CN117463382B - Ultra-fast preparation of porous Fe with strain effect 2 P/Co 2 Method for preparing P heterojunction catalyst and application thereof - Google Patents
Ultra-fast preparation of porous Fe with strain effect 2 P/Co 2 Method for preparing P heterojunction catalyst and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 76
- 238000000034 method Methods 0.000 title claims abstract description 44
- 230000000694 effects Effects 0.000 title claims abstract description 29
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- 239000000463 material Substances 0.000 claims abstract description 16
- KWSLGOVYXMQPPX-UHFFFAOYSA-N 5-[3-(trifluoromethyl)phenyl]-2h-tetrazole Chemical compound FC(F)(F)C1=CC=CC(C2=NNN=N2)=C1 KWSLGOVYXMQPPX-UHFFFAOYSA-N 0.000 claims abstract description 14
- 229910001379 sodium hypophosphite Inorganic materials 0.000 claims abstract description 14
- 239000011780 sodium chloride Substances 0.000 claims abstract description 12
- 239000001257 hydrogen Substances 0.000 claims abstract description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 8
- 150000003839 salts Chemical class 0.000 claims abstract description 8
- 239000002243 precursor Substances 0.000 claims description 50
- 239000011259 mixed solution Substances 0.000 claims description 48
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- 238000010438 heat treatment Methods 0.000 claims description 32
- 238000003756 stirring Methods 0.000 claims description 28
- 238000001291 vacuum drying Methods 0.000 claims description 25
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- 239000002904 solvent Substances 0.000 claims description 24
- 238000005406 washing Methods 0.000 claims description 18
- QMKYBPDZANOJGF-UHFFFAOYSA-N benzene-1,3,5-tricarboxylic acid Chemical compound OC(=O)C1=CC(C(O)=O)=CC(C(O)=O)=C1 QMKYBPDZANOJGF-UHFFFAOYSA-N 0.000 claims description 16
- 238000006243 chemical reaction Methods 0.000 claims description 13
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 12
- 238000001035 drying Methods 0.000 claims description 12
- 230000035939 shock Effects 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 9
- 229910021641 deionized water Inorganic materials 0.000 claims description 9
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical group [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 8
- 229920000877 Melamine resin Polymers 0.000 claims description 8
- 239000012298 atmosphere Substances 0.000 claims description 8
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 8
- 230000001681 protective effect Effects 0.000 claims description 8
- 150000001868 cobalt Chemical class 0.000 claims description 7
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 6
- 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 6
- 229910052757 nitrogen Inorganic materials 0.000 claims description 6
- 239000001301 oxygen Substances 0.000 claims description 6
- 229910052760 oxygen Inorganic materials 0.000 claims description 6
- 229910052786 argon Inorganic materials 0.000 claims description 4
- 239000013384 organic framework Substances 0.000 claims description 4
- CDVAIHNNWWJFJW-UHFFFAOYSA-N 3,5-diethoxycarbonyl-1,4-dihydrocollidine Chemical compound CCOC(=O)C1=C(C)NC(C)=C(C(=O)OCC)C1C CDVAIHNNWWJFJW-UHFFFAOYSA-N 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 3
- 229940011182 cobalt acetate Drugs 0.000 claims description 3
- 229910021446 cobalt carbonate Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 229940044175 cobalt sulfate Drugs 0.000 claims description 3
- 229910000361 cobalt sulfate Inorganic materials 0.000 claims description 3
- KTVIXTQDYHMGHF-UHFFFAOYSA-L cobalt(2+) sulfate Chemical compound [Co+2].[O-]S([O-])(=O)=O KTVIXTQDYHMGHF-UHFFFAOYSA-L 0.000 claims description 3
- ZOTKGJBKKKVBJZ-UHFFFAOYSA-L cobalt(2+);carbonate Chemical compound [Co+2].[O-]C([O-])=O ZOTKGJBKKKVBJZ-UHFFFAOYSA-L 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
- FJDJVBXSSLDNJB-LNTINUHCSA-N cobalt;(z)-4-hydroxypent-3-en-2-one Chemical compound [Co].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O FJDJVBXSSLDNJB-LNTINUHCSA-N 0.000 claims description 3
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 3
- RUTXIHLAWFEWGM-UHFFFAOYSA-H iron(3+) sulfate Chemical compound [Fe+3].[Fe+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O RUTXIHLAWFEWGM-UHFFFAOYSA-H 0.000 claims description 3
- 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 3
- YPJCVYYCWSFGRM-UHFFFAOYSA-H iron(3+);tricarbonate Chemical compound [Fe+3].[Fe+3].[O-]C([O-])=O.[O-]C([O-])=O.[O-]C([O-])=O YPJCVYYCWSFGRM-UHFFFAOYSA-H 0.000 claims description 3
- 229910000360 iron(III) sulfate Inorganic materials 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 239000003792 electrolyte Substances 0.000 abstract description 17
- 239000003795 chemical substances by application Substances 0.000 abstract description 4
- 238000005516 engineering process Methods 0.000 abstract description 4
- 239000002149 hierarchical pore Substances 0.000 abstract description 3
- 230000009471 action Effects 0.000 abstract description 2
- 150000002815 nickel Chemical class 0.000 abstract description 2
- 238000001308 synthesis method Methods 0.000 abstract description 2
- 239000006258 conductive agent Substances 0.000 abstract 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 80
- 239000011148 porous material Substances 0.000 description 45
- 238000012360 testing method Methods 0.000 description 42
- 230000003197 catalytic effect Effects 0.000 description 16
- 230000000052 comparative effect Effects 0.000 description 16
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 15
- 229910000510 noble metal Inorganic materials 0.000 description 15
- 239000000843 powder Substances 0.000 description 15
- 229910002804 graphite Inorganic materials 0.000 description 14
- 239000010439 graphite Substances 0.000 description 14
- 239000012299 nitrogen atmosphere Substances 0.000 description 12
- 238000009210 therapy by ultrasound Methods 0.000 description 10
- 238000005265 energy consumption Methods 0.000 description 7
- 229910052742 iron Inorganic materials 0.000 description 7
- 239000007788 liquid Substances 0.000 description 7
- 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 6
- 238000001354 calcination Methods 0.000 description 6
- 239000004570 mortar (masonry) Substances 0.000 description 6
- 238000005303 weighing Methods 0.000 description 6
- 238000000227 grinding Methods 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 229910052698 phosphorus Inorganic materials 0.000 description 5
- 238000001179 sorption measurement Methods 0.000 description 5
- 230000004888 barrier function Effects 0.000 description 4
- 239000007806 chemical reaction intermediate Substances 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 238000000197 pyrolysis Methods 0.000 description 4
- NCPXQVVMIXIKTN-UHFFFAOYSA-N trisodium;phosphite Chemical compound [Na+].[Na+].[Na+].[O-]P([O-])[O-] NCPXQVVMIXIKTN-UHFFFAOYSA-N 0.000 description 4
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical group [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 3
- 239000010411 electrocatalyst Substances 0.000 description 3
- 238000000643 oven drying Methods 0.000 description 3
- 238000011056 performance test Methods 0.000 description 3
