CN109728313A - A kind of novel carbinol fuel battery anode catalyst of self-supporting and preparation method thereof - Google Patents
A kind of novel carbinol fuel battery anode catalyst of self-supporting and preparation method thereof Download PDFInfo
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- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 title claims abstract description 96
- 239000003054 catalyst Substances 0.000 title claims abstract description 42
- 238000002360 preparation method Methods 0.000 title claims abstract description 36
- 239000000446 fuel Substances 0.000 title claims abstract description 31
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims abstract description 186
- 239000006260 foam Substances 0.000 claims abstract description 93
- 229910052759 nickel Inorganic materials 0.000 claims abstract description 93
- 239000002105 nanoparticle Substances 0.000 claims abstract description 32
- 238000000151 deposition Methods 0.000 claims abstract description 28
- 230000008021 deposition Effects 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- 238000005229 chemical vapour deposition Methods 0.000 claims abstract description 11
- 238000005520 cutting process Methods 0.000 claims abstract description 3
- 239000007789 gas Substances 0.000 claims description 38
- 229910021389 graphene Inorganic materials 0.000 claims description 31
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 30
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 20
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 claims description 20
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 10
- 229910052786 argon Inorganic materials 0.000 claims description 10
- 239000001257 hydrogen Substances 0.000 claims description 10
- 229910052739 hydrogen Inorganic materials 0.000 claims description 10
- 239000010453 quartz Substances 0.000 claims description 10
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 10
- 238000004062 sedimentation Methods 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 5
- 238000013461 design Methods 0.000 claims description 5
- 239000000758 substrate Substances 0.000 claims description 5
- 239000008246 gaseous mixture Substances 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract 1
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 48
- 230000003197 catalytic effect Effects 0.000 description 14
- 238000002484 cyclic voltammetry Methods 0.000 description 11
- 230000003647 oxidation Effects 0.000 description 9
- 238000007254 oxidation reaction Methods 0.000 description 9
- 229910002804 graphite Inorganic materials 0.000 description 6
- 239000010439 graphite Substances 0.000 description 6
- -1 graphite Alkene Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 229910052763 palladium Inorganic materials 0.000 description 5
- 238000006555 catalytic reaction Methods 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 238000004544 sputter deposition Methods 0.000 description 4
- 239000004964 aerogel Substances 0.000 description 3
- 239000012670 alkaline solution Substances 0.000 description 3
- 150000001336 alkenes Chemical class 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- 241000209094 Oryza Species 0.000 description 2
- 235000007164 Oryza sativa Nutrition 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 230000003749 cleanliness Effects 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000002708 enhancing effect Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 235000009566 rice Nutrition 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- ZZZCUOFIHGPKAK-UHFFFAOYSA-N D-erythro-ascorbic acid Natural products OCC1OC(=O)C(O)=C1O ZZZCUOFIHGPKAK-UHFFFAOYSA-N 0.000 description 1
- 206010054949 Metaplasia Diseases 0.000 description 1
- 230000010718 Oxidation Activity Effects 0.000 description 1
- 101150003085 Pdcl gene Proteins 0.000 description 1
- 229930003268 Vitamin C Natural products 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000010923 batch production Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000002485 combustion reaction Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007812 deficiency Effects 0.000 description 1
- 238000002242 deionisation method Methods 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
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- 238000010586 diagram Methods 0.000 description 1
- 201000006549 dyspepsia Diseases 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 238000004108 freeze drying Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 229910052738 indium Inorganic materials 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002386 leaching Methods 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000003863 metallic catalyst Substances 0.000 description 1
- 239000013528 metallic particle Substances 0.000 description 1
- 230000015689 metaplastic ossification Effects 0.000 description 1
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- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000012805 post-processing Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 238000004153 renaturation Methods 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
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- 238000002834 transmittance Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 238000009777 vacuum freeze-drying Methods 0.000 description 1
- 235000019154 vitamin C Nutrition 0.000 description 1
- 239000011718 vitamin C Substances 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 238000009736 wetting Methods 0.000 description 1
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention belongs to novel carbinol fuel areas, and in particular to a kind of novel carbinol fuel battery anode catalyst of self-supporting and preparation method thereof.Preparation method is that three-dimensional grapheme/nickel foam is prepared in tube furnace by the method for chemical vapor deposition: preparing PdNPs/ three-dimensional grapheme/nickel foam by the method for cluster-beam deposition: three-dimensional grapheme/nickel foam after cutting process is placed in deposit cavity, under vacuum conditions, Pd nanoparticle is deposited into three-dimensional grapheme/foam nickel surface, obtains PdNPs/ three-dimensional grapheme/nickel foam.Preparation process of the invention is quick, and the time is shorter, and preparing sample repeatability height can large-scale industrial production.
