CN110038604B - CuCo/Ti3C2TxComposite material and preparation method and application thereof - Google Patents
CuCo/Ti3C2TxComposite material and preparation method and application thereof Download PDFInfo
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- 229910016507 CuCo Inorganic materials 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- 239000000463 material Substances 0.000 title description 4
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 60
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 40
- 239000002131 composite material Substances 0.000 claims abstract description 29
- 238000006243 chemical reaction Methods 0.000 claims abstract description 18
- 239000008367 deionised water Substances 0.000 claims abstract description 16
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000000843 powder Substances 0.000 claims abstract description 14
- 238000005406 washing Methods 0.000 claims abstract description 13
- 238000001035 drying Methods 0.000 claims abstract description 12
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims abstract description 9
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 6
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims abstract description 5
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 claims abstract description 5
- 238000003756 stirring Methods 0.000 claims abstract description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims abstract description 5
- 239000000376 reactant Substances 0.000 claims abstract description 3
- 239000010949 copper Substances 0.000 claims description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 8
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 8
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 8
- 239000006228 supernatant Substances 0.000 claims description 8
- 229910052802 copper Inorganic materials 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920000557 Nafion® Polymers 0.000 claims description 4
- 229910017052 cobalt Inorganic materials 0.000 claims description 4
- 239000010941 cobalt Substances 0.000 claims description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims description 4
- 238000001291 vacuum drying Methods 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000005119 centrifugation Methods 0.000 claims description 2
- 239000003795 chemical substances by application Substances 0.000 claims description 2
- 238000004090 dissolution Methods 0.000 claims description 2
- 238000009830 intercalation Methods 0.000 claims description 2
- 230000002687 intercalation Effects 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- PIICEJLVQHRZGT-UHFFFAOYSA-N Ethylenediamine Chemical compound NCCN PIICEJLVQHRZGT-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 7
- 239000003054 catalyst Substances 0.000 abstract description 4
- 239000000138 intercalating agent Substances 0.000 abstract description 4
- 239000010405 anode material Substances 0.000 abstract description 2
- 150000001875 compounds Chemical class 0.000 description 11
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 11
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 10
- 229910000831 Steel Inorganic materials 0.000 description 10
- 239000010959 steel Substances 0.000 description 10
- 230000000694 effects Effects 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000002184 metal Substances 0.000 description 5
- 239000002244 precipitate Substances 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 4
- QGUAJWGNOXCYJF-UHFFFAOYSA-N cobalt dinitrate hexahydrate Chemical compound O.O.O.O.O.O.[Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QGUAJWGNOXCYJF-UHFFFAOYSA-N 0.000 description 4
- 230000000052 comparative effect Effects 0.000 description 4
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 4
- 238000004502 linear sweep voltammetry Methods 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- 239000000203 mixture Substances 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 238000005303 weighing Methods 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 239000010866 blackwater Substances 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 150000002736 metal compounds Chemical class 0.000 description 2
- 150000002739 metals Chemical class 0.000 description 2
- 229910000510 noble metal Inorganic materials 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 238000001075 voltammogram Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- GLCLQRXLJIMIEM-UHFFFAOYSA-N cobalt(2+) dinitrate trihydrate Chemical compound O.O.O.[Co++].[O-][N+]([O-])=O.[O-][N+]([O-])=O GLCLQRXLJIMIEM-UHFFFAOYSA-N 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 230000008034 disappearance Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 125000003916 ethylene diamine group Chemical group 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000000758 substrate Substances 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
- B01J27/20—Carbon compounds
- B01J27/22—Carbides
-
- B01J35/33—
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B1/00—Electrolytic production of inorganic compounds or non-metals
- C25B1/01—Products
- C25B1/02—Hydrogen or oxygen
- C25B1/04—Hydrogen or oxygen by electrolysis of water
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B11/00—Electrodes; Manufacture thereof not otherwise provided for
- C25B11/04—Electrodes; Manufacture thereof not otherwise provided for characterised by the material
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The invention discloses CuCo/Ti3C2TxComposite material and its preparation method and application. The preparation method comprises the following steps: in the presence of Ti3AlC2Adding LiF and concentrated HCl, stirring at room temperature for 72-75 h, centrifuging, adding an intercalator, performing ultrasonic treatment for 1-2 h, and centrifuging again to obtain Ti3C2TxA powder; mixing Ti3C2TxUltrasonically dispersing the powder in deionized water to obtain Ti3C2TxA black solution; adding copper nitrate and cobalt nitrate to Ti3C2TxDissolving the black solution in ultrasonic, adding an alkaline substance, adding the obtained mixed solution into a reaction kettle, keeping the temperature at 100 ℃ for 4-5 hours, centrifuging the obtained reactant, washing, and drying in vacuum to obtain CuCo/Ti3C2TxA composite material. CuCo/Ti of the invention3C2TxThe catalyst has better catalytic performance as an anode material for electrocatalytic water decomposition.