- 239000011574 phosphorus Substances 0.000 description 3
- 238000000634 powder X-ray diffraction Methods 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000035882 stress Effects 0.000 description 3
- 229910052723 transition metal Inorganic materials 0.000 description 3
- 150000003624 transition metals Chemical class 0.000 description 3
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 230000002776 aggregation Effects 0.000 description 2
- 239000012300 argon atmosphere Substances 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 230000002194 synthesizing effect Effects 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- WHXSMMKQMYFTQS-UHFFFAOYSA-N Lithium Chemical compound [Li] WHXSMMKQMYFTQS-UHFFFAOYSA-N 0.000 description 1
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 230000009194 climbing Effects 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
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- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000003837 high-temperature calcination Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- 150000002505 iron Chemical class 0.000 description 1
- 229910052744 lithium Inorganic materials 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910052748 manganese Inorganic materials 0.000 description 1
- 239000011572 manganese Substances 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
- 239000002114 nanocomposite Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Substances [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 1
- 239000007774 positive electrode material Substances 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 230000008646 thermal stress Effects 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/14—Phosphorus; Compounds thereof
- B01J27/185—Phosphorus; Compounds thereof with iron group metals or platinum group metals
- B01J27/1853—Phosphorus; Compounds thereof with iron group metals or platinum group metals with iron, cobalt or nickel
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/04—Mixing
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C—CHEMISTRY; METALLURGY
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- 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
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- C—CHEMISTRY; METALLURGY
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- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/054—Electrodes comprising electrocatalysts supported on a carrier
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- C25B11/051—Electrodes formed of electrocatalysts on a substrate or carrier
- C25B11/073—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material
- C25B11/091—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of at least one catalytic element and at least one catalytic compound; consisting of two or more catalytic elements or catalytic compounds
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
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Abstract
The invention discloses an ultra-fast preparation method of porous Fe with strain effect 2 P/Co 2 A method for preparing a P heterojunction catalyst and application thereof belong to the technical field of heterojunction catalyst material preparation. The invention uses hydrogen bond organic frame as support, sodium chloride as template agent and heat conductive agent, under the action of ferric salt, nickel salt and sodium hypophosphite, uses fast Joule thermal impact technology to prepare porous Fe 2 P/Co 2 P heterojunction catalysts. Porous Fe of the present invention 2 P/Co 2 P heterojunction catalyst at 10mAcm ‑2 And OER overpotential under 1MKOH electrolyte is less than or equal to 259.5mv. The synthesis method is simple, efficient and low in cost, and the prepared heterojunction catalyst has rich strain effect and hierarchical pore structure and shows excellent electrocatalytic OER activity in electrolyzed water.
Description
Technical Field
The invention belongs to the technical field of heterojunction material preparation, and in particular relates to ultra-fast preparation of porous Fe with strain effect 2 P/Co 2 A method of P heterojunction catalyst and application thereof.
Background
The global economic growth is limited by the consumption of fossil fuels and the worsening of environmental problems. These problems can be fundamentally solved using clean renewable energy sources. In the search for clean and sustainable energy, processes for electrocatalytic water splitting to produce hydrogen are considered one of the most promising processes. Since Oxygen Evolution Reaction (OER) is a multiple electron transfer step, the slow kinetics of the process greatly impedes the overall water splitting efficiency. The noble metal-based nanomaterial can significantly reduce OER (i.e., ruO 2 And IrO 2 ) But noble metal resources are insufficient, the cost is high, and the wide application of the high-voltage power supply is severely restricted. In order to solve the above problems, it is important to develop an efficient and stable non-noble metal electrocatalyst for OER.
Among the non-noble metal OER electrocatalysts that have been explored, transition Metal Phosphides (TMPs) have shown specific potential as high efficiency OER catalysts in that they have good electrical conductivity and excellent electrochemical activity. Research on the surface, and regulation of the electronic structure of the catalyst surface are effective strategies for promoting electrocatalytic water splitting reaction. Among them, interface engineering is one of means for adjusting electronic structures. Because the heterogeneous interface is constructed, a strain field can be induced in the catalyst, the electronic structure of an adsorption site is regulated, and the adsorption energy of the OER intermediate is optimized, so that the OER intrinsic activity is improved. However, the main method for constructing a heterogeneous interface in the transition metal phosphide is by a high-temperature calcination template method. The synthetic method has longer reaction time and higher energy consumption.
The Chinese patent document with publication number CN115915738A discloses a HOF-derived one-dimensional Ni-doped magnetic carbon-based nanocomposite and a preparation method thereof. The preparation method adopts the traditional pyrolysis calcination method, the heat preservation time is 2 hours at 600-900 ℃, and the heating rate is 2 ℃/min. The preparation method is time-consuming and energy-consuming, and can easily cause agglomeration of metal atoms, block mass transfer and block exposed active sites, thereby resulting in poor catalytic performance.
The Chinese patent document with publication number of CN113511692A discloses a preparation method and application of a short-time rapid thermal shock method for synthesizing a lithium-rich manganese-based positive electrode material. The preparation method mainly highlights the preparation of oxides of various elements and changes of grain sizes, namely a catalyst for forming single atoms, but the application of the patent does not relate to the grain sizes (single atoms) and the preparation of the oxides, and the OER performance of the oxides is lower.