Description
Technical field
The invention belongs to novel carbinol fuel areas, and in particular to a kind of novel carbinol anode of fuel cell of self-supporting is urged
Agent and preparation method thereof.
Background technique
Due to conventional fossil fuel resource gradually reduce and its adverse effect to environment, renewable and sustainable energy
The exploitation and use in source become more and more important.Fuel cell directly converts electricity for chemical energy by chemical reaction as a kind of
The energy source device of energy, the energy conversion efficiency of Yin Qigao, low pollution have attracted the extensive research of scientists.It is wherein straight
Methanol fuel cell is connect since fuel is easily obtained, high energy specific density and the characteristic that can be worked at low temperature are considered as
Extremely promising new energy device.However up to the present, the high cost and low stability of electrode material hinder direct methanol
The development of fuel cell in order to solve these problems and improves the catalytic performance of fuel cell, and many researchs, which are focused on, to be carried
Metal supported catalyst is on body to obtain stable metallic particles to promote catalytic efficiency.Pd and Pd base catalyst is due to its height
Abundance and low cost have higher catalytic activity to methanol in alkaline medium and have the anti-poisoning ability for being better than Pt, therefore Pd
Base catalyst can be used as the anode catalyst of good direct methanol fuel cell.The nanometer that most of conventional methods obtain
Grain has biggish size and shape, it is difficult to control the distribution of particle size also between indigestion particle properties and catalytic performance
Relationship.Although the method for liquid phase synthesis can prepare the Pd nanoparticle with narrow size distribution, particle surface is viscous
Attached pollutant is difficult to remove.The method very good solution of cluster-beam deposition these problems have cleaning to prepare
The Pd nanoparticle of surface and narrow size distribution has paved road.
The backing material of catalyst has a great impact to the catalytic performance of catalyst especially metallic catalyst, graphene
Due to its unique texture and excellent physicochemical properties, more and more concerns are attracted since two thousand four.Stone
Electron mobility that black alkene has many outstanding properties for example high, high specific surface area, high thermal coefficient, outstanding thermostabilization
Property, high hardness and outstanding light transmittance, therefore graphene is in the energy, biosensor, photovoltaic device and photoelectric device etc.
Field presents big advantage and application potential.
Graphene and metal nanoparticle is compound has shown outstanding methanol catalytic oxidation performance, such as: Tsang
People reports Pd nanometer particle load and presents order in alkaline solution on the graphene aerogel for being deposited on foam nickel surface
The satisfied methanol catalytic oxidation activity of people.Yuan et al. reports the well-distributed Au@Pt bimetal nano branch on graphene
Crystalline substance can significantly improve the electro catalytic activity and durability of methanol fuel cell.However most of stones for being used for methanol catalytic oxidation
Black alkene is the graphene oxide (rGO) of chemical method reduction, it has some intrinsic limitations such as noxious material in production process
It uses, low electric conductivity caused by the aggregation between the presence and graphene film of oxygen-containing group affects it and works as in electrochemical catalysis
In application.Compared with redox graphene, the graphene of chemical vapour deposition technique (CVD) preparation can effectively overcome this
A little disadvantages.The especially three-dimensional grapheme of chemical vapour deposition technique preparation, due to its large specific surface area, porosity height, thermal conductivity
It is the ideal material as absolute electrode well.
