CN111282586B - Preparation method and application of in-situ alumina coated titanium carbide catalyst - Google Patents
Preparation method and application of in-situ alumina coated titanium carbide catalyst Download PDFInfo
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- MTPVUVINMAGMJL-UHFFFAOYSA-N trimethyl(1,1,2,2,2-pentafluoroethyl)silane Chemical compound C[Si](C)(C)C(F)(F)C(F)(F)F MTPVUVINMAGMJL-UHFFFAOYSA-N 0.000 title claims abstract description 37
- 239000003054 catalyst Substances 0.000 title claims abstract description 23
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims abstract description 30
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims abstract description 22
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 20
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 18
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 18
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 14
- 230000003075 superhydrophobic effect Effects 0.000 claims abstract description 12
- 229910000029 sodium carbonate Inorganic materials 0.000 claims abstract description 11
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 10
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 10
- 238000003756 stirring Methods 0.000 claims abstract description 9
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- 239000002994 raw material Substances 0.000 claims abstract description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 45
- 238000006243 chemical reaction Methods 0.000 claims description 38
- 229910021529 ammonia Inorganic materials 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
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- 238000000034 method Methods 0.000 claims description 14
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- 230000015572 biosynthetic process Effects 0.000 claims description 8
- 238000003786 synthesis reaction Methods 0.000 claims description 8
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 7
- 239000000839 emulsion Substances 0.000 claims description 7
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- 150000002500 ions Chemical class 0.000 claims description 6
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 239000006185 dispersion Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 229920000557 Nafion® Polymers 0.000 claims description 3
- 238000005530 etching Methods 0.000 claims description 3
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 230000002194 synthesizing effect Effects 0.000 claims description 2
- 239000010936 titanium Substances 0.000 claims description 2
- 229910052719 titanium Inorganic materials 0.000 claims description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims 1
- 239000011247 coating layer Substances 0.000 claims 1
- 238000013329 compounding Methods 0.000 claims 1
- 238000004090 dissolution Methods 0.000 claims 1
- 238000011049 filling Methods 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 13
- 229910052782 aluminium Inorganic materials 0.000 abstract description 6
- 239000010411 electrocatalyst Substances 0.000 abstract description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 3
- 238000003889 chemical engineering Methods 0.000 abstract description 2
- 239000012847 fine chemical Substances 0.000 abstract description 2
- 238000005265 energy consumption Methods 0.000 abstract 1
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- 238000007254 oxidation reaction Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 14
- 239000000523 sample Substances 0.000 description 11
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- 229910052757 nitrogen Inorganic materials 0.000 description 7
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- 238000004519 manufacturing process Methods 0.000 description 6
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 238000000629 steam reforming Methods 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VRZJGENLTNRAIG-UHFFFAOYSA-N 4-[4-(dimethylamino)phenyl]iminonaphthalen-1-one Chemical compound C1=CC(N(C)C)=CC=C1N=C1C2=CC=CC=C2C(=O)C=C1 VRZJGENLTNRAIG-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere 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
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- 239000003337 fertilizer Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
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- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
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- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
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- 229910052709 silver Inorganic materials 0.000 description 1
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 229910001251 solid state electrolyte alloy Inorganic materials 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
-
- 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
-
- B01J35/33—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/32—Freeze drying, i.e. lyophilisation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/343—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of ultrasonic wave energy
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- C—CHEMISTRY; METALLURGY
- 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
-
- 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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts
Abstract
The invention discloses a preparation method and application of a super-hydrophobic in-situ alumina coated titanium carbide catalyst, and belongs to the technical fields of material preparation, electrocatalysis and fine chemical engineering. The electrocatalyst is prepared by taking sodium fluoride, commercial titanium aluminum carbide, N-methyl pyrrolidone, sodium carbonate, sodium hydroxide and polytetrafluoroethylene as raw materials, feeding in batches, heating and stirring under mild conditions, and using etched and dissolved aluminum ions as an aluminum source. The electrocatalyst prepared by the invention has good stability, large specific surface area, good electrocatalysis performance, good oxidation resistance, high thermal stability and the like. The preparation method has the advantages of simple and convenient preparation process, low energy consumption, low cost and larger application potential.
