CN110605131A - Three-dimensional nitrogen-doped carbon-based material loaded bimetallic phosphide bifunctional catalyst and preparation method and application thereof - Google Patents
Three-dimensional nitrogen-doped carbon-based material loaded bimetallic phosphide bifunctional catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 80
- 239000003575 carbonaceous material Substances 0.000 title claims abstract description 72
- 230000001588 bifunctional effect Effects 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 31
- 238000000034 method Methods 0.000 claims abstract description 27
- 230000003197 catalytic effect Effects 0.000 claims abstract description 25
- 150000003624 transition metals Chemical class 0.000 claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 21
- 229910052751 metal Inorganic materials 0.000 claims abstract description 20
- 239000002184 metal Substances 0.000 claims abstract description 20
- 238000001035 drying Methods 0.000 claims abstract description 17
- 239000002041 carbon nanotube Substances 0.000 claims abstract description 13
- 229910021393 carbon nanotube Inorganic materials 0.000 claims abstract description 13
- KIMPPGSMONZDMN-UHFFFAOYSA-N sodium;dihydrogen phosphite Chemical compound [Na+].OP(O)[O-] KIMPPGSMONZDMN-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000007853 buffer solution Substances 0.000 claims abstract description 7
- 239000000203 mixture Substances 0.000 claims abstract description 7
- 230000007935 neutral effect Effects 0.000 claims abstract description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims abstract description 7
- 229920000877 Melamine resin Polymers 0.000 claims abstract description 6
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims abstract description 6
- 230000009467 reduction Effects 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 20
- 239000002243 precursor Substances 0.000 claims description 17
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 13
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 10
- 229910021389 graphene Inorganic materials 0.000 claims description 7
- 238000011068 loading method Methods 0.000 claims description 7
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 6
- 230000009286 beneficial effect Effects 0.000 claims description 6
- 238000001816 cooling Methods 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- PVFSDGKDKFSOTB-UHFFFAOYSA-K iron(3+);triacetate Chemical compound [Fe+3].CC([O-])=O.CC([O-])=O.CC([O-])=O PVFSDGKDKFSOTB-UHFFFAOYSA-K 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- 229910021645 metal ion Inorganic materials 0.000 claims description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims description 3
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 3
- 230000002708 enhancing effect Effects 0.000 claims description 3
- 238000011065 in-situ storage Methods 0.000 claims description 3
- 229940071125 manganese acetate Drugs 0.000 claims description 3
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 3
- 239000002071 nanotube Substances 0.000 claims description 3
- 229940078494 nickel acetate Drugs 0.000 claims description 3
- 229910052698 phosphorus Inorganic materials 0.000 claims description 3
- 239000011574 phosphorus Substances 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- 230000002195 synergetic effect Effects 0.000 claims description 3
- 239000011521 glass Substances 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 claims description 2
- 239000002904 solvent Substances 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 6
- 229910052760 oxygen Inorganic materials 0.000 abstract description 6
- 239000001301 oxygen Substances 0.000 abstract description 6
- 230000008569 process Effects 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 238000010923 batch production Methods 0.000 abstract 1
- 238000004140 cleaning Methods 0.000 abstract 1
- 230000035484 reaction time Effects 0.000 abstract 1
- 229910002001 transition metal nitrate Inorganic materials 0.000 abstract 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical compound [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 13
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 12
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(iv) oxide Chemical compound O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 12
- 229910000510 noble metal Inorganic materials 0.000 description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 8
- 238000012360 testing method Methods 0.000 description 6
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 4
- 230000000630 rising effect Effects 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 3
- 239000000446 fuel Substances 0.000 description 3
