CN106268901A - A kind of nitrogen-doped graphene load P d/Ni catalyst and preparation method thereof - Google Patents
A kind of nitrogen-doped graphene load P d/Ni catalyst and preparation method thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
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- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 24
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 24
- 239000011591 potassium Substances 0.000 claims abstract description 24
- LGQLOGILCSXPEA-UHFFFAOYSA-L nickel sulfate Chemical compound [Ni+2].[O-]S([O-])(=O)=O LGQLOGILCSXPEA-UHFFFAOYSA-L 0.000 claims abstract description 11
- 229910002666 PdCl2 Inorganic materials 0.000 claims abstract description 8
- 229910000363 nickel(II) sulfate Inorganic materials 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 22
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- 230000000802 nitrating effect Effects 0.000 claims description 5
- 150000001336 alkenes Chemical class 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 239000004575 stone Substances 0.000 claims 1
- 238000006555 catalytic reaction Methods 0.000 abstract description 15
- 230000000694 effects Effects 0.000 abstract description 13
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- 239000002994 raw material Substances 0.000 abstract description 3
- 230000001147 anti-toxic effect Effects 0.000 abstract description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 41
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 26
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 12
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- 238000012360 testing method Methods 0.000 description 10
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- 239000001301 oxygen Substances 0.000 description 9
- 229910052760 oxygen Inorganic materials 0.000 description 9
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 229910052763 palladium Inorganic materials 0.000 description 8
- 230000009467 reduction Effects 0.000 description 8
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 7
- 229910052757 nitrogen Inorganic materials 0.000 description 7
- 239000002245 particle Substances 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- 238000002484 cyclic voltammetry Methods 0.000 description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
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- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000002131 composite material Substances 0.000 description 3
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- 238000003786 synthesis reaction Methods 0.000 description 3
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
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- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 231100000614 poison Toxicity 0.000 description 2
- 239000010970 precious metal Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000027756 respiratory electron transport chain Effects 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
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- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
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- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/33—Electric or magnetic properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/396—Distribution of the active metal ingredient
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Catalysts (AREA)
Abstract
The invention discloses one and have high catalytic activity, the nitrogen-doped graphene load P d/Ni catalyst of dispersibility, stability and antitoxin function admirable, it is mainly by NiSO4·6H2O, nitrogen-doped graphene, potassium borohydride and PdCl2The raw materials such as solution prepare；The invention discloses the preparation method of a kind of nitrogen-doped graphene load P d/Ni catalyst.Preparing nitrogen-doped graphene load P d/Ni catalyst in the present invention and have bigger desorption peaks area, its catalysis activity is more excellent, has higher redox catalysis performance, stability and bigger catalyst electrochemical active surface.
Description
Technical field
The present invention relates to catalyst and catalyst synthesis technology field, especially relate to a kind of nitrogen-doped graphene load P d/
Ni catalyst and preparation method thereof.
Background technology
Catalyst is that a class can accelerate chemical reaction rate but the material that do not changes of self physicochemical property, due to it
Can accelerate reaction rate, therefore in chemical reaction selection and synthesis for catalytic reaction extensively by being absorbed in.Due to noble metal
The electronic configuration characteristic of palladium atomic surface so that it is become catalyst important in a kind of chemical reaction, it has urges efficiently
Change performance, less size, the concern of surface activity advantages of higher extremely researcher, the most continuous in the application of catalytic field
Expand, there is very important problem.But it is easy to run off owing to traditional nano Pd catalyst exists in the reaction, is difficult to reclaim
Problem, serious constrain its in actual applications with the raising of catalytic performance.Graphene is at present the thinnest to be also
The advantages such as the hardest nano material, has resistivity low, and electron transfer speed is fast, so Graphene is in emerging catalyst field
Play important role, oxygen reduction reaction demonstrated higher catalysis activity and cyclical stability, therefore Graphene with
The catalyst that precious metal palladium is combined also progresses into the research range of researcher.
