CN110038604A - CuCo/Ti3C2TxComposite material and preparation method and application - Google Patents
CuCo/Ti3C2TxComposite material and preparation method and application Download PDFInfo
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- CN110038604A CN110038604A CN201910388121.0A CN201910388121A CN110038604A CN 110038604 A CN110038604 A CN 110038604A CN 201910388121 A CN201910388121 A CN 201910388121A CN 110038604 A CN110038604 A CN 110038604A
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- 229910016507 CuCo Inorganic materials 0.000 title claims abstract description 47
- 238000002360 preparation method Methods 0.000 title claims abstract description 27
- 239000000463 material Substances 0.000 title claims description 11
- 229910009819 Ti3C2 Inorganic materials 0.000 claims abstract description 61
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 35
- 239000002131 composite material Substances 0.000 claims abstract description 33
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 17
- 239000008367 deionised water Substances 0.000 claims abstract description 15
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 15
- 238000000354 decomposition reaction Methods 0.000 claims abstract description 12
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000005119 centrifugation Methods 0.000 claims abstract description 10
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims abstract description 8
- 238000006243 chemical reaction Methods 0.000 claims abstract description 8
- 239000000243 solution Substances 0.000 claims abstract description 8
- 239000000138 intercalating agent Substances 0.000 claims abstract description 7
- 238000001291 vacuum drying Methods 0.000 claims abstract description 7
- 238000004090 dissolution Methods 0.000 claims abstract description 6
- 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
- 238000002604 ultrasonography Methods 0.000 claims abstract description 5
- 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 4
- 239000000376 reactant Substances 0.000 claims abstract description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 16
- 238000005406 washing Methods 0.000 claims description 16
- 238000000034 method Methods 0.000 claims description 15
- 239000000047 product Substances 0.000 claims description 13
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethyl sulfoxide Natural products CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 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
- 239000007787 solid Substances 0.000 claims description 6
- 229920000557 Nafion® Polymers 0.000 claims description 4
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- 239000007788 liquid Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 2
- 125000003916 ethylene diamine group Chemical group 0.000 claims description 2
- 239000000725 suspension Substances 0.000 claims description 2
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 239000010405 anode material Substances 0.000 abstract description 2
- 239000010949 copper Substances 0.000 description 14
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 9
- 229910052751 metal Inorganic materials 0.000 description 8
- 239000002184 metal Substances 0.000 description 8
- WOCIAKWEIIZHES-UHFFFAOYSA-N ruthenium(IV) oxide Inorganic materials O=[Ru]=O WOCIAKWEIIZHES-UHFFFAOYSA-N 0.000 description 8
- 238000004502 linear sweep voltammetry Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000001035 drying Methods 0.000 description 6
- 229910052802 copper Inorganic materials 0.000 description 5
- 229910000831 Steel Inorganic materials 0.000 description 4
- 239000010941 cobalt Substances 0.000 description 4
- 235000013495 cobalt Nutrition 0.000 description 4
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-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
- 230000000694 effects Effects 0.000 description 4
- OQUOOEBLAKQCOP-UHFFFAOYSA-N nitric acid;hexahydrate Chemical compound O.O.O.O.O.O.O[N+]([O-])=O OQUOOEBLAKQCOP-UHFFFAOYSA-N 0.000 description 4
- 239000010959 steel Substances 0.000 description 4
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 3
- 239000003054 catalyst Substances 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 229910017052 cobalt Inorganic materials 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 230000001376 precipitating effect Effects 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 229910002651 NO3 Inorganic materials 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 239000010953 base metal Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000013522 chelant Substances 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 229910000765 intermetallic Inorganic materials 0.000 description 1
- HTXDPTMKBJXEOW-UHFFFAOYSA-N iridium(IV) oxide Inorganic materials O=[Ir]=O HTXDPTMKBJXEOW-UHFFFAOYSA-N 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000002927 oxygen compounds Chemical class 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/20—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 present invention discloses a kind of CuCo/Ti3C2TxComposite material and preparation method and application.Preparation method includes the following steps: in Ti3AlC2In, LiF and dense HCl is added, after 72~75h is stirred at room temperature, intercalator is added in centrifugation, and 1~2h of ultrasound is centrifuged again, obtains Ti3C2TxPowder；By Ti3C2TxPowder ultrasonic is scattered in deionized water, obtains Ti3C2TxDark solution；Ti is added in copper nitrate and cobalt nitrate3C2TxIn dark solution, after ultrasonic dissolution, alkaline matter is added, gained mixed solution is added in reaction kettle, at 100 DEG C, keeps 4~5h, and gained reactant is centrifuged, and is washed, and vacuum drying obtains CuCo/Ti3C2TxComposite material.CuCo/Ti of the invention3C2TxAs the anode material of electro-catalysis water decomposition, there is preferable catalytic performance.