Tsang, Chi-Him A. et al. reported a kind of anode catalyst of methanol fuel cell in 2014.To adopt
Graphene oxide is prepared with modified Hummer's method, the graphene oxide of 120mg freeze-drying is scattered in 20ml deionization
To obtain 6mg ﹒ ml in water-1Graphene oxide dispersion.Different amounts of K2PdCl6(8,16 and 80 mg) is added into graphite
Alkene dispersion liquid is continuously stirred at room temperature 30min and obtains the PdCl well mixed6 2-- GO mixed liquor (1,5 and 10 mM Pd4+From
Son).Clean nickel foam is impregnated into PdCl6 2-Ultrasound 20min in-GO mixed liquor, then aging 2h at room temperature.It will leaching
The nickel foam sample soaked is transferred to comprising being kept in the ascorbic solution of 0.5g (143 mM, 20 ml) at a temperature of 40 DEG C
For 24 hours to obtain the Pd/ graphene hydrogel for being carried on foam nickel surface.Pd/ graphene hydrogel/foam nickel electrode be placed in from
Three days are impregnated in sub- water to remove remaining vitamin C and Pd4+Ion.Clean Pd/ graphene hydrogel/foam nickel electrode
Vacuum freeze drying 48h obtains Pd/ graphene aerogel/nickel foam under conditions of -80 DEG C.It is prepared by this method
Pd/ graphene aerogel/foam nickel electrode is close to the peak current of methanol oxidation at cyclic voltammetry 50 times in alkaline solution
Degree is 788 A ﹒ g-1, corresponding peak current ratio If/ IbIt is 3.03.But above-mentioned technology has the disadvantage that 1. preparation methods
It is quite time-consuming.It can be seen that, which needs to expend time a couple of days from preparation process.2. the sample prepared cannot
Guarantee cleanliness.Because being related to a variety of chemical reagent during the preparation process, go to handle these although devoting a tremendous amount of time energy
Remaining chemical reagent, but a small number of chemical agent residues still are had, therefore cleanliness will not be too high.3. the weight of preparation process
Renaturation is not good enough.Because whole preparation flow very complicated will be greatly reduced sample in view of all kinds of errors of preparation process
Repeatability.4. the methanol oxidation performance of the sample prepared is not high enough.The graphene gas used in sample preparation procedure
Gel, the humidification of electric conductivity are not too by force, to cause it limited to the enhancing of catalytic performance.The palladium prepared is received
Rice corpuscles size is uncontrollable and wider distribution, affects catalytic performance.
Summary of the invention
For the deficiencies in the prior art, the novel carbinol anode of fuel cell that the present invention provides a kind of self-supporting is urged
Agent and preparation method thereof, the preparation process is quick, and the time is shorter, prepares sample repeatability height, can high-volume industry
Metaplasia produces.
In order to achieve the above-mentioned object of the invention, the invention adopts the following technical scheme:
A kind of novel carbinol fuel battery anode catalyst of self-supporting, the novel carbinol fuel battery anode catalyst are
PdNPs/ three-dimensional grapheme/nickel foam, wherein the Pd nanoparticle is deposited on three-dimensional grapheme/foam nickel surface；Deposition 20
The Pd nanoparticle of min Pd nanoparticle/three-dimensional grapheme/nickel foam sample anodic peak current density has reached 3259.4
MA ﹒ mg-1。
A kind of preparation method of the novel carbinol fuel battery anode catalyst of self-supporting, comprising the following steps:
(1) three-dimensional grapheme/nickel foam is prepared in tube furnace by the method for chemical vapor deposition:
(2) PdNPs/ three-dimensional grapheme/nickel foam is prepared by the method for cluster-beam deposition: by three after cutting process
Dimension graphene/nickel foam is placed in deposit cavity, under vacuum conditions, Pd nanoparticle is deposited to three-dimensional grapheme/foam
Nickel surface obtains PdNPs/ three-dimensional grapheme/nickel foam, wherein the Pd nanoparticle is prepared by cluster-beam deposition system
It obtains.
Preferably, the specific steps of the step (1) are as follows: be used to nickel foam to do growth substrate and catalyst, by foam
Nickel is put into quartz tube furnace middle section and is passed through volume ratio with the flow of 350-450sccm as the mixing of the hydrogen and argon gas of 5-9:100
Gas is annealed at 1000-1200 DEG C 30 min again；Methane gas, 1000-1200 DEG C of constant temperature are passed through with 9-12 sccm flow
25-45 min, stopping are passed through methane gas, and quartz tube furnace is 5-9:100 hydrogen in the volume ratio of 350-450 sccm flow
With argon gas it is mixed gas protected under, with 100-120 DEG C ﹒ min-1Cooling rate be cooled to room temperature, obtain being carried in nickel foam
Graphene, i.e. three-dimensional grapheme/nickel foam.
