CN107123817A - A kind of three metal alloy support type graphene nano Porous materials and its preparation method and application - Google Patents
A kind of three metal alloy support type graphene nano Porous materials and its preparation method and application Download PDFInfo
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Abstract
The present invention relates to a kind of three metal alloys support type graphene nano Porous materials and its preparation method and application.The edge that the material is evenly distributed on grapheme nano-pore carrier by three kinds of metal alloy nanoparticles by roasting is obtained, and it is that water is solvent using phthalocyanine metal and graphene as raw material, in hydro-thermal reaction 6 24 hours at 120 180 DEG C.Obtained product is subjected to high-temperature roasting in 600 800 DEG C under an inert atmosphere again, alloy support type graphene nano Porous materials are obtained.The composite is due to the formation of its high specific surface area porous structure, cooperateing between the metal alloy being evenly distributed and nano-pore and strong electronic action, and the formation of N M keys significantly improves its catalytic oxidation-reduction activity and cyclical stability.In addition, this method technique is simple, it is easy to regulate and control and can prepare on a large scale, have broad application prospects.
Description
Technical field
The present invention relates to a kind of three metal alloys support type graphene nano Porous materials and its preparation method and application, it will
The composite is prepared into electrode, can be used for catalytic oxidation-reduction reaction.
Background technology
Proton Exchange Membrane Fuel Cells is one of widest technology of sustainable energy area research.But, the device
Cathodic oxygen reduction（ORR）Dynamics is slow, and Pt/C catalyst costs are higher, hinder its commercial applications.Therefore, in dimension
The use that Pt is reduced while holding the preferable catalytic activity of ORR and stability is most important.It is to realize that Pt and transition metal, which are combined,
The excellent method of this target, this method can not only reduce Pt consumption, can also improve ORR catalytic activity.Reason is
The characteristic of transition metal causes Pt d to be moved with center to low-lying level and weakens Pt and the bond energy of oxidation intermediates.With binary Pt-
M alloys are compared, and ternary Pt-M alloys show preferably ORR catalytic performances.Synthesis on Pt based alloys has been achieved for very
Big progress, still, transition metal is easily decomposes in the research of early stage, and stability can not meet the requirement of people.Therefore,
The ternary metal Pt-M for the high activity and stability that design and synthesis meet people's demand seems particularly important.
Interaction between metal nanoparticle and carrier has a significant impact to the activity and stability of catalyst.Metal
Nano rice attached bag covers the great interest for causing people on the carbon carrier, because this not only protects metal ion to be not dissolved
And then increase the corrosion resistance of catalyst, it can be combined with metal nanoparticle and the intrinsic chemical property of carbon carrier and then generation
New characteristic.Much reported about the method for coating metal nanoparticle on the carbon carrier.But, by metal bag in carbon
Nano-pore is less as the research of efficient elctro-catalyst.Unique carbon nano-pore structure exposes specific and limited table
Face, and reactant molecule can only contact the active metal sites being limited in carbon nano-pore, be catalyzed so as to be carried with traditional carbon
The agent catalytic performances different compared to generation.Therefore, easy and fine synthetic method should be developed and be encapsulated in carbon nanometer to obtain
Metal nanoparticle in pore structure is used for catalyticing research.
The content of the invention
The problem of existing for prior art, it is an object of the invention to provide a kind of three metal alloys support type graphene
Mano-porous material and its preparation method and application, it modifies the composite onto electric shock, for catalytic oxidation-reduction reaction.
Described a kind of three metal alloys support type graphene nano Porous materials, it is characterised in that the material is by three kinds of metals
The edge that alloy nano particle is evenly distributed on grapheme nano-pore carrier by roasting is obtained, three kinds of metal alloys nanometer
Particle is the phthalocyanine metal precursor containing abundant N sources, and its N sources weight/mass percentage composition is 1-8%, promotes N during roasting
It is doped on grapheme nano-pore carrier.