The Chinese patent document with publication number of CN114196971A discloses a preparation method of a noble metal doped bimetallic phosphide catalyst for electrochemical full water decomposition. The method comprises the steps of synthesizing noble metal doped bimetallic phosphide by a hydrothermal method, and calcining the noble metal doped bimetallic phosphide and sodium hypophosphite in a tubular manner by a traditional calcining method to obtain a noble metal doped heterojunction. The method adopts the traditional pyrolysis method, has the defects of few active sites of the catalyst and the like, and has limited improvement on the catalytic performance after being doped with noble metal, namely the overpotential of OER in electrolyte of 1M KOH is 303 mV (10 mA cm) -2 ) With commercial RuO 2 Catalytic performance is as good as (321.6 mV@10 mA cm) -2 )。
Disclosure of Invention
The invention aims to provide a method for preparing porous Fe with strain effect in ultra-fast way 2 P/Co 2 The method of the P heterojunction catalyst can solve the problems that the reaction time is long, metal atoms are easy to gather and block the exposure of active sites in the traditional pyrolysis method catalyst preparation process, and the activity of the catalyst is low. The method of the invention prepares the porous Fe with strain effect by utilizing the Joule heat high-temperature impact technology under the action of taking a hydrogen bond organic framework as a support, sodium chloride as a template agent, a heat conduction agent, ferric salt, nickel salt and sodium hypophosphite 2 P/Co 2 Compared with the traditional electrolytic water catalyst, the P heterojunction catalyst has the advantages of low cost, simple synthesis method and higher electric catalytic OER performance.
In order to solve the problems, the invention provides an ultra-fast preparation method for porous Fe with strain effect 2 P/Co 2 A method of P heterojunction catalyst comprising the steps of:
(1) Dissolving melamine and trimesic acid in a solvent I, performing ultrasonic reaction at room temperature for 1-3h, and obtaining hydrogen bond organic frame materials (HOFs) after centrifugation, washing and vacuum drying;
(2) HOFs and sodium chloride are dissolved in a solvent II to prepare a mixed solution A; dissolving ferric salt and cobalt salt in a solvent II to prepare a mixed solution B; dropwise adding the mixed solution B into the mixed solution A under stirring to obtain mixed solution C, stirring until the solvent in the mixed solution C is completely volatilized, and drying in vacuum to obtain a precursor D;
(3) Carrying out quick joule thermal shock on the precursor D in a protective atmosphere to obtain a precursor E;
(4) Mixing the precursor E with sodium hypophosphite, performing rapid joule thermal shock under a protective atmosphere, centrifuging, washing, and vacuum drying to obtain porous Fe 2 P/Co 2 P heterojunction catalysts.
Further, in the step (1), the solvent I is methanol or ethanol; the washing condition is ethanol washing for three to five times; the vacuum drying conditions are as follows: drying at 40-80deg.C for 6-14 hr;
in the step (2), the solvent II is one of methanol, ethanol or water; the vacuum drying conditions are drying temperature: 40-80 ℃ and drying time: 2-4h;
in the step (3), the protective atmosphere is argon or nitrogen;
in the step (4), the protective atmosphere is argon or nitrogen; the washing condition is that deionized water is washed for three to five times; the vacuum drying conditions are as follows: drying at 40-80deg.C for 2-4 hr.
Further, in the step (2), the ferric salt is one of ferric chloride, ferric nitrate, ferric sulfate, ferric acetate, ferric carbonate or ferric acetylacetonate; the cobalt salt is one of cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt carbonate or cobalt acetylacetonate.
Further, in the step (1), the dosage proportion of the melamine, the trimesic acid and the solvent I is 0.8-1mmol:1mmol:25-30ml.
Further, in the step (2), the dosage ratio of the hydrogen bond organic framework material, sodium chloride and the solvent II is 200mg:200-1000mg:10-20ml.
Further, in the step (2), the dosage ratio of the ferric salt, the cobalt salt and the solvent II is 0.3mmol to 0.3-0.9mmol:5-10ml.
Further, in the step (3), the rapid joule thermal shock temperature is 900-1100 ℃; the heating rate of the Joule heat is 1500-2500 ℃/s; the number of joule heat impact is 3-5.
Further, in the step (4), the mass ratio of the precursor E to the sodium hypophosphite is 1:1-5.
Further, in the step (4), the rapid joule heat impact temperature is 500-1000 ℃; the heating rate of the Joule heat is 1500-2500 ℃/s; the number of joule heat impact is 5-7.
The invention also provides the porous Fe with the strain effect prepared by the method 2 P/Co 2 Application of P heterojunction, the porous Fe 2 P/Co 2 The P heterojunction is used for Oxygen Evolution Reaction (OER) in alkaline water.
In the invention, the joule heat impact is that the room temperature is raised to the target temperature, and then the room temperature is naturally cooled to the room temperature, which is expressed as one time.
The invention has the beneficial effects that:
(1) The invention forms the transition metal porous Fe rich in stress in the extreme environment of rapid temperature rise and drop by utilizing the rapid Joule thermal shock technology 2 P/Co 2 The P heterojunction effectively builds a rich stress field in the heterojunction material by utilizing the thermal stress generated by the temperature difference between the inside and the outside of the heterojunction material in the rapid temperature rise process and the lattice stress generated by lattice mismatch in the heterojunction; the strain effect obviously adjusts the electronic structures of active sites Fe and Co, optimizes the binding energy of the active sites Fe and Co and a reaction intermediate, further reduces the overpotential and improves the catalytic performance.
(2) Porous Fe prepared by the invention 2 P/Co 2 The porous structure of the P heterojunction catalyst enhances desorption of oxygen of a product, the heterojunction structure is beneficial to exposure of an active site and optimizes the binding energy barrier of the P heterojunction catalyst and O or OH or OOH, and the porous structure cooperate to improve OER catalytic performance in 1M KOH electrolyte.
(3) The method is simple, efficient and low in cost, and the prepared heterojunction catalyst has rich strain effect and porous Fe 2 P/Co 2 P heterojunction catalyst at 10mA cm -2 The OER overpotential in the 1M KOH electrolyte is 258.1-259.5mv, which is superior to the catalyst obtained by the traditional preparation method and the commercial noble metal catalyst, and shows excellent electrocatalytic OER activity.