Preferably, the density of step (1) nickel foam is 350 g ﹒ m-2 , with a thickness of 1.5 mm.
Preferably, the step (2) is deposited as double-sided deposition, and every face sedimentation time is 20min.
Preferably, the design parameter of step (2) deposition is as shown below:
| Background vacuum | 2×10-4 Pa |
| Sputter gas flow | 40 sccm |
| Buffer gas flow | 60 sccm |
| Sputtering power | 35watt |
| Condense distance | 7.5 cm |
| Deposition rate | 0.42 Å/s |
Compared with prior art, the invention has the following advantages:
1. the time that the preparation process needs is shorter, preparing a sample, it is only necessary to 2h；And the preparation method can magnify i.e.
Multiple samples are made simultaneously, preparation time can be further saved；
2. the chemical vapor deposition that the preparation method is related to and the preparation flow that Cluster Beam system is all ultra-clean, are preparing
Extra impurity will not be introduced in the process and the sample prepared is not necessarily to post-processing.The process repeatability is high, can advise greatly
Mould batch production；
3. graphene and nickel foam that the preparation process obtains are combined closely and electric conductivity with higher, and Pd nano particle ruler
It is very little to be evenly distributed and be preferably in the Dispersion on surface of graphene；
4. the Pd nanoparticle/nickel foam and Pd nano particle/graphite alkene/nickel foam sample methanol catalytic oxidation with higher
Activity, the sample in alkaline solution at cyclic voltammetry 25 times to methanol oxidation peak current density be 3259.4 A ﹒ g-1,
Corresponding peak current ratio If/ IbIt is 4.7.
Detailed description of the invention
Fig. 1 is the preparation flow figure of Pd nano particle/graphite alkene/nickel foam combination electrode of the present invention；
Fig. 2 is that PdNPs modifies cyclic voltammetry figure of the three-dimensional grapheme/nickel foam in 1 M KOH solution；
Fig. 3 is that PdNPs modifies three-dimensional grapheme/nickel foam in 1 M KOH/1 M CH3Cyclic voltammetry figure in OH；
Fig. 4 is PdNPs/ three-dimensional grapheme/nickel foam in 1 M KOH/1 M CH3Time current curve graph in OH, wherein electricity
- 0.13 V of position；
Fig. 5 is PdNPs/ three-dimensional grapheme/nickel foam multiple cyclic voltammetry peak current density variation diagram；
Description of symbols: nickel foam 1, three-dimensional grapheme/nickel foam 2, Pd nano particle 3, chemical vapor deposition 4, cluster beam
Stream deposition 5.
Specific embodiment
Below by specific embodiment, invention is further described in detail.But those skilled in the art will manage
Solution, the following example is merely to illustrate the present invention, and should not be taken as limiting the scope of the invention.Specific skill is not specified in embodiment
Art or condition person, described technology or conditions carry out to specifications according to the literature in the art.
