CN106807427A - A kind of embedded porous nitrogen phosphorus doping carbon material of transition metal and its preparation method and application - Google Patents
A kind of embedded porous nitrogen phosphorus doping carbon material of transition metal and its preparation method and application Download PDFInfo
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- CN106807427A CN106807427A CN201710046677.2A CN201710046677A CN106807427A CN 106807427 A CN106807427 A CN 106807427A CN 201710046677 A CN201710046677 A CN 201710046677A CN 106807427 A CN106807427 A CN 106807427A
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- transition metal
- carbon material
- agar
- phosphorus doping
- nitrogen phosphorus
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- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 33
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 32
- YUWBVKYVJWNVLE-UHFFFAOYSA-N [N].[P] Chemical compound [N].[P] YUWBVKYVJWNVLE-UHFFFAOYSA-N 0.000 title claims abstract description 31
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 57
- 229920001817 Agar Polymers 0.000 claims abstract description 45
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 43
- 239000008272 agar Substances 0.000 claims abstract description 40
- 239000003054 catalyst Substances 0.000 claims abstract description 29
- 229910052698 phosphorus Inorganic materials 0.000 claims abstract description 24
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000011574 phosphorus Substances 0.000 claims abstract description 22
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 15
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 12
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims abstract description 8
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims abstract description 8
- 230000008569 process Effects 0.000 claims abstract description 8
- 125000000383 tetramethylene group Chemical group [H]C([H])([*:1])C([H])([H])C([H])([H])C([H])([H])[*:2] 0.000 claims abstract description 8
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 6
- 239000000834 fixative Substances 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 17
- 238000010438 heat treatment Methods 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 16
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 15
- 239000001301 oxygen Substances 0.000 claims description 15
- 229910052760 oxygen Inorganic materials 0.000 claims description 15
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 14
- 239000012153 distilled water Substances 0.000 claims description 14
- 239000007789 gas Substances 0.000 claims description 11
- 239000000463 material Substances 0.000 claims description 11
- 229910052759 nickel Inorganic materials 0.000 claims description 11
- 238000006722 reduction reaction Methods 0.000 claims description 11
- 229910052742 iron Inorganic materials 0.000 claims description 10
- 239000000499 gel Substances 0.000 claims description 7
- 230000009467 reduction Effects 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- 230000001681 protective effect Effects 0.000 claims description 6
- 238000004108 freeze drying Methods 0.000 claims description 5
- 229910052751 metal Inorganic materials 0.000 claims description 5
- 239000002184 metal Substances 0.000 claims description 5
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 239000012467 final product Substances 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 239000011572 manganese Substances 0.000 claims description 4
- 150000003839 salts Chemical class 0.000 claims description 4
- 230000006641 stabilisation Effects 0.000 claims description 4
- 238000011105 stabilization Methods 0.000 claims description 4
- 229910002651 NO3 Inorganic materials 0.000 claims description 3
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- 239000000446 fuel Substances 0.000 claims description 3
- 239000001307 helium Substances 0.000 claims description 3
- 229910052734 helium Inorganic materials 0.000 claims description 3
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 claims description 3
- 239000000017 hydrogel Substances 0.000 claims description 3
- 239000007769 metal material Substances 0.000 claims description 3
- 239000000843 powder Substances 0.000 claims description 3
- 239000012266 salt solution Substances 0.000 claims description 3
- 238000005406 washing Methods 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 230000008859 change Effects 0.000 claims description 2
- 230000015271 coagulation Effects 0.000 claims description 2
- 238000005345 coagulation Methods 0.000 claims description 2
- 239000007772 electrode material Substances 0.000 claims description 2
- 238000007710 freezing Methods 0.000 claims description 2
- 230000008014 freezing Effects 0.000 claims description 2
- 238000012545 processing Methods 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 14
- 238000005087 graphitization Methods 0.000 abstract description 8
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 239000002994 raw material Substances 0.000 abstract description 3
- 229910001030 Iron–nickel alloy Inorganic materials 0.000 description 28
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 description 9
- 230000000694 effects Effects 0.000 description 7
- 239000000047 product Substances 0.000 description 5
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 4
- 239000001257 hydrogen Substances 0.000 description 4
- 229910052739 hydrogen Inorganic materials 0.000 description 4
- 238000006555 catalytic reaction Methods 0.000 description 3