Drawings
FIG. 1 shows the precursor D of step (2), the precursor E of step (3) and the porous Fe of step (4) in example 1 2 P/Co 2 The pore size distribution map of the NLDFT model of the P heterojunction catalyst was determined by the nitrogen full adsorption test at 77K (N 2 -BET) test results;
FIG. 2 is porous Fe in example 1 2 P/Co 2 Scanning Electron Microscope (SEM) images of P heterojunction catalysts;
FIG. 3 is porous Fe in example 1 2 P/Co 2 P heterojunction catalysisX-ray powder diffraction (XRD) pattern of the agent;
FIG. 4 is a porous Fe in example 1 2 P/Co 2 An interface high resolution imaging (HR-TEM) image of the P heterojunction;
FIG. 5 is porous Fe in example 1 2 P/Co 2 P heterojunction catalyst, fe in comparative example 1 2 P/Co 2 P-7, fe in comparative example 2 2 P, co in comparative example 3 2 P, commercial RuO 2 Is an electrocatalytic oxygen evolution LSV curve.
Detailed Description
The present invention will be further described with reference to examples and drawings, but the scope of the present invention is not limited thereto.
In the present invention, all the equipment, raw materials and the like are commercially available or commonly used in the industry unless otherwise specified.
Example 1
(1) 1mmol of trimesic acid and 0.83mmol of melamine are added into 28ml of methanol for ultrasonic treatment for 3 hours to form white turbid liquid, and then the white turbid liquid is centrifugally washed with ethanol for three times; placing the washed product into an oven, and vacuum drying for 10 hours at 40 ℃ to obtain HOFs;
(2) 200mg of HOFs and 200mg of NaCl are weighed and placed in a 50mL beaker, then 15mL of ethanol is added, ultrasonic treatment is carried out for 10min, and then stirring is carried out for 1h at 600rpm, so as to obtain a mixed solution A;
weighing 0.3mmol of ferric chloride and 0.3mmol of cobalt chloride, dissolving in 5ml of ethanol, and stirring at 600rpm for 5min to obtain a mixed solution B;
dropwise adding the mixed solution B into the mixed solution A under the condition that the mixed solution A rotates at 280rpm, adjusting the rotating speed to 600rpm after the mixed solution B is completely added, and continuously stirring overnight until the solvent is completely volatilized; after stirring, vacuum drying is carried out in an oven at 40 ℃ for 3 hours to obtain a precursor D, and grinding is carried out by a mortar until the precursor D is uniformly powdered;
(3) Placing the 300mg precursor D in a groove of a graphite sample table of a quick heating device for joule heat, and performing joule heat impact for 4 times in a nitrogen atmosphere, wherein the joule heat impact temperature is 900 ℃, and the heating rate is 1500 ℃/s, so as to obtain a precursor E;
(4) 20mg of precursor E and 50mg sodium phosphite are respectively placed at the left end and the right end of a groove of a graphite sample table of the quick heating device for Joule heat, joule heat impact is carried out for 5 times in a nitrogen atmosphere, the Joule heat impact temperature is 800 ℃, and the heating rate is 1500 ℃/s; centrifuging and washing the prepared powder with deionized water for three times, and vacuum drying at 40deg.C for 3 hr to obtain porous Fe 2 P/Co 2 P heterojunction catalyst, named Fe 2 P/Co 2 P-1 heterojunction.
Performing nitrogen total adsorption (N) on the precursor D in the step (2) 2 -BET), see fig. 1; n is carried out on the precursor E in the step (3) 2 Pore size test of BET, see fig. 1; for porous Fe in step (4) 2 P/Co 2 P heterojunction catalyst N 2 BET aperture, scanning Electron Microscope (SEM) morphology, X-ray powder diffraction (XRD) structure, high resolution imaging (HR-TEM) test, see FIGS. 1, 2, 3, 4, respectively.
As can be seen from fig. 1, the pore diameter of the precursor D in the step (2) ranges from 0.2 nm to 20nm, which represents a microporous and mesoporous hierarchical pore structure; in the step (3), the pore diameter range of the precursor E is 0.2-30nm, and the pore diameter range is enlarged, which is expressed as a microporous and mesoporous multi-level pore structure; porous Fe in step (4) 2 P/Co 2 The pore diameter of the P heterojunction catalyst ranges from 0.2 nm to 120nm, and the P heterojunction catalyst is expressed as a multi-level pore structure with micropores, mesopores and macropores.
As can be seen from FIG. 2, porous Fe 2 P/Co 2 The morphology of the P heterojunction catalyst is mainly presented as nano particles, so that the contact area of the catalyst and electrolyte is increased.
As can be seen from FIG. 3, porous Fe 2 P/Co 2 The P heterojunction catalyst has Fe 2 P and Co 2 P two phases constitute, indicating the structure of heterojunction formation.
As can be seen from FIG. 4, porous Fe 2 P/Co 2 The atomic configuration at the interface of the P heterojunction catalyst is changed due to the strain effect, which is helpful for adjusting the electronic structures of the active sites Fe and Co, optimizing the binding energy of the active sites Fe and Co and the reaction intermediate, and reducing the binding energy of the active sites Fe and Co and the reaction intermediateLow reaction energy barrier, and further improving the catalytic performance.
Porous Fe obtained in the step (4) 2 P/Co 2 The P heterojunction catalyst is used for Oxygen Evolution (OER) application of electrocatalysis in alkaline water, and comprises the following application steps:
graphite rod is used as a counter electrode, hg/HgO is used as a reference electrode, and porous Fe is loaded 2 P/Co 2 The glassy carbon electrode of the P heterojunction (diameter 5mm, catalyst loading 40 μg) was used as the working electrode and the OER activity of the catalyst was tested in 1M KOH electrolyte, see fig. 5.
As can be seen from FIG. 5, porous Fe 2 P/Co 2 P heterojunction catalyst at 10mA cm -2 Subtracting the voltage of the theoretical electrolyzed water of 1.23V at the current density to obtain Fe 2 P/Co 2 The P-1 heterojunction electrocatalyst only requires an overpotential of 258.6 mV, far below commercial RuO 2 (321.6 mV@10 mA cm -2 ) Has industrial application prospect.
