalyst, Y.Jiang, D.-F.Niu, X.-S.Zhang, X.-G.Zhou, L.Niu, W.-K.Yuan, J.Power Sources 2012, 215, 130.), Wang improves the activity (X.Wang of catalyst by preparation PdIr alloy, Y.Tang, Y.Gao, T.Lu, J.Power Sources 2008, 175, 784.), Liu improves the activity (Z.Liu of catalyst by preparation PdSn alloy, X.Zhang, Electrochem.commun.2009, 11, 1667.), Zhang and Morales improves the stability (L.Zhang of catalyst by preparation PdCo alloy, L.Wan, Y.Ma, Y.Chen, Y.Zhou, Y.Tang, T.Lu, Appl.catal.B:Environ.2013, 138-139, 229., D.Morales-Acosta, J.Ledesma-Garcia, L.A.Godinez, H.G.Rodr í guez, L.
l.G.Arriaga, J.Power Sources2010,195,461.), Zhang improves stability (L.Zhang, Y.Tang, the J.Bao of catalyst by nonmetal phosphorus doping, T.Lu, C.Li, J.Power Sources 2006,162,177.), Winjobi improves the stability (O.Winjobi of catalyst by preparation PdPt alloy, Z.Zhang, C.Liang, W.Li, Electrochim.Acta 2010,55,4217.).But above-mentioned preparation method respectively has deficiency, as prepared Pd-M (M=Pt, Ir, Sn, Au, Co etc.) although can improve the activity of catalyst to a certain extent, under battery context, the dissolving of M is assembled but is fatal part, Pd, Pt, Au etc. can not be widely deployed and apply as noble metal simultaneously, and current technical merit is only limited to conceptual phase; Though nonmetal phosphorus doping can improve the stability of catalyst to a certain extent, however very limited to the raising of catalytic activity.
In addition, in order to reduce resistance to mass tranfer, improving catalyst noble metal load capacity is also improve a kind of method of battery performance, but under high carrying capacity condition, noble metal nano particles is easily reunited, the utilance of noble metal can be reduced, simultaneously too high noble metal carrying capacity for realizing the low cost of fuel cell, economic benefit has weak point.Therefore, how to develop a kind of low noble metal carrying capacity, have high catalytic activity to have the catalyst of high stable performance extremely urgent simultaneously.
Summary of the invention
The present invention will solve technical problem of the prior art, the method for making of the direct formic acid anode of fuel cell eelctro-catalyst Pd-CoP/C of a kind of high-performance ultralow palladium carrying capacity is provided, the method is simple to operate, mild condition, can obtain the load type palladium catalyst of ultralow palladium carrying capacity, super-active, superelevation palladium utilance.
In order to solve the problems of the technologies described above, technical scheme of the present invention is specific as follows:
A method for making of the direct formic acid anode of fuel cell eelctro-catalyst Pd-CoP/C of high-performance ultralow palladium carrying capacity, comprises the steps:
(1) be scattered in water by carrier and cobalt chloride hexahydrate, after ultrasonic disperse, stirring, at 100 ~ 120 DEG C, evaporating water obtains the first complex carrier;
(2) under 800 DEG C of nitrogen protections, one hour is reacted by after described first complex carrier and hydration inferior sodium phosphate mixed grinding, products therefrom porphyrize, wash three times respectively with distilled water and absolute ethyl alcohol, then 60 ~ 80 DEG C of vacuumize 12 ~ 24 hours, obtains the second complex carrier;
(3) described second complex carrier is scattered in ethylene glycol, adds the acid of chlorine palladium, after ultrasonic disperse, stirring, obtain the first suspension-turbid liquid;
(4) by under described first suspension-turbid liquid stirring at room temperature with NaOH adjust ph, obtain the second suspension-turbid liquid;
(5) by described second suspension-turbid liquid microwave, after washing, drying, anode electrocatalyst Pd-CoP/C is obtained.
In technique scheme, described in step (1), carrier is active carbon, carbon nano-tube or Graphene.
In technique scheme, described in step (1), the mass ratio of carrier and described cobalt chloride hexahydrate is 310mg:1000mg ~ 2910mg:1000mg.
In technique scheme, described in step (2), the mass ratio of the first complex carrier and described hydration inferior sodium phosphate is 390mg:1000mg ~ 1800mg:1000mg.
In technique scheme, described in step (3), the mass volume ratio of the second complex carrier and described ethylene glycol is 140 ~ 190mg:80mL ~ 150mL.
In technique scheme, described in step (3), the mass ratio of the second complex carrier and the acid of described chlorine palladium is 140 ~ 190mg:10 ~ 60mg.
In technique scheme, the time of ultrasonic disperse described in step (1) and step (3) is 20min ~ 60min.
In technique scheme, described in step (4) with NaOH adjust ph for 9 ~ 12.