Such as Chinese patent publication No. CN101966453A, patent announcement day is on February 9th, 2011, this disclosure of the invention one
Plant the preparation method of Pd/ graphene nano electro-catalyst, negative including the preparation of Graphene, the functionalization of Graphene and Graphene
Carrying the steps such as Pd nanometer, prepared Pd/ graphene nano catalyst has the highest catalysis activity.And for example Chinese patent publication No.
CN105126830A, be December in 2015 9 patent announcement day, a kind of graphene-supported palladium catalyst of this disclosure of the invention and
Preparation method and application, its raw material includes according to parts by volume: A material 2～10 parts, ethylene glycol 30～50 parts, Graphene 100～
150 parts, KTiNbO5Nanometer sheet solution 5～20 parts, wherein, the raw material of A material includes PdCl2It is 30～37% hydrochloric acid with concentration,
PdCl2It is 0.01～0.1:10～40 with the w/v g:ml of hydrochloric acid；This invention also discloses a kind of graphene-supported palladium
The preparation method of catalyst；The graphene-supported palladium catalyst of this invention changes prior synthesizing method, it is not necessary to add surface activity
Agent, material particle size is little, simple to operate, and post processing is reclaimed simple, and reaction condition is gentle, green, economical.Above two Graphene
Multiple composite palladium catalyst and synthetic method thereof, although the method with synthesis is simple, the Graphene composite palladium catalysis prepared
It is high that agent has catalytic efficiency, but still suffer from composite catalyst and easily reunite, the shortcoming such as dispersibility, less stable, and it is urged
Change activity also to have much room for improvement.
Summary of the invention
For solving the problems referred to above, the invention provides one and there is high catalytic activity, dispersibility, stability and antitoxin performance
Excellent nitrogen-doped graphene load P d/Ni catalyst；
Present invention also offers one and can improve nitrogen-doped graphene load P d/Ni catalyst activity and stability,
Prevent the nitrogen-doped graphene load P d/Ni method for preparing catalyst of nitrogen-doped graphene load P d/Ni catalyst agglomeration.
For achieving the above object, the technical solution used in the present invention is as follows:
A kind of nitrogen-doped graphene load P d/Ni catalyst, is prepared by the component of following weight portion: NiSO4·6H2O1 part, mixes
Nitrogen Graphene 4～6 parts, potassium borohydride 20～25 parts；Also comprise the PdCl of appropriate 0.05mol/L2Solution, make Ni Yu Pd mole
Ratio is 1:2～4.
Graphene be at present the thinnest be also the hardest nano material, there is resistivity low, electron transfer speed
The advantage such as fast, plays important role in emerging electrochmical power source, Graphene has bigger ratio table as the carrier of catalyst
The advantages such as area, good electrical conductivity and mechanical performance, are possible not only to reduce the load capacity of precious metals pd/Ni, reduce cost, also
The catalysis activity of catalyst can be effectively improved；After Graphene nitrating, oxygen reduction reaction is demonstrated higher catalysis activity
And cyclical stability.
Pd base catalyst is considered as a class catalyst the highest to hydrogen reduction electro catalytic activity, but pure Pd surface has
The factors such as more serious inertia, price are high, poisonous, with the alloy formed by Pd Yu Ni, can improve the dispersibility of Pd particle, subtract
Few reunion, strengthens electrochemical active surface, improves activity, dispersibility, stability, and therefore Pd based alloy catalyst is expected to conduct
There is the oxidation reduction catalyst of preferable catalytic performance, the nano metal Pd grain when the ratio of Pd Yu Ni is suitable, in catalyst
Son is less, is evenly distributed, and can improve Pd poison resistance, has preferable oxidoreduction electro catalytic activity and stability.