Embodiment 1
The preparation method of the novel carbinol fuel battery anode catalyst of a kind of self-supporting as shown in Figure 1:, the novel carbinol combustion
Material cell anode catalyst is PdNPs/ three-dimensional grapheme/nickel foam, and the preparation method comprises the following steps:
(1) three-dimensional grapheme/nickel foam 2 is prepared in tube furnace by the method for chemical vapor deposition 4: is 350 g ﹒ by density
m-2, with a thickness of 1.5 mm nickel foam 1 be used to do growth substrate and catalyst, by nickel foam 1 be put into quartz tube furnace middle section with
The flow of 400sccm is passed through the hydrogen that volume ratio is 7:100 and the mixed gas of argon gas is annealed at 1000 DEG C 30 min again；With
10 sccm flows are passed through methane gas, 1000 DEG C of 30 min of constant temperature, and stopping is passed through methane gas, and quartz tube furnace is 400
The volume ratio of sccm flow be 7:100 hydrogen and argon gas it is mixed gas protected under, with 100 DEG C ﹒ min-1Cooling rate be cooled to
Room temperature obtains being carried on the graphene in nickel foam, i.e. three-dimensional grapheme/nickel foam 2；
(2) PdNPs/ three-dimensional grapheme/nickel foam is prepared by the method for cluster-beam deposition: 0.5 × 0.5 will be cut into
cm2Three-dimensional grapheme/nickel foam 2 be placed in deposit cavity, under vacuum conditions, Pd nanoparticle 3 is deposited into three-dimensional stone
Black 2 surface of alkene/nickel foam, obtains PdNPs/ three-dimensional grapheme/nickel foam, wherein the Pd nanoparticle 3 is sunk by Cluster Beam
5 systems of product prepare, described to be deposited as double-sided deposition, and every face sedimentation time is 20min；Below the design parameter of the deposition
It is shown:
| Background vacuum | 2×10-4 Pa |
| Sputter gas flow | 40 sccm |
| Buffer gas flow | 60 sccm |
| Sputtering power | 35watt |
| Condense distance | 7.5 cm |
| Deposition rate | 0.42 Å/s |
Embodiment 2
A kind of preparation method of the novel carbinol fuel battery anode catalyst of self-supporting, the novel carbinol anode of fuel cell
Catalyst is PdNPs/ three-dimensional grapheme/nickel foam, and the preparation method comprises the following steps:
(1) three-dimensional grapheme/nickel foam is prepared in tube furnace by the method for chemical vapor deposition: is 350 g ﹒ m by density-2 , with a thickness of 1.5 mm nickel foam be used to do growth substrate and catalyst, by nickel foam be put into quartz tube furnace middle section with
The flow of 350sccm is passed through the hydrogen that volume ratio is 5:100 and the mixed gas of argon gas is annealed at 1000 DEG C 30 min again；With
9sccm flow is passed through methane gas, 1000 DEG C of 25 min of constant temperature, and stopping is passed through methane gas, and quartz tube furnace is in 350 sccm
The volume ratio of flow be 5:100 hydrogen and argon gas it is mixed gas protected under, with 100 DEG C ﹒ min-1Cooling rate be cooled to room temperature,
Obtain being carried on the graphene in nickel foam, i.e. three-dimensional grapheme/nickel foam；
(2) PdNPs/ three-dimensional grapheme/nickel foam is prepared by the method for cluster-beam deposition: 0.5 × 0.5 will be cut into
cm2Three-dimensional grapheme/nickel foam be placed in deposit cavity, under vacuum conditions, Pd nanoparticle is deposited into three-dimensional graphite
Alkene/foam nickel surface obtains PdNPs/ three-dimensional grapheme/nickel foam, wherein the Pd nanoparticle is by cluster-beam deposition system
System prepares, described to be deposited as double-sided deposition, and every face sedimentation time is 20min, and the design parameter of the deposition is as shown below:
| Background vacuum | 2×10-4 Pa |
| Sputter gas flow | 40 sccm |
| Buffer gas flow | 60 sccm |
| Sputtering power | 35watt |
| Condense distance | 7.5 cm |
| Deposition rate | 0.42 Å/s |
Embodiment 3
A kind of preparation method of the novel carbinol fuel battery anode catalyst of self-supporting, the novel carbinol anode of fuel cell
Catalyst is PdNPs/ three-dimensional grapheme/nickel foam, and the preparation method comprises the following steps:
(1) three-dimensional grapheme/nickel foam is prepared in tube furnace by the method for chemical vapor deposition: is 350 g ﹒ m by density-2, with a thickness of 1.5 mm nickel foams be used to do growth substrate and catalyst, by nickel foam be put into quartz tube furnace middle section with
The flow of 450sccm is passed through the hydrogen that volume ratio is 9:100 and the mixed gas of argon gas is annealed at 1200 DEG C 30 min again；
