CN105618060B - Difunctional VPO catalysts of graphene/nickel iron houghite and its preparation method and application - Google Patents
Difunctional VPO catalysts of graphene/nickel iron houghite and its preparation method and application Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 61
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 32
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 30
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 150000001875 compounds Chemical class 0.000 claims abstract description 44
- 238000006243 chemical reaction Methods 0.000 claims abstract description 26
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 15
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 15
- 239000001301 oxygen Substances 0.000 claims abstract description 15
- 229910000863 Ferronickel Inorganic materials 0.000 claims abstract description 9
- 238000006722 reduction reaction Methods 0.000 claims abstract description 9
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims abstract description 5
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims abstract description 5
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 48
- 239000000243 solution Substances 0.000 claims description 26
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 25
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 17
- 239000007788 liquid Substances 0.000 claims description 15
- 239000006185 dispersion Substances 0.000 claims description 14
- 238000001035 drying Methods 0.000 claims description 12
- 229940044631 ferric chloride hexahydrate Drugs 0.000 claims description 10
- NQXWGWZJXJUMQB-UHFFFAOYSA-K iron trichloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].Cl[Fe+]Cl NQXWGWZJXJUMQB-UHFFFAOYSA-K 0.000 claims description 10
- LAIZPRYFQUWUBN-UHFFFAOYSA-L nickel chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Ni+2] LAIZPRYFQUWUBN-UHFFFAOYSA-L 0.000 claims description 10
- 239000000446 fuel Substances 0.000 claims description 9
- 229910021645 metal ion Inorganic materials 0.000 claims description 9
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical class OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 8
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical compound [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 claims description 6
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 235000019270 ammonium chloride Nutrition 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 3
- 239000007787 solid Substances 0.000 claims description 3
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- -1 graphite Alkene Chemical class 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229910002804 graphite Inorganic materials 0.000 claims 1
- 239000010439 graphite Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 19
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 15
- 230000003197 catalytic effect Effects 0.000 abstract description 13
- 238000006555 catalytic reaction Methods 0.000 abstract description 6
- 230000009467 reduction Effects 0.000 abstract description 5
- 229910052751 metal Inorganic materials 0.000 abstract description 2
- 239000002184 metal Substances 0.000 abstract description 2
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- 239000003513 alkali Substances 0.000 abstract 1
- 150000003839 salts Chemical class 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 16
- 230000008569 process Effects 0.000 description 12
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 11
- 239000006260 foam Substances 0.000 description 10
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- 238000005119 centrifugation Methods 0.000 description 7
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- 239000010953 base metal Substances 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 230000027756 respiratory electron transport chain Effects 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 3
- 238000004220 aggregation Methods 0.000 description 3
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- 239000013078 crystal Substances 0.000 description 3
- 239000010410 layer Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
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- 125000004432 carbon atom Chemical group C* 0.000 description 2
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- 239000003863 metallic catalyst Substances 0.000 description 2
- 239000011943 nanocatalyst Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 230000002441 reversible effect Effects 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000004094 surface-active agent Substances 0.000 description 2
- 239000000454 talc Substances 0.000 description 2
- 229910052623 talc Inorganic materials 0.000 description 2
- 235000012222 talc Nutrition 0.000 description 2
- 238000002604 ultrasonography Methods 0.000 description 2
- 239000011165 3D composite Substances 0.000 description 1
- VTLYFUHAOXGGBS-UHFFFAOYSA-N Fe3+ Chemical compound [Fe+3] VTLYFUHAOXGGBS-UHFFFAOYSA-N 0.000 description 1
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 230000009471 action Effects 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 125000000129 anionic group Chemical group 0.000 description 1
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- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
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- 239000003638 chemical reducing agent Substances 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
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- 230000007773 growth pattern Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 229910000000 metal hydroxide Inorganic materials 0.000 description 1
- 150000004692 metal hydroxides Chemical class 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- LVIYYTJTOKJJOC-UHFFFAOYSA-N nickel phthalocyanine Chemical compound [Ni+2].C12=CC=CC=C2C(N=C2[N-]C(C3=CC=CC=C32)=N2)=NC1=NC([C]1C=CC=CC1=1)=NC=1N=C1[C]3C=CC=CC3=C2[N-]1 LVIYYTJTOKJJOC-UHFFFAOYSA-N 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000004575 stone Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000010408 sweeping Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 238000012353 t test Methods 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
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- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/755—Nickel
-
- 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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/18—Carbon
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/88—Processes of manufacture
- H01M4/8825—Methods for deposition of the catalytic active composition
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- H—ELECTRICITY
- 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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
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- 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
Electro-catalysis application the present invention relates to nonmetallic difunctional VPO catalysts of a kind of graphene/nickel iron houghite and preparation method thereof and in alkaline medium to oxygen evolution reaction and oxygen reduction reaction.The catalyst is using micella as template, successively under hydro-thermal and reducing condition, ferronickel houghite is assembled into spherical porous graphene oxide/ferronickel houghite compound is formed on graphene.This method includes：First graphene oxide and metal salt are distributed in micella, synthesize graphene oxide/houghite compound under hydrothermal condition after introducing alkali source, obtained product obtains the catalyst through hydrazine hydrate reduction.VPO catalysts prepared by the present invention have high analysis oxygen and oxygen reduction catalytic activity, good stability and excellent methanol tolerance concurrently in the basic conditions, and raw materials used cost is low, preparation method is simple, easily operated, are easy to mass produce.
