CN115763845B - Preparation method of chromium-based inorganic matter coupled transition metal nitrogen-doped carbon catalyst - Google Patents
Preparation method of chromium-based inorganic matter coupled transition metal nitrogen-doped carbon catalyst Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 239000011651 chromium Substances 0.000 title claims abstract description 43
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 title claims abstract description 33
- 229910052804 chromium Inorganic materials 0.000 title claims abstract description 33
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 27
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 27
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- 229910052723 transition metal Inorganic materials 0.000 title claims abstract description 21
- 150000003624 transition metals Chemical class 0.000 title claims abstract description 21
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 50
- 238000000034 method Methods 0.000 claims abstract description 32
- 239000011780 sodium chloride Substances 0.000 claims abstract description 25
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 21
- 150000003863 ammonium salts Chemical class 0.000 claims abstract description 18
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 16
- 238000005406 washing Methods 0.000 claims abstract description 16
- 229910052751 metal Inorganic materials 0.000 claims abstract description 13
- 239000002184 metal Substances 0.000 claims abstract description 13
- 150000003839 salts Chemical class 0.000 claims abstract description 13
- 150000001844 chromium Chemical class 0.000 claims abstract description 12
- 239000007787 solid Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 50
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 33
- 238000010438 heat treatment Methods 0.000 claims description 22
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 claims description 19
- 238000003756 stirring Methods 0.000 claims description 17
- 239000002243 precursor Substances 0.000 claims description 16
- 239000008247 solid mixture Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 13
- 239000000446 fuel Substances 0.000 claims description 12
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 10
- 239000001301 oxygen Substances 0.000 claims description 10
- 229910052760 oxygen Inorganic materials 0.000 claims description 10
- 230000001681 protective effect Effects 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 239000002131 composite material Substances 0.000 claims description 9
- 239000004570 mortar (masonry) Substances 0.000 claims description 9
- 150000002500 ions Chemical class 0.000 claims description 8
- 238000002390 rotary evaporation Methods 0.000 claims description 8
- 238000000227 grinding Methods 0.000 claims description 7
- 238000000967 suction filtration Methods 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 7
- 239000012498 ultrapure water Substances 0.000 claims description 7
- 238000001291 vacuum drying Methods 0.000 claims description 7
- 230000008878 coupling Effects 0.000 claims description 6
- 238000010168 coupling process Methods 0.000 claims description 6
- 238000005859 coupling reaction Methods 0.000 claims description 6
- 238000006722 reduction reaction Methods 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 5
- 239000004202 carbamide Substances 0.000 claims description 5
- 238000006243 chemical reaction Methods 0.000 claims description 5
- PHFQLYPOURZARY-UHFFFAOYSA-N chromium trinitrate Chemical compound [Cr+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PHFQLYPOURZARY-UHFFFAOYSA-N 0.000 claims description 4
- 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 claims description 4
- 229920000877 Melamine resin Polymers 0.000 claims description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 3
- MWVTWFVJZLCBMC-UHFFFAOYSA-N 4,4'-bipyridine Chemical compound C1=NC=CC(C=2C=CN=CC=2)=C1 MWVTWFVJZLCBMC-UHFFFAOYSA-N 0.000 claims description 2
- 229910021555 Chromium Chloride Inorganic materials 0.000 claims description 2
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 2
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 2
- MQRWBMAEBQOWAF-UHFFFAOYSA-N acetic acid;nickel Chemical compound [Ni].CC(O)=O.CC(O)=O MQRWBMAEBQOWAF-UHFFFAOYSA-N 0.000 claims description 2
- QSWDMMVNRMROPK-UHFFFAOYSA-K chromium(3+) trichloride Chemical compound [Cl-].[Cl-].[Cl-].[Cr+3] QSWDMMVNRMROPK-UHFFFAOYSA-K 0.000 claims description 2
- GRWVQDDAKZFPFI-UHFFFAOYSA-H chromium(III) sulfate Chemical compound [Cr+3].[Cr+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O GRWVQDDAKZFPFI-UHFFFAOYSA-H 0.000 claims description 2
- 229940011182 cobalt acetate Drugs 0.000 claims description 2
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 2
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 2
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 2
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 2
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims description 2
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 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 2
- 238000002156 mixing Methods 0.000 claims description 2
- 229940078494 nickel acetate Drugs 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims 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 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- 238000005303 weighing Methods 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 20
- 238000012546 transfer Methods 0.000 abstract description 5
- 239000006185 dispersion Substances 0.000 abstract description 4
- 229910052742 iron Inorganic materials 0.000 abstract description 4
