CN113355691A - Preparation method of manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst - Google Patents
Preparation method of manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst Download PDFInfo
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- CN113355691A CN113355691A CN202010679228.3A CN202010679228A CN113355691A CN 113355691 A CN113355691 A CN 113355691A CN 202010679228 A CN202010679228 A CN 202010679228A CN 113355691 A CN113355691 A CN 113355691A
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- titanium carbide
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- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 148
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 title claims abstract description 135
- 239000002135 nanosheet Substances 0.000 title claims abstract description 130
- 229910052748 manganese Inorganic materials 0.000 title claims abstract description 121
- 239000011572 manganese Substances 0.000 title claims abstract description 121
- 239000003054 catalyst Substances 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 60
- 239000002159 nanocrystal Substances 0.000 title claims abstract description 54
- 238000002360 preparation method Methods 0.000 title claims abstract description 25
- 239000006185 dispersion Substances 0.000 claims description 28
- 229910017052 cobalt Inorganic materials 0.000 claims description 25
- 239000010941 cobalt Substances 0.000 claims description 25
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 25
- 239000000243 solution Substances 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 22
- 239000002243 precursor Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 17
- 239000012266 salt solution Substances 0.000 claims description 16
- 150000001868 cobalt Chemical class 0.000 claims description 15
- 150000002696 manganese Chemical class 0.000 claims description 15
- 238000003756 stirring Methods 0.000 claims description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 14
- 238000005406 washing Methods 0.000 claims description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 11
- 238000004108 freeze drying Methods 0.000 claims description 10
- 239000011259 mixed solution Substances 0.000 claims description 9
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 8
- PQXKHYXIUOZZFA-UHFFFAOYSA-M lithium fluoride Chemical compound [Li+].[F-] PQXKHYXIUOZZFA-UHFFFAOYSA-M 0.000 claims description 8
- 238000001035 drying Methods 0.000 claims description 7
- 229940011182 cobalt acetate Drugs 0.000 claims description 6
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 6
- 229940071125 manganese acetate Drugs 0.000 claims description 6
- UOGMEBQRZBEZQT-UHFFFAOYSA-L manganese(2+);diacetate Chemical compound [Mn+2].CC([O-])=O.CC([O-])=O UOGMEBQRZBEZQT-UHFFFAOYSA-L 0.000 claims description 6
- -1 titanium-aluminum-carbon Chemical compound 0.000 claims description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical group [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 4
- 238000003760 magnetic stirring Methods 0.000 claims description 4
- MIVBAHRSNUNMPP-UHFFFAOYSA-N manganese(2+);dinitrate Chemical group [Mn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MIVBAHRSNUNMPP-UHFFFAOYSA-N 0.000 claims description 4
- 239000000843 powder Substances 0.000 claims description 4
- 229910021380 Manganese Chloride Inorganic materials 0.000 claims description 3
- GLFNIEUTAYBVOC-UHFFFAOYSA-L Manganese chloride Chemical compound Cl[Mn]Cl GLFNIEUTAYBVOC-UHFFFAOYSA-L 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 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
- 239000008367 deionised water Substances 0.000 claims description 3
- 229910021641 deionized water Inorganic materials 0.000 claims description 3
- 235000002867 manganese chloride Nutrition 0.000 claims description 3
- 239000011565 manganese chloride Substances 0.000 claims description 3
- 229940099607 manganese chloride Drugs 0.000 claims description 3
- 229940099596 manganese sulfate Drugs 0.000 claims description 3
- 235000007079 manganese sulphate Nutrition 0.000 claims description 3
- 239000011702 manganese sulphate Substances 0.000 claims description 3
- SQQMAOCOWKFBNP-UHFFFAOYSA-L manganese(II) sulfate Chemical compound [Mn+2].[O-]S([O-])(=O)=O SQQMAOCOWKFBNP-UHFFFAOYSA-L 0.000 claims description 3
- 239000002244 precipitate Substances 0.000 claims description 3
- 239000006228 supernatant Substances 0.000 claims description 3
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 26
- 230000000694 effects Effects 0.000 abstract description 12
- 230000002195 synergetic effect Effects 0.000 abstract description 6
- 230000001351 cycling effect Effects 0.000 abstract 1
- 229910052739 hydrogen Inorganic materials 0.000 description 19
- 239000001257 hydrogen Substances 0.000 description 19
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 14
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000000463 material Substances 0.000 description 9
- 239000010410 layer Substances 0.000 description 8
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 8
- 239000000047 product Substances 0.000 description 7
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 229910000314 transition metal oxide Inorganic materials 0.000 description 6