Description
Technical Field
The invention belongs to the field of electrocatalytic water decomposition, and particularly relates to CuCo/Ti3C2TxAs anode material, certain voltage is applied to promote the oxygen gas separation rate in the electrolytic cell, thereby improving the water decomposition efficiency.
Background
Today, serious environmental crisis forces researchers to turn their attention to cleaner, more efficient means of energy conversion. Electrochemical water splitting, on the other hand, is one of the most attractive routes to clean energy. However, four electrons (2H) are transferred due to the reaction process2O→O2+4H++4e), the Oxygen Evolution Reaction (OER) rate is slow and the reaction is severely hampered. With efficient but expensive RuO2And IrO2Compared with noble metal electrocatalysts, the application of cheap metals in the field of electrocatalysis water decomposition is a significant research content.
However, the electrocatalytic effect of cheap metals has certain limitations, and the catalytic efficiency is lowAnd requires a large applied voltage. Ti3C2Tx (MXene) is a kind of group with good conductivity, many groups with strong electronegativity like-F and-O etc. on the surface, and it is easy to combine with metal to produce chelate, so as to promote the electron transmission efficiency.
Disclosure of Invention
In order to solve the above-mentioned problems, it is an object of the present invention to provide Ti3C2Tx (MXene) and a compound containing cobalt and copper are combined together under the heating condition to prepare a composite CuCo/Ti with improved electrocatalytic water decomposition performance3C2Tx。
Another object of the present invention is to use CuCo/Ti3C2TxThe composite material is applied to the field of electrocatalytic water decomposition, and has a better electrocatalytic effect compared with that of single cobalt and copper in the electrocatalytic anode water oxidation process.
The technical scheme adopted by the invention is as follows: CuCo/Ti3C2TxThe preparation method of the composite material comprises the following steps:
1) in the presence of Ti3AlC2Adding LiF solid, slowly adding concentrated hydrochloric acid, stirring at room temperature for 72-75 h, centrifuging, discarding supernatant, centrifugally washing the obtained product with deionized water, adding an intercalator, performing ultrasonic treatment for 1-2 h, centrifuging again, discarding supernatant, centrifugally washing the obtained product with deionized water, and vacuum drying to obtain Ti3C2TxA powder;
2) mixing Ti3C2TxUltrasonically dispersing the powder in deionized water to obtain Ti3C2TxA black solution; adding copper nitrate and cobalt nitrate to Ti3C2TxDissolving the black solution in ultrasonic, adding an alkaline substance, uniformly mixing, adding the obtained mixed solution into a reaction kettle, keeping the temperature of the reaction kettle at 100 ℃ for 4-5 hours, centrifuging the obtained reactant, washing, and drying in vacuum to obtain CuCo/Ti3C2TxA composite material.
Further, in the step 1), the ratio of the LiF solid to the concentrated hydrochloric acid is as follows: 0.1g LiF per 1ml concentrated HCl was added.
Further, in the step 1), Ti is added according to the mass ratio3AlC2LiF solid 1: 1.
Further, in the step 1), the centrifugation is carried out at 8500 rpm.
Further, in step 1), the intercalation agent is dimethyl sulfoxide.
Further, in the step 1), the temperature of the vacuum drying is 40-60 ℃.
Further, in the step 2), the ratio of copper nitrate to cobalt nitrate is 1: 1-6 according to the amount of the substance.
Further, in step 2), the alkaline substance is ethylenediamine.
CuCo/Ti prepared by the method3C2TxUse of a composite material in electrocatalytic water splitting. The method comprises the following steps: the CuCo/Ti prepared by the method3C2TxAdding the composite material into a mixed liquid of absolute ethyl alcohol and Nafion, and performing ultrasonic dispersion to obtain a suspension; and (3) taking the suspended liquid to drop on a glassy carbon electrode, drying in vacuum to form a three-electrode system by taking a Pt wire as a counter electrode and Ag/AgCl as a reference electrode, and realizing the electrocatalytic water decomposition process.
The beneficial effects of the invention are:
1. the raw materials used in the invention are cheap and easily available, and Ti3C2TxThe preparation process is easy and safe, and the adopted metal compounds are cobalt nitrate hexahydrate and copper nitrate trihydrate, which are non-noble metal substances.