Description
Technical field
The invention belongs to electrocatalytic decomposition water fields, specifically by CuCo/Ti3C2TxAs anode material, add certain electricity
Pressure promotes oxygen evolution rate in electrolytic cell, to improve water decomposition efficiency.
Background technique
Nowadays, serious environmental crisis forces researcher that attention steering is more cleaned, and more effective energy converts hand
Section.On the other hand, it is one of the approach for obtaining the most attraction of clean energy resource that electro-chemical water, which decomposes,.However, since it was reacted
Journey need to shift four electronics (2H2O→O2+4H++ 4e), oxygen evolution reaction (OER) rate is slow, reacts seriously hampered.
With effective but expensive RuO2And IrO2Equal noble metal electrocatalysts are compared, and cheap metal is applied in electro-catalysis water decomposition
Field will be a significant research contents.
However, the electro-catalysis effect of cheap metal have certain limitation, catalytic efficiency is low, and need applied voltage compared with
Greatly.Ti3C2Tx (MXene) is that a kind of electric conductivity is preferable, there are many surfaces stronger group of the electronegativity such as-F ,-O, is easy and metal
In conjunction with generating chelate, promote electron-transport efficiency with this.
Summary of the invention
In order to solve the above-mentioned technical problem, an object of the present invention is by Ti3C2Tx (MXene) and the change containing cobalt and copper
It closes object to be combined together in a heated condition, preparing has the composite material CuCo/Ti for improving electro-catalysis water dispersible energy3C2Tx。
The second object of the present invention is to by CuCo/Ti3C2TxComposite material is applied to electro-catalysis water decomposition field, urges in electricity
Change anode water oxidation process, has with the electro-catalysis effect compared to individual cobalt and copper and significantly improve.
The technical solution adopted by the present invention is that: CuCo/Ti3C2TxThe preparation method of composite material, includes the following steps:
1) in Ti3AlC2In, LiF solid is added, is slowly added to concentrated hydrochloric acid, after 72~75h is stirred at room temperature, supernatant is abandoned in centrifugation
After products therefrom deionized water centrifuge washing, intercalator is added in liquid, and 1~2h of ultrasound is centrifuged again, abandons supernatant, gained production
After object uses deionized water centrifuge washing again, vacuum drying obtains Ti3C2TxPowder；
2) by Ti3C2TxPowder ultrasonic is scattered in deionized water, obtains Ti3C2TxDark solution；By copper nitrate and nitric acid
Ti is added in cobalt3C2TxIn dark solution, after ultrasonic dissolution, alkaline matter is added, is uniformly mixed, gained mixed solution is added to
In reaction kettle, at 100 DEG C, 4~5h is kept, gained reactant is centrifuged, and is washed, and vacuum drying obtains CuCo/Ti3C2TxIt is compound
Material.
Further, in step 1), LiF solid and concentrated hydrochloric acid proportion are: 0.1g LiF is added in every 1ml concentrated hydrochloric acid.