In technique scheme, described in step (5), microwave irradiation time is 60s ~ 300s.
In technique scheme, washing described in step (5) adopts deionized water to wash.
The invention has the beneficial effects as follows:
The method for making of the direct formic acid anode of fuel cell eelctro-catalyst Pd-CoP/C of a kind of high-performance provided by the invention ultralow palladium carrying capacity, relative to existing commercial catalysts, the inventive method with the addition of CoP in the carrier as altogether/co-catalyst.In order to study different CoP content to the Electrochemical Performances of catalyst, the present invention controls different CoP content when Kaolinite Preparation of Catalyst, thus takes into account CoP content when obtaining most high catalytic activity and best stability.Experiment proves, the catalyst adopting the inventive method to prepare has remarkable chemical property, and its processing method is easy and simple to handle, and fabrication cycle is shorter; The carrying capacity of precious metal palladium is reduced while electrochemistry and battery performance obtain obviously promoting.In addition, method provided by the invention is simple to operate, mild condition, without the need to surfactant or template, therefore without the need to the operating procedure such as washing process of complexity, is easy to large-scale production.
Accompanying drawing explanation
Below in conjunction with the drawings and specific embodiments, the present invention is described in further detail.
Fig. 1 is the cyclic voltammetry curves of six kinds of catalyst in formic acid solution;
Fig. 2 is X-ray diffraction (XRD) curve of five kinds of carriers;
Fig. 3 is X-ray diffraction (XRD) curve of six kinds of catalyst;
Fig. 4 is X-ray photoelectron spectroscopic analysis (XPS) curve of six kinds of catalyst;
Fig. 5 is the transmission electron microscope photo of catalyst under 20nm scale (TEM) prepared by embodiment 1;
Fig. 6 is the transmission electron microscope photo of catalyst under 20nm scale (TEM) prepared by embodiment 2;
Fig. 7 is the transmission electron microscope photo of catalyst under 20nm scale (TEM) prepared by embodiment 3;
Fig. 8 is the transmission electron microscope photo of catalyst under 20nm scale (TEM) prepared by embodiment 4;
Fig. 9 is the transmission electron microscope photo of catalyst under 20nm scale (TEM) prepared by embodiment 5;
Figure 10 is the transmission electron microscope photo of catalyst under 20nm scale (TEM) of comparative example 1 business;
Figure 11 is the cell polarization curves of catalyst in embodiment 3 and comparative example 1;
Figure 12 is the stability test curve of catalyst in embodiment 3 and comparative example 1.
Embodiment
Below in conjunction with accompanying drawing, the present invention is described in detail.
A method for making of the direct formic acid anode of fuel cell eelctro-catalyst Pd-CoP/C of high-performance ultralow palladium carrying capacity, concrete steps and condition as follows:
(1) be scattered in water by carrier and cobalt chloride hexahydrate, after ultrasonic disperse 20min ~ 60min, stirring, at 100 ~ 120 DEG C, evaporating water obtains the first complex carrier; Described carrier is active carbon, carbon nano-tube or Graphene; The mass ratio of described carrier and described cobalt chloride hexahydrate is 310mg:1000mg ~ 2910mg:1000mg.
(2) under 800 DEG C of nitrogen protections, one hour is reacted by after described first complex carrier and hydration inferior sodium phosphate mixed grinding, products therefrom porphyrize, wash three times respectively with distilled water and absolute ethyl alcohol, then 60 ~ 80 DEG C of vacuumize 12 ~ 24 hours, obtains the second complex carrier; The mass ratio of described first complex carrier and described hydration inferior sodium phosphate is 390mg:1000mg ~ 1800mg:1000mg.
(3) described second complex carrier is scattered in ethylene glycol, adds the acid of chlorine palladium, after ultrasonic disperse 20min ~ 60min, stirring, obtain the first suspension-turbid liquid; The mass volume ratio of described second complex carrier and described ethylene glycol is 140 ~ 190mg:80mL ~ 150mL; The mass ratio of described second complex carrier and the acid of described chlorine palladium is 140 ~ 190mg:10 ~ 60mg.
(4) by under described first suspension-turbid liquid stirring at room temperature with NaOH adjust ph for 9 ~ 12, obtain the second suspension-turbid liquid;
(5) by described second suspension-turbid liquid microwave 60s ~ 300s, adopt that deionized water carries out washing, obtain anode electrocatalyst Pd-CoP/C after drying.
In order to understand the present invention further, below in conjunction with embodiment, the preferred embodiment of the invention is described, but should be appreciated that these describe just for further illustrating the features and advantages of the present invention, instead of limiting to the claimed invention.The performance catalyst based to Pd due to the mass percentage of amount in CoP/C complex carrier of CoP has material impact, and therefore embodiment enumerates the performance of the catalyst corresponding when mass percentage is 10% ~ 50% in CoP/C complex carrier with the content investigating CoP respectively.