- DTNVUQFDRPOYFY-UHFFFAOYSA-L nickel(2+);diacetate;hexahydrate Chemical compound O.O.O.O.O.O.[Ni+2].CC([O-])=O.CC([O-])=O DTNVUQFDRPOYFY-UHFFFAOYSA-L 0.000 description 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 208000021251 Methanol poisoning Diseases 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- QXZUUHYBWMWJHK-UHFFFAOYSA-N [Co].[Ni] Chemical compound [Co].[Ni] QXZUUHYBWMWJHK-UHFFFAOYSA-N 0.000 description 2
- POTRNMJIMIESGR-UHFFFAOYSA-L cobalt(2+);diacetate;hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].CC([O-])=O.CC([O-])=O POTRNMJIMIESGR-UHFFFAOYSA-L 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 238000003795 desorption Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000002803 fossil fuel Substances 0.000 description 2
- ZAUUZASCMSWKGX-UHFFFAOYSA-N manganese nickel Chemical compound [Mn].[Ni] ZAUUZASCMSWKGX-UHFFFAOYSA-N 0.000 description 2
- 239000002082 metal nanoparticle Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- 229910052684 Cerium Inorganic materials 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- GMZLXCKOIKUDTO-UHFFFAOYSA-L O.O.O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O Chemical compound O.O.O.O.O.O.[Mn+2].CC([O-])=O.CC([O-])=O GMZLXCKOIKUDTO-UHFFFAOYSA-L 0.000 description 1
- 208000005374 Poisoning Diseases 0.000 description 1
- QVYYOKWPCQYKEY-UHFFFAOYSA-N [Fe].[Co] Chemical compound [Fe].[Co] QVYYOKWPCQYKEY-UHFFFAOYSA-N 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- FQMNUIZEFUVPNU-UHFFFAOYSA-N cobalt iron Chemical compound [Fe].[Co].[Co] FQMNUIZEFUVPNU-UHFFFAOYSA-N 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000009849 deactivation Effects 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 229910052761 rare earth metal Inorganic materials 0.000 description 1
- 238000012827 research and development Methods 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000004083 survival effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
-
- B01J35/33—
-
- B01J35/40—
-
- B01J35/61—
-
- 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
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- 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
-
- 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
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
-
- 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 three-dimensional nitrogen-doped carbon-based material loaded bi-metal phosphide bifunctional catalyst and a preparation method and application thereof. The catalyst is a composite material consisting of double transition metal phosphide and nitrogen-doped carbon nanotubes. Firstly, mixing melamine and carbon nano tubes according to a certain mass ratio for heat treatment to prepare a three-dimensional nitrogen-doped carbon material; then mixing a certain proportion of double transition metal nitrate into the aqueous solution of the three-dimensional nitrogen-doped carbon material, and drying the mixture on the surface of an inert electrode; then electrodepositing for 0.5-1.5 minutes in neutral buffer solution, cleaning and drying; and finally reacting with sodium dihydrogen phosphite for 2 hours at 350 ℃ in a nitrogen atmosphere to obtain the catalyst. The catalyst has excellent catalytic oxygen evolution performance (OER) under alkaline conditions, also has efficient catalytic oxygen reduction function (ORR), and is low in price of raw materials, simple in process, short in reaction time and suitable for batch production.
Description
Technical Field
The invention belongs to the technical field of new energy such as fuel cells, water splitting desorption oxygen and the like, and particularly relates to a three-dimensional nitrogen-doped carbon-based material loaded bi-metal phosphide dual-function catalyst, and a preparation method and application thereof.
Background
Energy is a material basis on which human society relies on survival and development. At present, about 85 percent of the global energy consumption is caused by the combustion of fossil fuel, and the combustion of the fossil fuel causes CO in the atmosphere2Concentrations continue to rise cumulatively and eventually contribute to the greenhouse effect and global warming. Therefore, efficient and low-cost clean energy is actively researched and developed in various countries around the world. New energy technologies such as fuel cells (especially proton exchange membrane fuel cells), water splitting devices and metal-air batteries are important directions for research at present [ chem.Rev.2015,115,9869-9921]. Conventional noble metals (Pt, Ir,Ru, etc.) and alloys thereof have good catalytic activities for oxygen reduction (ORR) and Oxygen Evolution (OER), but are expensive and susceptible to poisoning and deactivation, which severely restricts the development of these energy technologies. Therefore, the non-noble metal double-effect catalyst with high efficiency, stability and low price becomes a research and development hotspot of new energy technology.