The preparation method of three described metal alloy support type graphene nano Porous materials, it is characterised in that including following step
Suddenly：
1）By graphene ultrasonic disperse in water, graphene solution is obtained；
2）To step 1）Graphene solution in add three kinds of phthalocyanine metal precursors, terpyridyls, ultrasound and after stirring,
It is fitted into water heating kettle at 120-180 DEG C hydro-thermal reaction 6-24 hours, is cooled to progress decompression suction filtration after room temperature, then filter cake is used
Distilled water and ethanol washing, then be dried in vacuo at 60-100 DEG C, obtain three metal load type grapheme materials；
3）By step 2）Three obtained metal load type grapheme materials carry out high-temperature roasting processing under an inert atmosphere, obtain three
Metal alloy support type graphene nano Porous materials.
A kind of preparation method of described three metal alloys support type graphene nano Porous materials, it is characterised in that step 1）
In graphene solution in graphene concentration be 0.4-1mg/mL.
A kind of preparation method of described three metal alloys support type graphene nano Porous materials, it is characterised in that step 2）
In phthalocyanine metal be phthalocyanine platinum, Cobalt Phthalocyanine, FePC, Nickel Phthalocyanine, CuPc in any three kinds, the mol ratio of three kinds of metals
For 1-3:1-3:1-3, three kinds of phthalocyanine metals preferably are combined as Pt:Fe:Co、Pt:Fe:Cu、Pt:Co:Cu、Pt:Fe:Ni、Pt:
Co:Ni or Pt:Cu:Ni, its molar ratio is preferably 3:1:1.
A kind of preparation method of described three metal alloys support type graphene nano Porous materials, it is characterised in that step 2）
The mass ratio that feeds intake of the auxiliary material that middle terpyridyl is phthalocyanine metal to be combined with graphene, terpyridyl and graphene is 1:
0.3-0.4, preferably 1:0.35.
A kind of preparation method of described three metal alloys support type graphene nano Porous materials, it is characterised in that step 3）
In inert atmosphere be nitrogen, argon gas or helium, inert gas flow is 20-100mL/min, preferably 40mL/min.
A kind of preparation method of described three metal alloys support type graphene nano Porous materials, it is characterised in that step 3）
In high-temperature roasting processing be specially：600-800 DEG C is warming up to 1-10 DEG C/min speed, 1-6 hours are incubated, it is last natural
Room temperature is down to, preferably soaking time is 2 hours.
Application of the three described metal alloy support type graphene nano Porous materials in catalytic oxygen reduction reaction.
Described application, it is characterised in that three metal alloy support type graphene nano Porous materials are prepared into electrode, is used
In catalytic oxygen reduction reaction.
By using above-mentioned technology, compared with prior art, beneficial effects of the present invention are as follows：
The present invention synthesizes three metal alloy support type grapheme nano-pore materials of novelty by easy and lower-cost method
Material, the composite is due to the formation of its high-specific surface area, loose structure, and the metal alloy being evenly distributed is received with graphene carrier
Collaboration and strong electronic action between metre hole, the formation of N-M keys significantly improve its catalytic oxidation-reduction activity and cyclical stability,
And better than the activity and stability of platinum carbon catalyst；Its preparation method technique is simple, it is easy to regulates and controls and can make on a large scale
It is standby, provided newly to design and develop the new metal load type graphene nano Porous materials for being used for energy storage and reforming unit
Thinking, have broad application prospects.
Brief description of the drawings
Fig. 1 a are 100 nanometers of PtCoFe/NPG 700 transmission electron microscope picture；
Fig. 1 b are 5 nanometers of PtCoFe/NPG 700 transmission electron microscope picture；
Fig. 2 is PtCoFe/NPG, Pt/NPG and graphene under different temperatures（G）X-ray diffractogram；
Fig. 3 is PtCoFe/NPG and graphene under different temperatures（G）Raman x ray diffration pattern x；
Fig. 4 is PtCoFe/NPG and graphene under different temperatures（G）X-ray photoelectron spectroscopy wide range figure；
Fig. 5 is the N of PtCoFe/NPG under different temperatures2Adsorption/desorption curve figure；
Fig. 6 is the graph of pore diameter distribution of PtCoFe/NPG under different temperatures；
Fig. 7 is the linear volt-ampere curve figure of PtCoFe/NPG and Pt/C under different temperatures, and disc rotation speed is 1600rpm；
Fig. 8 is PtCoFe/NPG electrode process transfer electron numbers corresponding with Pt/C and G linear volt-ampere curve under different temperatures,
Current potential selection is calculated in -0.6 Fu Chu；
Fig. 9 is different three metal alloys support type graphene nano Porous materials and Pt/C linear volt-ampere curve figure；
Figure 10 is PtCoFe/NPG 700 and Pt/C stability test figure；
Figure 11 is PtCoFe/NPG 700 and Pt/C methanol tolerance test chart.