2. In the invention, a hydrothermal method is adopted to prepare CuCo/Ti3C2TxComposite material, action of metal compound in alkali solution and Ti3C2TxUnder the condition of stronger electronegativity of surface-OH, -O and-F, in Ti3C2TxThe surface of the copper substrate is grown with the oxide of the cobalt and copper bimetallic.
3. In the present invention, CuCo/Ti is used3C2TxThe electrocatalysis process with the composite material as the catalyst has CuCo bimetal, CuCo any one metal and Ti3C2TxExhibit excellent catalytic effects.
Drawings
FIG. 1 shows Ti in example 13AlC2Scanning Electron Micrograph (SEM).
FIG. 2 is Ti prepared in example 13C2TxScanning Electron Micrograph (SEM).
FIG. 3 shows Ti in example 13AlC2And Ti3C2TxX powder diffraction pattern (XRD).
FIG. 4 is a graph of CuCo/Ti in example 23C2TxCuCo oxide, RuO2、Cu/Ti3C2TxAnd Ti3C2TxWater-resolved Linear Sweep Voltammogram (LSV).
FIG. 5 is a graph of CuCo oxide and Ti in different ratios for example 33C2TxA water-resolved Linear Sweep Voltammogram (LSV) of the composite was formed.
Detailed Description
Hereinafter, an embodiment of the present invention will be described in detail with reference to the accompanying examples, which are intended to more clearly understand the present invention, but the present invention is not limited to the embodiment.
Example 1.
(I) CuCo/Ti3C2TxPreparation of composite materials
1、MXene(Ti3C2Tx) The preparation of (1):
adding 0.2g Ti into the centrifuge tube3AlC2Slowly adding a mixed solution of 0.2g of LiF and 2ml of concentrated hydrochloric acid, stirring at room temperature for 72 hours, centrifuging at 8500 revolutions, discarding the supernatant, adding deionized water into the obtained product, centrifuging and washing at 8500 revolutions for 6 times, adding 1ml of DMSO (dimethyl sulfoxide) into the obtained product as an intercalator, performing ultrasonic treatment for 1 hour to increase Ti content3C2TxCentrifuging at 8500 r, removing supernatant, adding deionized water, centrifuging at 8500 r for 6 times, and cooling at 60 deg.CVacuum drying to remove water to obtain dried Ti with few layers3C2TxAnd (3) powder.
2、CuCo/Ti3C2TxPreparation of composite materials
Weighing 10mg of less Ti3C2TxThe powder was ultrasonically dispersed in 1ml of deionized water to obtain Ti3C2TxBlack aqueous solution.
0.07218g (0.03mol) of copper nitrate trihydrate and 0.261927g (0.09mol) of cobalt nitrate hexahydrate were weighed and added to Ti3C2TxDissolving the mixture in black water solution by ultrasonic wave, and adding 2ml of glycol to obtain a mixed solution.
Pouring the obtained mixed solution into a steel bottle reaction kettle, putting into an oven, keeping at 100 deg.C for 3 hr to obtain dark green precipitate, centrifuging, washing, and oven drying to remove water to obtain CuCo/Ti3C2TxAnd (3) powder.
(II) detection
FIG. 1 is Ti in example 13AlC2Scanning Electron Micrograph (SEM) of (1), as can be seen from FIG. 1, Ti3AlC2Is a substance having a laminar texture in which Al is present.
FIG. 2 is Ti prepared in example 13C2TxAs can be seen from fig. 2, after stripping off Al by etching, a clear gap appears between the layers.
FIG. 3 shows MXene (Ti) in example 13C2Tx) And Ti3AlC2X-ray diffraction pattern (XRD). As can be seen from FIG. 3, in Ti3AlC2The disappearance of the peak at about 40 degrees in the middle, the shift of the peak at the (002) crystal plane to the left and the broadening, indicating MXene (Ti)3C2Tx) The etching was successful.
Example 2.
Effect of coating different composites on Water Oxidation of electrocatalytic Anode
Preparation of the catalyst
1. The invention-CuCo/Ti3C2Tx: the product prepared in example 1 was taken.
2. Comparative example 1-CuCo oxide: 0.07218g (0.03mol) of copper nitrate trihydrate and 0.261927g (0.09mol) of cobalt nitrate hexahydrate were weighed, 1ml of water was added, ultrasonic decomposition was performed, and 2ml of ethylene glycol was added to obtain a mixed solution. Pouring the obtained mixed solution into a steel cylinder reaction kettle, putting the steel cylinder reaction kettle into an oven, keeping the steel cylinder reaction kettle at 100 ℃ for 3 hours, generating brown precipitate in the process, and removing water through centrifugal washing and drying to obtain CuCo oxide.