It is passed through methane gas, 1200 DEG C of 45 min of constant temperature with 12 sccm flows, stopping is passed through methane gas, and quartz tube furnace is 450
The volume ratio of sccm flow be 9:100 hydrogen and argon gas it is mixed gas protected under, with 120 DEG C ﹒ min-1Cooling rate be cooled to
Room temperature obtains being carried on the graphene in nickel foam, i.e. three-dimensional grapheme/nickel foam；
(2) PdNPs/ three-dimensional grapheme/nickel foam is prepared by the method for cluster-beam deposition: 0.5 × 0.5 will be cut into
cm2Three-dimensional grapheme/nickel foam be placed in deposit cavity, under vacuum conditions, Pd nanoparticle is deposited into three-dimensional graphite
Alkene/foam nickel surface obtains PdNPs/ three-dimensional grapheme/nickel foam, wherein the Pd nanoparticle is by cluster-beam deposition system
System prepares, described to be deposited as double-sided deposition, and every face sedimentation time is 20min, and the design parameter of the deposition is as shown below:
| Background vacuum | 2×10-4 Pa |
| Sputter gas flow | 40 sccm |
| Buffer gas flow | 60 sccm |
| Sputtering power | 35watt |
| Condense distance | 7.5 cm |
| Deposition rate | 0.42 Å/s |
The resulting PdNPs/ three-dimensional grapheme of embodiment 1/nickel foam is subjected to following performance detection:
The test of electrochemically active specific surface area (ECSA): can be passed through based on the cyclic voltammetry curve tested in 1 M KOH
The quality of Pd nanoparticle obtains on the reduction peak area and sample of PdO to calculate, and acquired results are as shown in Figure 2: electrochemistry
Specific surface area active gradually reduces as cyclic voltammetry number increases, and reaches and stablizes when recycling 30 times, therefore we
It selects cyclic voltammetry the 30th time curve calculating ECSA, calculates and obtain Pd nanoparticle/three-dimensional grapheme/nickel foam
ECSA value be 109.4 m2 g-1.Such a high ECSA is better than many three-dimensional grapheme gold-supporteds in the prior art
Belong to the catalyst of sample such as: Pd/3D folds graphene (40.9 m2﹒ g-1), PdCu/3D graphene platelet (65.3 m2﹒ g-1) and Pt/3D nitrogen-doped graphene (52.2 m2﹒ g-1).The result shows that Pd nanoparticle/three-dimensional grapheme/nickel foam phase
More active points are illustrated for other catalyst, in this way more than active point be advantageously possible for the catalysis oxidation of methanol.
It is 50 mV ﹒ s sweeping speed to obtain sample to the catalytic oxidation performance of methanol-1Under conditions of, we are by sample
It is put into comprising 1 M CH3Cyclic voltammetry is carried out in the 1 M KOH of OH.It is as shown in Figure 3: 20 min Pd nanoparticles of deposition
Pd nanoparticle/three-dimensional grapheme/nickel foam sample anodic peak current density reached 3259.4 mA ﹒ mg-1.It is high in this way
Current density be highest compared with the Pd/nickel foam or Pd/ three-dimensional grapheme elctro-catalyst that are previously reported.Pd receives
Rice corpuscles/three-dimensional grapheme/nickel foam sample enhancing catalytic activity can be attributed to the high electronics transfer speed of three-dimensional grapheme
Degree and high active surface area.On the other hand, many researchers think forward scan peak current density (If) and reverse scan
Peak current density (Ib) ratio can be used to evaluate tolerance of the catalyst to electrode surface to carbonaceous mesophase product accumulation.Compared with
Big IfWith IbRatio show that catalyst surface has adsorbed lower carbonaceous mesophase product.Pd nanoparticle/three-dimensional grapheme/
Nickel foam illustrates higher If/IbRatio, so good anti-interference ability may be attributed to the big activity of Pd nanoparticle and compare table
The three-dimensional structure of area and elctro-catalyst these can reduce the factor of the absorption of intermediate toxic product.
The long-time stability of elctro-catalyst are the key factors that it is applied in methanol fuel cell.Pd nanoparticle
Son/three-dimensional grapheme/nickel foam elctro-catalyst long-time stability are under the current potential of -0.13 V in 1 M CH3OH+1 M
Testing time current curve obtains in KOH solution.As shown in Figure 4: in entire test process, sedimentation time is the Pd of 20 min
NPs/ three-dimensional grapheme/nickel foam shows slower fall off rate and high current density.This phenomenon shows Pd NPs/
Three-dimensional grapheme/nickel foam (20 min) has preferable Electrocatalytic Oxidation of Methanol stability.