Embodiment
Technical scheme is described further with specific embodiment below, but protection scope of the present invention is not limited
In this：
The PtCoFe/NPG 700 of embodiment 1 synthesis
1）Weigh 12mg graphenes to add in 15mL distilled water, ultrasonic 30min makes it be uniformly dispersed, obtain solubility for 0.8mg/mL
Graphene solution；
2）14.4mg phthalocyanine platinum is weighed respectively, and 4.0mg Cobalt Phthalocyanines, 4.0mg FePCs and 4.2mg terpyridyls are placed in above-mentioned stone
In black alkene solution, be stirred for making for 1 hour its fully dispersed after ultrasonic 30min mixed liquor, then, mixed liquor is transferred to polytetrafluoro
It is placed in constant temperature blast drying oven and is reacted 8 hours at 170 DEG C in ethene water heating kettle, after sealing, naturally cools to room temperature, suction filtration
And washed with distilled water and ethanol to be placed in after 3 times in 80 DEG C of vacuum drying chamber respectively and dry, obtain three metal load type graphite
Alkene material；
3）Dried three metal load types grapheme material is placed in tube furnace in N2Under protection, using heating rate as 2 DEG C/
Min is warming up to 700 DEG C, is calcined 2 hours in 700 DEG C, room temperature is naturally cooled to afterwards, gained final product is designated as PtCoFe/NPG
700。
The PtCoFe/NPG 700 obtained to the present embodiment carries out transmission electron microscope observation, as a result sees Fig. 1 a and figure
1b.From Fig. 1 a and Fig. 1 b, loose structure is presented in the PtCoFe/NPG 700 that the present embodiment is obtained, and metal nanoparticle is equal
It is even to be distributed in a nanometer bore edges, and twins' shape structure is presented.
The metal alloy support type graphene nano Porous materials of platinum ferro-cobalt three that the present invention is obtained are as fuel battery negative pole oxygen
The application of reducing catalyst, its performance test methods are as follows：
Weigh the metal alloy support type grapheme nano-pore material catalyst sample of ferro-cobalt three prepared by 1mg be put into 4mL from
In heart pipe, the absolute ethyl alcohol of the Nafion solution and 900 μ L that measure 100 μ L successively with liquid-transfering gun is added in centrifuge tube, is then put
It is fully ultrasonic in Ultrasound Instrument, form it into dispersed slurries.Working electrode is polished and cleaned with aluminum oxide polishing powder
Totally, the slurries for pipetting 10 μ L are equably applied on the working electrode (s, are then placed under infrared lamp and are dried.Electrocatalysis characteristic is surveyed
Examination is to be carried out at room temperature using the CHI760E three-electrode cells system of Shanghai Chen Hua.Using platinum filament as to electrode, Ag/
AgCl（3M KCl）Electrode is reference electrode, and the glass-carbon electrode for scribbling elctro-catalyst is working electrode（Electrode diameter is 4mm, electricity
Pole-face product is about 0.1256cm2）.Electrolyte used is 0.1M KOH solutions.Lead to O first before testing230 min, make electrolyte
In saturation oxygen condition, surface sweeping speed is 20mVs-1, disc rotation speed is from 400 to 2025rpm.
The PtCoFe/NPG 600 of embodiment 2 synthesis
1）Be the same as Example 1.
2）Be the same as Example 1.
3）Sintering temperature is 600 DEG C, other be the same as Examples 1.Obtained final product is designated as PtCoFe/NPG 600.
Catalytic oxygen reduction reaction performance test conditions are identical with embodiment 1.
