CN116905021A - Preparation method and application of high-dispersion supported MXene electrocatalyst - Google Patents
Preparation method and application of high-dispersion supported MXene electrocatalyst Download PDFInfo
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- 239000006185 dispersion Substances 0.000 title claims abstract description 47
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 41
- 238000002360 preparation method Methods 0.000 title claims abstract description 18
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 76
- 150000003839 salts Chemical class 0.000 claims abstract description 41
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 38
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 claims abstract description 19
- 239000002184 metal Substances 0.000 claims abstract description 19
- 238000002156 mixing Methods 0.000 claims abstract description 14
- 239000000203 mixture Substances 0.000 claims abstract description 13
- KWGKDLIKAYFUFQ-UHFFFAOYSA-M lithium chloride Chemical compound [Li+].[Cl-] KWGKDLIKAYFUFQ-UHFFFAOYSA-M 0.000 claims abstract description 12
- 239000003054 catalyst Substances 0.000 claims abstract description 11
- 238000000227 grinding Methods 0.000 claims abstract description 11
- XKRFYHLGVUSROY-UHFFFAOYSA-N argon Substances [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims abstract description 10
- 229910052786 argon Inorganic materials 0.000 claims abstract description 10
- 238000010438 heat treatment Methods 0.000 claims abstract description 10
- 239000000463 material Substances 0.000 claims abstract description 10
- 238000004108 freeze drying Methods 0.000 claims abstract description 9
- 238000005406 washing Methods 0.000 claims abstract description 8
- 230000009467 reduction Effects 0.000 claims description 21
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 14
- 229910052799 carbon Inorganic materials 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 10
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 9
- 229920000557 Nafion® Polymers 0.000 claims description 8
- 229910052709 silver Inorganic materials 0.000 claims description 8
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 7
- FOIXSVOLVBLSDH-UHFFFAOYSA-N Silver ion Chemical compound [Ag+] FOIXSVOLVBLSDH-UHFFFAOYSA-N 0.000 claims description 7
- 239000012528 membrane Substances 0.000 claims description 7
- 229910052697 platinum Inorganic materials 0.000 claims description 7
- 239000004332 silver Substances 0.000 claims description 7
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical group [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 7
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 6
- 239000012498 ultrapure water Substances 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 3
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 3
- 239000002105 nanoparticle Substances 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 2
- 150000002739 metals Chemical class 0.000 claims description 2
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 2
- 238000006243 chemical reaction Methods 0.000 abstract description 13
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 abstract description 7
- 239000001257 hydrogen Substances 0.000 abstract description 7
- 229910052739 hydrogen Inorganic materials 0.000 abstract description 7
- 230000003197 catalytic effect Effects 0.000 abstract description 6
- 239000000047 product Substances 0.000 description 11
- 239000007789 gas Substances 0.000 description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 9
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 8
- 239000008367 deionised water Substances 0.000 description 8
- 229910021641 deionized water Inorganic materials 0.000 description 8
- 239000007788 liquid Substances 0.000 description 7
- 239000000243 solution Substances 0.000 description 7
- 238000005303 weighing Methods 0.000 description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- 238000005868 electrolysis reaction Methods 0.000 description 6
- 238000003181 co-melting Methods 0.000 description 5
- 239000003792 electrolyte Substances 0.000 description 5
- 238000011068 loading method Methods 0.000 description 5
- 238000011056 performance test Methods 0.000 description 5
- 239000010453 quartz Substances 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 239000002904 solvent Substances 0.000 description 5
- 238000009210 therapy by ultrasound Methods 0.000 description 5
- 238000004817 gas chromatography Methods 0.000 description 4
- 239000001103 potassium chloride Substances 0.000 description 4
- 235000011164 potassium chloride Nutrition 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000000460 chlorine Substances 0.000 description 3
- 239000010949 copper Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052801 chlorine Inorganic materials 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000007599 discharging Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000000921 elemental analysis Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000007710 freezing Methods 0.000 description 1
- 230000008014 freezing Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 229910052752 metalloid Inorganic materials 0.000 description 1
