CN106268899A - A kind of preparation method of nitrogen-doped graphene Pt-supported catalyst - Google Patents
A kind of preparation method of nitrogen-doped graphene Pt-supported catalyst Download PDFInfo
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- CN106268899A CN106268899A CN201610565524.4A CN201610565524A CN106268899A CN 106268899 A CN106268899 A CN 106268899A CN 201610565524 A CN201610565524 A CN 201610565524A CN 106268899 A CN106268899 A CN 106268899A
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 98
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 97
- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 59
- 238000000034 method Methods 0.000 claims abstract description 49
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims abstract description 43
- 229910052700 potassium Inorganic materials 0.000 claims abstract description 43
- 239000011591 potassium Substances 0.000 claims abstract description 43
- 229910002666 PdCl2 Inorganic materials 0.000 claims abstract description 26
- 230000008569 process Effects 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012153 distilled water Substances 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 18
- 101150003085 Pdcl gene Proteins 0.000 claims abstract description 15
- FGUUSXIOTUKUDN-IBGZPJMESA-N C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 Chemical compound C1(=CC=CC=C1)N1C2=C(NC([C@H](C1)NC=1OC(=NN=1)C1=CC=CC=C1)=O)C=CC=C2 FGUUSXIOTUKUDN-IBGZPJMESA-N 0.000 claims abstract description 9
- 238000012545 processing Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 9
- 238000001914 filtration Methods 0.000 claims abstract description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 24
- 229910021529 ammonia Inorganic materials 0.000 claims description 12
- 239000002994 raw material Substances 0.000 claims description 8
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 3
- GNFTZDOKVXKIBK-UHFFFAOYSA-N 3-(2-methoxyethoxy)benzohydrazide Chemical compound COCCOC1=CC=CC(C(=O)NN)=C1 GNFTZDOKVXKIBK-UHFFFAOYSA-N 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 2
- BDAGIHXWWSANSR-UHFFFAOYSA-N Formic acid Chemical compound OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 29
- 230000003647 oxidation Effects 0.000 description 15
- 238000007254 oxidation reaction Methods 0.000 description 15
- 235000019253 formic acid Nutrition 0.000 description 14
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 11
- 238000006555 catalytic reaction Methods 0.000 description 11
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 10
- 239000008151 electrolyte solution Substances 0.000 description 9
- 239000000446 fuel Substances 0.000 description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 6
- 238000002484 cyclic voltammetry Methods 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 229910052757 nitrogen Inorganic materials 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 5
- 230000000694 effects Effects 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 230000000802 nitrating effect Effects 0.000 description 5
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 239000013078 crystal Substances 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- 229910002804 graphite Inorganic materials 0.000 description 4
- 239000010439 graphite Substances 0.000 description 4
- 229910052760 oxygen Inorganic materials 0.000 description 4
- 238000010408 sweeping Methods 0.000 description 4
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 238000003795 desorption Methods 0.000 description 3
- -1 graphite Alkene Chemical class 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229920000557 Nafion® Polymers 0.000 description 2
- 238000001354 calcination Methods 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000008187 granular material Substances 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000005245 sintering Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229910052593 corundum Inorganic materials 0.000 description 1
- 229960000935 dehydrated alcohol Drugs 0.000 description 1
- 238000001514 detection method Methods 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
- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 229910001385 heavy metal Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000452 restraining effect Effects 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 125000000542 sulfonic acid group Chemical group 0.000 description 1
- 235000011149 sulphuric acid Nutrition 0.000 description 1
- 239000001117 sulphuric acid Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229910001845 yogo sapphire Inorganic materials 0.000 description 1
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
-
- B01J35/33—
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- 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
-
- 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
Abstract
The present invention relates to the preparation method of a kind of nitrogen-doped graphene Pt-supported catalyst, the method comprises the following steps: nitrogen-doped graphene a) joins supersound process in distilled water and obtains nitrogen-doped graphene solution；B) by PdCl2Be dissolved in the water the PdCl that prepared concentration is 0.05mol/L2Solution, by PdCl after supersound process2The pH value of solution is adjusted to 7～8；C) potassium borohydride is joined in enough distilled water and make its positive good dissolving prepare solution of potassium borohydride；D) PdCl that the nitrogen-doped graphene solution prepared by step a is prepared with step b2Solution mixes, and mixed solution is heated to 50～60 DEG C；E) mixed solution after processing through step d is slowly added to solution of potassium borohydride；F) mixed solution after adding potassium borohydride reacts at 50～60 DEG C；G) by reacted for step f product through sucking filtration, washing, dried prepared nitrogen-doped graphene Pt-supported catalyst.