The PtCoFe/NPG 800 of embodiment 3 synthesis
1）Be the same as Example 1.
2）Be the same as Example 1.
3）Sintering temperature is 800 DEG C, other be the same as Examples 1.Obtained final product is designated as PtCoFe/NPG 800.
Catalytic oxygen reduction reaction performance test conditions are identical with embodiment 1.
The Pt/NPG of embodiment 4 synthesis
1）Be the same as Example 1.
2）Only it is phthalocyanine platinum with a kind of phthalocyanine metal, other be the same as Examples 1.
3）Be the same as Example 1.Obtained final product is designated as Pt/NPG.
Catalytic oxygen reduction reaction performance test conditions are identical with embodiment 1.
The synthesis of other the three metal alloys support type graphene nano Porous materials of embodiment 5
1）Be the same as Example 1.
2）Using different phthalocyanine metals（Phthalocyanine platinum, Cobalt Phthalocyanine, FePC, Nickel Phthalocyanine, CuPc）, other be the same as Examples
1。
3）Be the same as Example 1.Obtained final product is designated as PtCoCu/NPG, PtCoNi/NPG, PtFeCu/NPG,
PtFeNi/NPG, and PtCuNi/NPG.
Catalytic oxygen reduction reaction performance test conditions are identical with embodiment 1.
PtCoFe/NPG-1 700 synthesis under the different metal ratio of embodiment 6
1）Weigh 6mg graphenes to add in 15mL distilled water, ultrasonic 30min makes it be uniformly dispersed, obtain solubility for 0.4mg/mL
Graphene solution；
2）Weigh 4.95mg phthalocyanine platinum respectively, 4.0mg Cobalt Phthalocyanines, 4.0mg FePCs and 1.14mg terpyridyls are placed in above-mentioned
In graphene solution, other be the same as Examples 1.
3）Be the same as Example 1.Obtained final product is designated as PtCoFe/NPG-1 700
Catalytic oxygen reduction reaction performance test conditions are identical with embodiment 1.
PtCoFe/NPG-2 700 synthesis under the different metal ratio of embodiment 7
1）Weigh 15mg graphenes to add in 15mL distilled water, ultrasonic 30min makes it be uniformly dispersed, it is 1mg/mL's to obtain solubility
Graphene solution；
2）4.95mg phthalocyanine platinum is weighed respectively, and 4.0mg Cobalt Phthalocyanines, 12mg FePCs and 4.2mg terpyridyls are placed in above-mentioned stone
In black alkene solution, other be the same as Examples 1.
3）Be the same as Example 1.Obtained final product is designated as PtCoFe/NPG-2 700
Catalytic oxygen reduction reaction performance test conditions are identical with embodiment 1.
Comparative example：
Using commercialized 20% Pt/C as comparative sample, its performance test methods is as follows：Weigh the catalyst sample prepared by 1mg
It is put into 4mL centrifuge tube, the absolute ethyl alcohol of the Nafion solution and 900 μ l that measure 100 μ l successively with liquid-transfering gun adds centrifugation
Guan Zhong, is subsequently placed in Ultrasound Instrument fully ultrasound, forms it into dispersed slurries.With aluminum oxide polishing powder by working electrode
Polish and clean up, the slurries for pipetting 10 μ l are equably applied on the working electrode (s, be then placed under infrared lamp and dry.With
The electrode is working electrode, using platinum plate electrode as to electrode, using Ag/AgCl as the three-electrode system of reference electrode, is satisfied in oxygen
Linear sweep voltammetry test is carried out in 0.1 M of sum KOH solution, sweep speed is 20 mV/s.
All samples and comparative example business Pt/C (20% load capacity) electrochemical property test that the present invention is obtained
And X-ray diffraction, Raman x ray diffraction, x-ray photoelectron power spectrum, N2Adsorption/desorption curve and pore-size distribution result referring to Fig. 2-
Figure 10, Fig. 2, which are shown in 26 ° of position, a very wide diffraction maximum, is identified as graphene（002）Crystallographic plane diffraction peak.