Example 2
(1) 1mmol of trimesic acid and 0.8mmol of melamine are added into 25ml of ethanol for ultrasonic treatment for 2 hours to form white turbid liquid, and then the white turbid liquid is centrifugally washed four times by ethanol; placing the washed product into an oven, and vacuum drying for 6 hours at 40 ℃ to obtain HOFs;
(2) 200mg of HOFs and 200mg of NaCl are weighed and placed in a 50mL beaker, then 10mL of water is added, ultrasonic treatment is carried out for 10min, and then stirring is carried out for 1h at 600rpm, so as to obtain a mixed solution A;
weighing 0.3mmol of ferric nitrate and 0.6mmol of cobalt nitrate, dissolving in 8ml of water, and stirring at 600rpm for 5min to obtain a mixed solution B;
dropwise adding the mixed solution B into the mixed solution A under the condition that the mixed solution A rotates at 280rpm, adjusting the rotating speed to 600rpm after the mixed solution B is completely added, and continuously stirring overnight until the solvent is completely volatilized; after stirring, drying in a drying oven at 60 ℃ for 2 hours in vacuum to obtain a precursor D, and grinding the precursor D into uniform powder by using a mortar;
(3) Placing the 300mg precursor D in a groove of a graphite sample table of a quick heating device for joule heat, and performing joule heat impact for 3 times in an argon atmosphere, wherein the joule heat impact temperature is 1000 ℃, and the heating rate is 2000 ℃/s, so as to obtain a precursor E;
(4) Respectively placing 20mg of precursor E and 20mg of sodium hypophosphite at the left end and the right end of a groove of a graphite sample table of the quick heating device for Joule heat, and performing Joule heat impact for 5 times in an argon atmosphere, wherein the Joule heat impact temperature is 1000 ℃, and the heating rate is 2000 ℃/s; centrifuging and washing the prepared powder with deionized water for four times, and vacuum drying at 60deg.C for 2 hr to obtain porous Fe 2 P/Co 2 P heterojunction, named Fe 2 P/Co 2 P-2 heterojunction.
For the porous Fe obtained in the step (4) 2 P/Co 2 P heterojunction N 2 Pore size test of BET and OER Performance application test, see Table 1, the method of OER Performance application test is the same as that of example 1.
As is clear from Table 1, porous Fe 2 P/Co 2 The pore diameter range of the P heterojunction catalyst is 0.2-115nm, and the P heterojunction catalyst has a multi-level pore structure with micropores, mesopores and macropores; in 1M KOH electrolyte, 10mA cm -2 Fe at current density of (2) 2 P/Co 2 The OER overpotential of the P-2 heterojunction is 259.1mV, far below that of commercial RuO 2 Noble metal catalyst (321.6 mV@10 mA cm) -2 ) Has industrial application prospect.
Example 3
(1) 1mmol of trimesic acid and 1mmol of melamine are added into 30ml of methanol for ultrasonic treatment for 3 hours to form white turbid liquid, and then the white turbid liquid is centrifugally washed with ethanol for five times; placing the washed product into an oven, and vacuum drying for 14h at 60 ℃ to obtain HOFs;
(2) 200mg of HOFs and 600mg of NaCl are weighed and placed in a 50mL beaker, then 20mL of methanol is added, ultrasonic treatment is carried out for 10min, and then stirring is carried out for 1h at 600rpm, thus obtaining a mixed solution A;
weighing 0.3mmol of ferric sulfate and 0.3mmol of cobalt sulfate, dissolving in 10ml of methanol, and stirring at 600rpm for 5min to obtain a mixed solution B;
dropwise adding the mixed solution B into the mixed solution A under the condition that the mixed solution A rotates at 280rpm, adjusting the rotating speed to 600rpm after the mixed solution B is completely added, and continuously stirring overnight until the solvent is completely volatilized; after stirring, the mixture was dried in an oven at 80℃for 4 hours under vacuum to give precursor D, which was ground to a uniform powder with a mortar.
(3) Placing the 300mg precursor D in a groove of a graphite sample stage of a quick heating device for joule heat, and performing joule heat impact for 3 times in a nitrogen atmosphere, wherein the joule heat impact temperature is 1100 ℃, and the heating rate is 2500 ℃/s, so as to obtain a precursor E;
(4) Respectively placing 20mg of precursor E and 50mg of sodium hypophosphite at the left end and the right end of a groove of a graphite sample table of the quick heating device for Joule heat, and performing Joule heat impact for 7 times in a nitrogen atmosphere, wherein the Joule heat impact temperature is 600 ℃, and the heating rate is 2500 ℃/s; centrifuging and washing the prepared powder with deionized water for five times, and vacuum drying at 80deg.C for 4 hr to obtain porous Fe 2 P/Co 2 P heterojunction catalyst, named Fe 2 P/Co 2 P-3 heterojunction.
For the porous Fe obtained in the step (4) 2 P/Co 2 P heterojunction catalyst N 2 Pore size test of BET and OER Performance application test, see Table 1, the method of OER Performance application test is the same as that of example 1.
As is clear from Table 1, porous Fe 2 P/Co 2 The pore diameter range of the P heterojunction catalyst is 0.2-120nm, and the P heterojunction catalyst has a multi-level pore structure with micropores, mesopores and macropores; in 1M KOH electrolyte, 10mA cm -2 Fe at current density of (2) 2 P/Co 2 The OER overpotential of the P-3 heterojunction is 258.9mV, far below that of commercial RuO 2 Noble metal catalyst (321.6 mV@10 mA cm) -2 ) Has industrial application prospect.
Example 4
(1) Step (1) as in example 1;
(2) 200mg of HOFs and 1000mg of NaCl are weighed and placed in a 50mL beaker, then 10mL of ethanol is added, ultrasonic treatment is carried out for 10min, and then stirring is carried out for 1h at 600rpm, thus obtaining a mixed solution A;
weighing 0.3mmol of ferric acetate and 0.9mmol of cobalt acetate, dissolving in 5ml of ethanol, and stirring at 600rpm for 5min to obtain a mixed solution B;
dropwise adding the mixed solution B into the mixed solution A under the condition that the mixed solution A rotates at 280rpm, adjusting the rotating speed to 600rpm after the mixed solution B is completely added, and continuously stirring overnight until the solvent is completely volatilized; after stirring, vacuum drying is carried out in an oven at 60 ℃ for 3 hours to obtain a precursor D, and grinding is carried out by a mortar until the precursor D is uniformly powdered;
(3) Placing the 300mg precursor D in a groove of a graphite sample table of a quick heating device for joule heat, and performing joule heat impact for 5 times in a nitrogen atmosphere, wherein the joule heat impact temperature is 900 ℃, and the heating rate is 1500 ℃/s, so as to obtain a precursor E;
(4) 20mg of precursor E and 100 mg sodium phosphite are respectively placed at the left end and the right end of a groove of a graphite sample table of the quick heating device for joule heat, the joule heat impact is carried out for 7 times in the nitrogen atmosphere, the joule heat impact temperature is 500 ℃, and the heating rate is 1800 ℃/s; centrifuging and washing the prepared powder with deionized water for three times, and vacuum drying at 60deg.C for 3 hr to obtain porous Fe 2 P/Co 2 P heterojunction catalyst, named Fe 2 P/Co 2 P-4 heterojunction.