- 239000010411 electrocatalyst Substances 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- IWHAVVGLVXIYBA-UHFFFAOYSA-N [S-2].[Mn+2].[Co+2].[S-2] Chemical compound [S-2].[Mn+2].[Co+2].[S-2] IWHAVVGLVXIYBA-UHFFFAOYSA-N 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000007547 defect Effects 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 229910009819 Ti3C2 Inorganic materials 0.000 description 3
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 238000006555 catalytic reaction Methods 0.000 description 3
- 238000013329 compounding Methods 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 125000000524 functional group Chemical group 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 238000001000 micrograph Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 239000002356 single layer Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- 229910003168 MnCo2O4 Inorganic materials 0.000 description 2
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000004202 carbamide Substances 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000002134 carbon nanofiber Substances 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- HJZMCWKYJQFMPG-UHFFFAOYSA-J cobalt(2+);manganese(2+);dicarbonate Chemical compound [Mn+2].[Co+2].[O-]C([O-])=O.[O-]C([O-])=O HJZMCWKYJQFMPG-UHFFFAOYSA-J 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910021397 glassy carbon Inorganic materials 0.000 description 2
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 239000011165 3D composite Substances 0.000 description 1
- 229920000557 Nafion® Polymers 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- CYKMNKXPYXUVPR-UHFFFAOYSA-N [C].[Ti] Chemical compound [C].[Ti] CYKMNKXPYXUVPR-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 230000004931 aggregating effect Effects 0.000 description 1
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 description 1
- 239000012752 auxiliary agent Substances 0.000 description 1
- 230000001588 bifunctional effect Effects 0.000 description 1
- 239000012876 carrier material Substances 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000010335 hydrothermal treatment Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000011065 in-situ storage Methods 0.000 description 1
- 230000000977 initiatory effect Effects 0.000 description 1
- UGKDIUIOSMUOAW-UHFFFAOYSA-N iron nickel Chemical group [Fe].[Ni] UGKDIUIOSMUOAW-UHFFFAOYSA-N 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 238000004502 linear sweep voltammetry Methods 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910001437 manganese ion Inorganic materials 0.000 description 1
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000007431 microscopic evaluation Methods 0.000 description 1
- 238000013508 migration Methods 0.000 description 1
- 230000005012 migration Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002064 nanoplatelet Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 239000011949 solid catalyst Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052596 spinel Inorganic materials 0.000 description 1
- 239000011029 spinel Substances 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 230000000087 stabilizing effect Effects 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000001132 ultrasonic dispersion Methods 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
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- B—PERFORMING OPERATIONS; TRANSPORTING
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
- B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/889—Manganese, technetium or rhenium
- B01J23/8892—Manganese
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Abstract
The invention provides a preparation method of a manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst, which relates to the field of electrode catalysts. According to the invention, manganese cobaltate nanocrystals uniformly grow on the two-dimensional titanium carbide nanosheets, the high electrocatalytic performance of manganese cobaltate and the excellent conductivity and stability of the titanium carbide nanosheets are simultaneously exerted, the synergistic enhancement effect between the manganese cobaltate nanocrystals and the titanium carbide nanosheets is realized, and the prepared electrode catalyst has good catalytic performance and good cycling stability.
Description
Technical Field
The invention relates to a preparation method of an electrode catalyst, in particular to a preparation method of a manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst.
Background
With the increasing demand for energy and the increasing problem of environmental pollution, the search for clean and sustainable energy has become an urgent problem for human society. Hydrogen, as an efficient, clean and environmentally friendly energy source, has attracted the eye of more and more scientists. However, hydrogen is not naturally occurring and must be prepared by a process. The electro-catalysis hydrogen evolution has the advantages of high efficiency, no pollution and wide raw material water source, is favored by people, and is very suitable for industrially preparing hydrogen. At present, the solid catalyst with the best electro-catalytic hydrogen evolution reaction activity is noble metal platinum, but the metal platinum has the defects of rare storage in the earth crust, high price, easy poisoning and unsuitability for large-scale commercial production. Therefore, the development of cheap and efficient non-noble metal hydrogen evolution electrode catalyst has great significance.