Transition metal (such as cobalt, nickel, iron and manganese) oxides have the advantages of low price, abundant reserves and the like, can form various crystal configurations, and are considered by many scientists to be catalytic materials capable of replacing noble metals. The Schuhmann group studied a series of perovskite-type transition metal oxides, which have good ORR and OER catalytic performances, but still need to be doped with a small amount of rare earth elements (La, Ce, etc.) [ Chemhyschem 2014,15,2810-2816 ]; a series of transition metal hydroxides prepared by Nocera et al, in which different crystalline structures were found to have a large influence on ORR and OER catalytic performance [ j.am.chem.soc.2012,134,6801-6809 ]. Although these materials have a certain catalytic potential, the synthesis process is complex, the preparation time is long, and the performance is still insufficient to meet the requirements of industrial production.
In summary, in order to solve the above technical problems in the prior art, the present invention provides a bi-metal phosphide bifunctional catalyst loaded on a three-dimensional nitrogen-doped carbon-based material, and a preparation method and an application thereof. The double transition metal phosphide has the synergistic effect of metal and phosphorus, and the catalytic performance of the double transition metal phosphide can be improved in a controllable manner by adjusting the metal species. The three-dimensional nitrogen-doped carbon-based material prepared by the invention is assisted in the double-transition metal phosphide bifunctional composite catalyst in the prior art. Therefore, the implementation method of the invention can controllably prepare the three-dimensional nitrogen-doped carbon-based material and assist the double-transition metal phosphide double-function composite catalyst, and has important significance for widening the research direction of the double-function catalyst.
Disclosure of Invention
The invention provides a three-dimensional nitrogen-doped carbon-based material loaded bimetallic phosphide bifunctional catalyst, a preparation method and application thereof, and provides an ORR and OER bifunctional composite catalyst with short preparation time, simple process, controllable reaction and high activity and a preparation method thereof, wherein the specific technical scheme is as follows:
a bi-metal phosphide bi-functional catalyst loaded on a three-dimensional nitrogen-doped carbon-based material is a composite material consisting of the three-dimensional nitrogen-doped carbon-based material and bi-metal phosphide.
The preparation method of the three-dimensional nitrogen-doped carbon-based material loaded bimetallic phosphide bifunctional catalyst comprises the following steps:
the method comprises the following steps:
(1) weighing melamine and carbon nano tubes according to the mass ratio of 1.5:1, performing ultrasonic dispersion in a solvent uniformly, drying, and performing heat treatment at 550 ℃ for 2 hours to obtain a three-dimensional nitrogen-doped carbon-based material;
(2) ultrasonically stirring the three-dimensional nitrogen-doped carbon-based material and divalent metal ions uniformly by using an organic solution with the mass molar ratio of 1g to 0.3-0.6mol, and drying on the surface of an inert electrode;
(3) and placing the inert electrode of the load material in a negative electrode in a neutral phosphoric acid buffer solution, electrolyzing for 0.5-1.5 minutes under the current of-10 mA, washing and drying to obtain the precursor.
(4) And (3) reacting the precursor with sodium dihydrogen phosphite at 350 ℃ for 2 hours in a nitrogen atmosphere, and cooling to obtain the three-dimensional nitrogen-doped carbon-based material loaded bi-metal phosphide bi-functional composite catalyst.
The preparation method of the three-dimensional nitrogen-doped carbon-based material loaded bimetallic phosphide bifunctional catalyst comprises the following steps: in the step (2), the divalent metal ions include Ni2+，Fe2+，Co2+，Mn2+，Cu2+Either one or both of them.
The preparation method of the three-dimensional nitrogen-doped carbon-based material loaded bimetallic phosphide bifunctional catalyst comprises the following steps: in the step (3), the inert electrode is any one of conductive glass, a glassy carbon electrode and a platinum electrode.
The preparation method of the three-dimensional nitrogen-doped carbon-based material loaded bimetallic phosphide bifunctional catalyst comprises the following steps: the three-dimensional nitrogen-doped carbon-based material is a composition of melamine and carbon nanotubes, and the specific surface area reaches 150m 2/g.