Description
Technical Field
The invention belongs to the technical fields of material preparation, electrocatalysis and fine chemical engineering, and particularly relates to a preparation method and application of a super-hydrophobic in-situ alumina coated titanium carbide catalyst.
Background art ammonia is the second largest chemical produced in the world. Global ammonia production in 2015 approaches 1.46 million tons, with a projected 40% increase by 2050, and amino fertilizers help to supply food for the globally growing population (about 100 million by 2050). Ammonia can also play an important role in the development of clean transportation and can be used directly in ammonia fuel cells or indirectly in hydrogen fuel cells. Ammonia can be a superior energy carrier for hydrogen (e.g., 17.6 wt% hydrogen in liquid ammonia versus 12.5 wt% methanol) as compared to other conventional fuels. Therefore, sustainable ammonia production is critical to food energy chemistry.
Currently, ammonia production relies primarily on the industrial Haber-Bosch process. The Haber-Bosch process entails ammonia synthesis at high temperature and pressure using pure hydrogen, which is typically derived from steam reforming of natural gas; meanwhile, a large amount of carbon dioxide gas is generated in the steam reforming process of natural gas, and therefore, ammonia production is an important factor causing climate change. Finding new alternative methods for ammonia synthesis is of great scientific interest at present. Although the literature is still rare, a number of N-passes have been reported2And direct production of NH by electroreduction of water or steam3Electrocatalytic study of (a). Most of the research on the electrochemical production of ammonia is based on solid-state electrolytes at high temperatures and pressures. Other studies are also based on liquid electrolytes, such as organic solvents, ionic liquids, molten salts, high-pressure or ambient-pressure aqueous electrolytes. In these studies, transition metal complexes and materials have been generally used as catalysts. If the solvent water is directly used as the hydrogen proton source to replace hydrogen as the hydrogen proton source, the cost in the ammonia synthesis process can be greatly saved, the carbon dioxide emission in the reforming process is avoided, and the influence on the environment is reduced, so that the aqueous electrolyte method has the characteristics of simplicity and low cost. However, aqueous electrolyte approaches suffer from competitive hydrogen evolution, which limits overall efficiency, resulting in low overall reaction rates. Until now, the faradaic efficiency of aqueous reactions under ambient conditions has not substantially exceeded 10%.
Titanium carbide is a new two-dimensional material, with a single layer thickness typically less than 1 nm and lateral dimensions ranging from nanometers to micrometers. In addition, titanium carbide has abundant surface functional groups, such as hydroxyl, oxygen or fluorine. In the presence of complete metal atomic layers and surface functional groups, the titanium carbide has good electronic conductivity and hydrophilic property, and meanwhile, the titanium carbide has a highly ordered structure, and the property of the titanium carbide can be predicted by theoretical calculation. The titanium carbide has larger internal surface area due to the layered structure, the interplanar spacing of the titanium carbide after the intercalation of the N-methylpyrrolidone is further increased, the internal surface area is further enlarged, and the interlayer space of the titanium carbide is beneficial to the enrichment of nitrogen, so that the titanium carbide can become possible to be electrically reduced for nitrogen fixation.
Disclosure of Invention
The invention aims to provide a preparation method of a super-hydrophobic in-situ alumina coated titanium carbide catalyst and application of the catalyst in electrocatalysis.
In order to achieve the purpose, the invention adopts the following technical scheme:
a super-hydrophobic in-situ alumina coated titanium carbide catalyst is prepared by taking sodium fluoride, commercial titanium aluminum carbide, N-methyl pyrrolidone, sodium carbonate, sodium hydroxide and polytetrafluoroethylene as raw materials, feeding in batches, heating and stirring under mild conditions, and using aluminum ions dissolved out by etching as an aluminum source to prepare the high-performance super-hydrophobic in-situ alumina coated titanium carbide electrocatalyst for electrocatalytic nitrogen fixation, and specifically comprises the following steps:
1) taking 0.4 g of Ti3AlC2And 50 mL of NMP solution containing NaF (6 mol/L) are put into a plastic reactor, stirred and heated at the temperature of 60-100 ℃, the rotating speed is 1000 r/min, and the reaction time is 1-4 h.