Manganese cobaltate (MnCo)2O4) The mixed transition metal oxide is a typical mixed transition metal oxide with a spinel structure, has unique characteristics of a multi-valence transition metal oxide, has electrocatalytic performance generally superior to that of a single transition metal oxide, and is widely used for research in the field of electrode catalysis. However, the poor conductivity of manganese cobaltate limits the application of manganese cobaltate in the field of electro-catalytic hydrogen production to a certain extent. The introduction of high-conductivity materials as matrix materials reduces the charge transfer resistance of the composite catalyst, and improves the electrocatalytic activity of the composite system, which is a good solution. Titanium carbide (Ti)3C2Tx) The titanium-carbon composite material is a newly discovered two-dimensional layered material, and has excellent conductivity, unique metal performance and catalytic performance due to the stacked structure of the titanium atomic layer and the carbon atomic layer; can be used as an ideal conductive carrier material and can also be used as a catalyst auxiliary agent. So far, in the research focus of electrocatalytic hydrogen production, there are many researches on titanium carbide and its compound or manganese cobaltate as hydrogen evolution catalyst (ATTANAYAKE N H, ABEYWEERA S C, THENEUWARA A C, et al2 on Ti3C2(MXene)as an improved HER catalyst[J].J Mater Chem A,2018,6(35):16882-9.ZHANG X,SHAO B,SUN Z,et al.Platinum Nanoparticle-Deposited Ti3C2Tx MXene for Hydrogen Evolution Reaction[J].Industrial&Engineering Chemistry Research,2020,59(5):1822-8.DU X,FU J,ZHANG X.Construction of a MnCo2O4@NiyMx(S and P)crosslinked network for efficient electrocatalytic water splitting[J].Crystengcomm,2019,21(47):7293-302.LIN Y,YANG Z,CAO D,et al.Electro-deposition of nickel-iron nanoparticles on flower-like MnCo2O4 nanowires as an efficient bifunctional electrocatalyst for overall water splitting[J]Crystegcomm, 2020,22(8):1425-35.), however, few studies have been reported on the complex of a complex transition metal oxide with titanium carbide as the subject of study, particularly the complex of titanium carbide with manganese cobaltate.
Chinese patent publication No. CN107855128A discloses a method for preparing a cobalt manganese sulfide electrocatalyst, comprising the following characteristic steps: i. weighing cobalt salt, manganese salt and urea, dissolving the weighed cobalt salt, manganese salt and urea in water, and stirring to obtain a uniformly mixed solution; ii. Placing the solution and the carrier in a reaction kettle together for hydrothermal reaction to obtain supported cobalt manganese carbonate; and iii, placing the supported cobalt manganese carbonate into an aqueous solution containing a vulcanizing agent for a vulcanization reaction to obtain the supported cobalt manganese sulfide. However, it is obvious from a scanning electron microscope image that irreversible migration, agglomeration and stacking phenomena occur between the carrier carrying the cobalt manganese sulfide electrocatalyst and the cobalt manganese sulfide particles, which cause the reduction of the active surface area of the catalyst and the coverage of partial reaction active sites, thereby reducing the performance of the catalyst; but also results in a large overpotential in the hydrogen evolution reaction. Therefore, the development of a new preparation method, the increase of the specific surface of the composite system and the improvement of the electrocatalytic activity of the composite material have important significance.
Disclosure of Invention
In order to solve the defects in the prior art, the invention provides a preparation method of a manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst; the manganese cobaltate nanocrystals uniformly grow on the two-dimensional titanium carbide nanosheets, the high electrocatalytic performance of manganese cobaltate and the excellent conductivity and stability of the titanium carbide nanosheets are simultaneously exerted, the synergistic enhancement effect between the manganese cobaltate nanocrystals and the titanium carbide nanosheets is realized, the prepared electrode catalyst is large in the number of catalytic active sites, good in circulation stability and excellent in catalytic performance of the composite electrode catalyst.
A preparation method of a manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst comprises the following steps:
s1, preparing titanium carbide nanosheet dispersion liquid;
s2, adding a cobalt salt solution and a manganese salt solution into the titanium carbide nanosheet dispersion liquid obtained in the step S1, and uniformly stirring to obtain a precursor solution, wherein the total adding amount of the titanium carbide nanosheets, the cobalt element and the manganese element is 1-10: 1-10, wherein the addition amounts of the cobalt element and the manganese element are 2: 1;
s3, carrying out hydrothermal reaction on the precursor solution obtained in the step S2, then carrying out centrifugal washing and freeze drying to obtain the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst.