Description
Technical field：
The invention belongs to novel energy resource material technology and electrochemical catalysis field, and in particular to graphene/nickel iron class neatly
The difunctional VPO catalysts of stone；Further relate to the preparation method of the catalyst and its in the reaction of electrolyzed alkaline water Oxygen anodic evolution and fuel
Electro-catalysis application in cell cathode oxygen reduction reaction.
Background technology：
As the mankind are continuously increased to cleaning and sustainable energy demand, great effort has been put into height by scientists
In terms of the research and development of effect, low cost and environmentally friendly energy conversion and stocking system.Wherein oxygen reduction reaction (ORR) exists
The cathode reaction of generally existing in fuel cell and metal-air battery, oxygen evolution reaction (OER) then solar energy fuel synthesis and
Played an important role in water-splitting energy storage system.Therefore, catalyst particularly VPO catalysts have been to restrict new energy dress
The main bottleneck put.In view of the activity and stability of catalyst, the catalyst for ORR reactions mainly has Pt and its alloy,
And the catalyst for being used for OER mainly has IrO2Or RuO2, but these noble metals are very rare in nature, make current power supply
Apparatus cost is too high.Therefore, research and develop base metal VPO catalysts turns into hot subject of concern in the field.
Houghite (writing a Chinese character in simplified form LDH) is a kind of two-dimensional nano anionic clay, and it forms formula and is represented by [M1-x 2+Mx 3+
(OH)2]x+(An-)x/n·mH2O, the interlayer anion to be balanced each other by positively charged hydroxide layer and therewith electric charge form.By
In adjustable chemical composition, different electrochemical active metal ions such as Fe, Ni, Co, Mn may participate in metal hydroxides octahedral
The structure of body neatly rock layers, make LDH materials energy conversion and field of storage present good application prospect [X.Long,
Z.Wang,S.Xiao,Y.An and S.Yang.Transition metal based layered double
hydroxides tailored for energy conversion and storage.Materials Today(2015),
http://dx.doi.org/10.1016/j.mattod.2015.10.006].However, in actual application, LDH catalyst
The shortcomings of small specific surface area, poorly conductive, easy aggregation and stability difference also be present in material.In order to overcome LDH disadvantage mentioned above, grind
The material such as some carbon materials such as graphene (GR) and CNT (CNT) is generally intercalated in LDH interlayers by the person of studying carefully, and first can be improved
The electric conductivity of composite, second prevent LDH from assembling, improve its stability.GR is a kind of sp2Hydbridized carbon atoms composition has
The two-dimensional material of one carbon atom thickness, has the specific surface area (~2600m of superelevation2/ g) and excellent electric conductivity (~106S/
Cm), the charge transfer and mass-transfer efficiency in electrocatalytic reaction can be greatly improved.And negatively charged graphene oxide (GO)
With the positively charged other static buildup of the face-to-face molecular level of LDH nanometer sheets, the transition metal-catalyzed center in LDH can be made with leading
The sp of electricity2Hydbridized carbon atoms are in close contact, and greatly shorten diffusion length [X.Long, the et of electrolyte
al.Angew.Chem.126(2014)7714–7718.].Although LDH and GR compound can solve by electrostatic assembly
The problems such as LDH material conductivities difference and aggregation, but the specific surface area for further improving composite is still that exploitation efficient electric is urged
The significant challenge of agent.