- 239000002159 nanocrystal Substances 0.000 abstract description 4
- 239000011812 mixed powder Substances 0.000 abstract description 3
- 239000002253 acid Substances 0.000 abstract description 2
- 238000000137 annealing Methods 0.000 abstract description 2
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 abstract 1
- 238000001914 filtration Methods 0.000 abstract 1
- 229910017053 inorganic salt Inorganic materials 0.000 abstract 1
- 238000012360 testing method Methods 0.000 description 19
- 230000000052 comparative effect Effects 0.000 description 18
- 239000000047 product Substances 0.000 description 15
- 230000010287 polarization Effects 0.000 description 11
- 238000003763 carbonization Methods 0.000 description 10
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 10
- 230000008569 process Effects 0.000 description 6
- 238000013112 stability test Methods 0.000 description 6
- 239000006227 byproduct Substances 0.000 description 5
- 238000005087 graphitization Methods 0.000 description 5
- 239000011261 inert gas Substances 0.000 description 5
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 5
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 4
- 229910000510 noble metal Inorganic materials 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium atom Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 description 3
- 230000007774 longterm Effects 0.000 description 3
- 230000009467 reduction Effects 0.000 description 3
- 230000027756 respiratory electron transport chain Effects 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- AFCARXCZXQIEQB-UHFFFAOYSA-N N-[3-oxo-3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propyl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(CCNC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 AFCARXCZXQIEQB-UHFFFAOYSA-N 0.000 description 2
- 238000001237 Raman spectrum Methods 0.000 description 2
- 230000032683 aging Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 229910002092 carbon dioxide Inorganic materials 0.000 description 2
- 239000001569 carbon dioxide Substances 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000007806 chemical reaction intermediate Substances 0.000 description 2
- 230000007797 corrosion Effects 0.000 description 2
- 238000005260 corrosion Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000010411 electrocatalyst Substances 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 230000007246 mechanism Effects 0.000 description 2
- 239000002135 nanosheet Substances 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- 229910020676 Co—N Inorganic materials 0.000 description 1
- 238000001069 Raman spectroscopy Methods 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 239000000306 component Substances 0.000 description 1
- 239000008358 core component Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005868 electrolysis reaction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 229910052741 iridium Inorganic materials 0.000 description 1
- -1 iron ions Chemical class 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 125000001477 organic nitrogen group Chemical group 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000012353 t test Methods 0.000 description 1
Classifications
-
- 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
A preparation method of a chromium-based inorganic matter coupled transition metal nitrogen doped carbon catalyst, belonging to the field of electrocatalysis. The method takes a prepared metal M-bipyridine solution as a starting point, then sodium chloride, chromium salt and organic ammonium salt are sequentially added into the solution, and the solution is stirred to dissolve solids and evaporated to dryness to obtain mixed powder; and then annealing, template removing, acid washing, suction filtering and drying are carried out to obtain the catalyst. Has the following advantages: introducing a chromium salt inorganic carrier into an M-N-C atomic-level dispersion catalyst to replace a conventional carbon carrier by a molten salt template method, wherein the method is applicable to various metal-nitrogen co-doped carbon catalysts (such as Fe, cu, ni and the like); the catalyst is ultrathin two-dimensional sheet-shaped formed by interconnecting nanocrystals, so that the mass transfer capacity can be effectively improved; the introduction of the chromium-based inorganic salt can improve Faraday efficiency, catalytic activity and durability under high-current and long-time working conditions, and is obviously superior to commercial platinum carbon catalysts and transition metal nitrogen doped carbon.
Description
Technical Field
The invention belongs to the field of new energy materials, and particularly relates to a composite catalyst prepared by using a two-dimensional flaky chromium-based inorganic substance as a carrier and coupling a transition metal nitrogen-doped carbon-type atomic distribution material (M-N-C, M is one or more of Fe, co, cu and Ni), which is applied to places such as fuel cells, metal-air cell cathode Oxygen Reduction Reaction (ORR), electrolytic water oxygen precipitation reaction (OER) and the like.
Background
The electrocatalyst is one of the core components of many novel energy conversion devices such as fuel cells, metal-air cells, water electrolysis engineering and the like. Currently, electrocatalysts are still based on noble metal catalytic materials, such as Pt, pd, ru and Ir, and are the most advanced oxygen electrode catalysts. However, their high price and limited reserves have greatly limited the development of the new energy industry. Therefore, it is necessary to develop a non-noble metal catalyst having high catalytic performance in place of the noble metal catalyst.