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 and urge
The preparation method of agent.
Background technology
Along with the fast development of science, the consumption of the energy is increasingly severe, and the pollution caused is the most increasing, and we are urgent
Ground needs to find a kind of to integrate environmental protection, energy-conservation, efficient clean energy resource.And the high conversion that fuel cell possesses, pollute
Property is little, and the scope of application is wide and valuing researches.The wherein Proton Exchange Membrane Fuel Cells manufacturing cost mistake with hydrogen as fuel
Height, thus cannot be carried out commercially producing；Although DMFC uses simple, cost is suitable, but because methanol has
Stronger volatility, and there is toxicity, not environmentally, the most not ideal enough.In recent years, by nonhazardous, and possesses methanol fuel cell
The aminic acid fuel battery of advantage is shown one's talent, and being recognized as by the public is the ideal source of portable type electronic product.
Along with our further investigation to direct methanoic acid fuel cell, it has been found that formic acid anion and nafion film
In sulfonic acid group there is bigger electrostatic influence, mutually exclusive, permeability is low, so its electrochemical oxidation is relatively good；With
And its theoretical potential and proton conductivity also higher than direct formic acid fuel.Thus, direct methanoic acid fuel cell will have one
Individual wide business development space, is also to solve the one of mankind's fuel contamination to wish greatly.
Such as Chinese patent publication No. CN105597743A, patent disclosure day is on May 23rd, 2016, discloses a kind of oxidation
The preparation method of alumina supporter Pt-supported catalyst, catalyst prepared by the method is alumina support Pt-supported catalyst, although
This method has prepared the Pd catalyst with good catalytic activity under relatively low content of beary metal, but this kind of catalyst
There is alumina support hinders the situations such as catalytic efficiency lifting, Pd skewness in the carrier to exist simultaneously so that utilize the party
The heavy metal Pd catalyst that method prepares still suffers from the situations such as catalytic efficiency is relatively low.
Summary of the invention
For solve the problems referred to above, the present invention provide one can improve nitrogen-doped graphene Pt-supported catalyst catalysis activity and
Stability, prevents the nitrogen-doped graphene Pt-supported catalyst preparation method that nitrogen-doped graphene Pt-supported catalyst is reunited.
For achieving the above object, the technical solution used in the present invention is as follows:
The preparation method of a kind of nitrogen-doped graphene Pt-supported 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) by PdCl2It is dissolved in enough distilled water and prepares PdCl2Solution, makes PdCl2The concentration of solution is 0.05mol/L,
By PdCl after supersound process2The pH value of solution is adjusted to 7～8；
C) potassium borohydride is joined in enough distilled water and make its positive good dissolving prepare solution of potassium borohydride；
D) PdCl that the nitrogen-doped graphene solution prepared by step a is prepared with step b2Solution mixes, and will mix molten
Liquid is heated to 50～60 DEG C；
E) mixed solution after processing through step d is slowly added to solution of potassium borohydride；
F) mixed solution after adding potassium borohydride reacts 6～8 hours at 50～60 DEG C；
G) by reacted for step f product through sucking filtration, washing, dried prepared nitrogen-doped graphene Pt-supported catalyst.
As preferably, in step e, the mixed solution after processing through step d is slowly added to solution of potassium borohydride, makes every
The addition of minute potassium borohydride is 30 weight portions.
As preferably, the reaction in step f is carried out in a nitrogen atmosphere.
As preferably, in step g, it is dried at a temperature of 70～80 DEG C after product washing.
As preferably, described nitrogen-doped graphene Pt-supported catalyst is to be prepared by the raw material of following weight portion: nitrating graphite
Alkene 60～90 parts, PdCl215～30 parts, potassium borohydride 300～320 parts.Graphene be at present the thinnest be also the hardest
Nano material, there is resistivity low, the advantages such as electron transfer speed is fast, play important role in emerging electrochmical power source,
Graphene has the advantages such as bigger specific surface area, good electrical conductivity and mechanical performance as the carrier of catalyst, not only may be used
To reduce the load capacity of precious metals pd, reduce cost, moreover it is possible to be effectively improved the catalysis activity of catalyst；After Graphene nitrating,
Oxygen reduction reaction is demonstrated higher catalysis activity and cyclical stability.