2) Adding 0.05-0.2 g of sodium carbonate and 50-100 muL of polytetrafluoroethylene PTFE emulsion (content 40 wt%) into the suspension obtained by the reaction, adjusting the pH value to 10 by using 4 mol/L of sodium hydroxide solution, continuously stirring and reacting for 0.5-2 h at 60 ℃ and 1000 r/min, and then placing the mixture into an ultrasonic machine (frequency 40 kHz and power 100W) for ultrasonic reaction for 1 h.
3) And centrifuging the reaction solution in a centrifugal machine of 3500 r/min to remove the solvent, and washing the reaction solution by using absolute ethyl alcohol and deionized water respectively until the ion solubility of the solution is lower than 10 ppm. And finally, transferring the sample into a freeze dryer to carry out freeze drying for 6 hours at the temperature of-18 ℃ to obtain a sample.
The resulting superhydrophobic in situThe alumina coated titanium carbide catalyst is mainly used for electrochemically synthesizing ammonia. The method comprises the following specific steps: dispersing 2 mg of the catalyst in a dispersion liquid consisting of 225 muL ethanol, 225 muL water and 50 muL nafion, and after one hour of ultrasonic dispersion, taking 50 muL dispersed liquid drops in 1 x 1 cm-2The working electrode is made on the carbon paper, and then the traditional three-electrode system is used for electrocatalytic synthesis of ammonia.
The invention has the following remarkable advantages:
(1) the preparation method has simple preparation conditions, and the N-methylpyrrolidone is firstly utilized to intercalate the titanium carbide material, so that the prepared material layer spacing is increased, more surface defects can be exposed, and more reaction active centers can be provided.
(2) The electrode material is subjected to hydrophobic treatment by creatively utilizing the polytetrafluoroethylene solution, so that the material has super-hydrophobicity, the hydrogen evolution reaction in electrochemical nitrogen fixation is inhibited, and the Faraday efficiency of the nitrogen fixation reaction is improved.
(3) The alumina coating is creatively generated in situ to form a strong composite structure of alumina-titanium carbide-polytetrafluoroethylene, and a novel super-hydrophobic in situ alumina coated titanium carbide catalyst is prepared for the first time.
(4) The super-hydrophobic in-situ alumina coated titanium carbide catalyst is creatively prepared by using N-methyl pyrrolidone, polytetrafluoroethylene, sodium carbonate and aluminum ions generated by etching in a synergistic manner, and the problems that the preparation process of the previously reported titanium carbide catalyst material is complex, and the alumina coating and the super-hydrophobicity of the catalyst can be realized by multiple processes are solved.
Drawings
FIG. 1 is an X-ray powder diffraction pattern (XRD) of the superhydrophobic in-situ alumina-coated titanium carbide catalyst obtained in example 1.
FIG. 2 is a scanning electron microscope image of the super-hydrophobic in-situ alumina-coated titanium carbide catalyst electrocatalyst obtained in example 2.
FIG. 3 is a graph comparing the ammonia content in the solution after electrochemical nitrogen fixation of the superhydrophobic in-situ alumina-coated titanium carbide catalyst obtained in example 2 with bias voltage applied, bias voltage not applied, and a blank.
FIG. 4 is a test of hydrophilicity and hydrophobicity of the titanium carbide material prepared in example 1.
Detailed Description
In order to make the present invention more comprehensible, the technical solutions of the present invention are further described below with reference to specific embodiments, but the present invention is not limited thereto.
Example 1
Take 0.4 g Ti3AlC2And 50 mL of NMP solution containing NaF (6 mol/L) are put into a plastic reactor, stirred and heated at 60 ℃, the rotating speed is 1000 r/min, and the reaction time is 4 h. 0.2 g of sodium carbonate and 50 muL of PTFE emulsion (content: 40%) are added into the suspension obtained by the reaction, the pH value is adjusted to 10 by using 4 mol/L sodium hydroxide solution, the reaction is continuously stirred for 0.5 h at 60 ℃ and 1000 r/min, and then the mixture is placed in an ultrasonic machine (frequency: 40 kHz, power: 100W) for ultrasonic reaction for 1 h. And centrifuging the reaction solution in a centrifugal machine of 3500 r/min to remove the solvent, and washing the reaction solution by using absolute ethyl alcohol and deionized water respectively until the ion solubility of the solution is lower than 10 ppm. And finally, transferring the sample into a freeze dryer for freeze drying to obtain a sample.