According to the invention, titanium aluminum carbon is used for selectively etching aluminum to generate two-dimensional accordion-shaped titanium carbide nanosheets, two-dimensional single-layer or few-layer carbon nitride nanosheets are generated through ultrasonic stripping, a manganese cobaltate/titanium carbide mixture precursor is prepared, the addition ratio of the manganese cobaltate/titanium carbide mixture precursor and the titanium carbide precursor is strictly controlled, and the manganese cobaltate is combined on the surface of a titanium carbide substrate through a hydrothermal reaction. Wherein, the two-dimensional titanium carbide nanosheet material is used as a substrate, and the manganese cobaltate nanoparticles uniformly grow on the titanium carbide nanosheets, so that the particles are small in size; the abundant functional groups on the surface of the titanium carbide can promote the nucleation growth of the manganese cobaltate, effectively disperse the manganese cobaltate nanoparticles, prevent the manganese cobaltate nanoparticles from aggregating and growing up, increase active sites in unit area and greatly improve the effective utilization rate of the manganese cobaltate. And the manganese cobaltate nanoparticles are positioned among the titanium carbide nanosheets and are crosslinked with each other to form an open 3D-like network structure, so that the stacking phenomenon of the titanium carbide nanosheets is reduced, and the specific surface area of the catalyst is increased. Secondly, the titanium carbide has strong conductivity, and can make up the defect of insufficient conductivity of the manganese cobaltate as a carrier, and improve the overall electron mobility of the composite material, thereby improving the electrocatalytic efficiency of the manganese cobaltate. In addition, the titanium carbide has the specific catalytic activity of metal, and the synergistic enhancement effect between the manganese cobaltate and the titanium carbide can further improve the electrocatalytic performance of the compound.
Further, in step S2, the addition amount of the titanium carbide nanosheet to the total amount of the cobalt element and the manganese element is 1 to 5: 1 to 5.
Further, in step S2, the addition amount of the titanium carbide nanosheets to the total amount of the cobalt element and the manganese element is 1: 0.73. the titanium carbide nanosheet is high in content and low in total addition of cobalt and manganese, so that although the dispersibility and conductivity of manganese cobaltate can be enhanced, due to the fact that the titanium carbide nanosheet is poor in electrocatalytic performance or low in manganese cobaltate content, catalytic active sites are reduced, and catalytic activity is reduced; correspondingly, the content of the titanium carbide nanosheet is low, the total addition amount of the cobalt element and the manganese element is high, although the catalytic sites are increased, the agglomeration of a large amount of manganese cobaltate is increased, so that the effective catalytic active sites are reduced, and meanwhile, the conductivity of the manganese cobaltate is poor, so that the catalytic activity is also reduced. Therefore, through a large number of experiments, most preferably, the addition amount of the titanium carbide nanosheet to the total of the cobalt element and the manganese element is 1: 0.73.
further, in step S2, the cobalt salt is cobalt nitrate, cobalt acetate, cobalt sulfate, cobalt acetate, or cobalt chloride; the manganese salt is manganese nitrate, manganese acetate, manganese sulfate, manganese acetate or manganese chloride. The method is not limited to the cobalt salt and the manganese salt provided by the invention, as long as manganese cobaltate can be generated in the titanium carbide nanosheet dispersion liquid, and uniform growth of manganese cobaltate nanoparticles on the titanium carbide nanosheets can be realized.
Further, in step S1, the concentration of the titanium carbide nanosheet dispersion is 0.1 to 5 g/L.
Further, in step S2, the stirring conditions are: magnetic stirring at 0-100 deg.C for 1-20 h.
Further, in step S3, the hydrothermal reaction conditions are: the reaction time is 2-48h at 60-200 ℃.
Further, in step S3, the number of times of centrifugal washing is 1 to 10, and the drying pressure during freeze drying is 10 to 200 Pa.
Further, in step S1, the preparation of the titanium carbide nanosheet dispersion specifically includes the steps of:
p1, slowly adding commercial titanium-aluminum-carbon powder into a mixed solution of concentrated hydrochloric acid and lithium fluoride, and magnetically stirring for 1-60h at the temperature of 20-80 ℃;
and P2, adding deionized water into the mixed solution obtained in the step P1, carrying out ultrasonic treatment for 1-60min, then carrying out centrifugal water washing until no supernatant exists in the solution, and removing the precipitate to obtain the titanium carbide nanosheet dispersion.
The method is characterized in that a mixed solution of lithium fluoride and hydrochloric acid is adopted to etch an aluminum atomic layer in the aluminum titanium carbide to generate two-dimensional accordion-shaped titanium carbide nanosheets, the specific surface area of the formed layered structure is obviously increased compared with that before etching, and then two-dimensional single-layer or few-layer carbon nitride nanosheets are generated through ultrasonic stripping. In the etching process, the Al atomic layer is replaced by electronegative functional groups such as-OH, -F and ═ O, and the electronegative functional groups positioned on the surface can play a role in stabilizing the manganese cobaltate nanoparticles, so that the activity of the manganese cobaltate nanoparticles is prevented from being reduced due to agglomeration in the catalysis process.
The invention achieves the following beneficial technical effects:
1. according to the preparation method of the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst, the prepared electrode catalyst is large in specific surface area, large in number of catalytic active sites, good in circulation stability and excellent in catalytic performance. The manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst prepared by the method has good application prospect and economic benefit in the fields of electrolytic hydrogen production and the like.