- 239000002086 nanomaterial Substances 0.000 description 3
- 235000006408 oxalic acid Nutrition 0.000 description 3
- 239000011148 porous material Substances 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 238000012360 testing method Methods 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000001588 bifunctional effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000009826 distribution Methods 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 239000003292 glue Substances 0.000 description 2
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 2
- KBJMLQFLOWQJNF-UHFFFAOYSA-N nickel(ii) nitrate Chemical compound [Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O KBJMLQFLOWQJNF-UHFFFAOYSA-N 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- UMPKMCDVBZFQOK-UHFFFAOYSA-N potassium;iron(3+);oxygen(2-) Chemical compound [O-2].[O-2].[K+].[Fe+3] UMPKMCDVBZFQOK-UHFFFAOYSA-N 0.000 description 2
- 238000004064 recycling Methods 0.000 description 2
- 238000002336 sorption--desorption measurement Methods 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 230000007704 transition Effects 0.000 description 2
- 238000001291 vacuum drying Methods 0.000 description 2
- 229910016874 Fe(NO3) Inorganic materials 0.000 description 1
- 229910021380 Manganese Chloride Inorganic materials 0.000 description 1
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 230000010757 Reduction Activity Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- NNBFNNNWANBMTI-UHFFFAOYSA-M brilliant green Chemical compound OS([O-])(=O)=O.C1=CC(N(CC)CC)=CC=C1C(C=1C=CC=CC=1)=C1C=CC(=[N+](CC)CC)C=C1 NNBFNNNWANBMTI-UHFFFAOYSA-M 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 description 1
- 229910001981 cobalt nitrate Inorganic materials 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000002079 cooperative effect Effects 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 125000005842 heteroatom Chemical group 0.000 description 1
- 150000002500 ions Chemical group 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 239000010977 jade Substances 0.000 description 1
- 235000002867 manganese chloride Nutrition 0.000 description 1
- 239000011565 manganese chloride Substances 0.000 description 1
- 229940099607 manganese chloride Drugs 0.000 description 1
- 229940099596 manganese sulfate Drugs 0.000 description 1
- 235000007079 manganese sulphate Nutrition 0.000 description 1
- 239000011702 manganese sulphate Substances 0.000 description 1
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical compound [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 description 1
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- AOPCKOPZYFFEDA-UHFFFAOYSA-N nickel(2+);dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O AOPCKOPZYFFEDA-UHFFFAOYSA-N 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000037361 pathway Effects 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010970 precious metal Substances 0.000 description 1
- 150000003222 pyridines Chemical class 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- -1 transition metal salt Chemical class 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
- H01M4/9075—Catalytic material supported on carriers, e.g. powder carriers
- H01M4/9083—Catalytic material supported on carriers, e.g. powder carriers on carbon or graphite
-
- 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 invention provides a kind of embedded porous nitrogen phosphorus doping carbon material of transition metal, it is using agar as carbon source, simultaneously as the fixative of metal ion, ethylenediamine tetramethylene phosphoric acid (EDTMPA) is nitrogen, phosphorus source, obtained microporous mesoporous structure is simultaneously deposited, and metallic equally distributed porous nitrogen phosphorus doping carbon material in carbon carrier.Relative to prior art, preparation method of the present invention is simple, the cost of raw material is low, and the specific surface area of nitrogen, the doping efficiency of phosphorus and catalyst nanoparticles can be effectively improved, obtained porous nitrogen phosphorus doping carbon material has surface-active area higher, degree of graphitization higher, current density when catalyst reacts can be effectively improved, excellent electro catalytic activity is shown with dynamics process faster.
Description
Technical field
The invention discloses embedded porous nitrogen phosphorus doping carbon material of a kind of transition metal and its preparation method and application, category
In doping type carbon nanomaterial technical field.
Background technology
Demand with the energy increasingly increases, and people are also gradually increasing to the attention rate of regenerative resource.Hydrogen is used as one
The renewable and clean energy resource of high-energy-density is planted, substitute fossil fuels is expected to as a kind of novel energy.In view of preparing hydrogen
Cost and purity, current maximally effective method is photocatalytic water.However, the yield of hydrogen is analysed by its crucial half-reaction-oxygen
Go out what reaction (OER) was determined.OER is an extremely slow process of dynamics process, it is necessary to catalyst accelerates reaction and reduces
Overpotential, so as to obtain energy conversion efficiency higher.In the past few decades, noble metal catalyst such as RuO2、IrO2Recognized
To be active highest OER catalyst, but they are expensive and reserves are rare, limit its commercial applications, therefore people
It is sought for the element of some rich reserves and is prepared into catalyst.