The preparation method of the three-dimensional nitrogen-doped carbon-based material loaded bimetallic phosphide bifunctional catalyst comprises the following steps: the bimetallic phosphide is nano-particles with the diameter of 5-20 nm.
The preparation method of the three-dimensional nitrogen-doped carbon-based material loaded bimetallic phosphide bifunctional catalyst comprises the following steps: the specific surface area of the three-dimensional nitrogen-doped carbon-based material loaded double-metal phosphide double-function composite catalyst reaches 420m2/g。
The preparation method of the three-dimensional nitrogen-doped carbon-based material loaded bimetallic phosphide bifunctional catalyst comprises the following steps: in the step (3), the precursors of the transition metal phosphide are sodium dihydrogen phosphite and any two of nickel acetate, iron acetate, cobalt acetate, manganese acetate and copper acetate.
The preparation method of the three-dimensional nitrogen-doped carbon-based material loaded bimetallic phosphide bifunctional catalyst comprises the following steps: the preparation method of the precursor of the transition metal phosphide can be divided into two steps:
1) loading a transition metal: loading transition metal elements by using an in-situ electrochemical reduction method;
2) phosphorization of transition metal: the phosphating of the transition metal was carried out with sodium dihydrogen phosphite at 350 ℃ under nitrogen.
In addition, the invention also provides application of the bimetallic phosphide dual-function catalyst loaded on the three-dimensional nitrogen-doped carbon-based material, wherein the three-dimensional nitrogen-doped carbon-based material has a typical spatial configuration of uniform cross support of a graphene sheet layer and a nanotube, the size of the nitrogen-doped graphene sheet layer is nano-scale, and the nitrogen-doped graphene sheet layer is 100-300 nm; the diameter of the nitrogen-doped carbon nanotube is 8-15nm, the length of the nitrogen-doped carbon nanotube is 100nm-1 mu m, the material has a larger specific surface area, and also has good conductivity and a large number of three-dimensional space structures, and the doping of nitrogen element in the material provides more active sites, the three-dimensional nitrogen-doped carbon-based material is beneficial to the effective load of transition metal, and is beneficial to enhancing the ORR and OER catalytic performance of the composite catalyst, the double-transition metal phosphide has the synergistic effect of metal and phosphorus, and the catalytic performance of the double-transition metal phosphide is improved in a controllable manner by adjusting the metal type.
Compared with the prior art, the invention has the following beneficial effects:
1) the raw materials are cheap, easy to prepare and rich in reserves.
2) The preparation method simplifies the process, shortens the flow and is easy to control.
3) The synthesized composite catalyst has a large effective specific surface area, clear components and clear catalytic activity centers.
4) The composite catalyst synthesized by the invention has dual-functional catalytic performance of ORR and OER under an alkaline condition, the ORR performance is close to that of a commercial 20 wt% platinum/carbon catalyst, the potential of the OER when the current density reaches 10mA/cm2 is close to that of mesoporous ruthenium dioxide reported in the literature, and the methanol poisoning resistance is superior to that of a commercial noble metal catalyst.
Drawings
Fig. 1 is a Scanning Electron Microscope (SEM) atlas of the three-dimensional nitrogen-doped carbon-based material supported nickel-iron bimetallic phosphide bifunctional composite catalyst of the present invention.
Fig. 2 is a Transmission Electron Microscope (TEM) map of the three-dimensional nitrogen-doped carbon-based material supported nickel iron bimetallic phosphide bifunctional composite catalyst of the present invention.
Fig. 3 is a BET nitrogen isothermal adsorption and desorption curve of the three-dimensional nitrogen-doped carbon-based material loaded nickel-iron bimetallic phosphide bifunctional composite catalyst.
FIG. 4 is an ORR polarization curve of the three-dimensional nitrogen-doped carbon-based material supported nickel-iron bimetallic phosphide dual-function composite catalyst and 20 wt% Pt/C.
FIG. 5 is an I-t curve of the methanol poisoning resistance test of the three-dimensional nitrogen-doped carbon-based material supported nickel-iron bimetallic phosphide dual-function composite catalyst and 20 wt% Pt/C.