In order to prepare the elctro-catalyst with bigger serface, nickelous and ferric iron are dissolved in GO ethylene glycol by the present invention
In solution, surfactant is added after well mixed, is transferred to after mixing dissolving in reactor under hydrothermal condition, using micella as template
Graphene oxide/ferronickel houghite (GO/LDH) spherical nano-complex is prepared, is made spherical porous after hydrazine hydrate reduction
Graphene/nickel iron houghite (rGO/LDH) nanocatalyst.Spherical porous rGO/LDH is prepared using the method at present to be catalyzed
Agent and the catalyst have not been reported for electrolyzed alkaline water anode OER and fuel battery negative pole ORR research.
Reverse micelle template of the present invention, reactant is set to be limited in the reversed micelle of surfactant composition,
So as to be prepared for the rGO/LDH catalyst of class reversed micelle pattern, the preparation method eliminates LDH and the compound mistake of graphene
Journey, spherical porous rGO/LDH catalyst is obtained；Not only increase the electric conductivity and specific surface area of catalyst, and gained oxygen
Catalyst effectively reduces OER and ORR overpotential, passes through rotating disk electrode (r.d.e) (RDE) and rotating ring disk electrode (r.r.d.e)
(RRDE) it is 4 electronic catalytic mechanism to show its ORR process, is ideal ORR courses of reaction.Elctro-catalyst obtained by this method
The synergy of LDH and rGO in terms of electro-catalysis is given full play to, to exploitation novel electrochemical catalyst and energy conversion and storage
Memory device has important theoretical and practical significance.
The content of the invention：
In view of the shortcomings of the prior art and the demand of this area research and application, an object of the present invention are to provide one
The kind difunctional VPO catalysts of graphene/nickel iron houghite；I.e. using micella as template, under hydrothermal conditions, first by ferronickel class water
Talcum, which is assembled on GO, forms GO/LDH compounds, is then reduced to form the spherical porous nano catalyst of rGO/LDH,
The second object of the present invention is to provide a kind of preparation side of the difunctional VPO catalysts of graphene/nickel iron houghite
Method, specifically include following steps：
(a) preparation of GO/LDH compounds
A certain amount of GO is scattered in ethylene glycol, makes its concentration be 1.0~1.5mg/mL, ultrasonic disperse 1 hour,
3000rpm centrifugations 10min removes unstripped GO, the GO dispersion liquids peeled off, dispersion liquid 20mL is taken, by certain mol proportion
Nickel dichloride hexahydrate and ferric chloride hexahydrate are added thereto, and it is 0.04mol/L to make metal ion total concentration, and stirring makes its complete
Dissolving, is then slowly added into 0.2~0.6g dodecyl sodium sulfates, it is at the uniform velocity instilled 10mL after all dissolving under stirring condition
Ethylene glycol solution containing 0.16g NaOH, the mixed liquor is moved into reactor, 24h, reaction solution centrifugation point are reacted in 180 DEG C
From rear, washed three times with deionized water and ethanol respectively, be GO/LDH compounds after drying；
(b) preparation of rGO/LDH VPO catalysts
The GO/LDH compounds of gained in step (a) are scattered in the aqueous solution, it is 1.0mg/ml to make its concentration, is pipetted
The 100ml solution, it is separately added into the μ L of hydrazine hydrate 50 that mass fraction is 35% and the aqueous ammonium chloride solution that mass fraction is 27%
350 μ L, are transferred in reactor after stirring, and react 1h under the conditions of 180 DEG C, gained solid sample spent after centrifuging from
Sub- water and ethanol washing three times, difunctional VPO catalysts rGO/LDH is obtained after drying.
The mol ratio of Nickel dichloride hexahydrate and ferric chloride hexahydrate is 3 wherein described in step (a)：1, institute in step (b)
The VPO catalysts obtained are in hollow ball-shape, and average grain diameter is 210~290nm, and specific surface area is in 132.63~186.64m2/g。
The three of the object of the invention are to provide a kind of difunctional VPO catalysts of graphene/nickel iron houghite in electrolyzed alkaline water
Application in anode OER and fuel battery negative pole ORR.