In a platinum group metal-free catalyst, a transition metal nitrogen-doped carbon-atom-dispersed material (M-N-C), i.e., MN with intercalation of atomic dispersion and nitrogen coordination in the carbon plane x Sites for oxygen reduction, oxygen Evolution (OER) and carbon dioxide reduction (CO) 2 RR) and the like, and shows good performance and good application prospect. The extremely high surface-to-volume ratio of M-N-C improves the catalysis of each atomEfficiency, improved uniformity of active sites, and the ability to tailor the guest environment, all of which are not only attractive for industrial applications, but also attractive for in-depth understanding of atomic-scale catalytic mechanisms. Despite their great progress in terms of activity and site structure, there is an urgent need to improve durability due to insufficient knowledge of their degradation mechanism during operation. Further research and improvement of M-N-C catalysts is still needed to facilitate practical use, particularly at high currents, and long term stability of the catalysts in severe battery testing.
Disclosure of Invention
Aiming at the defects of the catalytic activity and stability of the traditional transition metal nitrogen doped carbon catalyst M-N-C (M is one or more of Fe, co, cu and Ni), a two-dimensional flaky chromium-based inorganic substance is used as a carrier to couple the M-N-C as a catalyst, and the catalytic durability of the obtained catalyst is obviously higher than that of the traditional M-N-C catalyst and the latest commercial 20% Pt/C catalyst.
In order to achieve the above purpose, the technical scheme adopted by the invention is as follows:
a preparation method of a chromium-based inorganic matter coupled transition metal nitrogen doped carbon catalyst comprises the following steps:
step one: preparing a metal M-bipyridine solution:
weighing metal M salt and bipyridine, respectively dissolving in ultrapure water at room temperature, mixing the two solutions after complete dissolution to obtain orange-yellow solution, and stirring at room temperature to enable M ions and bipyridine to fully coordinate and grow;
step two: preparation of M-Cr-organic ammonium salt mixed precursor:
sequentially adding sodium chloride, chromium salt and organic ammonium salt into the orange-yellow solution obtained in the step one, and stirring to completely dissolve the solid; placing the solution on a heating platform, removing water in the solution by a rotary evaporation method to obtain a solid mixture, and placing the solid mixture in a vacuum oven for vacuum heating and drying to remove residual water to obtain an M-Cr-organic ammonium salt mixed precursor;
step three: preparation of chromium-based inorganic matter coupled M-N-C composite catalyst:
putting the precursor obtained in the second step into a mortar for full grinding, and then putting the mortar into a tube furnace for calcination treatment under a protective atmosphere; dispersing the calcined product into an aqueous solution, and removing a sodium chloride template through multiple times of water washing; to remove metal M clusters that may be present, the template-removed product is dispersed into dilute H 2 SO 4 And (3) in the aqueous solution, continuously stirring at 80 ℃ for 5 hours, and performing water washing, suction filtration and vacuum drying to obtain the chromium-based inorganic matter coupling transition metal nitrogen doped carbon catalyst.
Further, in the first step, the molar ratio of the metal M salt to the bipyridine is 1:1 to 4.
In the first step, the metal M salt is one or more of ferric nitrate, ferric chloride, ferric acetate, ferrous nitrate, ferrous chloride, ferrous acetate, cobalt nitrate, cobalt chloride, cobalt acetate, copper nitrate, copper chloride, copper acetate, nickel nitrate, nickel chloride and nickel acetate, and the bipyridine is 2,2 '-bipyridine or 4,4' -bipyridine.
In the second step, the input amount of the sodium chloride is determined according to the volume of the M-bipyridine solution, 0.5g of sodium chloride is corresponding to each milliliter of solution, and the molar ratio of the chromium salt to the metal M salt is 1-8: 1, the mass ratio of the organic ammonium salt to the chromium salt is 3:1.
in the second step, the chromium salt is one of chromium chloride, chromium sulfate and chromium nitrate, and the organic ammonium salt is one of urea, melamine, dicyandiamide and ammonium citrate.
Further, in the third step, the protective atmosphere is Ar or N 2 The calcining temperature is 650-800 ℃, the time is 1-3h, and the heating rate is 2-10 ℃/min.
The chromium-based inorganic matter coupled transition metal nitrogen doped carbon catalyst prepared by the method.
The chromium-based inorganic matter coupling transition metal nitrogen doped carbon catalyst prepared by the method is applied to a fuel cell, a metal-air cell cathode Oxygen Reduction Reaction (ORR) and an electrolytic water oxygen precipitation reaction (OER).
Compared with the prior art, the invention has the beneficial effects that:
(1) The invention can introduce the chromium-based inorganic carrier into the M-N-C atomic level dispersion catalyst to replace the conventional carbon carrier by a simple and effective molten salt template method, so as to synthesize various ultra-stable catalysts with different components and structures, can control the form of the chromium-based inorganic carrier by changing the selection of organic nitrogen ammonium salt, can control the nano-scale of the catalyst by changing the input amount of a sodium chloride template, and has the advantages of green color temperature, simplicity and great universality.