As preferably, nitrogen-doped graphene is prepared by following methods:
Add graphene oxide in proper ammonia and ultrasonic disperse, afterwards the solution after dispersion is joined hydro-thermal anti-
Answer in still, then react 4～6 hours at a temperature of 200～250 DEG C, at 70 DEG C after cooling, sucking filtration, washing after having reacted
Under be dried 10～14 hours prepared nitrogen-doped graphenes；The most every 1 gram of graphene oxide adds 150 milliliters of ammonia.
The preparation method of a kind of nitrogen-doped graphene load P d/Ni catalyst, comprises the following steps:
A) nitrogen-doped graphene joins supersound process in distilled water make it be uniformly dispersed to obtain nitrogen-doped graphene solution；
B) potassium borohydride is joined distilled water makes it fully dissolve prepared solution of potassium borohydride；
C) by PdCl2Solution and NiSO4·6H2O joins in nitrogen-doped graphene solution and supersound process；
D) solution of potassium borohydride that step b prepares is slowly added in the solution that step c prepares, afterwards at 50 DEG C of N2Protect
Protect lower reaction 5～7 hours；
E) will through step d reacted product sucking filtration, wash, dry after prepare Pd/Ni be combined nitrogen-doped graphene catalyst.
Therefore, the method have the advantages that
(1) there is bigger desorption peaks area；
(2) catalysis activity is more excellent, has higher redox catalysis performance, stability and bigger catalyst electrification
Learn active surface area；
(3) increase the dispersibility of Pd nanoparticle, decrease the reunion of Pd particle.
Accompanying drawing explanation
Fig. 1 is the XRD figure spectrum of three groups of embodiments and comparative example catalyst；
Fig. 2 is the transmission electron microscope picture that embodiment 2 prepares catalyst；
Fig. 3 is the EDX figure that embodiment 2 prepares catalyst；
Fig. 4 is the cyclic voltammetry curve of embodiment 2 catalyst electrode under room temperature；
Fig. 5 is comparative example and the cyclic voltammetry curve of each embodiment catalyst electrode under room temperature；
Comparative example and the current of polarization curve of each embodiment catalyst electrode when Fig. 6 is disc rotation speed 1600r/min；
Comparative example and the current of polarization curve of each embodiment catalyst electrode when Fig. 7 is disc rotation speed 2000r/min；
Fig. 8 is embodiment 2 catalyst linear volt-ampere curve under different scanning speed.
Fig. 9 is the three-electrode electro Chemical pool structure schematic diagram that the present invention uses.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further illustrated.
Embodiment 1
A kind of nitrogen-doped graphene load P d/Ni catalyst, is prepared by the component of following weight portion: NiSO4·6H2O1 part, mixes
Nitrogen Graphene 4 parts, potassium borohydride 20 parts；Also comprise the PdCl of appropriate 0.05mol/L2Solution, the mol ratio making Ni Yu Pd is 1:
2；
Wherein, nitrogen-doped graphene is prepared by following methods:
Add graphene oxide in proper ammonia and ultrasonic disperse 10 minutes, afterwards the solution after dispersion is joined
In hydrothermal reaction kettle, then react 4 hours at a temperature of 200 DEG C, dry at 70 DEG C after cooling filtering and washing after having reacted
Dry 10 hours prepared nitrogen-doped graphenes；The most every 1 gram of graphene oxide adds 150 milliliters of ammonia.
The preparation method of a kind of nitrogen-doped graphene load P d/Ni catalyst, comprises the following steps:
A) nitrogen-doped graphene joins supersound process in distilled water make it be uniformly dispersed to obtain nitrogen-doped graphene solution；Its
In every gram of nitrogen-doped graphene add 360 milliliters of distilled water；
B) potassium borohydride is joined distilled water makes it fully dissolve prepared solution of potassium borohydride；Wherein every gram of hydroboration
Potassium adds 170 milliliters of distilled water；
C) by PdCl2Solution and NiSO4·6H2O joins in nitrogen-doped graphene solution and supersound process；
D) solution of potassium borohydride that step b prepares is slowly added in the solution that step c prepares, afterwards at 40 DEG C of N2Protect
Protect lower reaction 5 hours；
E) prepared Pd/Ni will be dried at 60 DEG C and is combined nitrating graphite after step d reacted product sucking filtration, washing
Alkene catalyst.