Pd NPs/ three-dimensional grapheme/nickel foam (20 min) electro-catalysis stability is also reacted to be surveyed in continuous cyclic voltammetric
It, can be by collecting I in examinationfValue assess the stability of catalyst.It is as shown in Figure 5: in preceding 50 cyclic voltammetries
In, Pd NPs/ three-dimensional grapheme/nickel foam (20 min) IfValue increases with the increase of cycle-index, this may
Be need the regular hour with catalyst wetting contact completely due to electrolyte and gradually with the increase electrolyte of cycle-index
Being in contact with catalyst leads to IfValue is gradually increased to peak.And after 200 cyclic voltammetries, Pd NPs/ three-dimensional graphite
Alkene/nickel foam (20 min) maintains the activity of opposite peak 82%, these are the result shows that Pd NPs/ three-dimensional grapheme/bubble
Foam nickel (20 min) electro-catalysis stability with higher.
The above is only preferred embodiments of the present invention, is not intended to limit the scope of the present invention,
Therefore any trickle amendment, equivalent variations and modification made to the above embodiment according to the technical essence of the invention, belong to
In the range of technical solution of the present invention.
Claims (6)
1. a kind of novel carbinol fuel battery anode catalyst of self-supporting, which is characterized in that the novel carbinol fuel cell
Anode catalyst is PdNPs/ three-dimensional grapheme/nickel foam, wherein the Pd nanoparticle is deposited on three-dimensional grapheme/foam
Nickel surface；Deposit Pd nanoparticle/three-dimensional grapheme/nickel foam sample anodic peak current density of 20min Pd nanoparticle
3259.4mA ﹒ mg is reached-1。
2. a kind of preparation method of the novel carbinol fuel battery anode catalyst of self-supporting described in claim 1, feature
It is, comprising the following steps:
(1) three-dimensional grapheme/nickel foam is prepared in tube furnace by the method for chemical vapor deposition:
(2) PdNPs/ three-dimensional grapheme/nickel foam is prepared by the method for cluster-beam deposition: by three after cutting process
Dimension graphene/nickel foam is placed in deposit cavity, under vacuum conditions, Pd nanoparticle is deposited to three-dimensional grapheme/foam
Nickel surface obtains PdNPs/ three-dimensional grapheme/nickel foam, wherein the Pd nanoparticle is prepared by cluster-beam deposition system
It obtains.
3. a kind of preparation method of the novel carbinol fuel battery anode catalyst of self-supporting according to claim 2,
It is characterized in that, the specific steps of the step (1) are as follows: be used to do growth substrate and catalyst for nickel foam, nickel foam is put into
Quartz tube furnace middle section with the flow of 350-450sccm be passed through volume ratio for 5-9:100 hydrogen and argon gas mixed gas again
Anneal 30min at 1000-1200 DEG C；Methane gas is passed through with 9-12sccm flow, 1000-1200 DEG C of constant temperature 25-45min,
Stopping is passed through methane gas, and quartz tube furnace is 5-9:100 hydrogen and argon gas gaseous mixture in the volume ratio of 350-450sccm flow
Under body protection, with 100-120 DEG C ﹒ min-1Cooling rate be cooled to room temperature, obtain being carried on the graphene in nickel foam, i.e., three
Tie up graphene/nickel foam.
4. a kind of preparation method of the novel carbinol fuel battery anode catalyst of self-supporting according to claim 2 or 3,
It is characterized in that, the density of step (1) nickel foam is 350g ﹒ m-2, with a thickness of 1.5mm.
5. a kind of preparation method of the novel carbinol fuel battery anode catalyst of self-supporting according to claim 2,
It is characterized in that, the step (2) is deposited as double-sided deposition, and every face sedimentation time is 20min.
6. a kind of preparation method of the novel carbinol fuel battery anode catalyst of self-supporting according to claim 2 or 5,
It is characterized in that, the design parameter of step (2) deposition is as shown below:
。
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