(2) The chromium-based inorganic matter coupled M-N-C catalyst of the invention is an ultrathin two-dimensional sheet structure composed of a plurality of interconnected nanocrystals. The two-dimensional structure is beneficial to the full contact between the active site and the reactant in the catalytic process, and the open structure at the two sides of the nano sheet can also effectively promote the efficiency of the mass transfer process and simplify the transportation path of reaction intermediate products and products. This also greatly improves the mass transfer capacity of the catalyst, due to the large number of pores between the crystals, allowing electrolyte and ions to be transported through the sheet.
(3) The chromium-based inorganic carrier introduced by the invention can improve the graphitization degree of M-N-C and enhance the conductivity of the catalyst. The introduction of the chromium-based inorganic matters can also induce electron spin polarization in the carbon layer where M-N-C is located, so that the catalytic selectivity and Faraday efficiency are improved, and the generation of byproducts is reduced. The chromium-based inorganic material has better thermodynamic and corrosion resistance capabilities relative to the carbon support, ensuring long-term stability of the catalyst at high currents and in severe battery testing.
In summary, the catalysts of the present invention are ultrathin, two-dimensional platelets composed of a plurality of interconnected nanocrystals. The chromium-based inorganic carrier is introduced into the M-N-C atomic-level dispersion catalyst to replace a conventional carbon carrier, so that the graphitization degree of the M-N-C is improved, the catalytic selectivity and Faraday efficiency are improved, and the durability of the catalyst under the conditions of high current and long-time working is improved.
Drawings
FIG. 1 is a flow chart of the preparation of examples 1-3 of the present invention;
FIG. 2 is the present inventionCoCN@Cr prepared in example 1 2 O 3 SEM images of (a);
FIG. 3 is FeCN@Cr prepared in example 2 of the present invention 2 O 3 SEM images of (a);
FIG. 4 is an SEM image of NiCN@CrN prepared in example 3 of the invention;
FIG. 5 is a CoCN@Cr prepared in example 1 of the invention 2 O 3 A TEM image of (a);
FIG. 6 is a CoCN@Cr prepared in example 1 of the invention 2 O 3 HRTEM images of (a);
FIG. 7 is a CoCN@Cr prepared in example 1 of the invention 2 O 3 XPS profile of N1s in CoCN prepared in comparative example 3;
FIG. 8 is a CoCN@Cr prepared in example 1 of the invention 2 O 3 XPS profile of Co 2p in CoCN prepared in comparative example 3;
FIG. 9 is a CoCN@Cr prepared in example 1 of the invention 2 O 3 Raman spectrum of CoCN prepared in comparative example 3;
FIG. 10 is a CoCN@Cr prepared in example 1 of the invention 2 O 3 Pt/C of comparative example 1, coCN prepared in comparative example 3, cr prepared in comparative example 4 2 O 3 Is a polar diagram of ORR (fuel cell);
FIG. 11 is a CoCN@Cr prepared in example 1 of the present invention 2 O 3 Catalytic efficiency test patterns of CoCN prepared in comparative example 3, including electron transfer number and byproduct H 2 O 2 Yield (fuel cell field);
FIG. 12 is a CoCN@Cr prepared in example 1 of the invention 2 O 3 The Pt/C of comparative example 1, the half cell of CoCN prepared in comparative example 3, was tested for i-t stability for 10 hours in succession (fuel cell and zinc-air cell fields);
FIG. 13 is a CoCN@Cr prepared in example 1 of the invention 2 O 3 I-t stability test patterns (fuel cell and zinc-air cell fields) for 50 hours in succession;
FIG. 14 is a CoCN@Cr prepared in example 1 of the invention 2 O 3 10000 cycles of aging of half cellTest patterns (fuel cell and zinc-air cell fields);
FIG. 15 is a CoCN@Cr prepared in example 1 of the present invention 2 O 3 Long-term charge-discharge cycle performance graphs (zinc-air battery field) of the Pt/c+ir/C mixtures of comparative examples 1 and 2 applied in ZABs;
FIG. 16 is FeCN@Cr prepared in example 2 of the present invention 2 O 3 ORR polarization diagram of Pt/C of comparative example 1 (fuel cell field);
FIG. 17 is an OER polarization diagram (electrolyzed water field) of NiCN@CrN prepared in example 3 of the present invention, ir/C of comparative example 2;
FIG. 18 is a chart of the stability test (electrolyzed water field) of the NiCN@CrN electrocatalytic OER prepared in example 3 of the present invention.