39.3 °, 46.2 °, 67.63 ° and 81.93 ° of diffraction maximum, corresponding is Pt（111）、（200）、（220）With（311）Crystal face,
It is face-centred cubic structure to show Pt/NPG（JCPDS 04-0802）.In addition, PtCoFe/NPG 600,700 and 800 diffraction pattern
Also explanation is face-centred cubic structure to spectrum.But PtCoFe/NPG 700 is compared with the position of PtCoFe/NPG 800 diffraction maximum
Pt/NPG moves 1.1 ° to high angle, shows that Co and Fe and Pt together form alloy structure（JCPDS-29-
0499）.Fig. 3 shows PtCoFe/NPG 700 (1.26) and PtCoFe/NPG 800 (1.33) ID/IGValue is maximum, explanation
They generate more faults of construction, and generate during PtCoFe alloy nano particles etching graphene more
Unordered carbon structure.As shown in Figure 4, C, N, O, Pt, Fe, Co are present in the composite.From Fig. 5-6, PtCoFe/
NPG 700 specific surface area is maximum, and its average pore size is 25nm；Fig. 7 shows PtCoFe/NPG 700 take-off potential and business
Platinum carbon is -0.07V quite, and its limiting current density is maximum.Fig. 8 explanation except graphene electron transfer number be 2 in addition to, other
The electron transfer number of several samples is 4.Fig. 9 illustrates that PtCoFe/NPG shows most excellent hydrogen reduction catalytic performance.From figure
As can be seen that after 2000 circle circulations, PtCoFe/NPG 700 remains 94.6%, and business platinum carbon under equal conditions in 10
Catalyst only remains 63.6% activity, illustrates that the catalyst of the present invention is more more stable than business platinum carbon catalyst.Figure 11 explanations
PtCoFe/NPG 700 has preferable methanol mithridatism.
The section Example of the present invention is the foregoing is only, not for limiting the present invention.In every case according to present invention institute
The equivalent changes and modifications done, all for protection scope of the present invention within.
Claims (9)
1. a kind of three metal alloys support type graphene nano Porous materials, it is characterised in that the material is by three kinds of metal alloy nanometers
Particle is evenly distributed on the edge of grapheme nano-pore carrier by roasting and obtained, three kinds of metal alloy nanoparticles be containing
There is the phthalocyanine metal precursor in abundant N sources, its N sources weight/mass percentage composition is 1-8%, promote N to be doped to stone during roasting
On black alkene nano-pore carrier.
2. the preparation method of three metal alloys support type graphene nano Porous materials according to claim 1, its feature exists
In comprising the following steps：
1）By graphene ultrasonic disperse in water, graphene solution is obtained；
2）To step 1）Graphene solution in add three kinds of phthalocyanine metal precursors, terpyridyls, ultrasound and after stirring,
It is fitted into water heating kettle at 120-180 DEG C hydro-thermal reaction 6-24 hours, is cooled to progress decompression suction filtration after room temperature, then filter cake is used
Distilled water and ethanol washing, then be dried in vacuo at 60-100 DEG C, obtain three metal load type grapheme materials；
3）By step 2）Three obtained metal load type grapheme materials carry out high-temperature roasting processing under an inert atmosphere, obtain three
Metal alloy support type graphene nano Porous materials.
3. a kind of preparation method of three metal alloys support type graphene nano Porous materials according to claim 2, it is special
Levy and be step 1）In graphene solution in graphene concentration be 0.4-1mg/mL.
4. a kind of preparation method of three metal alloys support type graphene nano Porous materials according to claim 2, it is special
Levy and be step 2）In phthalocyanine metal be phthalocyanine platinum, Cobalt Phthalocyanine, FePC, Nickel Phthalocyanine, CuPc in any three kinds, three kinds
The mol ratio of metal is 1-3:1-3:1-3.
5. a kind of preparation method of three metal alloys support type graphene nano Porous materials according to claim 2, it is special
Levy and be step 2）The auxiliary material that middle terpyridyl is phthalocyanine metal to be combined with graphene, terpyridyl and graphene feed intake
Mass ratio is 1:0.3-0.4, preferably 1:0.35.