2. The composite catalyst of the manganese cobaltate nanocrystalline uniformly grown on the two-dimensional titanium carbide nanosheet simultaneously exerts the higher electrocatalytic performance of the manganese cobaltate and the excellent conductivity and stability of the titanium carbide nanosheet, and realizes the synergistic enhancement effect between the manganese cobaltate nanocrystalline and the titanium carbide nanosheet.
3. The titanium-aluminum-carbon and manganese cobaltate are low in price, rich in sources, low in cost, simple and controllable in preparation method, good in repeatability, beneficial to large-scale production and high in practical value.
Drawings
FIG. 1 is a schematic flow diagram of the present invention;
fig. 2 is an X-ray diffraction (XRD) spectrum of titanium carbide nanosheets, manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalysts and titanium aluminum carbon powder prepared by the method of example 3 of the present invention;
FIG. 3 is a field emission scanning electron microscope (FE-SEM) photograph of manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst prepared by the method of example 3 (FIG. A, FIG. B) and comparative example 4 (FIG. C, FIG. D) of the present invention;
fig. 4 is a Transmission Electron Microscope (TEM) photograph of the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst prepared by the method of example 3 of the present invention;
FIG. 5 shows a manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst (MnCo) prepared by the method of embodiment 3 of the present invention2O4-Ti3C2Tx) With pure manganese cobaltate nanocrystals (MnCo)2O4) Titanium carbide nanosheet (Ti)3C2Tx) Linear sweep voltammetry of the material on electrocatalytic hydrogen production reaction (diagram A) and tafel slope comparison curve chart (diagram B);
fig. 6 is a stability test chart of the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst prepared by the method in embodiment 3 of the present invention.
Detailed Description
The technical solutions of the present invention will be described clearly and completely with reference to the accompanying drawings, and it is obvious that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
As shown in fig. 1, a preparation method of a manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst comprises the following steps:
s1, preparing titanium carbide nanosheet dispersion liquid with the concentration of 0.1-5 g/L;
s2, adding a cobalt salt solution and a manganese salt solution into the titanium carbide nanosheet dispersion liquid obtained in the step S1, and magnetically stirring for 1-20 hours at 0-100 ℃ to obtain a precursor solution, wherein the mass ratio of the titanium carbide nanosheets to the total additive amount of cobalt elements and manganese elements is 1-10: 1-10, wherein the addition amounts of the cobalt element and the manganese element are 2: 1;
the cobalt salt is any one or more of cobalt nitrate, cobalt acetate, cobalt sulfate, cobalt acetate or cobalt chloride; the manganese salt is any one or more of manganese nitrate, manganese acetate, manganese sulfate, manganese acetate or manganese chloride. The cobalt salt and the manganese salt can provide cobalt ions and manganese ions, and can produce similar effects, the invention is not discussed, and the following examples take cobalt nitrate and manganese nitrate as examples;
s3, placing the precursor solution obtained in the step S2 at 60-200 ℃ for hydrothermal reaction for 2-48h, centrifugally washing the obtained product for 1-10 times, and freeze-drying under the condition of 10-200Pa to obtain the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst.
In step S1, the method for preparing the titanium carbide nanosheet dispersion includes the steps of:
p1, slowly adding commercial titanium-aluminum-carbon powder into a 9mol/L concentrated hydrochloric acid and lithium fluoride mixed solution, and magnetically stirring for 1-60h at the temperature of 20-80 ℃;
and P2, adding deionized water into the mixed solution obtained in the step P1, carrying out ultrasonic treatment for 1-60min, then carrying out centrifugal water washing until no supernatant exists in the solution, and removing the precipitate to obtain the titanium carbide nanosheet dispersion.
The influence of the etching and ultrasonic dispersion conditions of titanium carbide on the dispersion degree of titanium carbide has been reported in the prior art, and the present application is not repeated herein, preferably, the magnetic stirring is performed for 30 hours at room temperature in step P1, and the ultrasonic stripping is performed for 30min at room temperature in step P2 as the preparation conditions of the present application, which are selected in the following examples. Meanwhile, through earlier tests, the changes of the stirring temperature and time, the hydrothermal reaction temperature and time and the like in the steps S2 and S3 have less influence on the shape and size of the manganese cobaltate nanocrystal, and the invention is not separately discussed.
Example 1
The preparation method of the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst comprises the following steps:
s1, preparing titanium carbide nanosheet dispersion liquid with the concentration of 0.1 g/L.