Detailed Description
The following description of the present invention refers to the accompanying drawings and examples, but is not limited to the same, and modifications and equivalents of the present invention can be made without departing from the spirit and scope of the present invention.
Preparing a metal M-bipyridine solution at room temperature, and stirring at room temperature to enable M ions and bipyridine to fully coordinate and grow; then adding sodium chloride solid, chromium salt solid and organic ammonium salt into the solution respectively, and stirring to completely dissolve the solid; placing the solution on a heating platform, removing water in the solution by a rotary evaporation method to obtain a solid mixture, and then placing the collected solid mixture in a vacuum oven for drying to obtain mixed powder; and finally, annealing the mixed powder in a protective atmosphere, washing to remove the sodium chloride template, and carrying out acid washing, suction filtration and drying procedures to obtain the chromium-based inorganic matter coupling transition metal nitrogen-doped carbon ultrastable catalyst.
The catalyst designed by the invention takes ultrathin two-dimensional sheet chromium-based inorganic matters formed by a plurality of interconnected nanocrystals as carriers, the two-dimensional structure is favorable for the full contact between active sites and reactants in the catalytic process, and the open structures on the two sides of the nanosheets can also effectively promote the mass transfer processThe efficiency of the reaction intermediate and the transportation route of the product are simplified. The presence of a large number of pores between the crystals allows the electrolyte and ions to be transported through the sheet, which can also greatly improve the mass transfer capacity of the catalyst. In addition, the introduced chromium-based inorganic carrier can improve the graphitization degree of M-N-C, enhance the conductivity of the catalyst, induce the spin polarization of electrons in a carbon layer where the M-N-C is positioned, improve the catalytic selectivity and Faraday efficiency, reduce the generation of byproducts and effectively inhibit the damage of active oxygen species to the active sites of the catalyst. Compared with the traditional carbon material, the chromium-based inorganic carrier has higher thermodynamic stability and corrosion resistance, so that the M-N-C coupled with the chromium-based inorganic carrier not only has higher catalytic activities such as ORR, OER and the like, but also has ultrahigh durability under high current and long-time circulation. In addition, the invention can introduce inorganic carrier into different types of M-N-C (M= Co, fe, cu, ni and the like) atomic fraction separation catalysts by a green and easy sodium chloride molten salt template method, and is widely applied to ORR, OER and carbon dioxide reduction (CO) 2 RR) and the like, and the energy conversion devices, further improves the practical value of the invention.
Example 1:
this example provides CoCN@Cr 2 O 3 The preparation method of the catalyst comprises the following steps:
1. preparing Co-bipyridine solution: weigh 24mg CoCl 2 ·6H 2 O and 48mg of 2,2 '-bipyridine are respectively dissolved into 20mL of ultrapure water, after the O and the 2' -bipyridine are completely dissolved, the two solutions are mixed to obtain orange-yellow solution, and the orange-yellow solution is stirred for 24 hours at normal temperature to enable Co ions and the bipyridine to fully coordinate and grow;
2. preparation of Co-Cr-organic ammonium salt mixed precursor: 20g of NaCl and 24mg of CrCl are respectively added into the solution prepared in the step one 2 And 72mg of organic ammonium salt and stirring to completely dissolve the solid. Then, placing the solution on a heating platform at 65 ℃, removing water in the solution by a rotary evaporation method to obtain a solid mixture, and then placing the collected solid mixture in a vacuum oven for heating and drying to remove residual water;
3.Cr 2 O 3 preparation of coupled Co-N-C composite catalyst: and (3) putting the precursor obtained in the step (II) into a mortar for full grinding, and then putting into a tube furnace for calcination treatment under inert atmosphere. The protective atmosphere is Ar or N 2 Inert gas, carbonization temperature of 700 ℃, carbonization time of 2h and heating rate of 2 ℃/min. Subsequently, the calcined product was dispersed in an aqueous solution, and the sodium chloride template was removed by washing with water a plurality of times. To remove Co clusters which may be present, the template-removed product is dispersed to 0.5mol L -1 Is a dilute H of (2) 2 SO 4 In the aqueous solution, stirring continuously at 80 ℃ for 5 hours, and obtaining the final flaky Cr by a water washing, suction filtration and vacuum drying mode 2 O 3 Co-N-C coupled composite ultra-stable catalyst (CoCN@Cr) 2 O 3 )；
The flow of this embodiment is shown in fig. 1. The prepared CoCN@Cr under the process 2 O 3 The SEM, TEM and HRTEM morphologies of (1) are shown in FIG. 2, FIG. 5 and FIG. 6, the content of Co in ICP test is 1.02wt.%, and the CoCN@Cr morphology is shown in FIG. 7 and FIG. 8 2 O 3 XPS spectrum of Co 2p and N1s in the catalyst shows that Co in the catalyst is single-atom Co-N x FIG. 9 shows Raman spectra before and after the introduction of inorganic carrier, cr 2 O 3 The introduction of (3) increases the graphitization degree of the CoCN. CoCN@Cr 2 O 3 Catalyst ORR polarization test and catalytic efficiency test as shown in fig. 10 and 11, respectively, electron transfer and byproduct H 2 O 2 The yield indicates that Cr is introduced 2 O 3 The stability test of the catalyst in RDE is shown in FIG. 12, FIG. 13 and FIG. 14, the stability of the catalyst is greatly improved by the inorganic chromium salt, the current retention rate of the catalyst in the i-t test for 10 hours is 100%, the stability of the catalyst in ZABS battery is shown in FIG. 15 after long-time circulation, and the catalyst can be continuously and stably charged and discharged for more than 1500 hours.