As preferably, nitrogen-doped graphene Pt-supported catalyst is prepared by the raw material of following weight portion: nitrogen-doped graphene 80 parts,
PdCl225 parts, potassium borohydride 317 parts.
As preferably, nitrogen-doped graphene has following methods to prepare: add in the graphene oxide that weight portion is 30～35 parts
Enter the ammonia that weight portion is 2700～2800 parts, supersound process sufficiently long time so that it is in ink-like；By ink-like product with
Weight portion is that the ammonia of 2650～2750 parts is put in hydrothermal reaction kettle, reacts 4～6 hours at a temperature of 200～240 DEG C, system
Obtain nitrogen-doped graphene basic products；Nitrogen-doped graphene basic products is reacted 6～7 hours at 300～600 DEG C, prepares nitrating graphite
Alkene.
Therefore, the catalyst that the inventive method prepares has the advantages that (1) has bigger desorption peaks area；
(2) catalysis activity is more excellent, has higher redox catalysis performance, stability and bigger catalyst electro-chemical activity table
Area；(3) increase the dispersibility of Pd nanoparticle, decrease the reunion of Pd particle.
Accompanying drawing explanation
Fig. 1 is three battery structure schematic diagrams；
Fig. 2 is the XRD spectra of different embodiment gained catalyst；
Fig. 3 is the SEM figure of embodiment 2 and embodiment 3 gained catalyst；
Fig. 4 is that the EDX of embodiment 3 can spectrogram；
Fig. 5 is the cyclic voltammetry curve that each embodiment prepares that catalyst electrode surface sweeping speed in the electrolytic solution is 20mV/s；
Fig. 6 is the cyclic voltammetry curve that each embodiment prepares that catalyst electrode surface sweeping speed in the electrolytic solution is 50mV/s；
Fig. 7 is the cyclic voltammetry curve that each embodiment prepares that catalyst electrode surface sweeping speed in the electrolytic solution is 2mV/s
Fig. 8 is the cyclic voltammetry curve that each embodiment prepares that catalyst electrode surface sweeping speed in the electrolytic solution is 10mV/s
Fig. 9 is that each embodiment prepares catalysis electrode current of polarization curve under 0.4V constant potential；
Figure 10 is the PVI curve that each embodiment prepares under catalyst electrode 0.1mA constant current in the electrolytic solution；
Figure 11 is the PVI curve that embodiment 3 prepares under catalyst electrode different constant currents in the electrolytic solution；
Figure 12 is that to prepare catalyst electrode scanning speed in 0.5mol/L sulfuric acid solution be following of 50mV/s to each embodiment
Ring volt-ampere curve.
Detailed description of the invention
Below in conjunction with detailed description of the invention, the present invention is further illustrated.In the present invention, if not refering in particular to, all of
Part, percentage ratio are unit of weight, and the equipment used and raw material etc. are all commercially available or commonly used in the art.Following
Method in embodiment, if no special instructions, is the conventional method of this area.
Embodiment 1
A kind of nitrogen-doped graphene Pt-supported catalyst, is prepared by the raw material of following weight portion: nitrogen-doped graphene 60 parts,
PdCl215 parts, potassium borohydride 300 parts；
Wherein, nitrogen-doped graphene has following methods to prepare:
Adding the ammonia that weight portion is 2700 parts in the graphene oxide that weight portion is 30 parts, supersound process is sufficiently long
Time so that it is in ink-like；The ammonia that ink-like product and weight portion are 2650 parts is put in hydrothermal reaction kettle, at 200 DEG C
At a temperature of react 4 hours, prepare nitrogen-doped graphene basic products；Nitrogen-doped graphene basic products is reacted 6 hours at 300 DEG C, system
Obtain nitrogen-doped graphene；
Additionally graphene oxide is prepared by hummer method.