For the porous Fe obtained in the step (4) 2 P/Co 2 P heterojunction catalyst N 2 Pore size test of BET and OER Performance application test, see Table 1, the method of OER Performance application test is the same as that of example 1.
As is clear from Table 1, porous Fe 2 P/Co 2 The pore diameter range of the P heterojunction catalyst is 0.2-110nm, and the P heterojunction catalyst has a multi-level pore structure with micropores, mesopores and macropores; in 1M KOH electrolyte, 10mA cm -2 Fe at current density of (2) 2 P/Co 2 The OER overpotential of the P-4 heterojunction is 258.1mV, far below that of commercial RuO 2 Noble metal catalyst (321.6 mV@10 mA cm) -2 ) Has industrial application prospect.
Example 5
(1) 1mmol of trimesic acid and 0.85mol of melamine are added into 30ml of ethanol for ultrasonic treatment for 1h, white turbid liquid is formed, and then the solution is centrifugally washed with ethanol for three times; placing the washed product into an oven at 80 ℃ for vacuum drying for 6 hours to obtain HOFs;
(2) 200mg of HOFs and 600mg of NaCl are weighed and placed in a 50mL beaker, then 10mL of ethanol is added, ultrasonic treatment is carried out for 10min, and then stirring is carried out for 1h at 600rpm, thus obtaining a mixed solution A;
weighing 0.3mmol of ferric carbonate and 0.3mmol of cobalt carbonate, dissolving in 5ml of ethanol, and stirring at 600rpm for 5min to obtain a mixed solution B;
dropwise adding the mixed solution B into the mixed solution A under the condition that the mixed solution A rotates at 280rpm, adjusting the rotating speed to 600rpm after the mixed solution B is completely added, and continuously stirring overnight until the solvent is completely volatilized; after stirring, vacuum drying is carried out in an oven at 60 ℃ for 3 hours to obtain a precursor material D, and grinding is carried out by a mortar until the precursor material D is uniform in powder;
(3) Placing the 300mg precursor D in a groove of a graphite sample table of a quick heating device for joule heat, and performing joule heat impact for 4 times in a nitrogen atmosphere, wherein the joule heat impact temperature is 1000 ℃, and the heating rate is 2000 ℃/s, so as to obtain a precursor E;
(4) 20mg of precursor E and 50mg sodium phosphite are respectively placed at the left end and the right end of a groove of a graphite sample table of the quick heating device for joule heat, the joule heat impact is carried out for 7 times in the nitrogen atmosphere, the joule heat impact temperature is 600 ℃, and the heating rate is 2000 ℃/s; centrifuging the prepared powder with deionized water, washing for three times, and vacuum drying at 60deg.C for 3 hr to obtain porous Fe 2 P/Co 2 P heterojunction catalyst, named Fe 2 P/Co 2 -5 heterojunction.
For the porous Fe obtained in the step (4) 2 P/Co 2 P heterojunction catalyst N 2 Pore size test of BET and OER Performance application test, see Table 1, the method of OER Performance application test is the same as that of example 1.
As is clear from Table 1, porous Fe 2 P/Co 2 The pore diameter range of the P heterojunction catalyst is 0.2-110nm, and the P heterojunction catalyst has a multi-level pore structure with micropores, mesopores and macropores; in 1M KOH electrolyte, 10mA cm -2 Fe at current density of (2) 2 P/Co 2 The OER overpotential of the P-5 heterojunction is 259.0mV, far below that of commercial RuO 2 Noble metal catalyst (321.6 mV@10 mA cm) -2 ) Has industrial application prospect.
Example 6
(1) Step (1) as in example 1;
(2) 200mg of HOFs and 200mg of NaCl are weighed and placed in a 50mL beaker, then 10mL of ethanol is added, ultrasonic treatment is carried out for 10min, and then stirring is carried out for 1h at 600rpm, thus obtaining a mixed solution A;
weighing 0.3mmol of ferric acetylacetonate and 0.9mmol of cobalt acetylacetonate, dissolving in 5ml of ethanol, and stirring at 600rpm for 5min to obtain a mixed solution B;
dropwise adding the mixed solution B into the mixed solution A under the condition that the mixed solution A rotates at 280rpm, adjusting the rotating speed to 600rpm after the mixed solution B is completely added, and continuously stirring overnight until the solvent is completely volatilized; after stirring, vacuum drying is carried out in an oven at 60 ℃ for 3 hours to obtain a precursor material D, and grinding is carried out by a mortar until the precursor material D is uniform in powder;
(3) Placing the 300mg precursor D in a groove of a graphite sample table of a quick heating device for joule heat, and performing joule heat impact for 4 times in a nitrogen atmosphere, wherein the joule heat impact temperature is 900 ℃, and the heating rate is 2500 ℃/s, so as to obtain a precursor E;
(4) Respectively placing 20mg of precursor E and 20mg sodium phosphite at the left end and the right end of a groove of a graphite sample table of the quick heating device for Joule heat, and performing Joule heat impact for 6 times in a nitrogen atmosphere, wherein the Joule heat impact temperature is 600 ℃; the temperature rising rate is 2500 ℃/s; centrifuging and washing the prepared powder with deionized water for three times, and vacuum drying at 60deg.C for 3 hr to obtain porous Fe 2 P/Co 2 P heterojunction catalyst, named Fe 2 P/Co 2 -6 heterojunction.
For the porous Fe obtained in the step (4) 2 P/Co 2 P heterojunction catalyst N 2 Pore size test of BET and OER Performance application test, see Table 1, the method of OER Performance application test is the same as that of example 1.
As is clear from Table 1, porous Fe 2 P/Co 2 The pore diameter range of the P heterojunction catalyst is 0.2-110nm, and the P heterojunction catalyst has a multi-level pore structure with micropores, mesopores and macropores; in 1M KOH electrolyte, 10mA cm -2 Fe at current density of (2) 2 P/Co 2 P-6 heterologyThe OER overpotential of the mass junction is 259.5mV, which is far lower than commercial RuO 2 Noble metal catalyst (321.6 mV@10 mA cm) -2 ) Has industrial application prospect.