Example 2:
this example provides FeCN@Cr 2 O 3 The preparation method of the catalyst comprises the following steps:
1. preparing Fe-bipyridine solution: weigh 28mg FeCl 3 ·6H 2 O and 48mg of 2,2 '-bipyridine are respectively dissolved into 20mL of ultrapure water, after the O and the 2' -bipyridine are completely dissolved, the two solutions are mixed to obtain orange-yellow solution, and the orange-yellow solution is stirred for 24 hours at normal temperature to enable iron ions and the bipyridine to fully coordinate and grow;
2. preparing Fe-Cr-organic ammonium salt mixed precursor: 20g of NaCl and 24mg of CrCl are respectively added into the solution prepared in the step one 2 And 72mg urea and stirring to completely dissolve the solid. Then, placing the solution on a heating platform at 65 ℃, removing water in the solution by a rotary evaporation method to obtain a solid mixture, and then placing the collected solid mixture in a vacuum oven for heating and drying to remove residual water;
3. cr (Cr) 2 O 3 Preparation of coupled Fe-N-C composite catalyst: and (3) putting the precursor obtained in the step (II) into a mortar for full grinding, and then putting into a tube furnace for calcination treatment under inert atmosphere. The protective atmosphere is Ar inert gas, the carbonization temperature is 700 ℃, the carbonization time is 2 hours, and the heating rate is 2 ℃/min. Subsequently, the calcined product was dispersed in an aqueous solution, and the sodium chloride template was removed by washing with water a plurality of times. To remove Fe clusters which may be present, the template-removed product is dispersed to 0.5mol L -1 Is a dilute H of (2) 2 SO 4 In the aqueous solution, stirring continuously at 80 ℃ for 5 hours, and obtaining the final flaky Cr by a water washing, suction filtration and vacuum drying mode 2 O 3 Coupled Fe-N-C composite ultra-stable catalyst (FeCN@Cr) 2 O 3 )；
The flow of this embodiment is shown in fig. 1. FeCN@Cr prepared by the process 2 O 3 The SEM morphology of (2) is shown in FIG. 3, and the content of Fe is 1.52wt.% in ICP test, feCN@Cr 2 O 3 The ORR polarization test of the catalyst is shown in fig. 16, and the catalytic performance of the catalyst is obviously higher than that of the noble metal catalyst of comparative example 1, which represents a broad practical prospect in the field of fuel cells.
Example 3:
the embodiment provides a preparation method of a NiCN@CrN catalyst, which comprises the following steps:
1. preparing Ni-bipyridine solution: weigh 25mg NiCl 2 ·6H 2 O and 48mg of 2,2 '-bipyridine are respectively dissolved into 20mL of ultrapure water, after the O and the 2' -bipyridine are completely dissolved, the two solutions are mixed to obtain orange-yellow solution, and the orange-yellow solution is stirred for 24 hours at normal temperature to enable Co ions and the bipyridine to fully coordinate and grow;
2. preparation of Co-Cr-organic ammonium salt mixed precursor: 20g of NaCl and 24mg of CrCl are respectively added into the solution prepared in the step one 2 And 72mg melamine and stirring to completely dissolve the solid. Then, placing the solution on a heating platform at 65 ℃, removing water in the solution by a rotary evaporation method to obtain a solid mixture, and then placing the collected solid mixture in a vacuum oven for heating and drying to remove residual water;
3. preparation of CrN coupled Ni-N-C composite catalyst: and (3) putting the precursor obtained in the step (II) into a mortar for full grinding, and then putting into a tube furnace for calcination treatment under inert atmosphere. The protective atmosphere is Ar inert gas, the carbonization temperature is 650 ℃, the carbonization time is 2 hours, and the heating rate is 5 ℃/min. Subsequently, the calcined product was dispersed in an aqueous solution, and the sodium chloride template was removed by washing with water a plurality of times. To remove Ni clusters which may be present, the template-removed product is dispersed to 0.5mol L -1 Is a dilute H of (2) 2 SO 4 In the aqueous solution, continuously stirring for 5 hours at the temperature of 80 ℃, and obtaining the final flaky CrN coupled Ni-N-C composite ultra-stable catalyst (NiCN@CrN) through a water washing, suction filtration and vacuum drying mode;
the flow of this embodiment is shown in fig. 1. The SEM morphology of nicn@crn prepared under this process is shown in fig. 4, with ICP test Ni content of 1.34wt.%. OER polarization test of nicn@crn catalyst as shown in fig. 17, catalytic performance far exceeds that of comparative example 2. In addition, the stability test of the catalyst in RDE is shown in FIG. 18, and the catalyst performance is still excellent after 10000 times of aging, which represents that the catalyst has wide practical prospect in the field of fuel cells.