Raw materials usedly in following embodiment be the general chemical buied from the market.
Embodiment 1
(1) in the beaker containing 50mL intermediate water, add the Vulcan XC-72 of 0.60g cobalt chloride hexahydrate and the production of Cabot company of the 1.6889g U.S., 60min is stirred after ultrasonic 30min, then put into Muffle furnace 100 DEG C of evaporate to dryness moisture content and obtain black mixture, then be positioned in tube furnace after this black mixture 2.016g being added quartz boat together with 1.32g hydration inferior sodium phosphate, in nitrogen atmosphere, calcine 60min at 800 DEG C, wherein oxygen gas flow rate is 80cc min
-1, tube furnace from normal temperature with 5 DEG C of min
-1programming rate be warming up to 800 DEG C, obtained complex carrier is labeled as CoP/C-10% (wherein 10% represents the mass percentage of CoP in complex carrier).
(2) CoP/C-10%190mg obtained by step (1) is taken, add in the beaker containing 100mL ethylene glycol, add the chlorine palladium acid containing 10mg palladium simultaneously, 5h is stirred after ultrasonic 30min, then be 11.0 by NaOH adjust ph, immediately above-mentioned solution being put into power is that the microwave oven of 700W irradiates 3min to reduce the acid of chlorine palladium for Pd nano particle, and obtained catalyst is labeled as Pd-CoP/C-10%, and wherein palladium mass percentage is in the catalyst 5%.
(3) to containing 950 μ L ethanolic solutions beaker in add 50 μ L Aldrich produce, mass fraction be 5% Nafion solution, add the Pd-CoP/C-10% catalyst of preparation in 5mg step (2) more wherein, ultrasonic disperse 30min, obtains mixed solution; Get the above-mentioned solution of 5 μ L to drip and be applied on glass-carbon electrode, after room temperature is dried, obtain membrane electrode; With Hg/Hg
2cl
2electrode as reference electrode, Pt sheet as the three-electrode system to electrode, cyclic voltammetry is carried out in the sulfuric acid of the 0.5mol/L through nitrogen deoxygenation and the formic acid solution of 0.5mol/L, sweep speed is 50mV/s, result is see Fig. 1, Fig. 1 is the cyclic voltammetry curve of catalyst in formic acid solution, wherein, the cyclic voltammetry curve of commercial catalysts in formic acid solution that curve Pd/C-JM provides for comparative example 1, as shown in Figure 1, the mass ratio activity of the Pd-CoP/C-10% catalyst of embodiment 1 preparation is 1782.3mA mg
-1pd, mass ratio activity (the 783.1mA mg of the business Pd/C catalyst (Pd/C-JM) provided higher than comparative example 1 far away
-1pd).
(4) the CoP/C-10% carrier and the Pd-CoP/C-10% catalyst that take preparation in a certain amount of step (1) and step (2) survey XRD respectively.XRD spectrum as shown in Figures 2 and 3.Can find out that prepared carrier and catalyst and standard card match by Fig. 2 and Fig. 3.
(5) TEM (see Fig. 5) surveyed by the Pd-CoP/C-10% catalyst taking preparation in a certain amount of step (2).
(6) XPS (see Fig. 4) surveyed by the Pd-CoP/C-10% catalyst taking preparation in a certain amount of step (2).
Comparative example 1
(1) add in 950 μ L ethanolic solutions 50 μ L Johnson Mattery companies produce, mass fraction be 5% Nafion solution, add the 20%Pd/C catalyst (being labeled as Pd/C-JM) of 5mg business more wherein, ultrasonic disperse 30min, obtains mixed solution; Get the above-mentioned mixed solution of 5 μ L to drip and be applied on glass-carbon electrode, after room temperature is dried, obtain membrane electrode; With Hg/Hg
2cl
2electrode as reference electrode, Pt sheet as the three-electrode system to electrode, cyclic voltammetry is carried out in the sulfuric acid of the 0.5mol/L through nitrogen deoxygenation and the formic acid solution of 0.5mol/L, sweep speed is 50mV/s, result is see Fig. 1, Fig. 1 is the cyclic voltammetry curve of catalyst in formic acid solution, wherein, the cyclic voltammetry curve of commercial catalysts in formic acid solution that provide for comparative example 1 of curve Pd/C-JM.
(2) XRD (see Fig. 3) surveyed by the Pd/C-JM catalyst taking preparation in a certain amount of step (1).
(3) TEM surveyed by the Pd/C-JM catalyst taking preparation in a certain amount of step (1).It the results are shown in Figure 10, can find out that the palladium metal nano particle distribution of commercial catalysts is comparatively intensive, this is because carrying capacity is higher.
(4) XPS (see Fig. 4) surveyed by the Pd/C-JM catalyst taking preparation in a certain amount of step (1).