Example 2
Take 0.4 g Ti3AlC2And 50 mL of deionized water containing NaF (6 mol/L) are placed into a plastic reactor, stirred and heated at 80 ℃, the rotating speed is 1000 r/min, and the reaction time is 2 h. 0.05 g of sodium carbonate and 60 mu L of PTFE emulsion (content: 40%) are added into the suspension obtained by the reaction, the pH value is adjusted to 10 by using 4 mol/L sodium hydroxide solution, the reaction is continuously stirred at 60 ℃ and 1000 r/min for 0.5 h, and then the mixture is placed in an ultrasonic machine (frequency: 40 kHz and power: 100W) for ultrasonic reaction for 1 h. And centrifuging the reaction solution in a centrifugal machine of 3500 r/min to remove the solvent, and washing the reaction solution by using absolute ethyl alcohol and deionized water respectively until the ion solubility of the solution is lower than 10 ppm. And finally, transferring the sample into a freeze dryer for freeze drying to obtain a sample.
Example 3
Taking 0.4 g of Ti3AlC2And 50 mL of deionized water containing NaF (6 mol/L)Putting the mixture into a plastic reactor, stirring and heating the mixture at the temperature of 80 ℃, wherein the rotating speed is 1000 r/min, and the reaction time is 1 h. 0.2 g of sodium carbonate and 100 muL of PTFE emulsion (content: 40%) are added into the suspension obtained by the reaction, the pH value is adjusted to 10 by using 4 mol/L of sodium hydroxide solution, the reaction is continuously stirred for 2 hours at 60 ℃ and 1000 r/min, and then the mixture is placed in an ultrasonic machine (frequency: 40 kHz and power: 100W) for ultrasonic reaction for 1 hour. And centrifuging the reaction solution in a centrifugal machine of 3500 r/min to remove the solvent, and washing the reaction solution by using absolute ethyl alcohol and deionized water respectively until the ion solubility of the solution is lower than 10 ppm. And finally, transferring the sample into a freeze dryer for freeze drying to obtain a sample.
Example 4
Take 0.4 g Ti3AlC2And 50 mL of deionized water containing NaF (6 mol/L) are put into a plastic reactor, stirred and heated at 100 ℃, the rotating speed is 1000 r/min, and the reaction time is 1 h. Adding 0.1 g of sodium carbonate and 60 muL of PTFE emulsion (content: 40%) into the suspension obtained by the reaction, adjusting the pH value to 10 by using 4 mol/L of sodium hydroxide solution, continuously stirring and reacting for 0.5 h at 60 ℃ and 1000 r/min, and then placing the mixture into an ultrasonic machine (frequency: 40 kHz, power: 100W) for ultrasonic reaction for 1 h. And centrifuging the reaction solution in a centrifugal machine of 3500 r/min to remove the solvent, and washing with absolute ethyl alcohol and deionized water until the ionic solubility in the solution is lower than 10 ppm. And finally, transferring the sample into a freeze dryer for freeze drying to obtain a sample.
Application example 1
Dispersing 2 mg of a sample prepared by the method in a dispersion liquid consisting of 225 muL ethanol, 225 muL water and 50 muL nafion, and after one hour of ultrasonic dispersion, dropping 50 muL of the dispersion liquid in 1 x 1 cm-2The working electrode is made on the carbon paper. Then the traditional three-electrode system is used for electrocatalytic synthesis of ammonia.
Fig. 1 is an X-ray powder diffraction pattern of the titanium carbide electrocatalysts obtained in examples 1 to 4, and it can be seen from fig. 1 that the two-dimensional layered titanium carbide is successfully prepared by the method of the present invention, and after N-methylpyrrolidone intercalation treatment, the crystal plane (002), i.e., the peak position at 2 θ, is shifted forward, indicating that the interplanar spacing is significantly increased. The coating modification of the aluminum oxide and the polytetrafluoroethylene does not change the crystallinity of the titanium carbide material.