Comparative example 1:
the latest commercial 20% Pt/C (Comm.20% Pt/C) of a certain enterprise was purchased and used for testing directly without any treatment.
ORR polarization test of this example Comm.20% Pt/C is shown in FIG. 7. RDE stability test As shown in FIG. 10, the catalytic stability was far less than that of CoCN@Cr 2 O 3 。
Comparative example 2:
the latest commercial Ir/C (Comm.20% Ir/C) of a certain enterprise is purchased and directly used for testing without any treatment.
The OER polarization test for this example Comm.20% Ir/C is shown in FIG. 17.
Comparative example 3:
the steps of the CoCN which is prepared by the sodium chloride molten salt template method and is not introduced with inorganic carrier are as follows:
1. preparing Co-bipyridine solution: weigh 24mg CoCl 2 ·6H 2 O and 48mg of 2,2 '-bipyridine are respectively dissolved into 20mL of ultrapure water, after the O and the 2' -bipyridine are completely dissolved, the two solutions are mixed to obtain orange-yellow solution, and the orange-yellow solution is stirred for 24 hours at normal temperature to enable Co ions and the bipyridine to fully coordinate and grow;
2. preparation of Co-organic ammonium salt mixed precursor: to the solution prepared in the first step, 20g of NaCl and 75mg of urea were added, respectively, and the solid was completely dissolved by stirring. Then, placing the solution on a heating platform at 65 ℃, removing water in the solution by a rotary evaporation method to obtain a solid mixture, and then placing the collected solid mixture in a vacuum oven for heating and drying to remove residual water;
3. cr-free 2 O 3 Preparation of the coupled CoCN catalyst: and (3) putting the precursor obtained in the step (II) into a mortar for full grinding, and then putting into a tube furnace for calcination treatment under inert atmosphere. The protective atmosphere is Ar or N 2 Inert gas, carbonization temperature of 700 ℃, carbonization time of 2h and heating rate of 2 ℃/min. Subsequently, the calcined product was dispersed in an aqueous solution, and the sodium chloride template was removed by washing with water a plurality of times. To remove Co clusters which may be present, the template-removed product is dispersed to 0.5mol L -1 Is a dilute H of (2) 2 SO 4 In the aqueous solution, stirring continuously at 80 ℃ for 5 hours, and obtaining the final sheet-shaped Cr-free product by water washing, suction filtration and vacuum drying 2 O 3 Coupling ofCoCN；
The elemental valence analysis (XPS test) and graphitization degree (raman test) of CoCN prepared in this example are shown in fig. 7, 8 and 9, respectively; ORR polarization test, electron transfer number and H of CoCN 2 O 2 The yield test and the RDE stability test are shown in FIG. 10, FIG. 11 and FIG. 12, respectively. The ORR catalytic performance of CoCN is significantly lower than that of CoCN@Cr in example 1 2 O 3 Has higher by-product H 2 O 2 The yield proves that the catalytic efficiency is low, and the catalytic stability is far less than that of CoCN@Cr 2 O 3 。
Comparative example 4:
cr prepared by sodium chloride molten salt template method 2 O 3 The carrier comprises the following steps:
1. preparing a Cr-organic ammonium salt mixed precursor: 20g of NaCl and 24mg of CrCl were added to 40ml of ultrapure water, respectively 2 And 72mg urea and stirring to completely dissolve the solid. Then, placing the solution on a heating platform at 65 ℃, removing water in the solution by a rotary evaporation method to obtain a solid mixture, and then placing the collected solid mixture in a vacuum oven for heating and drying to remove residual water;
2. cr (Cr) 2 O 3 Preparation of inorganic matters: and (3) putting the precursor obtained in the step (II) into a mortar for full grinding, and then putting into a tube furnace for calcination treatment under inert atmosphere. The protective atmosphere is Ar or N 2 Inert gas, carbonization temperature of 700 ℃, carbonization time of 2h and heating rate of 2 ℃/min. Then dispersing the calcined product into aqueous solution, washing for multiple times to remove sodium chloride template, and vacuum-drying to obtain final sheet Cr 2 O 3 。
Cr prepared in this example 2 O 3 The ORR polarization tests of (2) are shown in figure 7, respectively. Cr (Cr) 2 O 3 ORR catalysis of (C) is not performed by CoCN@Cr 2 O 3 。