- 150000002738 metalloids Chemical class 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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Classifications
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- 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
- C25B11/075—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the electrocatalyst material consisting of a single catalytic element or catalytic compound
-
- 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
- C25B1/23—Carbon monoxide or syngas
-
- 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
- C25B11/055—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material
- C25B11/057—Electrodes formed of electrocatalysts on a substrate or carrier characterised by the substrate or carrier material consisting of a single element or compound
- C25B11/061—Metal or alloy
Abstract
The invention relates to a preparation method and application of a high-dispersion supported MXene electrocatalyst, and belongs to the technical field of novel catalyst preparation. The preparation method of the high-dispersion supported MXene electrocatalyst comprises the steps of grinding and mixing LiCl and KCl with a molar ratio of 1:0.5-1 uniformly to obtain molten salt, adding active metal salt and MXene material, continuously grinding, placing in a tubular furnace, heating to 450-1000 ℃ at a heating rate of 1-10 ℃/min under the protection of hydrogen-argon mixture, maintaining for 1-24 h, washing to remove the molten salt, and freeze-drying at-10-40 ℃ to obtain the high-dispersion supported MXene electrocatalyst, wherein the molar ratio of the active metal salt to MXene is 1:5-20. The high-dispersion supported MXene electrocatalyst prepared by the invention shows excellent catalytic conversion performance when used for reducing carbon dioxide, well inhibits hydrogen evolution reaction, has continuous stability and has higher Faraday efficiency.
Description
Technical Field
The invention relates to a preparation method and application of a high-dispersion supported MXene electrocatalyst, and belongs to the technical field of novel catalyst preparation.
Background
As fossil energy is continuously consumed, excessive emission of greenhouse gases causes serious environmental problems such as global warming, glacier melting, and the like. Carbon dioxide (CO) 2 ) Is an important greenhouse gas, and is used for capturing CO 2 The conversion into chemical raw materials or fuel can effectively reduce carbon emission, and the method is widely focused on. The CO is prepared by adopting an electrochemical method due to mild reaction conditions and controllable product distribution 2 Reduction to fuel or fine chemicals is reduction of CO 2 A method for discharging and realizing artificial carbon circulation, which has great prospect. The electrocatalyst is electrochemical reduction of CO 2 The core of the technology. The catalytic active metal is loaded on the surface of the carrier in a high dispersion form such as nano particles, atom clusters and the like, so that the exposure of active atoms can be increased, the number of surface active sites can be increased, and the intrinsic activity of the catalytic sites can be enhanced through unsaturated coordination effect, quantum size effect and metal-carrier interaction, so that the specific performance different from that of a common catalyst is endowed. The high-dispersion supported catalyst can achieve excellent catalytic effect usually only by small load, so that the utilization rate of active metal is greatly improved, and the cost is reduced.
MXene is a novel two-dimensional layered metal carbo/nitride material, has metalloid characteristics and high conductivity, has large specific surface area, contains a large amount of M-O and other electronegative functional groups, endows the material with good affinity to a reaction medium, and is suitable for preparing electrocatalysts. At present, there are still some problems to be overcome in preparing high dispersion supported MXene electrocatalyst: serious hydrogen evolution reaction in the catalytic reaction is difficult to inhibit; the dispersion state of the active metal on the surface of the carrier is uncontrollable, and the agglomeration effect is very easy to occur; and the catalyst loading is difficult to control. Zhao et al [1] By adjusting the synthesis conditions of the precursor MAX, the quaternary precursor Ti is synthesized at the high temperature of more than 1400 DEG C 3 (Al 1-x Cu x )C 2 (x=0-0.1), and then selectively etching to obtain the accordion MXene loaded high-dispersion copper catalystThe chemical agent consumes a large amount of energy under the harsh conditions of high temperature and the like in the preparation process, has low energy utilization rate, and has the defects of complex preparation process, low load capacity and the like.
Reference [1 ]]ZHAO Q,ZHANG C,HU R,et al.Selective Etching Quaternary MAX Phase toward Single Atom Copper Immobilized MXene(Ti 3 C 2 Cl x )for Efficient CO 2 Electroreduction to Methanol[J].ACS Nano,2021,15(3):4927-4936.