The preparation method of a kind of nitrogen-doped graphene Pt-supported 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) by PdCl2It is dissolved in enough distilled water and prepares PdCl2Solution, makes PdCl2The concentration of solution is 0.05mol/L,
By PdCl after supersound process2The pH value of solution is adjusted to 7；
C) potassium borohydride is joined in enough distilled water and make its positive good dissolving prepare solution of potassium borohydride；
D) PdCl that the nitrogen-doped graphene solution prepared by step a is prepared with step b2Solution mixes, and will mix molten
Liquid is heated to 50 DEG C；
E) mixed solution after processing through step d is slowly added to solution of potassium borohydride, makes potassium borohydride per minute
Addition is 30 weight portions；
F) mixed solution after adding potassium borohydride reacts 6 hours under 50 DEG C of nitrogen atmospheres；
G) by reacted for step f product through sucking filtration, washing, the dried nitrogen-doped graphene Pt-supported catalyst for preparing, dry
Dry carry out at a temperature of 70 DEG C.
Embodiment 2
A kind of nitrogen-doped graphene Pt-supported catalyst, is prepared by the raw material of following weight portion: nitrogen-doped graphene 80 parts,
PdCl225 parts, potassium borohydride 317 parts；
Wherein, nitrogen-doped graphene has following methods to prepare:
Adding the ammonia that weight portion is 2730 parts in the graphene oxide that weight portion is 35 parts, supersound process is sufficiently long
Time so that it is in ink-like；The ammonia that ink-like product and weight portion are 2730 parts is put in hydrothermal reaction kettle, at 210 DEG C
At a temperature of react 5 hours, prepare nitrogen-doped graphene basic products；Nitrogen-doped graphene basic products is reacted 6 hours at 400 DEG C, system
Obtain nitrogen-doped graphene；
Additionally graphene oxide is prepared by hummer method.
The preparation method of a kind of nitrogen-doped graphene Pt-supported 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) by PdCl2It is dissolved in enough distilled water and prepares PdCl2Solution, makes PdCl2The concentration of solution is 0.05mol/L,
By PdCl after supersound process2The pH value of solution is adjusted to 7.5；
C) potassium borohydride is joined in enough distilled water and make its positive good dissolving prepare solution of potassium borohydride；
D) PdCl that the nitrogen-doped graphene solution prepared by step a is prepared with step b2Solution mixes, and will mix molten
Liquid is heated to 50 DEG C；
E) mixed solution after processing through step d is slowly added to solution of potassium borohydride, makes potassium borohydride per minute
Addition is 30 weight portions；
F) mixed solution after adding potassium borohydride reacts 6 hours under 50 DEG C of nitrogen atmospheres；
G) by reacted for step f product through sucking filtration, washing, the dried nitrogen-doped graphene Pt-supported catalyst for preparing, dry
Dry carry out at a temperature of 70 DEG C.
Embodiment 3
A kind of nitrogen-doped graphene Pt-supported catalyst, is prepared by the raw material of following weight portion: nitrogen-doped graphene 90 parts,
PdCl230 parts, potassium borohydride 320 parts；
Wherein, nitrogen-doped graphene has following methods to prepare:
Adding the ammonia that weight portion is 2800 parts in the graphene oxide that weight portion is 35 parts, supersound process is sufficiently long
Time so that it is in ink-like；The ammonia that ink-like product and weight portion are 2750 parts is put in hydrothermal reaction kettle, at 240 DEG C
At a temperature of react 6 hours, prepare nitrogen-doped graphene basic products；To react 7 hours at nitrogen-doped graphene basic products 600 DEG C, prepare
Nitrogen-doped graphene；
Additionally graphene oxide is prepared by hummer method.
The preparation method of a kind of nitrogen-doped graphene Pt-supported 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) by PdCl2It is dissolved in enough distilled water and prepares PdCl2Solution, makes PdCl2The concentration of solution is 0.05mol/L,
By PdCl after supersound process2The pH value of solution is adjusted to 8；
C) potassium borohydride is joined in enough distilled water and make its positive good dissolving prepare solution of potassium borohydride；
D) PdCl that the nitrogen-doped graphene solution prepared by step a is prepared with step b2Solution mixes, and will mix molten
Liquid is heated to 60 DEG C；
E) mixed solution after processing through step d is slowly added to solution of potassium borohydride, makes potassium borohydride per minute
Addition is 30 weight portions；
F) mixed solution after adding potassium borohydride reacts 8 hours under 60 DEG C of nitrogen atmospheres；
G) by reacted for step f product through sucking filtration, washing, the dried nitrogen-doped graphene Pt-supported catalyst for preparing, dry
Dry carry out at a temperature of 80 DEG C.