(5) take preparation in a certain amount of step (1) Pd/C-JM catalyst and add successively wherein deionized water,
aqueous isopropanol also makes it to be uniformly dispersed by ultrasonic, stirring, wherein
mass fraction is 15% in the catalyst, and by finely dispersed slurries spraying instrument direct spraying on anode carbon paper TGP-H-060 (10wt%PTFE), Pd/C-JM catalyst loading is 0.3mg cm
-2, be prepared into anode electrode.
(6) get a certain amount of Vulcan XC-72 carbon dust and add successively wherein deionized water, isopropyl alcohol and by ultrasonic, stir make it to be uniformly dispersed, add mass fraction be again the PTFE solution of 20% and be uniformly dispersed, by finely dispersed slurries, blade coating is on negative electrode carbon paper TGP-H-030 (20wt%PTFE) by hand, and VulcanXC-72 carbon dust carrying capacity is 2mg cm
-2, dry under natural conditions, form microporous layers, carbon paper and microporous layers form gas diffusion layers.
(7) take the black catalyst of a certain amount of Pt and add successively wherein deionized water,
aqueous isopropanol also makes it to be uniformly dispersed by ultrasonic, stirring, wherein
mass fraction is 10% in the catalyst, and be sprayed into by finely dispersed slurries spraying instrument on gas diffusion layers prepared by (6) step, the black catalyst loading of Pt is 4mg cm
-2, be prepared into cathode electrode.
(8) by anode prepared by step (5),
the negative electrode prepared of 115 films and step (7) in hot press 130 DEG C, under 3MPa, hot pressing 120s obtains membrane electrode.
Be arranged on by this membrane electrode in an active direct methanoic acid fuel cell, at 30 DEG C, test its polarization and discharge performance, formic acid concn is 3M, and test result is as shown in Pd/C-JM curve in Figure 11 and Figure 12.In Figure 11, Pd/C-JM curve is voltage and the power curve of membrane electrode prepared by the present embodiment test when discharging with 3M formic acid solution at 30 DEG C, and in Figure 11, abscissa is discharge current density, and ordinate is discharge voltage, and secondary ordinate is power density.In Figure 12, Pd/C-JM curve is the voltage curve of membrane electrode prepared by the present embodiment test when discharging for a long time under constant voltage 0.35V with 3M formic acid solution at room temperature 30 DEG C, and in figure, abscissa is discharge time, and ordinate is discharge current density.
Embodiment 2
(1) in the beaker containing 50mL intermediate water, add the Vulcan XC-72 of 1.20g cobalt chloride hexahydrate and the production of Cabot company of the 1.5016g U.S., 60min is stirred after ultrasonic 30min, then put into Muffle furnace 110 DEG C of evaporate to dryness moisture content and obtain black mixture, then be positioned in tube furnace after this black mixture 2.157g being added quartz boat together with 2.64g hydration inferior sodium phosphate, in nitrogen atmosphere, calcine 90min at 800 DEG C, wherein oxygen gas flow rate is 80cc min
-1, tube furnace from normal temperature with 5 DEG C of min
-1programming rate be warming up to 800 DEG C, obtained complex carrier is labeled as CoP/C-20% (wherein 20% represents the mass percentage of CoP in complex carrier).
(2) CoP/C-20%190mg obtained by step (1) is taken, add in the beaker containing 100mL ethylene glycol, add the chlorine palladium acid containing 10mg palladium simultaneously, 5h is stirred after ultrasonic 30min, then be 11.0 by NaOH adjust ph, immediately above-mentioned solution being put into power is that the microwave oven of 700W irradiates 3min to reduce the acid of chlorine palladium for Pd nano particle, and obtained catalyst is labeled as Pd-CoP/C-20%, and wherein palladium mass percentage is in the catalyst 5%.
(3) to containing 950 μ L ethanolic solutions beaker in add 50 μ L Aldrich produce, mass fraction be 5% Nafion solution, add the Pd-CoP/C-20% catalyst of preparation in 5mg step (2) more wherein, ultrasonic disperse 30min, obtains mixed solution; Get the above-mentioned mixed solution of 5 μ L to drip and be applied on glass-carbon electrode, after room temperature is dried, obtain membrane electrode; With Hg/Hg
2cl
2electrode as reference electrode, Pt sheet as the three-electrode system to electrode, cyclic voltammetry is carried out in the sulfuric acid of the 0.5mol/L through nitrogen deoxygenation and the formic acid solution of 0.5mol/L, sweep speed is 50mV/s, result is see Fig. 1, Fig. 1 is the cyclic voltammetry curve of catalyst in formic acid solution, wherein, the cyclic voltammetry curve of commercial catalysts in formic acid solution that curve Pd/C-JM provides for comparative example 1, as shown in Figure 1, the mass ratio activity of the Pd-CoP/C-20% catalyst of embodiment 2 preparation is 2076.1mA mg
-1pd, mass ratio activity (the 783.1mA mg of the business Pd/C catalyst (Pd/C-JM) provided higher than comparative example 1 far away
-1pd).