S2, adding a cobalt salt solution and a manganese salt solution into the titanium carbide nanosheet dispersion liquid obtained in the step S1, and magnetically stirring for 1 hour at 0 ℃ to obtain a manganese cobaltate/titanium carbide nanosheet precursor solution; the total addition amount of the titanium carbide nanosheets and the cobalt and manganese elements is 1: 10, the addition amounts of the cobalt element and the manganese element are 2: 1;
s3, placing the manganese cobaltate/titanium carbide nanosheet precursor solution obtained in the step S2 at 60 ℃ for hydrothermal reaction for 2 hours, centrifugally washing the obtained product for 2 times, and freeze-drying under the drying pressure of 10Pa to obtain the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst.
Example 2
The preparation method of the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst comprises the following steps:
s1, preparing titanium carbide nanosheet dispersion liquid with the concentration of 2 g/L.
S2, adding a cobalt salt solution and a manganese salt solution into the titanium carbide nanosheet dispersion liquid obtained in the step S1, and magnetically stirring for 10 hours at 80 ℃ to obtain a manganese cobaltate/titanium carbide nanosheet precursor solution; the total addition amount of the titanium carbide nanosheets and the cobalt and manganese elements is 1: 5, the addition amounts of the cobalt element and the manganese element are 2: 1;
s3, placing the manganese cobaltate/titanium carbide nanosheet precursor solution obtained in the step S2 at 100 ℃ for hydrothermal reaction for 12 hours, centrifugally washing the obtained product for 5 times, and freeze-drying under the drying pressure of 25Pa to obtain the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst.
Example 3
The preparation method of the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst comprises the following steps:
s1, preparing titanium carbide nanosheet dispersion liquid with the concentration of 2 g/L.
S2, adding a cobalt salt solution and a manganese salt solution into the titanium carbide nanosheet dispersion liquid obtained in the step S1, and magnetically stirring for 10 hours at 80 ℃ to obtain a manganese cobaltate/titanium carbide nanosheet precursor solution; the total addition amount of the titanium carbide nanosheets and the cobalt and manganese elements is 1: 0.73, wherein the addition amounts of the cobalt element and the manganese element are 2: 1;
s3, placing the manganese cobaltate/titanium carbide nanosheet precursor solution obtained in the step S2 at 100 ℃ for hydrothermal reaction for 12 hours, centrifugally washing the obtained product for 5 times, and freeze-drying under the drying pressure of 25Pa to obtain the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst.
Example 4
The preparation method of the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst comprises the following steps:
s1, preparing titanium carbide nanosheet dispersion liquid with the concentration of 2 g/L.
S2, adding a cobalt salt solution and a manganese salt solution into the titanium carbide nanosheet dispersion liquid obtained in the step S1, and magnetically stirring for 10 hours at 80 ℃ to obtain a manganese cobaltate/titanium carbide nanosheet precursor solution; the total addition amount of the titanium carbide nanosheets and the cobalt and manganese elements is 5: 1, the addition amounts of the cobalt element and the manganese element are 2: 1;
s3, placing the manganese cobaltate/titanium carbide nanosheet precursor solution obtained in the step S2 at 100 ℃ for hydrothermal reaction for 12 hours, centrifugally washing the obtained product for 5 times, and freeze-drying under the drying pressure of 25Pa to obtain the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst.
Example 5
The preparation method of the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst comprises the following steps:
s1, preparing titanium carbide nanosheet dispersion liquid with the concentration of 5 g/L.
S2, adding a cobalt salt solution and a manganese salt solution into the titanium carbide nanosheet dispersion liquid obtained in the step S1, and magnetically stirring for 20 hours at 100 ℃ to obtain a manganese cobaltate/titanium carbide nanosheet precursor solution; the total addition amount of the titanium carbide nanosheets and the cobalt and manganese elements is 10: 1, the addition amounts of the cobalt element and the manganese element are 2: 1;
s3, placing the manganese cobaltate/titanium carbide nanosheet precursor solution obtained in the step S2 at 200 ℃ for hydrothermal reaction for 48h, centrifugally washing the obtained product for 10 times, and freeze-drying under the drying pressure of 200Pa to obtain the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst.
Comparative example 1
The comparative example 1 differs from the example 3 in that, in step S2, the addition amount of the titanium carbide nanosheets to the total of cobalt and manganese elements is 25: 1.
comparative example 2
Comparative example 2 differs from example 3 in that, in step S2, the addition amount of the titanium carbide nanosheets to the total of cobalt and manganese elements is 1: 25.
comparative example 3
Comparative example 3 differs from example 3 in that, in step S2, the titanium carbide nanoplatelets are replaced with an equal amount of a common carbon Nanofiber (NCF) material.