Preparing 2PdNi/N-Graphene catalyst by embodiment 1, N-Graphene is nitrogen-doped graphene.
Embodiment 2
A kind of nitrogen-doped graphene load P d/Ni catalyst, is prepared by the component of following weight portion: NiSO4·6H2O1 part, mixes
Nitrogen Graphene 5 parts, potassium borohydride 23 parts；Also comprise the PdCl of appropriate 0.05mol/L2Solution, the mol ratio making Ni Yu Pd is 1:
3；
Wherein, nitrogen-doped graphene is prepared by following methods:
Add graphene oxide in proper ammonia and ultrasonic disperse 12 minutes, afterwards the solution after dispersion is joined
In hydrothermal reaction kettle, then react 5 hours at a temperature of 210 DEG C, dry at 70 DEG C after cooling filtering and washing after having reacted
Dry 12 hours prepared nitrogen-doped graphenes；The most every 1 gram of graphene oxide adds 150 milliliters of ammonia.
The preparation method of a kind of nitrogen-doped graphene load P d/Ni catalyst, comprises the following steps:
A) nitrogen-doped graphene joins supersound process in distilled water make it be uniformly dispersed to obtain nitrogen-doped graphene solution；Its
In every gram of nitrogen-doped graphene add 375 milliliters of distilled water；
B) potassium borohydride is joined distilled water makes it fully dissolve prepared solution of potassium borohydride；Wherein every gram of hydroboration
Potassium adds 190 milliliters of distilled water；
C) by PdCl2Solution and NiSO4·6H2O joins in nitrogen-doped graphene solution and supersound process；
D) solution of potassium borohydride that step b prepares is slowly added in the solution that step c prepares, afterwards at 50 DEG C of N2Protect
Protect lower reaction 6 hours；
E) prepared Pd/Ni will be dried at 70 DEG C and is combined nitrating graphite after step d reacted product sucking filtration, washing
Alkene catalyst.
Preparing 3PdNi/N-Graphene catalyst by embodiment 2, N-Graphene is nitrogen-doped graphene.
Embodiment 3
A kind of nitrogen-doped graphene load P d/Ni catalyst, is prepared by the component of following weight portion: NiSO4·6H2O1 part, mixes
Nitrogen Graphene 6 parts, potassium borohydride 25 parts；Also comprise the PdCl of appropriate 0.05mol/L2Solution, the mol ratio making Ni Yu Pd is 1:
4；
Wherein, nitrogen-doped graphene is prepared by following methods:
Add graphene oxide in proper ammonia and ultrasonic disperse 15 minutes, afterwards the solution after dispersion is joined
In hydrothermal reaction kettle, then react 6 hours at a temperature of 250 DEG C, dry at 70 DEG C after cooling filtering and washing after having reacted
Dry 14 hours prepared nitrogen-doped graphenes；The most every 1 gram of graphene oxide adds 150 milliliters of ammonia.
The preparation method of a kind of nitrogen-doped graphene load P d/Ni catalyst, comprises the following steps:
A) nitrogen-doped graphene joins supersound process in distilled water make it be uniformly dispersed to obtain nitrogen-doped graphene solution；Its
In every gram of nitrogen-doped graphene add 390 milliliters of distilled water；
B) potassium borohydride is joined distilled water makes it fully dissolve prepared solution of potassium borohydride；Wherein every gram of hydroboration
Potassium adds 195 milliliters of distilled water；
C) by PdCl2Solution and NiSO4·6H2O joins in nitrogen-doped graphene solution and supersound process；
D) solution of potassium borohydride that step b prepares is slowly added in the solution that step c prepares, afterwards at 55 DEG C of N2Protect
Protect lower reaction 5～7 hours；
E) prepared Pd/Ni will be dried at 65 DEG C and is combined nitrating graphite after step d reacted product sucking filtration, washing
Alkene catalyst.