Disclosure of Invention
The invention aims to provide a preparation method of a high-dispersion supported MXene electrocatalyst for carbon dioxide reduction. The invention utilizes the lithium chloride and potassium chloride fused salt at high temperature, wherein the active metal salt is dissolved, the two-dimensional flaky MXene is immersed in the fused salt, then the fused salt is washed off by water, and the fused salt is freeze-dried, thus obtaining the high-dispersion supported MXene electrocatalyst.
The preparation method of the high-dispersion supported MXene electrocatalyst comprises the steps of grinding and mixing LiCl and KCl with a molar ratio of 1:0.5-1 uniformly to obtain molten salt, adding active metal salt and MXene material, continuously grinding, placing in a tubular furnace, heating to 450-1000 ℃ at a heating rate of 1-10 ℃/min under the protection of hydrogen-argon mixture, maintaining for 1-24 h, washing to remove the molten salt, and freeze-drying at-10-40 ℃ to obtain the high-dispersion supported MXene electrocatalyst, wherein the molar ratio of the active metal salt to MXene is 1:5-20.
In the above technical scheme, in the hydrogen-argon mixture, the hydrogen accounts for 8% by volume.
In the above technical scheme, the amount of the molten salt is such that the reaction can proceed smoothly, and preferably the mass ratio of the active metal salt to the molten salt is 1:100-10000.
Preferably, the active metal salt is AgCl or CuCl 2 And SnCl 2 One of them.
Preferably, the MXene is a sheet material having an MXene layer number of 10 layers or less.
Preferably, the MXene is Ti 3 C 2 、Nb 2 C、Cr 2 C and Ti 2 One of C.
It is another object of the present invention to provide a highly dispersed supported MXene electrocatalyst prepared by the above method.
Further, the high-dispersion supported MXene electrocatalyst supports active metals on the surface of two-dimensional flaky MXene in a nanoparticle or atom cluster high-dispersion form.
It is a further object of the present invention to provide the use of the highly dispersed supported MXene electrocatalyst described above as a carbon dioxide reduction catalyst.
Further, uniformly mixing the high-dispersion supported MXene electrocatalyst with ethanol, nafion solution and ultrapure water, performing ultrasonic dispersion for 20-40 min, uniformly dripping the obtained dispersion on carbon paper, and naturally airing to obtain a working electrode; the silver/silver ion electrode is used as a reference electrode, the platinum sheet electrode is used as a counter electrode, the Nafion 115 or 117 proton exchange membrane is used, the H-type electrolytic cell is used as a reactor, and the electrocatalytic reduction of carbon dioxide is carried out in an electrochemical workstation.
The beneficial effects of the invention are as follows: the preparation method provided by the invention is simple and easy to implement, and the chlorine on the surface of the MXene is blocked in a molten salt system, so that hydrogen evolution reaction during electrocatalytic reduction is effectively inhibited; the production cost of raw materials such as lithium chloride, potassium chloride molten salt, active metal salt and the like is low; the type, the load capacity and the surface dispersion state of the carrier can be effectively regulated and controlled; the high-dispersion supported MXene electrocatalyst prepared by the invention shows excellent catalytic conversion performance when used for reducing carbon dioxide, well inhibits hydrogen evolution reaction, has continuous stability and has higher Faraday efficiency.
Drawings
FIG. 1 is a scanning electron microscope picture of a preparation of an MXene-supported highly dispersed Ag electrocatalyst according to example 1 of the invention. As can be seen from FIG. 1, the MXene-loaded high-dispersion Ag electrocatalyst prepared by the molten salt method has no change of the original two-dimensional sheet structure of MXene.
FIG. 2 is a drawing of the preparation of Ti according to example 1 of the present invention 3 C 2 And (3) an energy spectrometer picture of the MXene loaded high-dispersion Ag electrocatalyst. Elemental analysis results from EDS of FIG. 2, MXene-supported highly dispersed Ag electrocatalystTogether, C, ti and Ag. C and Ti element Total content of element52.18 of a shape of 52.18wt.% and 45.52wt.% while the Ag element is only 2.3wt.%, and is uniformly distributed.