FIG. 6 is an OER polarization curve of the three-dimensional nitrogen-doped carbon-based material loaded nickel-iron bimetallic phosphide dual-function composite catalyst and 20 wt% Pt/C.
Detailed Description
The invention is further described below with reference to the figures and examples.
EXAMPLE 1
Ultrasonically dispersing 450mg of melamine (national drug group chemical reagent Co., Ltd., analytical purity) and 300mg of carbon nanotubes (Chinese academy of sciences organic chemistry Co., Ltd.) in ultrapure water for 30 minutes, drying at 80 ℃, and carrying out heat treatment at 550 ℃ for 2 hours under nitrogen to obtain a three-dimensional nitrogen-doped carbon-based material (3D-C);
ultrasonically dispersing 500mg of three-dimensional nitrogen-doped carbon-based material, 1g of nickel acetate hexahydrate and 1g of ferric acetate hexahydrate in 5mL of ethanol for 1 hour, and drying the mixed solution on the surface of a glassy carbon electrode at 80 ℃;
in a neutral phosphoric acid buffer solution, taking the inert glassy carbon electrode of the load mixture as a working electrode, a platinum wire as a counter electrode and a Saturated Calomel Electrode (SCE) as a reference electrode, electrolyzing for 1 minute under the current of-10 mA, washing for 5 times by using ultrapure water, and drying to obtain a precursor;
and (3) reacting the precursor with 200mg of sodium dihydrogen phosphite at 350 ℃ for 2 hours at the temperature rising speed of 2.5 ℃/min in the nitrogen atmosphere, and cooling to obtain the three-dimensional nitrogen-doped carbon-based material loaded nickel-iron bimetallic phosphide bifunctional composite catalyst.
EXAMPLE 2
Adopts a standard three-electrode system to load a nickel-iron bimetallic phosphide dual-function composite catalyst (NiP) on a three-dimensional nitrogen-doped carbon-based material2/FeP23D-C) carrying out an ORR catalytic performance test. The testing apparatus is a CH Instrument Model 760D potentistat system. The Hg/HgO electrode is a reference electrode, the C rod is a counter electrode, and the glassy carbon electrode is a working electrode. The solution was 0.1M KOH, the scan rate was 10mV/s, the electrode rotation speed was 1600rpm, and the temperature was room temperature. Before testing, the electrolyte was saturated with oxygen for 30 minutes, the retention time was set to 30s, and the ring voltage was set to 0.8V. As can be seen from the figure, NiP2/FeP2The initial potential of the/3D-C catalyst is 0.020V, which is shifted by 18mV compared with the initial potential (0.002V) of Pt/C; NiP2/FeP2Half of a/3D-C catalystThe wave potential is-0.115V, which is shifted by 10mV more than the half-starting potential (-0.105V) of Pt/C; NiP2/FeP2The limiting current density of the/3D-C catalyst is slightly larger than that of Pt/C. The result shows that the three-dimensional nitrogen-doped carbon-based material loaded nickel-iron bimetallic phosphide dual-function composite catalyst (NiP)2/FeP2ORR catalytic activity of/3D-C) was slightly better than that of commercial 20 wt% Pt/C.
EXAMPLE 3
Adopts a standard three-electrode system to load a nickel-iron bimetallic phosphide dual-function composite catalyst (NiP) on a three-dimensional nitrogen-doped carbon-based material2/FeP2the/3D-C) methanol resistance test. The Hg/HgO electrode is a reference electrode, the C rod is a counter electrode, and the glassy carbon electrode is a working electrode. The solution was 0.1M KOH, the scan rate was 10mV/s, the electrode rotation speed was 1600rpm, the temperature was room temperature, and the test voltage was-0.4V. It can be seen from the figure that 2M methanol, NiP, was added at around 300s2/FeP2The catalytic current of the/3D-C is not changed obviously, while the catalytic current of the Pt/C is reduced sharply. The results show that NiP2/FeP2The catalytic capability of the/3D-C catalyst is not obviously affected after methanol is added, namely the three-dimensional nitrogen-doped carbon-based material loaded nickel-iron bimetallic phosphide dual-functional composite catalyst (NiP)2/FeP2the/3D-C) methanol resistance is significantly better than commercial 20 wt% Pt/C.