Embodiment 4
A kind of nitrogen-doped graphene Pt-supported catalyst, is prepared by the raw material of following weight portion: nitrogen-doped graphene 80 parts,
PdCl225 parts, potassium borohydride 317 parts；
Wherein, nitrogen-doped graphene has following methods to prepare:
Adding the ammonia that weight portion is 2730 parts in the graphene oxide that weight portion is 35 parts, supersound process is sufficiently long
Time so that it is in ink-like；The ammonia that ink-like product and weight portion are 2730 parts is put in hydrothermal reaction kettle, at 210 DEG C
At a temperature of react 5 hours, prepare nitrogen-doped graphene；
Additionally graphene oxide is prepared by hummer method.
The preparation method of a kind of nitrogen-doped graphene Pt-supported 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) by PdCl2It is dissolved in enough distilled water and prepares PdCl2Solution, makes PdCl2The concentration of solution is 0.05mol/L,
By PdCl after supersound process2The pH value of solution is adjusted to 7.5；
C) potassium borohydride is joined in enough distilled water and make its positive good dissolving prepare solution of potassium borohydride；
D) PdCl that the nitrogen-doped graphene solution prepared by step a is prepared with step b2Solution mixes, and will mix molten
Liquid is heated to 50 DEG C；
E) mixed solution after processing through step d is slowly added to solution of potassium borohydride, makes potassium borohydride per minute
Addition is 30 weight portions；
F) mixed solution after adding potassium borohydride reacts 6 hours under 50 DEG C of nitrogen atmospheres；
G) by reacted for step f product through sucking filtration, washing, the dried nitrogen-doped graphene Pt-supported catalyst for preparing, dry
Dry carry out at a temperature of 70 DEG C.
The impact of performance characterizes:
1. detection method
A. prepared by catalysis electrode: claims 5mgPd/N-Graphene in plastic test tube, adds 15 μ L Nafion and 2 times
Dehydrated alcohol, in supersonic cleaning machine ultrasonic 20 minutes to ink-like (10 points are changed water once), pipette 27 μ L with liquid-transfering gun and be loaded in
The cleaned glass carbon surface of a diameter of 4mm (uses Al2O3Vitreous carbon after polishing), make load electrode；
B. the structural characterization of catalyst: after sample ultrasonic, carries out XRD test, Cu target, A=0.143124nm；
C. Catalysis experiments device and electrochemical property test:
Use three-electrode system, as it is shown in figure 1, include: catalysis electrode, reference electrode: saturated calomel electrode；Auxiliary electricity
Pole: platinum electrode, is used for conducting electric current.Use CV, LSV and IT Study of Catalyst electrocatalysis characteristic to formic acid oxidation.CV is permissible
Observe the current peak (between-0.2V～0.8V, sweep speed is 50mV/s to sweep limits) of the catalysis oxidation of catalyst；
LSV may determine that the initial oxidation current potential of catalyst；It can record formic acid electrocatalytic oxidation galvanic current and change over (constant potential
For 0.4V).Electrolyte is 1mol/L HCOOH+0.5mol/L H2SO4(being the most all referred to as electrolyte).It is passed through in the electrolytic solution
20min obtains nitrogen to remove the dissolved oxygen in electrolyte, can carry out electrochemical property test.
2. the performance test results:
A.XRD test result:
As in figure 2 it is shown, we can see that from figure the diffraction maximum of (002) crystal face at reduced graphene at 2 θ is
On the position of 26.5 °, Pd crystal (111), (200), (220), 2 θ of diffraction maximum of (311) crystal face are respectively 40.118 °,
46.658 °, 68.119 °, 82.098 °, illustrate that catalyst that different sintering temperature processes is by the Pd of cubic plane core structure and stone
Ink alkene composition.From figure, we have further appreciated that (002) crystal face of 600 DEG C of calcination process rear catalysts moves to right, according to formula:
2d sin θ=λ, it can be deduced that θ is the biggest, and d is the least, namely reduced graphene spacing between layers diminishes, and makes graphite
Alkene structure shortrange order, electric conductivity improves.