Preparing 4PdNi/N-Graphene, N-Graphene by embodiment 3 is nitrogen-doped graphene.
In above-described embodiment, graphene oxide uses hummers method to prepare.
Comparative example
Comparative example uses the Pd/N-Graphene catalyst that the preparation method of above-described embodiment prepares the Ni that undopes.
The impact of performance characterizes:
1. detection method:
A. prepared by catalysis electrode: first use Al2O3Glass-carbon electrode is polished to minute surface by polishing powder, washing, and dried for standby weighs
5g catalyst, is separately added into 30 μ L dehydrated alcohol and 15 μ LNafion, ultrasonic 3 times, pipettes 2.5 μ L catalyst and be coated in vitreous carbon table
It is dried on face and prepares catalysis electrode；
B. the structural characterization of catalyst: after sample ultrasonic, carries out XRD test, Cu target, A=0.143124nm；
C. catalyst experiment device and chemical property detection:
Using three-electrode system, catalyst electrode, platinum plate electrode, saturated calomel electrode, the sulfuric acid solution of 0.5mol/L is
Electrolyte；Use linear scanning method (LSV), the hydrogen reduction chemical property of the technique study catalyst such as cyclic voltammetry (CV)；
This detection is divided into two backgrounds, under oxygen background, is passed through 30min oxygen, connects each electrode, carries out (CV) test；Nitrogen
Under background, it is passed through 5min, 15min, 30min successively, removes the dissolved oxygen of electrolyte；
After rotating circular disk test device leads to oxygen 30min, under different rotating speeds, carry out the linear surface sweeping research of hydrogen reduction respectively,
This experiment is all carried out at room temperature 25 DEG C.Experimental equipment is shown in Fig. 1, and in Fig. 1, label 1,2,3,4 is respectively electrode；Work
Electrode；Reference electrode；Glass membrane.
2. the performance test results:
A.XRD test result:
As it is shown in figure 1,2 θ are 39.7 °, 46.1 °, be four crystal face characteristic diffraction peaks of Pd respectively at 68.2 ° and 82.3 °,
The diffraction maximum of the crystal face of 39.7 ° is maximum, it can be seen that after mixing Ni, the characteristic diffraction peak of Pd (111) crystal face is right
Move, illustrate that the incorporation of Ni element makes parameter diminish.
B.TEM test result:
Observe embodiment 2 with TEM respectively and prepare the grain morphology of catalyst, and testing example 2 prepares the EDX of catalyst
Spectrogram, i.e. characterizes embodiment 2 and prepares the elementary composition of catalyst.Such as Fig. 2, shown in transmission electron microscope picture, metallic particles is uniformly dispersed,
Particle diameter is about 3nm, as shown in Fig. 3, EDX scheme, mainly has Pd, N, Ni and C element, shows that N element is successfully adulterated.
C. electrochemical property test result:
At room temperature, 0.5mol/LH2SO4In solution, it is worth catalyst electricity with the scanning speed testing example 2 of 20mV/S
The Cyclic voltamogram of pole；From fig. 4, it can be seen that oxygen is passed through lower situation, there is downward reduction peak at the peak of 0.5V in this catalyst,
Along with the prolongation of the time that is passed through of nitrogen, this peak intensity constantly weakens, and can confirm that the electroreduction peak that peak is oxygen of 0.5V；
Fig. 5 is at room temperature comparative example and the cyclic voltammetry curve of embodiment catalyst electrode, and each group embodiment prepares
Catalyst has hydrogen desorption oxidation peak, and area is essentially the same greatly, and compared with the catalyst that comparative example prepares, its desorption peaks area increases
Greatly, illustrate that Ni element improves the dispersibility of Pd particle, reduce and reunite, strengthen electrochemical active surface；Wherein embodiment 2 is made
The catalyst obtained, i.e. the desorption peaks area of 3PdNi/N-Graphene catalyst is maximum.