(4) XRD (see Fig. 2 and Fig. 3) surveyed respectively by the CoP/C-20% carrier and the Pd-CoP/C-20% catalyst that take preparation in a certain amount of step (1) and step (2).
(5) TEM (see Fig. 6) surveyed by the Pd-CoP/C-20% catalyst taking preparation in a certain amount of step (2).
(6) XPS (see Fig. 4) surveyed by the Pd-CoP/C-20% catalyst taking preparation in a certain amount of step (2).
Embodiment 3
(1) in the beaker containing 50mL intermediate water, add the Vulcan XC-72 of 1.20g cobalt chloride hexahydrate and the production of Cabot company of the 0.876g U.S., 60min is stirred after ultrasonic 30min, then put into Muffle furnace 120 DEG C of evaporate to dryness moisture content and obtain black mixture, then be positioned in tube furnace after this black mixture 1.5313g being added quartz boat together with 2.64g hydration inferior sodium phosphate, in nitrogen atmosphere, calcine 120min at 800 DEG C, wherein oxygen gas flow rate is 80cc min
-1, tube furnace from normal temperature with 5 DEG C of min
-1programming rate be warming up to 800 DEG C, obtained complex carrier is labeled as CoP/C-30% (wherein 30% represents the mass percentage of CoP in complex carrier).
(2) CoP/C-30%190mg obtained by step (1) is taken, add in the beaker containing 100mL ethylene glycol, add the chlorine palladium acid containing 10mg palladium simultaneously, 5h is stirred after ultrasonic 30min, then be 11.0 by NaOH adjust ph, immediately above-mentioned solution being put into power is that the microwave oven of 700W irradiates 3min to reduce the acid of chlorine palladium for Pd nano particle, and obtained catalyst is labeled as Pd-CoP/C-30%, and wherein palladium mass percentage is in the catalyst 5%.
(3) to containing 950 μ L ethanolic solutions beaker in add 50 μ L Aldrich produce, mass fraction be 5% Nafion solution, add the Pd-CoP/C-30% catalyst of preparation in 5mg step (2) more wherein, ultrasonic disperse 30min, obtains mixed solution; Get the above-mentioned mixed solution of 5 μ L to drip and be applied on glass-carbon electrode, after room temperature is dried, obtain membrane electrode; With Hg/Hg
2cl
2electrode as reference electrode, Pt sheet as the three-electrode system to electrode, cyclic voltammetry is carried out in the sulfuric acid of the 0.5mol/L through nitrogen deoxygenation and the formic acid solution of 0.5mol/L, sweep speed is 50mV/s, result is see Fig. 1, Fig. 1 is the cyclic voltammetry curve of catalyst in formic acid solution, wherein, the cyclic voltammetry curve of commercial catalysts in formic acid solution that curve Pd/C-JM provides for comparative example 1, as shown in Figure 1, the mass ratio activity of the Pd-CoP/C-30% catalyst of embodiment 3 preparation is 2757.5mA mg
-1pd, mass ratio activity (the 783.1mA mg of the business Pd/C catalyst (Pd/C-JM) provided higher than comparative example 1 far away
-1pd).
(4) XRD (see Fig. 2 and Fig. 3) surveyed respectively by the CoP/C-30% carrier and the Pd-CoP/C-30% catalyst that take preparation in a certain amount of step (1) and step (2).
(5) TEM (see Fig. 7) surveyed by the Pd-CoP/C-30% catalyst taking preparation in a certain amount of step (2).
(6) XPS (see Fig. 4) surveyed by the Pd-CoP/C-30% catalyst taking preparation in a certain amount of step (2).
(7) take preparation in a certain amount of step (2) Pd-CoP/C-30% catalyst and add successively wherein deionized water,
aqueous isopropanol also makes it to be uniformly dispersed by ultrasonic, stirring, wherein
mass fraction is 15% in the catalyst, and by finely dispersed slurries spraying instrument direct spraying on anode carbon paper TGP-H-060 (10wt%PTFE), in Pd-CoP/C-30% catalyst, the carrying capacity of Pd is 0.3mg cm
-2, be prepared into anode electrode.
(8) get a certain amount of Vulcan XC-72 carbon dust and add successively wherein deionized water, isopropyl alcohol and by ultrasonic, stir make it to be uniformly dispersed, add mass fraction be again the PTFE solution of 20% and be uniformly dispersed, by finely dispersed slurries, blade coating is on negative electrode carbon paper TGP-H-030 (20wt%PTFE) by hand, and VulcanXC-72 carbon dust carrying capacity is 2mg cm
-2, dry under natural conditions, form microporous layers, carbon paper and microporous layers form gas diffusion layers.