In these catalyst, iron, cobalt, nickel, manganese have activity relatively higher.But this kind of transition elements of iron, cobalt, nickel, manganese
The electric conductivity of the compound of formation is unsatisfactory, while relatively low specific surface area also limit its further development.It is near several
Some of year report that the heteroatomic doping such as nitrogen, phosphorus can further lift the electro catalytic activity of non-precious metal catalyst, and
With carbon material as carrier, the electric conductivity of transition element compound can be improved, reach the purpose of the current density for improving catalyst.
But at present, research related in the prior art still suffers from some defects, such as nitrogen, phosphorus doping efficiency it is low, it is made
Material electrocatalysis characteristic difference for obtaining etc..
The content of the invention
Goal of the invention：For above-mentioned technical problem, the invention provides a kind of embedded porous nitrogen phosphorus doping of transition metal
Carbon material and its preparation method and application.
Technical scheme：To achieve the above object of the invention, mixed the invention provides a kind of embedded porous nitrogen phosphorus of transition metal
Miscellaneous carbon material, it is using agar as carbon source, while as the fixative of metal ion, ethylenediamine tetramethylene phosphoric acid
(EDTMPA) it is nitrogen, phosphorus source, obtained microporous mesoporous structure is simultaneously deposited, and metallic is equally distributed porous in carbon carrier
Nitrogen phosphorus doping carbon material.
It is preferred that, the transition metal be iron, cobalt, nickel, manganese in one or several.
It is present invention also offers the preparation method of the embedded porous nitrogen phosphorus doping carbon material of the transition metal including following
Step：Transition metal and ethylenediamine tetramethylene phosphoric acid are formed the complex of stabilization, recycling agar can be miscible with water, and
The characteristic of stabilization hydrogel can be formed, complex is fixed in agar gel, then frozen drying, high temperature thermal reduction
The carbon-supported metal material of nitrogen, phosphorus doping is prepared, the porous nitrogen phosphorus doping carbon material is obtained final product.
It is preferred that, the preparation method of the embedded porous nitrogen phosphorus doping carbon material of transition metal is comprised the following steps：
(1) salt of transition metal is dissolved in distilled water and forms solution；
(2) to the excessive ethylenediamine tetramethylene phosphoric acid solution of addition in metal salt solution obtained in step (1)；
(3) preparation of aqueous agar solution：By in agar powder or agar strip addition distilled water, micro-boiling, stirring to fine jade are heated to
Fat is completely dissolved, and stops heating, agar solution temperature is maintained at 40-100 DEG C；
(4) by the agar solution of obtained solution addition step (3) in step (2), treat that its natural coagulation forms gel,
Then obtained gel is carried out into freeze-drying process；
(5) agar gel in step (4) by freezing processing is carried out into high-temperature heat treatment, and is continually fed into protection gas
Body, carbonization, centrifuge washing obtains final product the material.
Further preferably, the salt of transition metal is the nitrate of transition metal in the step (1).
Further preferably, the content of nitrogen and phosphorus is controlled in 5-80% in the final resulting solution of the step (2).
Further preferably, in the step (3) agar and distilled water mass ratio (1-80)：100.
Further preferably, freeze-drying uses freeze drier in the step (4), and the temperature of freeze drier is -10
~-55 DEG C, air pressure is≤150Pa.
Further preferably, the condition of step (5) the high temperature heat treatment is：With the heating rate liter of 1~10 DEG C/min
To 400~1000 DEG C, protective gas 30~200mL/min of flow velocity is incubated 2~6h；Protective gas is in nitrogen, argon gas, helium
One or several gases for mixing in any proportion.
The present invention finally there is provided the application of the embedded porous nitrogen phosphorus doping carbon material of the transition metal, make by the material
For electrode material is used for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalyst, i.e., for decomposition water reaction and fuel electricity
The catalyst in pond.With commercialization RuO2Porous nano particle with the nitrogen that undopes, phosphorus is compared, porous nitrogen-phosphor codoping transition metal
Nano material shows activity higher in oxygen evolution reaction, is embodied in lower overpotential and bigger electric current is close
Degree, and be a kind of bifunctional catalyst with good oxygen reduction activity.