FIG. 3 is an X-ray diffraction pattern of the preparation of an MXene-supported highly dispersed Ag electrocatalyst according to example 1 of the invention. As can be seen from FIG. 3, in the XRD pattern of the MXene-supported highly dispersed Ag electrocatalyst prepared by the molten salt method, only about 8.5 degrees of MXene (002) crystal face diffraction peak exists, no obvious Ag simple substance characteristic peak is observed, and it is indicated that Ag is supported on two-dimensional flaky MXene (Ti 3 C 2 ) A surface.
Detailed Description
The following non-limiting examples will enable those of ordinary skill in the art to more fully understand the invention and are not intended to limit the invention in any way.
The test methods described in the following examples, unless otherwise specified, are all conventional; the reagents and materials, unless otherwise specified, are commercially available.
In the following examples, the molten salts were prepared by grinding for 30min at a molar ratio of LiCl to KCl of 1:0.7.
In the following examples, the hydrogen-argon mixture gas has a hydrogen content of 8% by volume.
In the following examples, the two-dimensional sheet-like MXene was prepared as follows: adding 75mL of concentrated hydrochloric acid into 25mL of deionized water to prepare 100mL of 9M hydrochloric acid; 8g of LiF is added into the prepared hydrochloric acid, and stirred at 600rpm until the LiF is completely dissolved, so as to form a mixed solution; adding 5g including but not limited to Ti to the mixed solution 3 AlC 2 、Nb 2 AlC、Cr 2 AlC and Ti 2 One of AlC, MAX, is stirred at 600rpm and reacts for 48 hours at 35 ℃; centrifuging the suspension after reaction at 3500rpm, and washing the precipitate to neutrality by deionized water; dispersing the precipitate in 200mL deionized water, performing ultrasonic treatment for 4h, shaking vigorously until the solution becomes colloid, centrifuging the dispersion at 7000rpm, freezing the upper liquid by liquid nitrogen, and performing low-temperature freeze drying to obtain two-dimensional flaky MXene.
Example 1
(1) Weighing 100mg of two-dimensional sheet Ti 3 C 2 For standby according to the mole with MXeneWeighing 8.6mgAgCl according to the molar ratio of 1:10, adding the AgCl into a 10g mixed salt system, uniformly mixing, fully grinding for 30min, loading the mixture into a quartz boat, heating to 700 ℃ at 3 ℃/min in a tube furnace under the protection of hydrogen-argon mixed gas, maintaining the temperature for 2h, repeatedly washing the mixture with deionized water, removing molten salt, and freeze-drying the mixture at-20 ℃ to obtain the high-dispersion Ag-supported MXene electrocatalyst.
(2) Uniformly mixing 5mg of high-dispersion Ag supported MXene electrocatalyst with 260 mu L of ethanol, 40 mu L of LNafion solution and 700 mu L of ultrapure water, carrying out ultrasonic treatment for 40min, uniformly dripping 50 mu L of the obtained dispersion liquid on 10 mm/10 mm carbon paper, and naturally airing to obtain a working electrode; using silver/silver ion electrode as reference electrode, platinum sheet electrode as counter electrode, using Nafion 115 proton exchange membrane, in deep CO-melting solvent electrolyte, using H-type electrolytic cell as reactor, performing electrocatalytic reduction carbon dioxide performance test on electrochemical workstation, detecting gas phase product by gas chromatography, and calculating to obtain CO 2 Faraday efficiency of reduction to CO and other products. At constant potential electrolysis of-2.0V, the local current density is 5.1mA cm -2 The faraday efficiency of CO generation is as high as 93.7%.
Example 2
(1) Weighing 100mg of two-dimensional sheet Ti 3 C 2 For standby, 8.0mg of CuCl is weighed according to the molar ratio of MXene of 1:10 2 Adding into 10g molten salt system, mixing uniformly, grinding for 30min, loading into quartz boat, heating to 700 deg.C at 3 deg.C/min under the protection of hydrogen-argon mixture, maintaining for 2 hr, repeatedly washing with deionized water, removing molten salt, and freeze drying at-10deg.C to obtain high-dispersion Cu-loaded MXene electrocatalyst.