(9) take the black catalyst of a certain amount of Pt and add successively wherein deionized water,
aqueous isopropanol also makes it to be uniformly dispersed by ultrasonic, stirring, wherein
mass fraction is 10% in the catalyst, and be sprayed into by finely dispersed slurries spraying instrument on gas diffusion layers prepared by (8) step, the black catalyst loading of Pt is 4mg cm
-2, be prepared into cathode electrode.
(10) by anode prepared by step (7),
the negative electrode prepared of 115 films and step (9) in hot press 130 DEG C, under 3MPa, hot pressing 120s obtains membrane electrode.
Be arranged on by this membrane electrode in an active direct methanoic acid fuel cell, at 60 DEG C, test its polarization and discharge performance, formic acid concn is 3M, and test result is as shown in Pd-CoP/C-30% curve in Figure 11 and Figure 12.In Figure 11, Pd-CoP/C-30% curve is voltage and the power curve of membrane electrode prepared by the present embodiment test when discharging with 3M formic acid solution at 60 DEG C, and in figure, abscissa is discharge current density, and ordinate is discharge voltage, and secondary ordinate is power density.In Figure 12, Pd-CoP/C-30% curve is the voltage curve of membrane electrode prepared by the present embodiment test when discharging for a long time under constant voltage 0.35V with 3M formic acid solution at 60 DEG C, and in figure, abscissa is discharge time, and ordinate is discharge current density.
Embodiment 4
(1) in the beaker containing 50mL intermediate water, add the Vulcan XC-72 of 1.20g cobalt chloride hexahydrate and the production of Cabot company of the 0.5613g U.S., 60min is stirred after ultrasonic 30min, then put into Muffle furnace 120 DEG C of evaporate to dryness moisture content and obtain black mixture, then be positioned in tube furnace after this black mixture 1.2166g being added quartz boat together with 2.64g hydration inferior sodium phosphate, in nitrogen atmosphere, calcine 60min at 800 DEG C, wherein oxygen gas flow rate is 80cc min
-1, tube furnace from normal temperature with 5 DEG C of min
-1programming rate be warming up to 800 DEG C, obtained complex carrier is labeled as CoP/C-40% (wherein 40% represents the mass percentage of CoP in complex carrier).
(2) CoP/C-40%190mg obtained by step (1) is taken, add in the beaker containing 100mL ethylene glycol, add the chlorine palladium acid containing 10mg palladium simultaneously, 5h is stirred after ultrasonic 30min, then be 11.0 by NaOH adjust ph, immediately above-mentioned solution being put into power is that the microwave oven of 700W irradiates 3min to reduce the acid of chlorine palladium for Pd nano particle, and obtained catalyst is labeled as Pd-CoP/C-40%, and wherein palladium mass percentage is in the catalyst 5%.
(3) to containing 950 μ L ethanolic solutions beaker in add 50 μ L Aldrich produce, mass fraction be 5% Nafion solution, add the Pd-CoP/C-40% catalyst of preparation in 5mg step (2) more wherein, ultrasonic disperse 30min, obtains mixed solution; Get the above-mentioned mixed solution of 5 μ L to drip and be applied on glass-carbon electrode, after room temperature is dried, obtain membrane electrode; With Hg/Hg
2cl
2electrode as reference electrode, Pt sheet as the three-electrode system to electrode, cyclic voltammetry is carried out in the sulfuric acid of the 0.5mol/L through nitrogen deoxygenation and the formic acid solution of 0.5mol/L, sweep speed is 50mV/s, result is see Fig. 1, Fig. 1 is the cyclic voltammetry curve of catalyst in formic acid solution, wherein, the cyclic voltammetry curve of commercial catalysts in formic acid solution that curve Pd/C-JM provides for comparative example 1, as shown in Figure 1, the mass ratio activity of the Pd-CoP/C-40% catalyst of embodiment 4 preparation is 2076.1mA mg
-1pd, mass ratio activity (the 783.1mA mg of the business Pd/C catalyst (Pd/C-JM) provided higher than comparative example 1 far away
-1pd).
(4) XRD (see Fig. 2 and Fig. 3) surveyed respectively by the CoP/C-40% carrier and the Pd-CoP/C-40% catalyst that take preparation in a certain amount of step (1) and step (2).
(5) TEM (see Fig. 8) surveyed by the Pd-CoP/C-40% catalyst taking preparation in a certain amount of step (2).
(6) XPS (see Fig. 4) surveyed by the Pd-CoP/C-40% catalyst taking preparation in a certain amount of step (2).