EXAMPLE 4
Adopts a standard three-electrode system to load a nickel-iron bimetallic phosphide dual-function composite catalyst (NiP) on a three-dimensional nitrogen-doped carbon-based material2/FeP2the/3D-C) was tested for OER catalytic performance. The testing apparatus is a CH Instrument Model 760D potentistat system. The Saturated Calomel Electrode (SCE) is a reference electrode, the C rod is a counter electrode, and the glassy carbon electrode is a working electrode. The solution was 0.1M KOH, the scan rate was 10mV/s, the electrode rotation speed was 1600rpm, and the temperature was room temperature. As can be seen from the figure, NiP2/FeP2The potential of the/3D-C catalyst at 10mA/cm2 is 0.639V, and the catalyst is more noble metal RuO2(0.714V) and Pt/C (1.071V) were low at 10mA/cm 2. The result shows that the three-dimensional nitrogen-doped carbon-based material loaded nickel-iron bimetallic phosphide dual-functional composite catalysis is performedAgent (NiP)2/FeP2the/3D-C) has better catalytic activity on OER than the commercial noble metal catalysts RuO2 and Pt/C.
EXAMPLE 5
Ultrasonically dispersing 500mg of three-dimensional nitrogen-doped carbon-based material and 1g of nickel acetate hexahydrate and 1g of cobalt acetate hexahydrate in 5mL of ethanol for 1 hour, and drying the mixed solution on the surface of a glassy carbon electrode at 80 ℃; in a neutral phosphoric acid buffer solution, taking the inert glassy carbon electrode of the load mixture as a working electrode, a platinum wire as a counter electrode and a Saturated Calomel Electrode (SCE) as a reference electrode, electrolyzing for 1 minute under the current of-10 mA, washing for 5 times by using ultrapure water, and drying to obtain a precursor; and (3) reacting the precursor with 200mg of sodium dihydrogen phosphite at the temperature of 350 ℃ for 2 hours at the temperature rising speed of 2.5 ℃/min in a nitrogen atmosphere, and cooling to obtain the three-dimensional nitrogen-doped carbon-based material loaded nickel-cobalt bimetallic phosphide bifunctional composite catalyst. The potential of the catalyst at 10mA/cm2 is 0.715V, which is more noble than RuO catalyst2The potential at 10mA/cm2 (0.714V) was comparable to that at 10mA/cm2 (1.071V) of Pt/C. The result shows that the catalytic activity of the three-dimensional nitrogen-doped carbon-based material loaded nickel-cobalt bimetallic phosphide bifunctional composite catalyst on OER and the commercial noble metal catalyst RuO2Is equivalent to and superior to Pt/C.
Ultrasonically dispersing 500mg of three-dimensional nitrogen-doped carbon-based material, 1g of nickel acetate hexahydrate and 1g of manganese acetate hexahydrate in 5mL of ethanol for 1 hour, and drying the mixed solution on the surface of a glassy carbon electrode at 80 ℃; in a neutral phosphoric acid buffer solution, taking the inert glassy carbon electrode of the load mixture as a working electrode, a platinum wire as a counter electrode and a Saturated Calomel Electrode (SCE) as a reference electrode, electrolyzing for 1 minute under the current of-10 mA, washing for 5 times by using ultrapure water, and drying to obtain a precursor; and (3) reacting the precursor with 200mg of sodium dihydrogen phosphite at the temperature of 350 ℃ for 2 hours at the temperature rising speed of 2.5 ℃/min in a nitrogen atmosphere, and cooling to obtain the three-dimensional nitrogen-doped carbon-based material loaded nickel-manganese bi-metal phosphide dual-functional composite catalyst. The catalyst has a potential of 0.792V at 10mA/cm2, and is a more noble metal catalyst RuO2The potential at 10mA/cm2 (0.714V) was higher than that at 10mA/cm2 (1.071V). The results show three-dimensional nitrogen dopingThe catalytic activity of the carbon-based material loaded nickel-manganese bimetallic phosphide bifunctional composite catalyst on OER is slightly lower than that of a commercial noble metal catalyst RuO2Is superior to Pt/C.