Comparative example 1
The difference from example 1 is that the steps (3) and (4) are not changed. The specific operations of the step (3) and the step (4) are described as follows:
(3) Placing the 300mg precursor D in a tube furnace, heating the precursor D to 900 ℃ from room temperature in nitrogen atmosphere, and calcining the precursor D at 900 ℃ for 1 hour, wherein the heating rate is 5 ℃/min, so as to obtain a precursor E;
(4) Respectively placing 50mg of sodium hypophosphite and 20mg precursor E at the upper end and the lower end of a quartz tube of a tube furnace, calcining for 1 hour at 600 ℃ in a nitrogen atmosphere, wherein the heating rate is 5 ℃/min; centrifuging the prepared powder with deionized water, washing for three times, and vacuum drying to obtain porous Fe 2 P/Co 2 P heterojunction catalyst, named Fe 2 P/Co 2 -7 heterojunction.
For the porous Fe obtained in the step (4) 2 P/Co 2 P heterojunction N 2 Pore size test of BET and OER Performance application test, the test results are shown in Table 1, and the method of OER Performance application test is the same as that of example 1.
As is clear from Table 1, porous Fe 2 P/Co 2 The pore diameter range of the P heterojunction catalyst is 0.2-90nm, and the P heterojunction catalyst has a multi-level pore structure of micropores, mesopores and macropores; in 1M KOH electrolyte, 10mA cm -2 Fe at current density of (2) 2 P/Co 2 The OER overpotential of the P-7 heterojunction is 289.6mV, which is far higher than that of the porous Fe prepared by the application 2 P/Co 2 The catalytic activity of the P heterojunction is less than or equal to 259.5mv, and the energy consumption is high. This is due to the traditional pyrolysis mode, which is difficult to bring about the change of lattice strain, rich pore channels and easily exposed active sites, and results in poor performance.
Comparative example 2
The difference from example 1 is that no cobalt salt is added in step (2), and the other steps are unchanged, to obtain Fe 2 P。
For Fe 2 P N 2 Pore size test of BET and OER Performance application test, the test results are shown in Table 1, and the method of OER Performance application test is the same as that of example 1.
As is clear from Table 1, fe 2 The pore diameter of P is 0.2-100nm, and the P is a multi-stage pore structure of micropores, mesopores and macropores; in 1M KOH electrolyte, 10mA cm -2 Fe at current density of (2) 2 The OER overpotential of the P heterojunction is 369.7mV, which is far higher than that of the porous Fe prepared by the application 2 P/Co 2 The catalytic activity of the P heterojunction is less than or equal to 259.5mv, and the energy consumption is high. This is because the addition of a single element produces less channels during the reaction and does not have a synergistic effect of heterogeneous junctions, which makes it difficult to reduce the reaction energy barrier.
Comparative example 3
The difference from example 1 is that in step (2) no iron salt is added, the other steps are unchanged, co is obtained 2 P。
For Co 2 P N 2 Pore size test of BET and OER Performance application test, the test results are shown in Table 1, and the method of OER Performance application test is the same as that of example 1.
As can be seen from Table 1, co 2 The pore diameter of P is 0.2-100nm, and the P is a multi-stage pore structure of micropores, mesopores and macropores; in 1M KOH electrolyte, 10mA cm -2 Co at current density of (2) 2 The OER overpotential of the P heterojunction is 339.5mV, which is far higher than that of the porous Fe prepared by the application 2 P/Co 2 Catalytic Activity of P heterojunction (.ltoreq. 259.5 mv) and commercial RuO 2 (321.6 mV@10 mA cm -2 ) The energy consumption is high. This is because the addition of a single element produces less channels during the reaction and does not have the synergistic effect of heterogeneous junctions, which makes it difficult to reduce the reaction energy barrier; however, the catalytic effect of the reaction of Co metal is better than that of Fe metal, because Co is combined with O or OH or OOH in a better way.
Comparative example 4
The difference from example 1 is that there is no step (2), step (3), step (4), and the other steps are unchanged. And centrifuging, washing and drying HOFs to obtain HOFs powder.
N for HOFs powder 2 Pore size test of BETAnd OER performance application test, the test results are shown in table 1, and the OER performance application test method is the same as in example 1.
As shown in Table 1, the pore diameter of HOFs ranges from 0.2 to 10nm, and has a microporous and mesoporous structure; in 1M KOH electrolyte, 10mA cm -2 The OER overpotential of HOFs at current density of 549.5mV is far higher than that of porous Fe prepared by the method 2 P/Co 2 Catalytic Activity of P heterojunction (.ltoreq. 259.5 mv) and commercial RuO 2 (321.6 mV@10 mA cm -2 ) The energy consumption is high.
Comparative example 5
The difference from example 1 is that there are no steps (2) and (4), and the other steps are unchanged, and black powder is obtained after joule thermal shock.
Subjecting it to N 2 Pore size test of BET and OER performance test, the test results are shown in Table 1, and the method of OER performance application test is the same as in example 1.
As is clear from Table 1, the pore diameter of the carbonized HOFs ranges from 0.2 to 45nm, and the carbonized HOFs have a microporous and mesoporous hierarchical pore structure; in 1M KOH electrolyte, 10mA cm -2 The OER overpotential of HOFs at current density of 475.5mV is far higher than that of porous Fe prepared by the method 2 P/Co 2 Catalytic Activity of P heterojunction (.ltoreq. 259.5 mv) and commercial RuO 2 (321.6 mV@10 mA cm -2 ) The energy consumption is high.
Comparative example 6
The difference from example 1 is that in step (4), sodium hypophosphite is not present, and oxides are obtained after Joule thermal impact.
Subjecting it to N 2 Pore size test of BET and OER performance test, the test results are shown in Table 1, and the method of OER performance application test is the same as in example 1.
As can be seen from Table 1, the pore diameter of the oxide without the phosphorus exchange of sodium hypophosphite is 0.2-95nm, and the oxide has a multi-stage pore structure of micropores, mesopores and macropores; in 1M KOH electrolyte, 10mA cm -2 The OER overpotential of HOFs at current density of 323.5mV is far higher than that of porous Fe prepared by the method 2 P/Co 2 Catalytic Activity of P heterojunction (.ltoreq. 259.5 mv) and commercial RuO 2 (321.6 mV@10 mA cm -2 ) The energy consumption is high.