Embodiment 5
(1) in the beaker containing 50mL intermediate water, add the Vulcan XC-72 of 2.40g cobalt chloride hexahydrate and the production of Cabot company of the 0.7508g U.S., 60min is stirred after ultrasonic 30min, then put into Muffle furnace 120 DEG C of evaporate to dryness moisture content and obtain black mixture, then be positioned in tube furnace after this black mixture 2.06g being added quartz boat together with 5.28g hydration inferior sodium phosphate, in nitrogen atmosphere, calcine 60min at 800 DEG C, wherein oxygen gas flow rate is 80cc min
-1, tube furnace from normal temperature with 5 DEG C of min
-1programming rate be warming up to 800 DEG C, obtained complex carrier is labeled as CoP/C-50% (wherein 50% represents the mass percentage of CoP in complex carrier).
(2) CoP/C-50%190mg obtained by step (1) is taken, add in the beaker containing 100mL ethylene glycol, add the chlorine palladium acid containing 10mg palladium simultaneously, 5h is stirred after ultrasonic 30min, then be 11.0 by NaOH adjust ph, immediately above-mentioned solution being put into power is that the microwave oven of 700W irradiates 3min to reduce the acid of chlorine palladium for Pd nano particle, and obtained catalyst is labeled as Pd-CoP/C-50%, and wherein palladium mass percentage is in the catalyst 5%.
(3) to containing 950 μ L ethanolic solutions beaker in add 50 μ L Aldrich produce, mass fraction be 5% Nafion solution, add the Pd-CoP/C-50% catalyst of preparation in 5mg step (2) more wherein, ultrasonic disperse 30min, obtains mixed solution; Get the above-mentioned mixed solution of 5 μ L to drip and be applied on glass-carbon electrode, after room temperature is dried, obtain membrane electrode; With Hg/Hg
2cl
2electrode as reference electrode, Pt sheet as the three-electrode system to electrode, cyclic voltammetry is carried out in the sulfuric acid of the 0.5mol/L through nitrogen deoxygenation and the formic acid solution of 0.5mol/L, sweep speed is 50mV/s, result is see Fig. 1, Fig. 1 is the cyclic voltammetry curve of catalyst in formic acid solution, wherein, the cyclic voltammetry curve of commercial catalysts in formic acid solution that curve Pd/C-JM provides for comparative example 1, as shown in Figure 1, the mass ratio activity of the Pd-CoP/C-50% catalyst of embodiment 5 preparation is 1563.9mA mg
-1pd, mass ratio activity (the 783.1mA mg of the business Pd/C catalyst (Pd/C-JM) provided higher than comparative example 1 far away
-1pd).
(4) XRD (see Fig. 2 and Fig. 3) surveyed respectively by the CoP/C-50% carrier and the Pd-CoP/C-50% catalyst that take preparation in a certain amount of step (1) and step (2).
(5) TEM (see Fig. 9) surveyed by the Pd-CoP/C-50% catalyst taking preparation in a certain amount of step (2).
(6) XPS (see Fig. 4) surveyed by the Pd-CoP/C-50% catalyst taking preparation in a certain amount of step (2).
Embodiment 6
(1) in the beaker containing 50mL intermediate water, add the Vulcan XC-72 of 0.6g cobalt chloride hexahydrate and the production of Cabot company of the 1.746g U.S., 60min is stirred after ultrasonic 20min, then put into Muffle furnace 120 DEG C of evaporate to dryness moisture content and obtain black mixture, then be positioned in tube furnace after this black mixture 2.06g being added quartz boat together with 1.14g hydration inferior sodium phosphate, in nitrogen atmosphere, calcine 60min at 800 DEG C, wherein oxygen gas flow rate is 80cc min
-1, tube furnace from normal temperature with 5 DEG C of min
-1programming rate be warming up to 800 DEG C, obtained complex carrier is labeled as CoP/C-11.5% (wherein 11.5% represents the mass percentage of CoP in complex carrier).
(2) CoP/C-11.5%140mg obtained by step (1) is taken, add in the beaker containing 80mL ethylene glycol, add the chlorine palladium acid containing 60mg palladium simultaneously, 5h is stirred after ultrasonic 20min, then be 9.0 by NaOH adjust ph, immediately above-mentioned solution being put into power is that the microwave oven of 700W irradiates 1min to reduce the acid of chlorine palladium for Pd nano particle, and obtained catalyst is labeled as Pd-CoP/C-11.5%, and wherein palladium mass percentage is in the catalyst 30%.
Embodiment 7
(1) in the beaker containing 50mL intermediate water, add the Vulcan XC-72 of 0.6g cobalt chloride hexahydrate and the production of Cabot company of the 1.746g U.S., 60min is stirred after ultrasonic 20min, then put into Muffle furnace 120 DEG C of evaporate to dryness moisture content and obtain black mixture, then be positioned in tube furnace after this black mixture 2.06g being added quartz boat together with 1.14g hydration inferior sodium phosphate, in nitrogen atmosphere, calcine 60min at 800 DEG C, wherein oxygen gas flow rate is 80cc min
-1, tube furnace from normal temperature with 5 DEG C of min
-1programming rate be warming up to 800 DEG C, obtained complex carrier is labeled as CoP/C-11.5% (wherein 11.5% represents the mass percentage of CoP in complex carrier).