Ultrasonically dispersing 500mg of three-dimensional nitrogen-doped carbon-based material and 1g of ferric acetate hexahydrate and 1g of cobalt acetate hexahydrate in 5mL of ethanol for 1 hour, and drying the mixed solution on the surface of a glassy carbon electrode at 80 ℃; in a neutral phosphoric acid buffer solution, taking the inert glassy carbon electrode of the load mixture as a working electrode, a platinum wire as a counter electrode and a Saturated Calomel Electrode (SCE) as a reference electrode, electrolyzing for 1 minute under the current of-10 mA, washing for 5 times by using ultrapure water, and drying to obtain a precursor; and (3) reacting the precursor with 200mg of sodium dihydrogen phosphite at 350 ℃ for 2 hours at the temperature rising speed of 2.5 ℃/min in the nitrogen atmosphere, and cooling to obtain the three-dimensional nitrogen-doped carbon-based material loaded iron-cobalt bimetallic phosphide dual-function composite catalyst. The potential of the catalyst at 10mA/cm2 is 0.894V, which is more noble metal catalyst RuO2The potential at 10mA/cm2 (0.714V) was higher than that at 10mA/cm2 (1.071V). The result shows that the catalytic activity of the three-dimensional nitrogen-doped carbon-based material loaded cobalt-iron bimetallic phosphide bifunctional composite catalyst on OER is slightly lower than that of a commercial noble metal catalyst RuO2 and is better than that of Pt/C.
The three-dimensional nitrogen-doped carbon-based material prepared by the invention has a typical spatial configuration of uniform cross support of a graphene sheet layer and a nanotube, wherein the size of the nitrogen-doped graphene sheet layer is nano-scale and is 100-300 nm; the diameter of the nitrogen-doped carbon nano tube is 8-15nm, and the length of the nitrogen-doped carbon nano tube is 100nm-1 mu m. The material has a large specific surface area, good conductivity and a large number of three-dimensional void structures, and more active sites such as graphite nitrogen, pyridine nitrogen, pyrrole nitrogen and the like are provided by doping of nitrogen elements in the material. The three-dimensional nitrogen-doped carbon-based material is beneficial to effective loading of transition metal and enhancing the ORR and OER catalytic performance of the composite catalyst.
The precursor of the transition metal phosphide is sodium dihydrogen phosphite and any two of nickel acetate, iron acetate, cobalt acetate, manganese acetate and copper acetate, and the preparation method can be divided into two steps: 1) loading a transition metal: and loading the transition metal element by using an in-situ electrochemical reduction method. 2) Phosphorization of transition metal: the phosphating of the transition metal was carried out with sodium dihydrogen phosphite at 350 ℃ under nitrogen. The preparation method has the advantages of convenient operation, simple process and strong controllability, greatly shortens the preparation time and saves resources. The metal nano particles in the three-dimensional nitrogen-doped carbon-based material loaded double-metal phosphide double-function composite catalyst synthesized by the method are uniformly distributed, and the diameter of the metal nano particles is 5-20 nm.
Claims (10)
1. A three-dimensional nitrogen-doped carbon-based material loaded bi-metal phosphide bifunctional catalyst is characterized in that: the catalyst is a composite material consisting of a three-dimensional nitrogen-doped carbon-based material and a bimetallic phosphide.