Further, in step 1), in mass ratio, Ti3AlC2: LiF solid=1:1.
Further, in step 1), the centrifugation, revolving speed is 8500 revs/min.
Further, in step 1), the intercalator is dimethyl sulfoxide.
Further, in step 1), the vacuum drying temperature is 40~60 DEG C.
Further, in step 2), by the mass ratio of the material, copper nitrate: cobalt nitrate=1:1~6.
Further, in step 2), the alkaline matter is ethylenediamine.
The CuCo/Ti of above-mentioned method preparation3C2TxApplication of the composite material in electro-catalysis water decomposition.Method is as follows: will
The CuCo/Ti of above method preparation3C2TxComposite material is added in the mixing liquid of dehydrated alcohol and Nafion, ultrasonic disperse
Obtain suspension；It takes suspended drop on glass-carbon electrode, is dried in vacuo, as working electrode, Pt as to electrode, Ag/
AgCl is reference electrode, constitutes three-electrode system, realizes electro-catalysis water splitting processes.
The beneficial effects of the present invention are:
1, raw material used in the present invention is cheap and easy to get, Ti3C2TxPreparation process be relatively easy to safety, the metal of use
Compound is cabaltous nitrate hexahydrate and Gerhardite, is all base metal substance.
2, in the present invention, CuCo/Ti is prepared using hydro-thermal method3C2TxComposite material, the work of metallic compound alkali in the solution
With and Ti3C2TxUnder the conditions of the relatively strong electronegativity of surface-OH ,-O and-F, in Ti3C2TxSurface growth cobalt and copper bi-metal oxygen
Compound.
3, in the present invention, with CuCo/Ti3C2TxComposite material is the electro-catalysis process of catalyst, is had bis- relative to CuCo
Any one metal of metal, CuCo and Ti3C2TxAll show superior catalytic effect.
Detailed description of the invention
Fig. 1 is Ti in embodiment 13AlC2Scanning electron microscope (SEM) photograph (SEM).
Fig. 2 is the Ti prepared in embodiment 13C2TxScanning electron microscope (SEM) photograph (SEM).
Fig. 3 is Ti in embodiment 13AlC2And Ti3C2TxX powder diffraction image (XRD).
Fig. 4 is CuCo/Ti in embodiment 23C2Tx, CuCo oxide, RuO2、Cu/Ti3C2TxAnd Ti3C2TxWater decomposition
Linear sweep voltammetry comparison diagram (LSV).
Fig. 5 is the CuCo oxide and Ti of different proportion in embodiment 33C2TxThe water decomposition for forming composite material is linearly swept
Retouch a volt-ampere comparison diagram (LSV).
Specific embodiment
Below with reference to appended implementation legend detailed description of the present invention embodiment, this embodiment is in order to more clearly
Understand the present invention, but the present invention is not limited thereto embodiment.
Embodiment 1.
(1) CuCo/Ti3C2TxThe preparation of composite material
1、MXene(Ti3C2Tx) preparation:
0.2g Ti is added in centrifuge tube3AlC2, it is slowly added to the mixed liquor of 0.2gLiF and 2ml concentrated hydrochloric acid, is stirred at room temperature
After 72h, supernatant is abandoned in 8500 turns of centrifugations, and products therefrom adds deionized water by centrifuge washing, and centrifugal rotational speed is 8500 turns, is washed
Washing number is 6 times, 1ml DMSO is added in products therefrom as intercalator, ultrasound 1 hour increases Ti3C2TxInterlamellar spacing,
Supernatant is abandoned in 8500 turns of centrifugations, and products therefrom adds deionized water by centrifuge washing, and centrifugal rotational speed is 8500 turns, washing times
It is 6 times, products therefrom is dried in vacuo at 60 DEG C removes moisture, obtains few layer of dry Ti3C2TxPowder.