With agar as carbon source, ethylenediamine tetramethylene phosphoric acid (EDTMPA) is nitrogen, phosphorus source to the present invention, and transition metal salt is preceding
Body and pore creating material are driven, transition metal is formed into stable complex by with EDTMPA, recycling agar can be miscible with water,
40-100 DEG C of the characteristic that can form stabilization hydrogel, complex is fixed in agar gel；Frozen drying, high temperature
Thermal reduction prepares the carbon-supported metal material of nitrogen, phosphorus doping.Carbon-supported metal nano material prepared by the inventive method has many
Unique architectural feature such as hole, high-specific surface area, high graphitization degree, Heteroatom doping, to oxygen evolution reaction (OER) and oxygen also
Original reaction (ORR) shows catalysis activity higher, can be used for decomposition water reaction and fuel cell.Wherein loose structure is catalysis
Agent provides sufficiently large specific surface area, creates more avtive spots, is conducive to reactant more fully to be connect with catalyst
Touch, shorten the time that reaction needs, accelerate reaction process.
The advantage of the invention is that：Using agar as carbon source and fixative, it is capable of the metal ion of fixed ion form,
So that the dispersiveness of metallic is more preferable in high-temperature heat treatment；By the way of freeze-drying, the physics knot of gel is not destroyed
Structure；Using the coordination of EDTMPA and metal ion, make there is chemical bond between nitrogen phosphorus source and metal, improve nitrogen, phosphorus and mix
Miscellaneous efficiency；The slaine for using is nitrate, the effect with pore creating material, it is possible to increase the specific surface of catalyst nanoparticles
Product.With the commercialization RuO purchased from Aladdin reagent net2Compared with NiFe/C catalyst, with oxygen evolution reaction activity higher.
Specifically include：
With agar as carbon source and metal ion fixative, porous nitrogen-phosphor codoping transition metal is prepared by Gel Pathway and is received
Rice material has surface-active area higher, degree of graphitization higher, can effectively improve electricity when catalyst reacts
Current density.
Result shows obtained porous N, and P-NiFe/C nano particles are in oxygen evolution reaction (OER) and oxygen reduction reaction
(ORR) excellent electro catalytic activity and dynamics process faster are shown in, is good bifunctional catalyst.
Preparation method of the invention is simple, and raw material are cheap, is adapted to industrial mass production.
Technique effect：Relative to prior art, preparation method of the present invention is simple, and the cost of raw material is low, and can effectively carry
The specific surface area of nitrogen high, the doping efficiency of phosphorus and catalyst nanoparticles, obtained porous nitrogen phosphorus doping carbon material has
Surface-active area, degree of graphitization higher higher, can effectively improve current density when catalyst reacts, and represent
Go out excellent electro catalytic activity with dynamics process faster.
Brief description of the drawings
Fig. 1 is porous N prepared in accordance with the present invention, the transmission electron microscope figure spectrum of P-NiFe/C nano particles.
Fig. 2 is porous N prepared in accordance with the present invention, the scanning electron microscope diagram spectrum of P-NiFe/C nano particles.
Fig. 3 is the X ray diffracting spectrum of porous N, P-NiFe/C and NiFe/C prepared in accordance with the present invention.
Fig. 4 is porous N prepared in accordance with the present invention, the X-ray photoelectron spectroscopic analysis (XPS) of P-NiFe/C nano particles
Collection of illustrative plates.
Fig. 5 is the porous N of preparation under different temperatures, the Raman spectrogram of P-NiFe/C nano particles.
Fig. 6 is porous N prepared in accordance with the present invention, the graph of pore diameter distribution of P-NiFe/C nano particles.
Fig. 7 is porous N prepared in accordance with the present invention, the adsorption desorption curve map of P-NiFe/C nano particles.
Fig. 8 is porous N prepared in accordance with the present invention, P-NiFe/C, NiFe/C, pure agar, commercialization RuO2Oxygen separate out
Reaction (OER) curve map.
Fig. 9 is porous N prepared in accordance with the present invention, P-NiFe/C, NiFe/C, pure agar, commercialization RuO2Tafel it is bent
Line chart.
Figure 10 is porous N prepared in accordance with the present invention, P-NiFe/C rotating speed be 100,400,900,1600,2500rpm
Under the conditions of oxygen reduction reaction (ORR) curve map
Specific embodiment
Below in conjunction with the accompanying drawings and instantiation, the present invention is furture elucidated, it should be understood that these embodiments are merely to illustrate this
Rather than limitation the scope of the present invention, after the present invention has been read, those skilled in the art are to of the invention various etc. for invention
The modification of valency form falls within the application appended claims limited range.