The reverse micelle template that the present invention uses, the GO/LDH catalyst of class reversed micelle pattern is first prepared, made through reduction
It is standby to have obtained spherical porous rGO/LDH catalyst；Not only increase the electric conductivity and specific surface area of catalyst, and gained oxygen
Catalyst effectively reduces OER and ORR overpotential, the results showed that its ORR process is 4 electronic catalytic mechanism, is more to manage
The ORR courses of reaction thought.
Compared with prior art, the present invention has following major advantage and beneficial effect：
1) difunctional VPO catalysts of the present invention are base metal composite, raw materials used to be easy to buy and make
Standby, aboundresources and price is relatively low, it is low that it prepares cost on a large scale；
2) methanol tolerance that difunctional VPO catalysts of the present invention have had, in 0.1mol/L KOH electrolyte
1mol/L methanol is added, the catalytic activity of catalyst does not almost decay；
3) difunctional VPO catalysts of the present invention are a kind of novel three-dimensional composite, have preferable OER and ORR
Activity, there is significant advantage compared with the one-side ORR activity of base metal/non-metallic catalyst of current research report；
4) compared with commercialization 20wt% Pt/C catalyst, stability obtains difunctional VPO catalysts of the present invention
Significantly improve, can keep good catalytic activity in fuel cell long-term use；
5) difunctional VPO catalysts of the present invention OER activity, hence it is evident that be better than at present research report base metal/
Non-metallic catalyst, and activity is better than commercial RuO2Catalytic activity；
6) difunctional VPO catalysts preparation method of the present invention is simple, easily operated, is easy to mass produce.
Brief description of the drawings：
Fig. 1 is the scanning electron microscope (SEM) photograph (a) and transmission electron microscope picture (b) of the gained rGO/LDH compounds of embodiment 4.
Fig. 2 is the gained rGO/LDH compounds of embodiment 4 and the gained LDH of comparative example 1 XRD spectrum.
Fig. 3 is the gained rGO/LDH compounds of embodiment 4, the gained LDH of comparative example 1, the gained GO/LDH of comparative example 2 modifications Ni
The linear volt-ampere curve figure of foam electrode and naked OERNi foam electrodes.
Fig. 4 is that the gained rGO/LDH compounds of embodiment 4 modify Ni foam electrodes in 10mA/cm2Under P-t curve maps.
Fig. 5 is the gained rGO/LDH compounds of embodiment 4, the gained LDH of comparative example 1 and the gained GO/LDH of comparative example 2 modifications
The RDE linear volt-ampere curve figures of ORR.
Fig. 6 is the ORR kinetic curves that the gained rGO/LDH compounds of embodiment 4 are tested by RDE.
Fig. 7 is the ORR kinetic curves that the gained rGO/LDH compounds of embodiment 4 are tested by RRDE.
Fig. 8 is I-t curve map of the gained rGO/LDH compounds of embodiment 4 under 0.6V constant voltages.
Embodiment：
To further understand the present invention, the invention will be further described with reference to the accompanying drawings and examples, but not with
Any mode limits the present invention.