OER Performance test and N for examples 1-6 and comparative examples 1-6 2 Pore size test of BET is shown in table 1:
as is clear from comparative examples 1 to 6 and example 1, the conventional calcination method is far lower than the rapid high Wen Jiaoer thermal shock preparation method, and is mainly characterized by being easy to cause metal atom agglomeration, being difficult to generate lattice strain, and obstructing mass transfer and blocking exposed active sites, resulting in poor OER catalytic effect; fe of comparative example 2 and comparative example 3 2 P、Co 2 The OER catalytic effect of the P material is far lower than that of porous Fe 2 P/Co 2 P-heterojunction, mainly consisting in no heterojunction and smaller lattice strain and pore size range, results in low intrinsic activity and fewer binding sites to the reaction intermediates; HOFs material of comparative example 4 was more porous Fe 2 P/Co 2 The OER effect of the P heterojunction is poor and mainly comprises poor conductivity of HOFs, no rich pore channels and no heterogenous junction structure; the carbonized HOFs material of comparative example 5 was more porous Fe 2 P/Co 2 The P heterojunction has poor OER effect, mainly has no abundant pore channels, no heterogenous junction structure and no lattice strain, and further has poor performance in the OER field. The oxide of comparative example 6, which had no phosphorus exchange with sodium hypophosphite, had far lower OER performance than porous Fe 2 P/Co 2 P heterojunction mainly because sodium hypophosphite can realize phosphorus exchange to form a multi-level pore structure and Fe 2 P/Ni 2 P heterojunction and generates lattice strain, enhances adsorption to OH, adjusts electronic structures of active sites Fe and Co, optimizes the binding energy of the active sites Fe and Co and a reaction intermediate, so that OER performance of phosphide is far greater than that of oxide.
The quick Joule heat impact technology in the embodiment of the invention is from a quick Joule heat heating device, which consists of an electrode, a 316L vacuum cavity, a gas circuit device, a vacuum pump, a graphite sample table, a temperature measuring module and a data collecting system; the output voltage is 0-40V, the output current is 0-375A, the current climbing time is 1000ms, the sample test quantity is 300mg, the model is JH3.2, and the power supply is single-phase 220V/40A.
The above-described embodiments are provided to illustrate the gist of the present invention, but are not intended to limit the scope of the present invention. It will be understood by those skilled in the art that various modifications and equivalent substitutions may be made to the technical solution of the present invention without departing from the spirit and scope of the technical solution of the present invention.
Claims (8)
1. Ultra-fast preparation of porous Fe with strain effect 2 P/Co 2 A method of P heterojunction catalyst comprising the steps of:
(1) Dissolving melamine and trimesic acid in a solvent I, performing ultrasonic reaction at room temperature for 1-3h, and obtaining a hydrogen bond organic framework material after centrifugation, washing and vacuum drying;
(2) Dissolving hydrogen bond organic frame material and sodium chloride in a solvent II to prepare a mixed solution A; dissolving ferric salt and cobalt salt in a solvent II to prepare a mixed solution B; dropwise adding the mixed solution B into the mixed solution A under stirring to obtain mixed solution C, stirring until the solvent in the mixed solution C is completely volatilized, and drying in vacuum to obtain a precursor D;
(3) Carrying out quick joule thermal shock on the precursor D in a protective atmosphere to obtain a precursor E;
(4) Mixing the precursor E with sodium hypophosphite, performing rapid joule thermal shock under a protective atmosphere, centrifuging, washing, and vacuum drying to obtain porous Fe 2 P/Co 2 A P heterojunction catalyst;
in the step (3), the rapid Joule thermal shock temperature is 900-1100 ℃; the heating rate of the Joule heat is 1500-2500 ℃/s; the number of the Joule thermal shock is 3-5;
in the step (4), the rapid Joule thermal shock temperature is 500-1000 ℃; the heating rate of the Joule heat is 1500-2500 ℃/s; the number of joule heat impact is 5-7.
2. The ultra-fast preparing porous Fe with strain effect according to claim 1 2 P/Co 2 The method of the P heterojunction catalyst is characterized in that in the step (1), the solvent I is methanol or ethanol; the washing condition is ethanol washing for three to five times; the vacuum drying conditions are as follows: drying at 40-80deg.C for 6-14 hr; in the step (2), the solvent II is one of methanol, ethanol or water; the vacuum drying conditions are as follows: drying at 40-80deg.C for 2-4 hr; in the step (3), the protective atmosphere is argon or nitrogen; in the step (4), the protective atmosphere is argon or nitrogen; the washing condition is that deionized water is washed for three to five times; the vacuum drying conditions are as follows: drying at 40-80deg.C for 2-4 hr.
3. The ultra-fast preparing porous Fe with strain effect according to claim 1 2 P/Co 2 The method of the P heterojunction catalyst is characterized in that in the step (2), the ferric salt is one of ferric chloride, ferric nitrate, ferric sulfate, ferric acetate, ferric carbonate or ferric acetylacetonate; the cobalt salt is one of cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt acetate, cobalt carbonate or cobalt acetylacetonate.
4. The ultra-fast preparing porous Fe with strain effect according to claim 1 2 P/Co 2 The method of the P heterojunction catalyst is characterized in that in the step (1), the dosage proportion of melamine, trimesic acid and solvent I is 0.8-1mmol:1mmol:25-30ml.
5. The ultra-fast preparing porous Fe with strain effect according to claim 1 2 P/Co 2 The method of the P heterojunction catalyst is characterized in that in the step (2), the dosage ratio of hydrogen bond organic framework material, sodium chloride and solvent II is 200mg:200-1000mg:10-20ml.
6. The ultra-fast preparing porous Fe with strain effect according to claim 1 2 P/Co 2 A process for preparing a P heterojunction catalyst, characterized in that in the step (2), the dosage ratio of ferric salt, cobalt salt and solvent II is 0.3mmol:0.3-0.9mmol：5-10ml。
7. The ultra-fast preparing porous Fe with strain effect according to claim 1 2 P/Co 2 The method of the P heterojunction catalyst is characterized in that in the step (4), the mass ratio of the precursor E to the sodium hypophosphite is 1:1-5.
8. A porous Fe with strain effect prepared by the method as claimed in any one of claims 1 to 7 2 P/Co 2 The application of the P heterojunction is characterized in that the porous Fe 2 P/Co 2 The P heterojunction is applied to oxygen evolution reactions in alkaline water.
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