(2) Uniformly mixing 5mg of high-dispersion Cu-supported MXene electrocatalyst with 260 mu L of ethanol, 40 mu L of LNafion solution and 700 mu L of ultrapure water, carrying out ultrasonic treatment for 40min, uniformly dripping 50 mu L of the obtained dispersion liquid on 10 mm-10 mm carbon paper, and naturally airing to obtain a working electrode; using silver/silver ion electrode as reference electrode, platinum sheet electrode as counter electrode, using Nafion 115 proton exchange membrane, in deep co-melting solvent electrolyte, using H-type electrolytic cell as reactor, performing electrocatalytic reduction carbon dioxide performance test on electrochemical workstation, and detecting by gas chromatographyMeasuring gas phase product, obtaining CO by calculation 2 Faraday efficiency of reduction to CO and other products. At constant potential electrolysis of-2.2V, the local current density is 6.8mA cm -2 The faraday efficiency of CO generation is as high as 91.8%.
Example 3
(1) Weighing 100mg of two-dimensional sheet Ti 3 C 2 For standby, weighing 11.3mg of SnCl according to the molar ratio of MXene of 1:10 2 Adding into 10g of molten salt system, mixing uniformly, grinding for 30min, loading into quartz boat, heating to 700 deg.C at 3 deg.C/min under the protection of hydrogen-argon mixture, maintaining for 2h, washing with deionized water repeatedly, removing molten salt, and freeze drying at-20deg.C to obtain high-dispersion Sn-loaded MXene electrocatalyst.
(2) Uniformly mixing 5mg of high-dispersion Sn supported MXene electrocatalyst with 260 mu L of ethanol, 40 mu L of LNafion solution and 700 mu L of ultrapure water, carrying out ultrasonic treatment for 40min, uniformly dripping 50 mu L of the obtained dispersion liquid on 10 mm/10 mm carbon paper, and naturally airing to obtain a working electrode; using silver/silver ion electrode as reference electrode, platinum sheet electrode as counter electrode, using Nafion 115 proton exchange membrane, in deep CO-melting solvent electrolyte, using H-type electrolytic cell as reactor, performing electrocatalytic reduction carbon dioxide performance test on electrochemical workstation, detecting gas phase product by gas chromatography, and calculating to obtain CO 2 Faraday efficiency of reduction to CO and other products. At constant potential electrolysis of-2.2V, the local current density is 4.7mA cm -2 The faraday efficiency of CO generation is as high as 79.3%.
Example 4
(1) Weighing 100mg of two-dimensional sheet Ti 3 C 2 17.2mg of AgCl is weighed according to the molar ratio of 1:5 with MXene, added into a 10g molten salt system, uniformly mixed, fully ground for 30min, filled into a quartz boat, heated to 800 ℃ at 5 ℃/min under the protection of hydrogen-argon mixed gas in a tube furnace, maintained for 3h, repeatedly washed with deionized water, molten salt is removed, and the high-dispersion Ag-supported MXene electrocatalyst is obtained after freeze drying at-10 ℃.
(2) Mixing 5mg of high dispersion Fe supported MXene electrocatalyst with 260 mu L ethanol, 40 mu L LNafion solution and 700 mu L ultra pure waterUniformly and ultrasonically treating for 40min, uniformly dripping 50 mu L of the obtained dispersion liquid on 10 mm-10 mm carbon paper, and naturally airing to obtain a working electrode; using silver/silver ion electrode as reference electrode, platinum sheet electrode as counter electrode, using Nafion117 proton exchange membrane, in deep CO-melting solvent electrolyte, using H-type electrolytic cell as reactor, performing electrocatalytic reduction carbon dioxide performance test on electrochemical workstation, detecting gas phase product by gas chromatography, and calculating to obtain CO 2 Faraday efficiency of reduction to CO and other products. At constant potential electrolysis of-2.2V, the local current density is 5.5mA cm -2 The faraday efficiency of CO generation is as high as 91.3%.