Embodiment 1：
(a) preparation of GO/LDH compounds
A certain amount of GO is scattered in ethylene glycol, makes its concentration be 1.0mg/mL, ultrasonic disperse 1 hour, 3000rpm centrifugations
10min removes unstripped GO, the GO dispersion liquids peeled off, dispersion liquid 20mL is taken, by 3：1 mol ratio adds thereto
Nickel dichloride hexahydrate and ferric chloride hexahydrate, it is 0.04mol/L to make metal ion total concentration, and stirring is completely dissolved it, then
0.6g dodecyl sodium sulfates are slowly added to, it is at the uniform velocity instilled 10mL after all dissolving under stirring condition and contains 0.16g NaOH
Ethylene glycol solution, by the mixed liquor move into reactor in, in 180 DEG C react 24h, reaction solution centrifuge after, spend respectively
Ionized water and ethanol washing are GO/LDH compounds after drying three times；
(b) preparation of rGO/LDH VPO catalysts
The GO/LDH compounds of gained in step (a) are scattered in the aqueous solution, it is 1.0mg/ml to make its concentration, is pipetted
The 100ml solution, it is separately added into the μ L of hydrazine hydrate 50 that mass fraction is 35% and the aqueous ammonium chloride solution that mass fraction is 27%
350 μ L, are transferred in reactor after stirring, and react 1h under the conditions of 180 DEG C, gained solid sample spent after centrifuging from
Sub- water and ethanol washing three times, difunctional VPO catalysts rGO/LDH is obtained after drying.Its average grain diameter is 214nm, and specific surface area is
146.35m2/g。
Embodiment 2：
(a) preparation of GO/LDH compounds
A certain amount of GO is scattered in ethylene glycol, makes its concentration be 0.5mg/mL, ultrasonic disperse 1 hour, 3000rpm centrifugations
10min removes unstripped GO, the GO dispersion liquids peeled off, dispersion liquid 20mL is taken, by 3：1 mol ratio adds thereto
Nickel dichloride hexahydrate and ferric chloride hexahydrate, it is 0.04mol/L to make metal ion total concentration, and stirring is completely dissolved it, then
0.6g dodecyl sodium sulfates are slowly added to, it is at the uniform velocity instilled 10mL after all dissolving under stirring condition and contains 0.16g NaOH
Ethylene glycol solution, by the mixed liquor move into reactor in, in 180 DEG C react 24h, reaction solution centrifuge after, spend respectively
Ionized water and ethanol washing are GO/LDH compounds after drying three times；
(b) preparation of rGO/LDH VPO catalysts
Prepared according to the method and condition of step (b) in embodiment 1.Its average grain diameter is 288nm, and specific surface area is
163.47m2/g。
Embodiment 3：
(a) preparation of GO/LDH compounds
A certain amount of GO is scattered in ethylene glycol, makes its concentration be 1.0mg/mL, ultrasonic disperse 1 hour, 3000rpm centrifugations
10min removes unstripped GO, the GO dispersion liquids peeled off, dispersion liquid 20mL is taken, by 3：1 mol ratio adds thereto
Nickel dichloride hexahydrate and ferric chloride hexahydrate, it is 0.04mol/L to make metal ion total concentration, and stirring is completely dissolved it, then
0.2g dodecyl sodium sulfates are slowly added to, it is at the uniform velocity instilled 10mL after all dissolving under stirring condition and contains 0.16g NaOH
Ethylene glycol solution, by the mixed liquor move into reactor in, in 180 DEG C react 24h, reaction solution centrifuge after, spend respectively
Ionized water and ethanol washing are GO/LDH compounds after drying three times；
(b) preparation of rGO/LDH VPO catalysts
Prepared according to the method and condition of step (b) in embodiment 1.Its average grain diameter is 256nm, and specific surface area is
146.35m2/g。
Embodiment 4：
(a) preparation of GO/LDH compounds
A certain amount of GO is scattered in ethylene glycol, makes its concentration be 1.5mg/mL, ultrasonic disperse 1 hour, 3000rpm centrifugations
10min removes unstripped GO, the GO dispersion liquids peeled off, dispersion liquid 20mL is taken, by 3：1 mol ratio adds thereto
Nickel dichloride hexahydrate and ferric chloride hexahydrate, it is 0.04mol/L to make metal ion total concentration, and stirring is completely dissolved it, then
0.6g dodecyl sodium sulfates are slowly added to, it is at the uniform velocity instilled 10mL after all dissolving under stirring condition and contains 0.16g NaOH
Ethylene glycol solution, by the mixed liquor move into reactor in, in 180 DEG C react 24h, reaction solution centrifuge after, spend respectively
Ionized water and ethanol washing are GO/LDH compounds after drying three times；
(b) preparation of rGO/LDH VPO catalysts
Prepared according to the method and condition of step (b) in embodiment 1.Its average grain diameter is 210nm, and specific surface area is
132.63m2/g.Its average grain diameter is 236nm, specific surface area 146.35m2/g。
Comparative example 1：
(a) preparation of LDH hybrids
3 are pressed into 20mL deionized waters：1 mol ratio adds Nickel dichloride hexahydrate and ferric chloride hexahydrate, make metal from
Sub- total concentration is 0.04mol/L, and stirring is completely dissolved it, is then slowly added into 0.6g dodecyl sodium sulfates, stirring condition
Under make its all dissolving after at the uniform velocity instill the ethylene glycol solution that 10mL contains 0.16g NaOH, by the mixed liquor move into reactor
In, 24h is reacted in 180 DEG C, after reaction solution centrifuges, is washed three times with deionized water and ethanol respectively, is LDH after drying
Hybrid.