(2) CoP/C-11.5%190mg obtained by step (1) is taken, add in the beaker containing 150mL ethylene glycol, add the chlorine palladium acid containing 10mg palladium simultaneously, 5h is stirred after ultrasonic 60min, then be 12.0 by NaOH adjust ph, immediately above-mentioned solution being put into power is that the microwave oven of 700W irradiates 5min to reduce the acid of chlorine palladium for Pd nano particle, and obtained catalyst is labeled as Pd-CoP/C-11.5%, and wherein palladium mass percentage is in the catalyst 5%.
As seen from Figure 1, when CoP content is in the carrier 30%, corresponding Pd-CoP/C-30% catalyst has the highest current density, is 2757mA mg
-1pd is business 781mA mg
-13.53 times of Pd activity.As can be seen from Fig. 2 and Fig. 3, the catalyst prepared by each embodiment and the crystal property of carrier thereof are well, very identical with standard card.Pd-CoP/C-30% catalyst is all negative compared with the Pd 3d electron binding energy of other catalyst as shown in Figure 4 moves, and show to have stronger electronic effect between Pd and CoP, this is also the main cause that catalyst activity improves.Can find out that prepared catalyst pattern is better by Fig. 5 ~ 9, dispersiveness is higher without assembling.The domain size distribution of business Pd/C catalyst is comparatively intensive as seen from Figure 10, and this causes because its carrying capacity is higher.As shown in Figure 11, be that its maximum power density of direct methanoic acid fuel cell of preparing of anode catalyst is up to 149mW cm with Pd-CoP/C-30%
-2, be business Pd/C (43mW cm
-2) 3.46 times of catalyst.As shown in Figure 12, be that the stability of direct methanoic acid fuel cell prepared by anode catalyst is higher with Pd-CoP/C-30%, be suitable as scale utilization and extention.
To the above-mentioned explanation of the disclosed embodiments, be professional and technical personnel in the field are realized or uses the present invention.To be apparent for those skilled in the art to the multiple amendment of these embodiments, General Principle as defined herein can without departing from the spirit or scope of the present invention, realize in other embodiments.Therefore, the present invention can not be restricted to these embodiments shown in this article, but will meet the widest scope consistent with principle disclosed herein and features of novelty.
Claims (10)
1. a method for making of the direct formic acid anode of fuel cell eelctro-catalyst Pd-CoP/C of high-performance ultralow palladium carrying capacity, is characterized in that, comprise the steps:
(1) be scattered in water by carrier and cobalt chloride hexahydrate, after ultrasonic disperse, stirring, at 100 ~ 120 DEG C, evaporating water obtains the first complex carrier;
(2) under 800 DEG C of nitrogen protections, one hour is reacted by after described first complex carrier and hydration inferior sodium phosphate mixed grinding, products therefrom porphyrize, wash three times respectively with distilled water and absolute ethyl alcohol, then 60 ~ 80 DEG C of vacuumize 12 ~ 24 hours, obtains the second complex carrier;
(3) be scattered in ethylene glycol by described second complex carrier, add the acid of chlorine palladium, ultrasonic disperse obtains the first suspension-turbid liquid after stirring;
(4) by under described first suspension-turbid liquid stirring at room temperature with NaOH adjust ph, obtain the second suspension-turbid liquid;
(5) by described second suspension-turbid liquid microwave, after washing, drying, anode electrocatalyst Pd-CoP/C is obtained.
2. method for making according to claim 1, is characterized in that, described in step (1), carrier is active carbon, carbon nano-tube or Graphene.
3. method for making according to claim 1, is characterized in that, described in step (1), the mass ratio of carrier and described cobalt chloride hexahydrate is 310mg:1000mg ~ 2910mg:1000mg.
4. method for making according to claim 1, is characterized in that,
Described in step (2), the mass ratio of the first complex carrier and described hydration inferior sodium phosphate is 390mg:1000mg ~ 1800mg:1000mg.
5. method for making according to claim 1, is characterized in that, described in step (3), the mass volume ratio of the second complex carrier and described ethylene glycol is 140 ~ 190mg:80mL ~ 150mL.
6. method for making according to claim 1, is characterized in that, described in step (3), the mass ratio of the second complex carrier and the acid of described chlorine palladium is 140 ~ 190mg:10 ~ 60mg.
7. method for making according to claim 1, is characterized in that, the time of ultrasonic disperse described in step (1) and step (3) is 20min ~ 60min.
8. method for making according to claim 1, is characterized in that, described in step (4) with NaOH adjust ph for 9 ~ 12.
9. method for making according to claim 1, is characterized in that, described in step (5), microwave irradiation time is 60s ~ 300s.
10. method for making according to claim 1, is characterized in that, washing described in step (5) adopts deionized water to wash.
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