Embodiment 1：
(1) accurate a certain amount of Nickelous nitrate hexahydrate and Fe(NO3)39H2O (two kinds of slaines), are dissolved in distilled water
In.
(2) in metal salt solution add EDTMPA solution, formed clear emerald green solution, make nitrogen therein and
The content of phosphorus is controlled in 5-80%.
(3) by agar powder in beaker, the mass ratio (1-80) of distilled water, agar and distilled water is added：100, it is heated to
90 DEG C of agar are completely dissolved.
(4) by step (2) resulting solution addition agar solution, stirring, room temperature natural cooling forms gel.It is put into refrigerator
Pre-freeze, places into freeze drier vacuum drying, forms dry glue.Wherein freeze drier condition is：The temperature of freeze drier-
55 DEG C, air pressure is 80Pa.
(5) step (4) gained dry glue is put into tube furnace, in the heat treatment of inert atmosphere high temperature.Wherein, high temperature furnace treatment
Manage bar part is：In high temperature furnace, 750 DEG C are risen to the heating rate of 5 DEG C/min, nitrogen flow rate 30mL/min is incubated 3h；
(6) product centrifuge washing will be obtained after heat treatment, after vacuum drying, obtains pure porous N, P-NiFe/C nanometers
Grain, porous nitrogen phosphorus doping carbon material as of the present invention.
Embodiment 2
Same as Example 1, difference is that slaine used is nickel nitrate.
Embodiment 3
Same as Example 1, difference is that slaine used is that three oxalic acid close potassium ferrite.
Embodiment 4
Same as Example 1, difference is that slaine used is cobaltous sulfate.
Embodiment 5
Same as Example 1, difference is that slaine used is manganese chloride.
Embodiment 6
Same as Example 1, difference is that slaine used is nickel nitrate and cobaltous sulfate.
Embodiment 7
Same as Example 1, difference is that slaine used is that three oxalic acid close potassium ferrite and manganese sulfate.
Embodiment 8
Same as Example 1, difference is that slaine used is that three oxalic acid close nickel acid potassium and manganese nitrate.
Embodiment 9
Same as Example 1, difference is that slaine used is ferric nitrate and cobalt nitrate.
Embodiment 10
Same as Example 1, difference is as follows：
The content of nitrogen and phosphorus is controlled 5% in step (2) resulting solution；
The mass ratio 1 of agar and distilled water in step (3)：100, it is heated to 40-100 DEG C of agar and is completely dissolved；
- 10 DEG C of the temperature of freeze drier in step (4), air pressure is 10Pa；
Step (5) high temperature furnace treatment manage bar part is：In high temperature furnace, 400 DEG C are risen to the heating rate of 1 DEG C/min,
Nitrogen flow rate 30mL/min, is incubated 2h.
Embodiment 11
Same as Example 2, difference is as follows：
The content of nitrogen and phosphorus is controlled 80% in step (2) resulting solution；
The mass ratio 80 of agar and distilled water in step (3)：100, it is heated to 100 DEG C of agar and is completely dissolved；
- 55 DEG C of the temperature of freeze drier in step (4), air pressure is 150Pa；
Step (5) high temperature furnace treatment manage bar part is：In high temperature furnace, 1000 are risen to the heating rate of 10 DEG C/min
DEG C, nitrogen flow rate 200mL/min is incubated 6h.
Embodiment 12
Same as Example 3, difference is as follows：
The content of nitrogen and phosphorus is controlled 42% in step (2) resulting solution；
The mass ratio 40 of agar and distilled water in step (3)：100, it is heated to 70 DEG C of agar and is completely dissolved；
- 22 DEG C of the temperature of freeze drier in step (4), air pressure is 80Pa；
Step (5) high temperature furnace treatment manage bar part is：In high temperature furnace, 700 DEG C are risen to the heating rate of 5 DEG C/min,
Nitrogen flow rate 165mL/min, is incubated 4h.