B.SEM test result analysis:
As shown in Figure 3, it is seen that in different embodiments, the dispersing morphology of Pd granule changes, and it is mainly at nitrating graphite
Alkene produces impact through the roasting of different temperatures, and sintering temperature changes the agglomeration of Pd, improves dispersibility.Compared to reality
Executing example 2 roasting at 400 DEG C, the embodiment 3 catalyst Pd granule under 600 DEG C of roastings more disperses, and improves catalyst
Performance；
As shown in fig. 4, it can be seen that C, N, O, Pd are the elements that mainly comprises of nitrogen-doped graphene Pt-supported catalyst, explanation
Graphene success nitrating.
C. catalyst electrocatalysis characteristic in formic acid oxidation is catalyzed:
Fig. 5 and Fig. 6 is respectively this catalysis electrode cyclic voltammogram under 20mV and 50mV in the electrolytic solution.Can from figure
A peak of prominence produced by formic acid oxidation is occurred in that at about 0.1V to find out；Under 20mV, its formic acid of the catalyst of not roasting
Oxidation peak current electric current density is 17.83mA cm-2, and embodiment 1,2,3 processes the formic acid oxidation peak point current of rear catalyst
Density improves the most in various degree, respectively 39.49mA cm-2, 42.99mA cm-2With 62.82mA cm-2.And during 50mV, rule
Restraining similar, its formic acid oxidation peak current electric current density of catalyst after embodiment 4 processes is 29.94mA cm-2, embodiment 1,2,
After 3 process, its formic acid oxidation peak current density all increases, and embodiment 1,2,3 processes the peak current density of rear catalyst
It is respectively 29.94mA cm-2, 57.25mA cm-2, 62.98mA cm-2, 95.70mA cm-2.We can see that embodiment
The electric current density of 3 process rear catalysts is the highest, and the catalytic performance of this catalyst is optimal；
Fig. 7, Fig. 8 are respectively the LSV figure that this catalyst electrode scanning speed in the electrolytic solution is 2mV/s and 10mV/s.From
In it can be seen that an obvious oxidation peak, play peak position at about-0.12V, it can be seen that embodiment 3 processes rear catalyst and rises
Peak position the most the earliest, so the better performances of this catalyst.
D. catalyst stability in Formic Acid Catalytic Oxidation:
The study on the stability of catalyst is mainly by chronoa mperometric plot and the sign of time-measuring electric potential curve；
As it is shown in figure 9, the catalyst after different embodiments are processed, in 3600s, all occur in that downward trend, embodiment
Electric current density after 3 process declines the slowest, and its electric current density is consistently higher than other catalyst.Electrode inactivation causes electricity
Current density declines, and can produce CO, and these poisonous substances CO can accumulate at catalyst surface, accounts for during being because formic acid indirect oxidation
According to partially catalyzed active center, thus Pd electrode inactivates, and peak point current declines.Electrochemistry after embodiment 3 process is described
Stability is more preferably；
Figure 10 is that different embodiment prepares the chronoa mperometric plot that catalyst is made under the constant current of 0.1mA, and Figure 11 is real
Execute the chronoa mperometric plot that the catalyst of example 3 preparation is made respectively under 0.1mA, 0.3mA, 0.6mA constant current；From Figure 10 we
Can be seen that take-off potential is-0.075mV, wherein embodiment 3 preparation catalyst parallel voltage-0.05mV～-
0.04mV, embodiment 3 preparation at-0.035mV～-0.025mV, embodiment 1 preparation at-0.025mV～0.03mV, implement
Example 4 preparation at 0mV～0.075mV；The take-off potential that we can see that catalyst from Figure 11 is 0.12mV, then exists
Plateau potential under 0.1mA is between 0.18mV～0.20mV, and the plateau potential of 0.3mA is under 0.19mV～0.21mV, 0.6mA
Plateau potential at 0.25mV～0.28mV；Because Pd/N-Graphene catalyst is as the negative pole in battery, so parallel
Voltage is the lowest more good；Figure 10 and Figure 11 all illustrates that catalyst stability prepared by embodiment 3 is better than other temperature calcination and processes
After catalyst.