3. Comparative example 2 RuO2
4. Comparative example 3-Cu/Ti3C2Tx: weighing 10mg of less Ti3C2TxThe powder was ultrasonically dispersed in 1ml of deionized water to obtain Ti3C2TxBlack aqueous solution. 0.07218g (0.03mol) of copper nitrate trihydrate were weighed into Ti3C2TxDissolving the mixture in black water solution by ultrasonic wave, and adding 2ml of glycol to obtain a mixed solution. Pouring the obtained mixed solution into a steel bottle reaction kettle, putting the steel bottle reaction kettle into an oven, keeping the steel bottle reaction kettle at 100 ℃ for 3 hours to generate dark green precipitate in the process, and removing water by centrifugal washing and drying to obtain Cu/Ti3C2TxAnd (3) powder.
5. Comparative example 3-Ti3C2Tx: the product prepared in example 1 was taken.
(II) working electrode
Respectively taking 4mg of CuCo/Ti3C2TxComposite material, CuCo oxide, RuO2、Cu/Ti3C2TxAnd Ti3C2TxAdding 495 mul of deionized water, 500 mul of absolute ethyl alcohol and 5 mul of Nafion respectively, ultrasonically dispersing, and transferring 5 mul of mixed solution to an area of 0.07cm by using a liquid transfer gun-2And putting the glassy carbon electrode into a drying oven at 40 ℃ for drying to obtain glassy carbon electrodes coated with different compounds.
The performance of anodic water oxidation was evaluated in 1M KOH using a standard three-electrode system on a CHI 760D electrochemical workstation. Linear Sweep Voltammetry (LSV) rotation rate at 1600rpm,The scanning rate is 10mV s-1And (4) measuring. The glassy carbon electrodes coated with different compounds are used as working electrodes, Pt wires are used as counter electrodes, and Ag/AgCl is used as reference electrodes to form a three-electrode system. All potentials measured on Ag/AgCl electrodes according to E in the inventionvs RHE＝Evs Ag/AgCl+0.059pH +0.197 converted to a potential relative to RHE.
(III) results
As shown in FIG. 4, is CuCo/Ti3C2TxComposite material, CuCo oxide, RuO2、Cu/Ti3C2TxAnd Ti3C2TxWhen the electrocatalytic water decomposition of the materials is carried out on the linear sweep voltammetry curve, the comparison shows that the initial potential of the material designed by the invention is the lowest, and Evs RHE1.42V, close to the catalytic onset potential of commercial ruthenium dioxide, the catalytic onset potential of bimetallic mixtures is Evs RHE1.57V, much lower than CuCo/Ti3C2TxComposite material, metal alone or with Ti alone3C2TxHas no obvious effect, and CuCo/Ti has no obvious effect along with the increase of voltage3C2TxThe composite material has the advantages of quickest current density increase and higher catalysis rate.
Example 3.
Effect of different Co Compound and Cu Compound contents on electrocatalytic Water splitting Effect
Preparation of catalyst
1、MXene(Ti3C2Tx) The preparation of (1):
adding 0.2g Ti into the centrifuge tube3AlC2Slowly adding a mixed solution of 0.2g of LiF and 2ml of concentrated hydrochloric acid, stirring at room temperature for 72 hours, centrifuging at 8500 revolutions, discarding the supernatant, adding deionized water into the obtained product, centrifuging and washing at 8500 revolutions for 6 times, adding 1ml of DMSO (dimethyl sulfoxide) into the obtained product as an intercalator, performing ultrasonic treatment for 1 hour to increase Ti content3C2TxCentrifuging at 8500 r, removing supernatant, adding deionized water, centrifuging at 8500 r, and washingThe times are 6 times, and the obtained product is vacuum dried at 60 deg.C to remove water to obtain dried Ti with few layers3C2TxAnd (3) powder.
2、CuCo/Ti3C2TxPreparation of composite materials
Weighing 10mg of less Ti3C2TxThe powder was ultrasonically dispersed in 1ml of deionized water to obtain Ti3C2TxBlack aqueous solution.
Cobalt nitrate trihydrate and cobalt nitrate hexahydrate were weighed as in Table 1, and added to Ti3C2TxAfter ultrasonic dissolution in a black aqueous solution, 2ml of ethylene glycol was added to obtain a mixed solution.
Pouring the obtained mixed solution into a steel cylinder reaction kettle, putting the steel cylinder reaction kettle into an oven, keeping the steel cylinder reaction kettle at 100 ℃ for 3 hours to generate dark green precipitate in the process, and centrifugally washing and drying the precipitate to remove water to obtain CuCo/Ti3C2TxAnd (3) powder.