2、CuCo/Ti3C2TxThe preparation of composite material
It weighs 10mg and lacks layer Ti3C2TxPowder ultrasonic is dispersed in 1ml deionized water, obtains Ti3C2TxBlack aqueous solution.
0.07218g (0.03mol) Gerhardite and 0.261927g (0.09mol) cabaltous nitrate hexahydrate are weighed, is added
Enter to Ti3C2TxIn black aqueous solution, after ultrasonic dissolution, 2ml ethylene glycol is added, obtains mixed solution.
It by gained mixed solution, pours into steel cylinder reaction kettle, is put into baking oven, kept for 3 hours at 100 DEG C, this process produces
Raw blackish green precipitating, by centrifuge washing, drying removes moisture, obtains CuCo/Ti3C2TxPowder.
(2) it detects
Fig. 1 is Ti in embodiment 13AlC2Scanning electron microscope (SEM) photograph (SEM), from figure 1 it appears that Ti3AlC2It is with layer
The substance of shape texture, Al exist wherein.
Fig. 2 is the Ti prepared in embodiment 13C2TxScanning electron microscope (SEM) photograph (SEM), from figure 2 it can be seen that passing through etching
After peeling off Al, occurs clear gap between layers.
Fig. 3 is MXene (Ti in embodiment 13C2Tx) and Ti3AlC2X-ray diffraction spectrogram (XRD).As seen from Figure 3, exist
Ti3AlC2In 40 ° or so of spike disappear, the peak of (002) crystal face moves to left and broadens, and illustrates MXene (Ti3C2Tx) be etched into
Function.
Embodiment 2.
The influence that coating different composite object aoxidizes electro-catalysis anode water
(1) preparation of catalyst
1, of the invention --- CuCo/Ti3C2Tx: product prepared by Example 1.
2,0.07218g (0.03mol) Gerhardite and 0.261927g comparative example 1 --- CuCo oxide: are weighed
(0.09mol) cabaltous nitrate hexahydrate, is added 1ml water, and ultrasonic decomposition is added 2ml ethylene glycol, obtains mixed solution.Gained is mixed
Solution pours into steel cylinder reaction kettle, is put into baking oven, is kept for 3 hours at 100 DEG C, this process generates brown precipitate, passes through centrifugation
Washing, drying remove moisture, obtain CuCo oxide.
3, comparative example 2 --- RuO2
4, comparative example 3 --- Cu/Ti3C2Tx: it weighs 10mg and lacks layer Ti3C2TxPowder ultrasonic is dispersed in 1ml deionized water,
Obtain Ti3C2TxBlack aqueous solution.0.07218g (0.03mol) Gerhardite is weighed, Ti is added to3C2TxBlack aqueous solution
In, after ultrasonic dissolution, 2ml ethylene glycol is added, obtains mixed solution.Gained mixed solution is poured into steel cylinder reaction kettle, be put into baking
Case is kept for 3 hours at 100 DEG C, this process generates blackish green precipitating, and by centrifuge washing, drying removes moisture, obtains Cu/
Ti3C2TxPowder.
5, comparative example 3 --- Ti3C2Tx: product prepared by Example 1.
(2) working electrode
4mg CuCo/Ti is taken respectively3C2TxComposite material, CuCo oxide, RuO2、Cu/Ti3C2TxAnd Ti3C2Tx, respectively
495 μ l deionized waters, 500 μ l dehydrated alcohols and 5 μ l Nafion, ultrasonic disperse are added, gained mixed liquor is turned with liquid-transfering gun respectively
It is 0.07cm that 5 μ l drops, which are moved, in area-2Glass-carbon electrode on, be put into the drying of 40 DEG C of baking ovens, obtain the glass carbon of coating different composite object
Electrode.