Claims (8)
1. A preparation method of a chromium-based inorganic matter coupled transition metal nitrogen doped carbon catalyst is characterized by comprising the following steps of: the method comprises the following steps:
step one: preparing a metal M-bipyridine solution:
weighing metal M salt and bipyridine, respectively dissolving in ultrapure water at room temperature, mixing the two solutions after complete dissolution to obtain orange-yellow solution, and stirring at room temperature to enable M ions and bipyridine to fully coordinate and grow; the metal M salt is one or more of ferric nitrate, ferric chloride, ferric acetate, ferrous nitrate, ferrous chloride, ferrous acetate, cobalt nitrate, cobalt chloride, cobalt acetate, copper nitrate, copper chloride, copper acetate, nickel nitrate, nickel chloride and nickel acetate;
step two: preparation of M-Cr-organic ammonium salt mixed precursor:
sequentially adding sodium chloride, chromium salt and organic ammonium salt into the orange-yellow solution obtained in the step one, and stirring to completely dissolve the solid; placing the solution on a heating platform, removing water in the solution by a rotary evaporation method to obtain a solid mixture, and placing the solid mixture in a vacuum oven for vacuum heating and drying to remove residual water to obtain an M-Cr-organic ammonium salt mixed precursor; the input amount of the sodium chloride is determined according to the volume of the M-bipyridine solution, and each milliliter of the solution corresponds to 0.5g sodium chloride; the organic ammonium salt is one of urea, melamine, dicyandiamide and ammonium citrate;
step three: preparation of chromium-based inorganic matter coupled M-N-C composite catalyst:
putting the precursor obtained in the second step into a mortar for full grinding, and then putting the mortar into a tube furnace for calcination treatment under a protective atmosphere; dispersing the calcined product into an aqueous solution, and removing a sodium chloride template through multiple times of water washing; dispersing the template-removed product into dilute H 2 SO 4 And (3) in the aqueous solution, continuously stirring at 80 ℃ for 5h, and performing water washing, suction filtration and vacuum drying to obtain the chromium-based inorganic matter coupling transition metal nitrogen doped carbon catalyst.
2. The method for preparing the chromium-based inorganic matter-coupled transition metal nitrogen-doped carbon catalyst according to claim 1, which is characterized in that: in the first step, the molar ratio of the metal M salt to the bipyridine is 1: 1-4.
3. The method for preparing the chromium-based inorganic matter-coupled transition metal nitrogen-doped carbon catalyst according to claim 1, which is characterized in that: in the first step, the bipyridine is 2,2 '-bipyridine or 4,4' -bipyridine.
4. The method for preparing the chromium-based inorganic matter-coupled transition metal nitrogen-doped carbon catalyst according to claim 1, which is characterized in that: in the second step, the molar ratio of the chromium salt to the metal M salt is 1-8: 1, the mass ratio of the organic ammonium salt to the chromium salt is 3:1.
5. the method for preparing the chromium-based inorganic matter-coupled transition metal nitrogen-doped carbon catalyst according to claim 1, which is characterized in that: in the second step, the chromium salt is one of chromium chloride, chromium sulfate and chromium nitrate.
6. The method for preparing the chromium-based inorganic matter-coupled transition metal nitrogen-doped carbon catalyst according to claim 3, wherein the method comprises the following steps: in the third step, the protective atmosphere is Ar or N 2 The calcining temperature is 650-800 ℃, the time is 1-3h, and the heating rate is 2-10 ℃/min.
7. A chromium-based inorganic coupled transition metal nitrogen-doped carbon catalyst prepared by the method of any one of claims 1-6.
8. Use of a chromium-based inorganic coupled transition metal nitrogen-doped carbon catalyst prepared by the method of any one of claims 1-6 in fuel cells, metal-air cell cathode oxygen reduction reactions, and electrolytic water oxygen evolution reactions.
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