6. a kind of preparation method of three metal alloys support type graphene nano Porous materials according to claim 2, it is special
Levy and be step 3）In inert atmosphere be nitrogen, argon gas or helium, inert gas flow is 20-100mL/min, be preferably
40mL/min。
7. a kind of preparation method of three metal alloys support type graphene nano Porous materials according to claim 2, it is special
Levy and be step 3）In high-temperature roasting processing be specially：600-800 DEG C is warming up to 1-10 DEG C/min speed, 1-6 is incubated
Hour, last to be down to room temperature naturally, preferably soaking time is 2 hours.
8. a kind of three metal alloys support type graphene nano Porous materials according to claim 1 or 2 in catalytic oxygen also
Application in original reaction.
9. application according to claim 8, it is characterised in that by three metal alloy support type graphene nano Porous materials systems
For into electrode, for catalytic oxygen reduction reaction.
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109390594A (en) * | 2018-11-27 | 2019-02-26 | 浙江工业大学 | A kind of mesoporous platinum Pd-Co alloy nanosphere and preparation method thereof of catalysis Oxidation of Formic Acid reaction |
| CN109411773A (en) * | 2018-10-22 | 2019-03-01 | 浙江工业大学 | A kind of palladium copper-golden nanometer thorn-like elctro-catalyst and preparation method thereof |
| CN110554546A (en) * | 2019-09-26 | 2019-12-10 | 中国科学院长春光学精密机械与物理研究所 | Graphene phthalocyanine composite material and preparation method thereof |
| CN111193035A (en) * | 2019-12-03 | 2020-05-22 | 青岛大学 | Preparation method of strong pi-pi conjugated defective graphene and iron phthalocyanine composite material for oxygen reduction electrocatalyst |
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101703931A (en) * | 2009-11-25 | 2010-05-12 | 中国农业大学 | Load type palladium catalyst and preparation method thereof |
| CN104549363A (en) * | 2014-12-31 | 2015-04-29 | 江苏大学 | Nano-metal or metal alloy catalyst and preparing method thereof |
| CN105514379A (en) * | 2015-12-19 | 2016-04-20 | 台州市金博超导纳米材料科技有限公司 | lLithium battery negative material prepared by compounding spherical nano silicon and graphene and preparing method |
| CN106099125A (en) * | 2016-08-16 | 2016-11-09 | 深圳大学 | A kind of palladium stannum cobalt ternary-alloy nanocatalyst and preparation method and application |
-
2017
- 2017-04-11 CN CN201710231343.2A patent/CN107123817A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101703931A (en) * | 2009-11-25 | 2010-05-12 | 中国农业大学 | Load type palladium catalyst and preparation method thereof |
| CN104549363A (en) * | 2014-12-31 | 2015-04-29 | 江苏大学 | Nano-metal or metal alloy catalyst and preparing method thereof |
| CN105514379A (en) * | 2015-12-19 | 2016-04-20 | 台州市金博超导纳米材料科技有限公司 | lLithium battery negative material prepared by compounding spherical nano silicon and graphene and preparing method |
| CN106099125A (en) * | 2016-08-16 | 2016-11-09 | 深圳大学 | A kind of palladium stannum cobalt ternary-alloy nanocatalyst and preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| XING ZHONG 等: "Twin-like ternary PtCoFe alloy in nitrogen-doped graphene nanopores as a highly effective electrocatalyst for oxygen reduction", 《CATALYSIS SCIENCE &TECHNOLOGY》 * |
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| CN111193035A (en) * | 2019-12-03 | 2020-05-22 | 青岛大学 | Preparation method of strong pi-pi conjugated defective graphene and iron phthalocyanine composite material for oxygen reduction electrocatalyst |
| CN113555570A (en) * | 2020-04-24 | 2021-10-26 | 中国科学技术大学 | Graphene-loaded PtFeCo ternary alloy catalyst for catalytic oxidation of methanol and preparation method thereof |
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| CN113651356A (en) * | 2021-08-16 | 2021-11-16 | 电子科技大学 | Preparation method and application of titanium dioxide graphene complex with core-shell cavity structure |
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