Example 5
(1) Weighing 100mg of two-dimensional sheet Nb 2 And C, for standby, weighing 7.2mg of AgCl according to the molar ratio of the AgCl to the MXene of 1:10, adding the AgCl into 10g of molten salt system, uniformly mixing, fully grinding for 30min, loading the mixture into a quartz boat, heating to 600 ℃ at 10 ℃/min under the protection of hydrogen-argon mixed gas in a tube furnace, maintaining for 1h, repeatedly washing the mixture with deionized water, removing the molten salt, and freeze-drying the mixture at-10 ℃ to obtain the high-dispersion Ag-supported MXene electrocatalyst.
(2) Uniformly mixing 5mg of high-dispersion Ni supported MXene electrocatalyst with 260 mu L of ethanol, 40 mu L of LNafion solution and 700 mu L of ultrapure water, carrying out ultrasonic treatment for 40min, uniformly dripping 50 mu L of the obtained dispersion liquid on 10 mm/10 mm carbon paper, and naturally airing to obtain a working electrode; using silver/silver ion electrode as reference electrode, platinum sheet electrode as counter electrode, using Nafion 115 proton exchange membrane, in deep CO-melting solvent electrolyte, using H-type electrolytic cell as reactor, performing electrocatalytic reduction carbon dioxide performance test on electrochemical workstation, detecting gas phase product by gas chromatography, and calculating to obtain CO 2 Faraday efficiency of reduction to CO and other products. At constant potential electrolysis of-2.2V, the local current density is 5.6mA cm -2 The faraday efficiency of CO generation is as high as 87.2%.
According to the preparation method provided by the invention, chlorine on the surface of MXene is blocked in a molten salt system, so that hydrogen evolution reaction during electrocatalytic reduction is effectively inhibited; the kind of active metal, the load and the dispersion state of the carrier surface can be effectively regulated. The invention has high preparation efficiencyThe disperse supported MXene electrocatalyst for reducing carbon dioxide shows excellent catalytic conversion performance, and CO is prepared under constant potential electrolysis of-2.0V 2 The highest Faraday efficiency of CO conversion is 93.7%, and the catalyst material is an efficient electrocatalytic carbon dioxide reduction catalyst material.
Claims (9)
1. A preparation method of a high-dispersion supported MXene electrocatalyst is characterized by comprising the following steps:
grinding LiCl and KCl with the molar ratio of 1:0.5-1, uniformly mixing to obtain molten salt, adding active metal salt and MXene material, continuously grinding, placing in a tube furnace, heating to 450-1000 ℃ at the heating rate of 1-10 ℃/min under the protection of hydrogen-argon mixture, maintaining for 1-24 h, washing to remove the molten salt, and freeze-drying at-10 to-40 ℃ to obtain the high-dispersion supported MXene electrocatalyst, wherein the molar ratio of the active metal salt to the MXene is 1:5-20.
2. The method according to claim 1, characterized in that: the active metal salt is AgCl or CuCl 2 、SnCl 2 One of them.
3. The method according to claim 1, characterized in that: the MXene is a sheet material with MXene layers below 10 layers.
4. The method according to claim 1, characterized in that: the MXene is Ti 3 C 2 、Nb 2 C、Cr 2 C and Ti 2 One of C.
5. The method according to claim 1, characterized in that: the mass ratio of the active metal salt to the molten salt is 1:100-10000.
6. A highly dispersed supported MXene electrocatalyst made by the method of any one of claims 1 to 5.
7. The catalyst of claim 6, wherein: the high-dispersion supported MXene electrocatalyst loads active metals on the surface of two-dimensional flaky MXene in a nano particle or atom cluster high-dispersion form.
8. Use of the catalyst of claim 6 as a carbon dioxide reduction catalyst.
9. The use according to claim 8, characterized in that: uniformly mixing the high-dispersion supported MXene electrocatalyst according to claim 5 with ethanol, nafion solution and ultrapure water, performing ultrasonic dispersion for 20-40 min, uniformly dripping the obtained dispersion on carbon paper, and naturally airing to obtain a working electrode; the silver/silver ion electrode is used as a reference electrode, the platinum sheet electrode is used as a counter electrode, the Nafion 115 or 117 proton exchange membrane is used, the H-type electrolytic cell is used as a reactor, and the electrocatalytic reduction of carbon dioxide is carried out in an electrochemical workstation.
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