Comparative example 2：
(a) preparation of GO/LDH compounds
A certain amount of GO is scattered in ethylene glycol, makes its concentration be 1.0mg/mL, ultrasonic disperse 1 hour, 3000rpm centrifugations
10min removes unstripped GO, the GO dispersion liquids peeled off, dispersion liquid 20mL is taken, by 3：1 mol ratio adds thereto
Nickel dichloride hexahydrate and ferric chloride hexahydrate, it is 0.04mol/L to make metal ion total concentration, and stirring is completely dissolved it, then
0.6g dodecyl sodium sulfates are slowly added to, it is at the uniform velocity instilled 10mL after all dissolving under stirring condition and contains 0.16g NaOH
Ethylene glycol solution, by the mixed liquor move into reactor in, in 180 DEG C react 24h, reaction solution centrifuge after, spend respectively
Ionized water and ethanol washing are GO/LDH compounds after drying three times.
Fig. 1 is the scanning electron microscope (SEM) photograph (a) and transmission electron microscope picture (b) of the gained rGO/LDH compounds of embodiment 4.From figure (a)
As can be seen that in the case where surface-active forms reversed micelle template action, GO nanometer sheets and metal ion in micella interfacial assembly, with
GO and LDH is continuously increased, acted on by Micellar Gel, form the spherical classification nanostructure of three-dimensional order.From figure (b)
In then as can be seen that formed three-dimensional order rGO/LDH spherical nanoparticles be made up of the rGO of countless small LDH nanometer sheets,
There is obvious roughness on surface, and has many spaces among spherical particle, and it is porous nano particle to show this bead, so as to be in
Higher specific surface area is showed.
Fig. 2 is the gained rGO/LDH compounds of embodiment 4 and the gained LDH of comparative example 1 XRD spectrum.There is class water in LDH
The characteristic peak of talcum, illustrate that NiFe LDH crystal is successfully prepared, but due to its hexagonal piece growth pattern non-planar, but with
Graphene oxide layer is the different growth type of plane, so its (003) peak peak intensity is smaller.And (003) of rGO/LDH compounds
Peak intensity dramatically increases, and is attached to mainly due to rGO thin slices on LDH crystal faces, causes the LDH regular crystal forms degree of incorgruous stacking to obtain
Improvement has been arrived, so as to which peak intensity strengthens, rGO/LDH successful preparation, and the diffraction maximum without obvious rGO in figure has been illustrated, is
Because rGO is compound with LDH progress in a manner of thin slice, not with the presence of caused by the rGO for stacking state of aggregation.
Embodiment 5：
The catalyst of 10mg embodiments 4, comparative example 1 and the gained of comparative example 2 is scattered in 400 μ L ethanol and 20 μ L respectively
In polytetrafluoroethylsolution solution, after ultrasound mixes solution, 15 μ L slurry drops are taken to be applied to 1 × 1cm2On foam nickel electrode, treat that its is complete
Tabletting determines its OER electrocatalysis characteristic on CHI660D electrochemical workstations after drying；Similarly, respectively by 10mg embodiments
4th, the catalyst of comparative example 1 and the gained of comparative example 2 is scattered in 400 μ L ethanol and 15 μ L Nafion solutions, and ultrasound mixes molten
After liquid, 2 μ L slurry drops are taken to be applied to rotating ring disk electrode (r.r.d.e) (RRDE, 0.1256cm2) on, in CHI660D electricity after it is completely dried
Its ORR electrocatalysis characteristic is determined on chem workstation.
Using saturation Ag/AgCl electrodes as reference electrode, Pt electrodes are that sweeping speed is to electrode for above-mentioned electrocatalysis characteristic test
10mV/s, electrolyte need to carry out N for electrolyte before 0.1M KOH, OER catalytic performance tests2Saturated process, ORR catalytic performances are surveyed
Need to carry out O before examination2Saturated process.RDE test results are after Koutecky-Levich formula manipulation, by the K-L slopes of curve
(B) electron transfer number (n) can be calculated.