Anode water oxidation is assessed in 1M KOH using standard three electrode system on CHI 760D electrochemical workstation
Performance.The speed of rotation, sweep speed of the linear sweep voltammetry (LSV) in 1600rpm are 10mV s-1It is measured.To coat difference
The glass-carbon electrode of compound is working electrode, and Pt are used as to electrode, and Ag/AgCl is that reference electrode constitutes three-electrode system.This
All current potentials measured on Ag/AgCl electrode in invention, according to Evs RHE=Evs Ag/AgCl+ 0.059pH+0.197 is converted to phase
For the current potential of RHE.
(3) result
As shown in figure 4, being CuCo/Ti3C2TxComposite material, CuCo oxide, RuO2、Cu/Ti3C2TxAnd Ti3C2TxEqual materials
The electro-catalysis water decomposition linear sweep voltammetry curve of material can be seen that the take-off potential for the material that the present invention designs most by comparison
It is low, Evs RHE=1.42V, close to the catalysis take-off potential of commercialized ruthenic oxide, the catalysis take-off potential of bimetallic mixing
For Evs RHE=1.57V, well below CuCo/Ti3C2TxComposite material, independent metal or and independent Ti3C2TxCatalytic effect
All without remarkable result, as voltage increases, CuCo/Ti3C2TxThe current density of composite material is pushed the speed most fastly, catalysis speed
Rate is very fast.
Embodiment 3.
Influence of the content of different Co compounds and Cu compound to electro-catalysis water decomposition effect
(1) preparation of catalyst
1、MXene(Ti3C2Tx) preparation:
0.2g Ti is added in centrifuge tube3AlC2, it is slowly added to the mixed liquor of 0.2gLiF and 2ml concentrated hydrochloric acid, is stirred at room temperature
After 72h, supernatant is abandoned in 8500 turns of centrifugations, and products therefrom adds deionized water by centrifuge washing, and centrifugal rotational speed is 8500 turns, is washed
Washing number is 6 times, 1ml DMSO is added in products therefrom as intercalator, ultrasound 1 hour increases Ti3C2TxInterlamellar spacing,
Supernatant is abandoned in 8500 turns of centrifugations, and products therefrom adds deionized water by centrifuge washing, and centrifugal rotational speed is 8500 turns, washing times
It is 6 times, products therefrom is dried in vacuo at 60 DEG C removes moisture, obtains few layer of dry Ti3C2TxPowder.
2、CuCo/Ti3C2TxThe preparation of composite material
It weighs 10mg and lacks layer Ti3C2TxPowder ultrasonic is dispersed in 1ml deionized water, obtains Ti3C2TxBlack aqueous solution.
Three nitric hydrate cobalts and cabaltous nitrate hexahydrate are weighed by table 1, are added to Ti3C2TxIn black aqueous solution, ultrasonic dissolution
Afterwards, 2ml ethylene glycol is added, obtains mixed solution.
It by gained mixed solution, pours into steel cylinder reaction kettle, is put into baking oven, kept for 3 hours at 100 DEG C, this process produces
Raw blackish green precipitating, by centrifuge washing, drying removes moisture, obtains CuCo/Ti3C2TxPowder.
Table 1
| The mass ratio of the material | 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 |
(2) preparation of electrode
The content CuCo/Ti of 4mg difference Co compound and Cu compound is taken respectively3C2TxComposite material is separately added into 495 μ
L deionized water, 500 μ l dehydrated alcohols and 5 μ l Nafion, ultrasonic disperse, gained mixed liquor shift 5 μ l drops with liquid-transfering gun respectively
It is 0.07cm in area-2Glass-carbon electrode on, be put into the drying of 40 DEG C of baking ovens, obtain the glass-carbon electrode of coating different composite object.
Anode water oxidation is assessed in 1M KOH using standard three electrode system on CHI 760D electrochemical workstation
Performance.The speed of rotation, sweep speed of the linear sweep voltammetry (LSV) in 1600rpm are 10mV s-1It is measured.To coat difference
The glass-carbon electrode of compound is working electrode, and Pt are used as to electrode, and Ag/AgCl is that reference electrode constitutes three-electrode system.This
All current potentials measured on Ag/AgCl electrode in invention, according to Evs RHE=Evs Ag/AgCl+ 0.059pH+0.197 is converted to phase
For the current potential of RHE.