The electrochemical property test result of each embodiment catalyst under the most same rotating speed:
Comparative example and each embodiment catalyst electricity when Fig. 7 and Fig. 8 disc rotation speed is respectively 1600r/min and 2000r/min
The current of polarization curve of pole；As seen from the figure, all catalyst all have certain oxygen reduction activity, with comparative example catalyst electrode
Comparing, in addition to embodiment 1 catalyst electrode, the catalyst of other ratio is to being all demonstrated by preferably being catalyzed activity, and its electric current is close
Degree is all increasing；When current potential is 0V (vs.SCE), the hydrogen reduction limiting current density of embodiment 2 and 3 catalysis electrode is 0.631mA/
cm2And 0.723mA/cm2It point it is hydrogen reduction limiting current density 0.413mA/cm of comparative example catalysis electrode21.52 times and
1.75 again.
E. under different rotating speeds, embodiment 2 prepares the electrochemical property test result of catalyst:
Fig. 8 is that embodiment 2 prepares catalyst at 0.5mol/LH2SO4In electrolyte, difference sweeps speed lower linear volt-ampere curve figure,
It will be seen that along with the increase of rotating speed, the limiting current density of catalyst is all increasing, illustrate that embodiment 2 prepares catalysis
The hydrogen reduction of agent is irreversible.
3. Characterization result conclusion:
The catalyst that the catalyst prepared by three groups of embodiments is prepared than comparative example has higher hydrogen reduction catalytic
Energy and stability, electrochemical active surface is relatively big, due to the addition of nickel, improves the dispersibility of Pd nanoparticle, decreases
The reunion of Pd particle.The catalyst wherein prepared by embodiment 2, i.e. 3PdNi/N-Graphene catalyst electro-chemical activity
Largest surface area.
Claims (3)
1. a nitrogen-doped graphene load P d/Ni catalyst, it is characterised in that prepared by the component of following weight portion: NiSO4·
6H2O1 part, nitrogen-doped graphene 4～6 parts, potassium borohydride 20～25 parts；Also comprise the PdCl of appropriate 0.05mol/L2Solution, makes Ni
It is 1:2～4 with the mol ratio of Pd.
A kind of nitrogen-doped graphene load P d/Ni catalyst the most according to claim 1, it is characterised in that described nitrating stone
Ink alkene is prepared by following methods:
Add graphene oxide in proper ammonia and ultrasonic disperse, afterwards the solution after dispersion is joined hydrothermal reaction kettle
In, then react 4～6 hours at a temperature of 200～250 DEG C, be dried at 70 DEG C after cooling filtering and washing after having reacted
10～14 hours prepared nitrogen-doped graphenes；The most every 1 gram of graphene oxide adds 150 milliliters of ammonia.
3. the preparation method of a nitrogen-doped graphene load P d/Ni catalyst according to claim 1, it is characterised in that bag
Include following steps:
A) nitrogen-doped graphene joins supersound process in distilled water make it be uniformly dispersed to obtain nitrogen-doped graphene solution；
B) potassium borohydride is joined distilled water makes it fully dissolve prepared solution of potassium borohydride；
C) by PdCl2Solution and NiSO4·6H2O joins in nitrogen-doped graphene solution and supersound process；
D) solution of potassium borohydride that step b prepares is slowly added in the solution that step c prepares, afterwards at 40～55 DEG C of N2Protect
Protect lower reaction 5～7 hours；
E) will through step d reacted product sucking filtration, wash, dry after prepare Pd/Ni be combined nitrogen-doped graphene catalyst.
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