J-1=Jk -1+(Bω1/2)-1
B=0.62n F C0D0 2/3v1/6
Wherein F=96485C/mol, C0=1.2 × 10-3Mol/L, D0=1.9 × 10-5cm2/ s, v=0.01cm2/s。
RRDE test results can obtain electron transfer number (n) and H by following formula manipulation2O2Content：
N=4Id·(Id+Ir/N)
%H2O2=200Id/N·(Id+Ir/ N),
Wherein N=0.43.
Fig. 3 is the gained rGO/LDH compounds of embodiment 4, the gained LDH of comparative example 1, the gained GO/LDH of comparative example 2 modifications Ni
The linear volt-ampere curve figures of the OER of foam electrode and naked Ni foam electrodes.The starting of naked Ni foam electrodes is excessively electric as shown in the figure
Position is 396mV, and after LDH combined oxidation graphenes, OER starting overpotentials are down to 271mV by LDH 306mV, then pass through reduction
After agent processing, rGO/LDH starting overpotential is down to 209mV.Meanwhile when current density is 10mA/cm2When, rGO/LDH, GO/
Overpotential corresponding to LDH, LDH and naked Ni foam electrodes is respectively 140,158,194 and 310mV.As a result show that LDH passes through
RGO's is compound, significantly reduces its overpotential, this be mainly due to the LDH composite material conductives ability after compound rGO and
Electro-catalysis ability is obviously improved.
Fig. 4 is that the gained rGO/LDH compounds of embodiment 4 modify Ni foam electrodes in 10mA/cm2Under constant current test
Figure.As illustrated, by 9h continuous analysis oxygen process, rGO/LDH OER current potentials only there occurs minor variations, this mainly by
In the lasting precipitation of oxygen bubbles, the rGO/LDH catalyst of electrode surface is constantly impacted, so as to cause the micro of material to come off,
As can be seen here, rGO/LDH modification Ni foam electrodes good OER catalytic stabilities are shown in alkaline solution, have compared with
Long service life.
Fig. 5 is the gained rGO/LDH compounds of embodiment 4, the gained LDH of comparative example 1 and the gained GO/LDH of comparative example 2 modifications
The RDE linear volt-ampere curve figures of ORR.As illustrated, the compound GO of LDH, again after reducing agent is handled, catalyst rGO/LDH is to ORR
Take-off potential shuffled, Limited diffusion current density is also by -2.345mA/cm2Increase to -4.051mA/cm2, it is possible thereby to
Infer：RGO presence significantly improves the electronics conduction efficiency of rGO/LDH compounds, shows as in ORR steady-state process,
Current density has obtained significant increase, it is achieved thereby that the enhancing of ORR catalytic performances.
Fig. 6 is the kinetic parameter that the gained rGO/LDH compounds of embodiment 4 are obtained by the RDE ORR research institutes carried out.Knot
Fruit shows that electron transfer number mesh is about 3.6 in the ORR catalytic process, close to without H2O24 electronic transfer process of product, so as to say
The ORR processes of bright rGO/LDH modified electrodes catalysis are 4 ideal electron reaction mechanism.
Fig. 7 is the kinetic parameter that the gained rGO/LDH compounds of embodiment 4 are obtained by the RRDE ORR research institutes carried out.Knot
Fruit shows that electron transfer number mesh is about 3.6 in the ORR catalytic process, consistent with RDE test results, and 2 electron reactions are gone through
The H of journey2O2Product maintains less than 25% always, and it is 4 ideal electron reaction mechanism to further illustrate the ORR processes,
RGO/LDH VPO catalysts have good ORR catalytic activity.
Fig. 8 is constant voltage I-t test chart of the gained rGO/LDH compounds of embodiment 4 when 0.6V.As illustrated, anaerobic
RGO/LDH modified electrodes start logical oxygen without obvious operating current in environment after 20min, and response current is gradually lifted, this explanation
There occurs ORR reactions, and total overall reaction is ORR processes, and during about 2h ORR, its electric current has almost no change, and says
Bright rGO/LDH has good stability, and good catalytic activity can be kept in the long-term use of fuel cell, is instilling 1M
(1mL is instilled after methanol in about 50mL electrolyte), for using 20wt%Pt/C electrode currents decay 38% compared to business, rGO/
The current attenuation of LDH modified electrodes shows that rGO/LDH has the methanol tolerance interference better than commercialization noble metal electrode less than 10%
Performance, it can be used as the decorative material of pluralities of fuel cell cathode.