2. A method for preparing the three-dimensional nitrogen-doped carbon-based material supported bimetallic phosphide bifunctional catalyst as claimed in claim 1, wherein the method comprises the following steps:
the method comprises the following steps:
(1) weighing melamine and carbon nano tubes according to the mass ratio of 1.5:1, performing ultrasonic dispersion in a solvent uniformly, drying, and performing heat treatment at 550 ℃ for 2 hours to obtain a three-dimensional nitrogen-doped carbon-based material;
(2) ultrasonically stirring the three-dimensional nitrogen-doped carbon-based material and divalent metal ions uniformly by using an organic solution with the mass molar ratio of 1g to 0.3-0.6mol, and drying on the surface of an inert electrode;
(3) placing the inert electrode of the load material in a negative electrode in a neutral phosphoric acid buffer solution, electrolyzing for 0.5-1.5 minutes under the current of-10 mA, washing and drying to obtain a precursor;
(4) and (3) reacting the precursor with sodium dihydrogen phosphite at 350 ℃ for 2 hours in a nitrogen atmosphere, and cooling to obtain the three-dimensional nitrogen-doped carbon-based material loaded bi-metal phosphide bi-functional composite catalyst.
3. The method for preparing the three-dimensional nitrogen-doped carbon-based material supported bimetallic phosphide bifunctional catalyst as claimed in claim 2, wherein the method comprises the following steps: in the step (2), the divalent metal ions include Ni2+，Fe2+，Co2+，Mn2+，Cu2+Either one or both of them.
4. The method for preparing the three-dimensional nitrogen-doped carbon-based material supported bimetallic phosphide bifunctional catalyst as claimed in claim 3, wherein the method comprises the following steps: in the step (3), the inert electrode is any one of conductive glass, a glassy carbon electrode and a platinum electrode.
5. The method for preparing the three-dimensional nitrogen-doped carbon-based material supported bimetallic phosphide bifunctional catalyst as claimed in claim 4, wherein the method comprises the following steps: the three-dimensional nitrogen-doped carbon-based material is a composition of melamine and carbon nanotubes, and the specific surface area reaches 150m 2/g.
6. The method for preparing the three-dimensional nitrogen-doped carbon-based material supported bimetallic phosphide bifunctional catalyst as claimed in claim 5, wherein the method comprises the following steps: the bimetallic phosphide is nano-particles with the diameter of 5-20 nm.
7. The method of any one of claims 2-6, wherein the three-dimensional nitrogen-doped carbon-based material supported bi-metal phosphide bi-functional catalyst is prepared by: the specific surface area of the three-dimensional nitrogen-doped carbon-based material loaded double-metal phosphide double-function composite catalyst reaches 420m2/g。
8. The method for preparing the three-dimensional nitrogen-doped carbon-based material supported bimetallic phosphide bifunctional catalyst as claimed in claim 2, wherein the method comprises the following steps: in the step (3), the precursors of the transition metal phosphide are sodium dihydrogen phosphite and any two of nickel acetate, iron acetate, cobalt acetate, manganese acetate and copper acetate.
9. The method for preparing the three-dimensional nitrogen-doped carbon-based material supported bimetallic phosphide bifunctional catalyst as claimed in claim 8, wherein the method comprises the following steps: the preparation method of the precursor of the transition metal phosphide can be divided into two steps:
1) loading a transition metal: loading transition metal elements by using an in-situ electrochemical reduction method;
2) phosphorization of transition metal: the phosphating of the transition metal was carried out with sodium dihydrogen phosphite at 350 ℃ under nitrogen.
10. Use of the bi-metal phosphide-supported bifunctional catalyst as claimed in claim 9, wherein: the three-dimensional nitrogen-doped carbon-based material has a typical spatial configuration of uniform cross support of a graphene sheet layer and a nanotube, wherein the size of the nitrogen-doped graphene sheet layer is nano-scale and is 100-300 nm; the diameter of the nitrogen-doped carbon nanotube is 8-15nm, the length of the nitrogen-doped carbon nanotube is 100nm-1 mu m, the material has a larger specific surface area, and also has good conductivity and a large number of three-dimensional space structures, and the doping of nitrogen element in the material provides more active sites, the three-dimensional nitrogen-doped carbon-based material is beneficial to the effective load of transition metal, and is beneficial to enhancing the ORR and OER catalytic performance of the composite catalyst, the double-transition metal phosphide has the synergistic effect of metal and phosphorus, and the catalytic performance of the double-transition metal phosphide is improved in a controllable manner by adjusting the metal type.
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