Embodiment 13
Same as Example 4, difference is as follows：
The content of nitrogen and phosphorus is controlled 70% in step (2) resulting solution；
The mass ratio 60 of agar and distilled water in step (3)：100, it is heated to 80 DEG C of agar and is completely dissolved；
- 45 DEG C of the temperature of freeze drier in step (4), air pressure is 130Pa；
Step (5) high temperature furnace treatment manage bar part is：In high temperature furnace, 900 DEG C are risen to the heating rate of 8 DEG C/min,
Nitrogen flow rate 180mL/min, is incubated 5h.
Embodiment 14
Same as Example 5, difference is as follows：
The content of nitrogen and phosphorus is controlled 15% in step (2) resulting solution；
The mass ratio 10 of agar and distilled water in step (3)：100, it is heated to 80 DEG C of agar and is completely dissolved；
- 15 DEG C of the temperature of freeze drier in step (4), air pressure is 20Pa；
Step (5) high temperature furnace treatment manage bar part is：In high temperature furnace, 500 DEG C are risen to the heating rate of 3 DEG C/min,
Nitrogen flow rate 50mL/min, is incubated 3h.
Embodiment 15
Similar to Example 6, difference is in step 5, protective atmosphere is argon gas.
Embodiment 16
Similar to Example 7, difference is in step 5, protective atmosphere is helium.
Properties of product are detected：
Porous N prepared in accordance with the present invention, P-NiFe/C nano particles pattern is as shown in Figure 1, 2, it can be observed that substantially
Loose structure and dispersed particle.Metallic is evenly distributed in carbon carrier as can be seen from Figure 1, then may be used from Fig. 2
Clearly to find out the loose structure of product so that product has specific surface area very high,
Porous N, P-NiFe/C are with porous NiFe/C (carbon material without nitrogen phosphorus doping prepared by same procedure, similarly hereinafter) such as
Shown in Fig. 3, the change of crystal formation after N, P doping, it was demonstrated that heteroatomic successfully to adulterate.
As shown in figure 4, XPS figures illustrate the present invention preparation porous N, P-NiFe/C really containing N, P, Ni, Fe, C this
Several elements.
As shown in figure 5, according to Raman spectrum test result, spectrogram is in 1596cm-1And 1363cm-1Two peaks are occurred in that, point
Not Dui Ying carbon material G peaks and D peaks, generally use ID/IGRatio weighs the degree of graphitization of material, ID/IGIt is smaller, then material
Degree of graphitization is better.According to N, P-Ni that preparation under the conditions of 750 DEG C is can be seen that in collection of illustrative plates3Fe1The I of/CD/IGRatio is
0.81, illustrate that obtained catalyst has degree of graphitization higher, while ratio (0.92) and 700 of the value compared to 650 DEG C
DEG C ratio (0.87) have reduction, illustrate that, with the rising of temperature, the degree of graphitization of carbon material is also improved.Raman spectrum
The N that figure explanation is prepared, P-NiFe/C is mainly what is be made up of the relatively good graphitic carbon of crystallinity, when being conducive to electrocatalytic reaction
The transmission of electronics, so as to lift the current density of catalyst.
According to pore-size distribution Fig. 6 and adsorption desorption curve map 7, it can be seen that prepared nano particle exist it is microporous mesoporous simultaneously
The structure deposited, and micropore size is 1.6nm or so.N is calculated through DFT, P-NiFe/C has specific surface area higher
716.893m2g-1, be conducive to the lifting of material conductivity, and make catalyst that there are more avtive spots.
The electrocatalysis characteristic of N, P-Ni, Fe/C is characterized by carrying out OER tests in 0.1M KOH.As control,
We also use pure agar, commercialization RuO2, NiFe/C catalyst tested under the same conditions.According to Fig. 8, can see
It is 10mA cm to go out in current density-2When N, P-NiFe/C, commercialization RuO2, NiFe/C, the overpotential of pure agar exist respectively
0.41V, 0.41V, 0.46V and 0.67V.And the current density of N, P-NiFe/C has eventually exceeded commercialization RuO2.Preparing
Cheng Zhong, N are possible to form pyridine type compound with carbon, with sucting electronic effect, so that the current potential required for reducing catalytic reaction.
And the doping of P then changes the original lattice structure of Ni, Fe, this cooperative effect is conducive to the generation that OER reacts, so making to urge
Agent has outstanding OER performances.
According to Fig. 9, it can be seen that the Tafel slopes of N, P-Ni, Fe/C are less than commercialization RuO2, Tafel slopes are smaller, say
Bright dynamics process is faster, clearly demonstrate that porous N, and P-NiFe/C nano particles have better than commercialized catalyst and nitrogen-free
The performance of the NiFe/C catalyst of phosphorus doping.