(3) result
Fig. 5 is the CuCo/Ti of the content of different Co compounds and Cu compound3C2TxThe LSV image of composite material, by Fig. 5
As it can be seen that the increase of the mass ratio of the material with Cu and Co, take-off potential E vs RHE has apparent reduction, and as voltage increases
Greatly, current density increases faster, when the mass ratio of the material of Cu and Co is 1:6, the minimum 1.42V of overpotential and identical voltage
Under, highest current density is contrasted with Fig. 4 it can be found that the difference of CuCo additional amount will affect catalytic effect, and Ti3C2Tx's
Addition can promote bimetallic catalytic effect.
Claims (10)
1.CuCo/Ti3C2TxThe preparation method of composite material, which is characterized in that preparation method includes the following steps:
1) in Ti3AlC2In, LiF solid is added, is slowly added to concentrated hydrochloric acid, after 72~75h is stirred at room temperature, supernatant, institute are abandoned in centrifugation
After obtaining product deionized water centrifuge washing, intercalator is added, 1~2h of ultrasound is centrifuged again, abandons supernatant, products therefrom is again
After deionized water centrifuge washing, vacuum drying obtains Ti3C2TxPowder；
2) by Ti3C2TxPowder ultrasonic is scattered in deionized water, obtains Ti3C2TxDark solution；Copper nitrate and cobalt nitrate are added
Enter Ti3C2TxIn dark solution, after ultrasonic dissolution, alkaline matter is added, is uniformly mixed, gained mixed solution is added to reaction
In kettle, at 100 DEG C, 4~5h is kept, gained reactant is centrifuged, and is washed, and vacuum drying obtains CuCo/Ti3C2TxComposite material.
2. CuCo/Ti according to claim 13C2TxThe preparation method of composite material, which is characterized in that in step 1),
LiF solid and concentrated hydrochloric acid proportion are: 0.1g LiF is added in every 1ml concentrated hydrochloric acid.
3. CuCo/Ti according to claim 13C2TxThe preparation method of composite material, which is characterized in that in step 1), press
Mass ratio, Ti3AlC2: LiF solid=1:1.
4. CuCo/Ti according to claim 13C2TxThe preparation method of composite material, which is characterized in that in step 1), institute
Centrifugation is stated, revolving speed is 8500 revs/min.
5. CuCo/Ti according to claim 13C2TxThe preparation method of composite material, which is characterized in that in step 1), institute
Stating intercalator is dimethyl sulfoxide.
6. CuCo/Ti according to claim 13C2TxThe preparation method of composite material, which is characterized in that in step 1), institute
Stating vacuum drying temperature is 40~60 DEG C.
7. CuCo/Ti according to claim 13C2TxThe preparation method of composite material, which is characterized in that in step 2), press
The mass ratio of the material, copper nitrate: cobalt nitrate=1:1~6.
8. CuCo/Ti according to claim 13C2TxThe preparation method of composite material, which is characterized in that in step 2), institute
Stating alkaline matter is ethylenediamine.
9. the CuCo/Ti of method preparation according to any one of claims 1 to 83C2TxComposite material is in electro-catalysis water decomposition
In application.
10. application according to claim 9, which is characterized in that method is as follows: claim 1~7 is described in any item
The CuCo/Ti of method preparation3C2TxComposite material is added in the mixing liquid of dehydrated alcohol and Nafion, and ultrasonic disperse obtains
Suspension；It takes suspended drop on glass-carbon electrode, is dried in vacuo, as working electrode, Pt are used as to electrode, and Ag/AgCl is
Reference electrode constitutes three-electrode system, realizes electro-catalysis water splitting processes.
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