Comparative example 4
Comparative example 4 differs from example 3 in that, in step S2, a manganese cobaltate solution was added to the titanium carbide nanosheet dispersion of step S1, and magnetic stirring was performed at 80 ℃ for 10 hours to obtain a manganese cobaltate/titanium carbide nanosheet precursor solution.
Application case Performance characterization
The manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst prepared by the method of example 3 is taken as an example for performance characterization.
1) X-ray powder diffraction Pattern (XRD)
Fig. 2 is an X-ray powder diffraction pattern, i.e., XRD pattern, of the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst prepared by the method of example 3, from which characteristic peaks of the manganese cobaltate nanocrystal and titanium carbide nanosheet can be clearly seen, which indicates that the composite product contains the two components.
2) Microscopic analysis
Fig. 3A-B are field emission scanning electron microscope images of manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalysts, wherein fig. 3B is a partial enlarged view of fig. 3A. As can be seen in the figure, the catalyst has a very obvious single-layer or few-layer two-dimensional nanosheet structure, and the manganese cobaltate nanocrystals are uniformly distributed and grown on the two-dimensional titanium carbide sheet. When the preparation conditions of the method are changed, if manganese cobaltate and titanium carbide nanosheets are directly mixed for hydrothermal treatment (comparative example 4), a large amount of aggregated manganese cobaltate can be generated and cannot be uniformly dispersed on the two-dimensional nanosheets (as shown in fig. 3C-D), so that the manganese cobaltate can be grown in situ on the surfaces of the titanium carbide nanosheets by using a hydrothermal method, and manganese cobaltate nanocrystals which are uniform in appearance, small in particle size and uniform in dispersion can be formed.
Fig. 4 is a transmission electron microscope image of the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst. It can be seen that manganese cobaltate uniformly grows on the surface of the two-dimensional titanium carbide nanosheet layer, the volume of the manganese cobaltate crystal is kept in a nanoscale range, and the super-strong electrocatalytic performance of the manganese cobaltate crystal is ensured by the fine crystal size and high dispersity.
The results show that the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst has a two-dimensional nanostructure, the manganese cobaltate and the titanium carbide are well dispersed, the manganese cobaltate is uniform in shape, the specific surface area of the catalyst is large, and the number of active sites is large, so that the catalyst has higher catalytic performance and electrochemical activity.
3) Electrochemical hydrogen production reaction test
The experimental method comprises the following steps: electrocatalytic hydrogen production reaction tests were performed on an electrochemical workstation (CHI760E, shanghai chenhua instruments ltd). A standard three-electrode system is adopted, and a carbon rod, a Saturated Calomel Electrode (SCE) and a glassy carbon electrode (GCE, 3mm) coated with a composite catalytic material are respectively used as a counter electrode, a reference electrode and a working electrode. The working electrode was prepared using a typical method: 2mg of the three-dimensional composite catalytic material was dissolved in a mixed solution (475. mu.L of water, 475. mu.L of ethanol and 50. mu.L of 5% Nafion), sonicated for 30min, and then 5. mu.L of the above suspension was carefully dropped on the surface of the pretreated glassy carbon electrode (GCE, 3mm) and dried at room temperature. In the hydrogen evolution performance test, the hydrogen evolution performance is 0.5M H2SO4In the aqueous solution, the potential of the scanning electrode is 0.142 to-0.758V (vs RHE), and the potential scanning rate is 2mV s-1While, a polarization curve was measured. At room temperature, between-0.258 and-0.338V (vs RHE) at a scanning rate of 10mV s for 2000 cycles-1。
As can be seen from fig. 5A, the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst has the lowest reaction initiation potential and the highest current density, which indicates that the catalyst has good electrocatalytic performance; as can be seen from fig. 5B, the Tafel (Tafel) slope of the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst is the smallest, indicating that the catalytic activity of the catalyst is the best. Meanwhile, as shown in fig. 6, after a chronoamperometric test of 3000s, the current of the catalyst hardly decayed, indicating that it had excellent stability.
In addition, the composite electrode catalysts prepared by the methods of examples 1 to 5 and comparative examples 1 to 4 were subjected to hydrogen production catalytic activity tests, and the results are shown in table 1.
TABLE 1 Performance index of composite electrode catalysts prepared in examples 1 to 5 and comparative examples 1 to 4 for hydrogen generation reaction
The composite catalyst formed by compounding the two-dimensional layered material and the transition metal oxide can not only make up for the defect of insufficient conductivity or rare catalytic sites, but also can generate synergistic effect through compounding to enhance the electrocatalytic performance of the compound. The two-dimensional layered titanium carbide nanosheet has a large specific surface area, excellent conductivity and stability, but the electrocatalytic performance of the pure titanium carbide is not high, and the electrocatalyst with good overall performance can be obtained by compounding the titanium carbide nanosheet with manganese cobaltate which has excellent electrocatalytic activity but poor conductivity. The key to obtaining the excellent composite electrocatalyst is how to adjust the component proportion between the manganese cobaltate and the titanium carbide.