E. catalyst electrocatalysis characteristic in sulphuric acid measures:
It is this catalyst electrode CV figure in sulfuric acid electrolyte as shown in figure 12；Cyclic voltammetry curve is by three part groups
Become: Part I is the adsorption desorption process of hydrogen, occurs in-0.20V～+0.10V scope；Part II is the discharge and recharge of electric double layer
Process, in+0.10V～+0.30V scope；Part III is oxidation and the reducing zone of oxygen, in+0.30V～+0.80V scope；Aobvious
So, the catalyst after four kinds for the treatment of of different temperature all occurs in that the desorption peaks of hydrogen, and the peak value of desorption peaks is different and becomes rule.From figure
In it may be seen that these four catalyst urge electrochemistry effective active specific surface area size order be embodiment 3 > embodiment 2
> embodiment 1 > embodiment 4, so the effective active specific surface area of the catalyst of embodiment 3 preparation is maximum.
Claims (6)
1. the preparation method of a nitrogen-doped graphene Pt-supported catalyst, it is characterised in that comprise 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) by PdCl2It is dissolved in enough distilled water and prepares PdCl2Solution, makes PdCl2The concentration of solution is 0.05mol/L, ultrasonic
By PdCl after process2The pH value of solution is adjusted to 7～8；
C) potassium borohydride is joined in enough distilled water and make its positive good dissolving prepare solution of potassium borohydride；
D) PdCl that the nitrogen-doped graphene solution prepared by step a is prepared with step b2Solution mixes, and is heated by mixed solution
To 50～60 DEG C；
E) mixed solution after processing through step d is slowly added to solution of potassium borohydride；
F) mixed solution after adding potassium borohydride reacts 6～8 hours at 50～60 DEG C；
G) by reacted for step f product through sucking filtration, washing, dried prepared nitrogen-doped graphene Pt-supported catalyst.
The preparation method of a kind of nitrogen-doped graphene Pt-supported catalyst the most according to claim 1, it is characterised in that: described
In step e, the mixed solution after processing through step d is slowly added to solution of potassium borohydride, makes adding of potassium borohydride per minute
Entering amount is 30 weight portions.
The preparation method of a kind of nitrogen-doped graphene Pt-supported catalyst the most according to claim 1, it is characterised in that: described
Reaction in step f is carried out in a nitrogen atmosphere.
The preparation method of a kind of nitrogen-doped graphene Pt-supported catalyst the most according to claim 1, it is characterised in that: described
Step g in, product washing after at a temperature of 70～80 DEG C be dried.
The preparation method of a kind of nitrogen-doped graphene Pt-supported catalyst the most according to claim 1, it is characterised in that: this is urged
Agent is prepared by the raw material of following weight portion: nitrogen-doped graphene 60～90 parts, PdCl215～30 parts, potassium borohydride 300～320
Part.
The preparation method of a kind of nitrogen-doped graphene Pt-supported catalyst the most according to claim 5, it is characterised in that: described
Nitrogen-doped graphene have following methods prepare: in the graphene oxide that weight portion is 30～35 parts add weight portion be 2700～
The ammonia of 2800 parts, the supersound process sufficiently long time so that it is in ink-like；By ink-like product and weight portion be 2650～
The ammonia of 2750 parts is put in hydrothermal reaction kettle, reacts 4～6 hours at a temperature of 200～240 DEG C, prepares nitrogen-doped graphene pre-
Product；Nitrogen-doped graphene basic products is reacted 6～7 hours at 300～600 DEG C, prepares nitrogen-doped graphene.
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| CN106744755A (en) * | 2017-03-24 | 2017-05-31 | 福州大学 | The preparation method of black phosphorus nanometer sheet and noble metal nano particles composite |
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| CN110026236A (en) * | 2019-03-23 | 2019-07-19 | 大连理工大学 | A kind of Pd composite nano-catalyst and preparation method thereof for formic acid decomposing hydrogen-production |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106744755A (en) * | 2017-03-24 | 2017-05-31 | 福州大学 | The preparation method of black phosphorus nanometer sheet and noble metal nano particles composite |
| CN107042101A (en) * | 2017-06-02 | 2017-08-15 | 宁夏大学 | A kind of hydrogenation of carbon dioxide catalyst for methanol of doped graphene |
| CN110026236A (en) * | 2019-03-23 | 2019-07-19 | 大连理工大学 | A kind of Pd composite nano-catalyst and preparation method thereof for formic acid decomposing hydrogen-production |
| CN110026236B (en) * | 2019-03-23 | 2021-09-10 | 大连理工大学 | Pd composite nano catalyst for hydrogen production by formic acid decomposition and preparation method thereof |
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