Claims (4)
1. a kind of difunctional VPO catalysts of graphene/nickel iron houghite, it is characterised in that the catalyst is using micella as mould
Plate, under hydrothermal conditions, ferronickel houghite is first assembled into formation graphene oxide/ferronickel houghite on graphene oxide
Compound, is then reduced to form the spherical nano-complex of graphene/nickel iron houghite, and the graphene oxide is designated as
GO, graphene are designated as rGO, and ferronickel houghite is designated as LDH, and graphene oxide/ferronickel houghite is designated as GO/LDH, graphite
Alkene/ferronickel houghite is designated as rGO/LDH；
The preparation method of the difunctional VPO catalysts of graphene/nickel iron houghite, it is characterised in that including walking in detail below
Suddenly：
(a) preparation of GO/LDH compounds
A certain amount of GO is scattered in ethylene glycol, makes its concentration be 1.0~1.5mg/mL, ultrasonic disperse 1 hour, 3000rpm from
Heart 10min removes unstripped GO, and the GO dispersion liquids peeled off take dispersion liquid 20mL, added thereto by certain mol proportion
Enter Nickel dichloride hexahydrate and ferric chloride hexahydrate, it is 0.04mol/L to make metal ion total concentration, and stirring is completely dissolved it, so
After be slowly added to 0.2~0.6g dodecyl sodium sulfates, it is all at the uniform velocity instilled 10mL and is contained after dissolving under stirring condition
0.16g NaOH ethylene glycol solution, the mixed liquor is moved into reactor, 24h is reacted in 180 DEG C, reaction solution centrifuges
Afterwards, washed three times with deionized water and ethanol respectively, be GO/LDH compounds after drying；
(b) preparation of rGO/LDH VPO catalysts
The GO/LDH compounds of gained in step (a) are scattered in the aqueous solution, it is 1mg/ml to make its concentration, and pipetting 100ml should
Solution, the μ L of hydrazine hydrate 50 that mass fraction is 35% and the μ L of aqueous ammonium chloride solution 350 that mass fraction is 27% are separately added into, is stirred
It is transferred to after mixing uniformly in reactor, 1h is reacted under the conditions of 180 DEG C, gained solid sample uses deionized water and second after centrifuging
Alcohol is washed three times, and difunctional VPO catalysts rGO/LDH is obtained after drying.
A kind of 2. difunctional VPO catalysts of graphene/nickel iron houghite according to claim 1, it is characterised in that step
(a) mol ratio of Nickel dichloride hexahydrate described in and ferric chloride hexahydrate is 3：1.
A kind of 3. difunctional VPO catalysts of graphene/nickel iron houghite according to claim 1 or 2, it is characterised in that
The catalyst is in hollow ball-shape, and average grain diameter is 210~290nm, and specific surface area is in 132.63~186.64m2/g。
A kind of 4. difunctional VPO catalysts of graphene/nickel iron houghite according to claim 1 or 2, it is characterised in that
The catalyst is used for the reaction of electrolyzed alkaline water Oxygen anodic evolution and fuel battery negative pole oxygen reduction reaction.
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Inventor after: Zhan Tianrong Inventor after: Tian Xia Inventor after: Wang Zhiwei Inventor after: Zhang Yumei Inventor before: Zhan Tianrong Inventor before: Zhang Yumei Inventor before: Liu Xiaolin |
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Effective date of registration: 20190312 Address after: 230000 B-1512, west of Ganquan Road, Shushan District, Hefei, Anhui. Patentee after: Anhui Eagle Dragon Industrial Design Co., Ltd. Address before: 266000 Qingdao University of Science & Technology, 53 Zhengzhou Road, Shibei District, Qingdao, Shandong Patentee before: Qingdao University of Science & Technology |
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Effective date of registration: 20191217 Address after: Yaolin town forest farm, Tonglu County, Hangzhou City, Zhejiang Province Patentee after: Hangzhou xinlingfeng Lubricating Oil Co., Ltd Address before: Ganquan road Shushan District of Hefei City, Anhui Province, 230000 West hillock road to the South Wild Garden commercial office building room B-1512 Patentee before: Anhui Eagle Dragon Industrial Design Co., Ltd. |
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Granted publication date: 20171117 Termination date: 20201220 |