As can be seen from table 1, the composite electrode catalysts prepared by the methods of examples 1 to 5 have low overpotential, low Tafel slope and large exchange current density and high catalytic activity, compared to common composite forms such as using carbon Nanofibers (NCF) as a support material. With the increase of the content of the titanium carbide nanosheets in the composite electrode catalyst, the active surface area and the exchange current density of the catalyst are increased, the overpotential and the Tafel slope are correspondingly reduced, but the addition amount of the titanium carbide nanosheets is further increased, as shown in examples 4-5, the performance of the catalyst is reduced in comparison with example 3, and when the content of the titanium carbide nanosheets is increased to the content of the comparative example 1, the performance of the catalyst is sharply reduced; the reason is that the titanium carbide has poor electrocatalytic performance, a large amount of titanium carbide can reduce catalytic active sites, and the manganese cobaltate nanocrystal has low loading rate, so that the catalytic activity is further reduced; correspondingly, the data of the comparative example 2 and the examples 1 to 5 show that the content of the manganese cobaltate nanocrystal is high, the agglomeration of a large amount of manganese cobaltate grows up to reduce the catalytic activity sites, and meanwhile, the conductivity of the manganese cobaltate is poor, so that the catalytic activity is reduced. The proper addition proportion of the manganese cobaltate and the titanium carbide nanosheets is beneficial to comprehensively exerting the catalytic performances of the manganese cobaltate and the titanium carbide, and a synergistic effect is generated, so that high catalytic activity and catalytic stability are obtained.
Claims (9)
1. A preparation method of a manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst is characterized by comprising the following steps:
s1, preparing titanium carbide nanosheet dispersion liquid;
s2, adding a cobalt salt solution and a manganese salt solution into the titanium carbide nanosheet dispersion liquid obtained in the step S1, and uniformly stirring to obtain a precursor solution, wherein the total adding amount of the titanium carbide nanosheets, the cobalt element and the manganese element is 1-10: 1-10, wherein the addition amounts of the cobalt element and the manganese element are 2: 1;
s3, carrying out hydrothermal reaction on the precursor solution obtained in the step S2, then carrying out centrifugal washing and freeze drying to obtain the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst.
2. The preparation method of the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst as claimed in claim 1, wherein in step S2, the added amount of the titanium carbide nanosheets to the total amount of cobalt and manganese in a mass ratio of 1-5: 1 to 5.
3. The preparation method of the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst according to claim 2, wherein in step S2, the added amounts of the titanium carbide nanosheets and the total amount of cobalt and manganese elements are 1: 0.73.
4. the method for preparing a manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst as claimed in claim 1, wherein in step S2, the cobalt salt is cobalt nitrate, cobalt acetate, cobalt sulfate, cobalt acetate or cobalt chloride; the manganese salt is manganese nitrate, manganese acetate, manganese sulfate, manganese acetate or manganese chloride.
5. The method for preparing a manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst of claim 1, wherein in step S1, the concentration of the titanium carbide nanosheet dispersion is 0.1-5 g/L.
6. The preparation method of the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst as claimed in claim 1, wherein in step S2, the stirring conditions are: magnetic stirring at 0-100 deg.C for 1-20 h.
7. The preparation method of the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst as claimed in claim 1, wherein in step S3, the hydrothermal reaction conditions are: the reaction time is 2-48h at 60-200 ℃.
8. The method for preparing a manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst according to claim 1, wherein in step S3, the number of times of centrifugal washing is 1 to 10 times, and the drying pressure during freeze drying is 10 to 200 Pa.
9. The preparation method of the manganese cobaltate nanocrystal/titanium carbide nanosheet composite electrode catalyst of claim 1, wherein the step S1 of preparing the titanium carbide nanosheet dispersion specifically comprises the steps of:
p1, slowly adding commercial titanium-aluminum-carbon powder into a mixed solution of concentrated hydrochloric acid and lithium fluoride, and magnetically stirring for 1-60h at the temperature of 20-80 ℃;
and P2, adding deionized water into the mixed solution obtained in the step P1, carrying out ultrasonic treatment for 1-60min, then carrying out centrifugal water washing until no supernatant exists in the solution, and removing the precipitate to obtain the titanium carbide nanosheet dispersion.
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