TABLE 1
| Mass ratio of substances | 1:1 | 1:2 | 1:4 | 1:6 |
| Cu(NO3)3.3H2O/g | 0.1746 | 0.07218 | 0.07218 | 0.07218 |
| Co(NO3)2.6H2O/g | 0.1449 | 0.1449 | 0.1746 | 0.23194 |
Preparation of (II) electrode
Respectively taking 4mg of CuCo/Ti with different Co compound and Cu compound contents3C2TxAdding 495 mul of deionized water, 500 mul of absolute ethyl alcohol and 5 mul of Nafion into the composite material respectively, performing ultrasonic dispersion, and transferring 5 mul of mixed solution to a liquid transfer gun to form a drop with the area of 0.07cm-2And putting the glassy carbon electrode into a 40 ℃ oven for drying to obtain glassy carbon electrodes coated with different compounds.
The performance of anodic water oxidation was evaluated in 1M KOH on a CHI 760D electrochemical workstation using a standard three electrode system. Rotation rate of Linear Sweep Voltammetry (LSV) at 1600rpm, scan rate of 10mV s-1And (4) measuring. The glassy carbon electrodes coated with different compounds are used as working electrodes, Pt wires are used as counter electrodes, and Ag/AgCl is used as reference electrodes to form a three-electrode system. All potentials measured on Ag/AgCl electrodes according to E in the inventionvs RHE＝Evs Ag/AgCl+0.059pH +0.197 converted to a potential relative to RHE.
(III) results
FIG. 5 is a graph of CuCo/Ti for different Co compound and Cu compound contents3C2TxLSV image of composite material, as can be seen from FIG. 5, the initial potential E vs RHE is obviously reduced along with the increase of the quantity ratio of the Cu and Co substances, and the current density is increased faster along with the increase of the voltage, when the quantity ratio of the Cu and Co substances is 1:6, the overpotential is 1.42V at the lowest and the current density is the largest under the same voltage, and as can be seen from comparison with FIG. 4, the difference of CuCo addition quantity influences the catalytic effect, andTi3C2Txthe addition of (b) may promote the catalytic effect of the bimetal.
Claims (5)
1.CuCo/Ti3C2TxThe preparation method of the composite material is characterized in that the CuCo/Ti3C2TxThe composite material is formed of Ti3C2TxThe surface of the composite material is grown with the oxide of cobalt and copper bimetallic, and the preparation method comprises the following steps:
1) in the presence of Ti3AlC2Adding LiF solid, slowly adding concentrated hydrochloric acid, stirring at room temperature for 72-75 h, centrifuging, discarding supernatant, centrifugally washing the obtained product with deionized water, adding intercalation agent dimethyl sulfoxide, performing ultrasonic treatment for 1-2 h, centrifuging again, discarding supernatant, centrifugally washing the obtained product with deionized water, and performing vacuum drying to obtain Ti3C2TxPowder; in a mass ratio of Ti3AlC2 LiF solids = 1: 1; adding 0.1g LiF into 1mL of concentrated hydrochloric acid;
2) mixing Ti3C2TxUltrasonically dispersing the powder in deionized water to obtain Ti3C2TxA black solution; adding copper nitrate and cobalt nitrate to Ti3C2TxAdding an alkaline substance ethylenediamine into a black solution after ultrasonic dissolution, uniformly mixing, adding the obtained mixed solution into a reaction kettle, keeping the temperature at 100 ℃ for 4-5 hours, centrifuging the obtained reactant, washing, and drying in vacuum to obtain CuCo/Ti3C2TxA composite material; copper nitrate to cobalt nitrate = 1:6 by mass ratio.
2. CuCo/Ti according to claim 13C2TxThe preparation method of the composite material is characterized in that in the step 1), the centrifugation is carried out at the rotating speed of 8500 r/min.
3. CuCo/Ti according to claim 13C2TxThe preparation method of the composite material is characterized in that in the step 1), the vacuum drying is carried outThe temperature of (a) is 40-60 ℃.
4. CuCo/Ti prepared by the method according to any one of claims 1 to 33C2TxUse of a composite material in electrocatalytic water splitting.
5. Use according to claim 4, characterized in that the method is as follows: mixing CuCo/Ti3C2TxAdding the composite material into a mixed liquid of absolute ethyl alcohol and Nafion, and performing ultrasonic dispersion to obtain a suspension; and (3) taking the suspended liquid to drop on a glassy carbon electrode, drying in vacuum to form a three-electrode system by taking a Pt wire as a counter electrode and Ag/AgCl as a reference electrode, and realizing the electrocatalytic water decomposition process.
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