The hydrogen reduction performance of N, P-Ni, Fe/C is characterized by carrying out ORR tests in 0.1M KOH, is tested respectively
Rotating ring disk electrode (r.r.d.e) rotating speed is respectively 100,400,900,1600, the performance under the conditions of 2500rpm.Be can be seen that according to Figure 10, N,
The initial reduction current potential of P-Ni, Fe/C is 0.868V (vs RHE), belongs to more outstanding non noble metal oxygen reduction catalyst, and
With preferable limiting diffusion current, as fuel-cell catalyst there is certain commercialization to be worth.
Claims (10)
1. the embedded porous nitrogen phosphorus doping carbon material of a kind of transition metal, it is characterised in that its be using agar as carbon source, while
Used as the fixative of metal ion, ethylenediamine tetramethylene phosphoric acid (EDTMPA) is nitrogen, phosphorus source, obtained microporous mesoporous structure
And deposit, and metallic equally distributed porous nitrogen phosphorus doping carbon material in carbon carrier.
2. the embedded porous nitrogen phosphorus doping carbon material of transition metal according to claim 1, it is characterised in that the transition
Metal be iron, cobalt, nickel, manganese in one or several.
3. the preparation method of the embedded porous nitrogen phosphorus doping carbon material of transition metal described in any one of claim 1-2, its feature
It is to comprise the following steps：Transition metal and ethylenediamine tetramethylene phosphoric acid are formed the complex of stabilization, agar energy is recycled
It is enough miscible with water, and the characteristic for stablizing hydrogel can be formed, complex is fixed in agar gel, then low temperature cold is freezed
The carbon-supported metal material of nitrogen, phosphorus doping is prepared in dry, high temperature thermal reduction, obtains final product the porous nitrogen phosphorus doping carbon material.
4. the preparation method of the embedded porous nitrogen phosphorus doping carbon material of transition metal according to claim 3, its feature exists
In comprising the following steps：
(1) salt of transition metal is dissolved in distilled water and forms solution；
(2) to the excessive ethylenediamine tetramethylene phosphoric acid solution of addition in metal salt solution obtained in step (1)；
(3) preparation of aqueous agar solution：By in agar powder or agar strip addition distilled water, micro-boiling is heated to, stirred complete to agar
CL, stops heating, agar solution temperature is maintained at 40-100 DEG C；
(4) by the agar solution of obtained solution addition step (3) in step (2), treat that its natural coagulation forms gel, then
Obtained gel is carried out into freeze-drying process；
(5) agar gel in step (4) by freezing processing is carried out into high-temperature heat treatment, and is continually fed into protective gas, carbon
Change, centrifuge washing obtains final product the material.
5. the preparation method of the embedded porous nitrogen phosphorus doping carbon material of transition metal according to claim 4, its feature exists
In the salt of transition metal is the nitrate of transition metal in the step (1).
6. the preparation method of the embedded porous nitrogen phosphorus doping carbon material of transition metal according to claim 4, its feature exists
In the content of nitrogen and phosphorus is controlled in 5-80% in the final resulting solution of the step (2).
7. the preparation method of the embedded porous nitrogen phosphorus doping carbon material of transition metal according to claim 4, its feature exists
In the mass ratio (1-80) of agar and distilled water in the step (3)：100.
8. the preparation method of the embedded porous nitrogen phosphorus doping carbon material of transition metal according to claim 4, its feature exists
In, freeze-drying uses freeze drier in the step (4), and the temperature of freeze drier is -10~-55 DEG C, air pressure for≤
150Pa。
9. the preparation method of the embedded porous nitrogen phosphorus doping carbon material of transition metal according to claim 4, its feature exists
In the condition of step (5) the high temperature heat treatment is：400~1000 DEG C are risen to the heating rate of 1~10 DEG C/min, is protected
Shield 30~200mL/min of gas flow rate, is incubated 2~6h；Protective gas is pressed for one or several in nitrogen, argon gas, helium
The gas that arbitrary proportion is mixed.
10. the application of the embedded porous nitrogen phosphorus doping carbon material of transition metal described in any one of claim 1-2, its feature exists
In the material is used for oxygen evolution reaction (OER) and oxygen reduction reaction (ORR) catalyst as electrode material, i.e., for decomposing
Water reacts the catalyst with fuel cell.
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