FIG. 2 is a comparison of scanning electron micrographs of unreacted titanium aluminum carbide and example 2. As can be seen in the figure, the titanium aluminum carbide is a dense layered structure (FIG. 2, left). The two-dimensional layered titanium carbide material prepared by the method is of a nano-sheet stacked structure, and the aluminum-titanium carbide middle aluminum layer can be clearly seen to be stripped (figure 2, right). And the titanium carbide surface is covered with a slightly rough aluminum oxide and polytetrafluoroethylene composite layer.
Fig. 3 shows the ammonia yield after the nitrogen fixation reaction in the blank experiment under argon atmosphere using a three-electrode system with-0.3V bias and without bias after the titanium carbide material prepared in example 1 was prepared into an electrocatalytic working electrode, and the blank experiment was performed directly using 1 cm by 1 cm carbon paper without any solution added dropwise as a blank sample. The electrochemical reaction uses three-electrode system, the preparation electrode is used as the working electrode, the reference electrode is the silver/silver chloride electrode, the platinum sheet is used as the counter electrode, the ammonia content is measured with ion chromatography and indophenol blue spectrophotometry.
FIG. 4 is a test of hydrophilicity and hydrophobicity of the titanium carbide material prepared in example 1. As can be seen from the figure, the contact angle of water reaches 146 degrees, exhibiting superhydrophobicity.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (7)
1. A preparation method of an in-situ alumina coated titanium carbide catalyst for electrochemically synthesizing ammonia is characterized by comprising the following steps: the catalyst is sodium fluoride NaF and commercial titanium aluminum carbide Ti3AlC2N-methyl pyrrolidone NMP, sodium carbonate, sodium hydroxide and polytetrafluoroethylene PTFE are used as raw materials, and the specific preparation method comprises the following steps: etching and dissolving out an Al layer in commercial titanium aluminum carbide by using sodium fluoride, filling the space of the Al layer by using N-methylpyrrolidone to form layered titanium carbide, and adjusting the pH value of a reaction system by using sodium carbonate and sodium hydroxide to realize the dissolution of Al ions in the titanium carbideThe surface is converted into an aluminum oxide coating layer; meanwhile, the polytetrafluoroethylene emulsion is introduced to enable the polytetrafluoroethylene and the alumina layer to form close compounding, so that the super-hydrophobic in-situ alumina coated titanium carbide catalyst is finally obtained; the method specifically comprises the following steps:
1) take 0.4 g Ti3AlC2And 50 mL of NMP solution containing 6 mol/LNaF are put into a plastic reactor and stirred and heated for reaction;
2) adding 0.05-0.2 g of sodium carbonate and 50-100 muL of PTFE emulsion with the content of 40wt% into the suspension obtained by the reaction, adjusting the pH value to 10 by using 4 mol/L of sodium hydroxide solution, continuing stirring for reaction, and then carrying out ultrasonic reaction for 1 h;
3) centrifuging the reaction solution in a centrifugal machine of 3500 r/min to remove the solvent, washing with anhydrous ethanol and deionized water respectively until the ion solubility of the solution is lower than 10 ppm, and freeze-drying in a freeze dryer at-18 deg.C for 6 h to obtain the sample.
2. The method of claim 1, wherein: the stirring and heating reaction in the step 1) is specifically as follows: stirring and heating at 60-100 deg.C, rotating speed of 1000 r/min, and reaction time of 1-4 h.
3. The method of claim 1, wherein: the step 2) of continuously stirring the reaction specifically comprises the following steps: the reaction is continued to be stirred for 0.5 to 2 hours at the temperature of 60 ℃ and the speed of 1000 r/min.
4. The method of claim 1, wherein: the ultrasonic machine conditions of the ultrasonic reaction in the step 2) are as follows: frequency 40 kHz, power 100W.
5. An in situ alumina coated titanium carbide catalyst for the electrochemical synthesis of ammonia prepared by the process as claimed in any one of claims 1 to 4.
6. Use of the in situ alumina-coated titanium carbide catalyst of claim 5 for the electrochemical synthesis of ammonia.
7. Use according to claim 6, characterized in that: dispersing 2 mg of the catalyst in a dispersion liquid consisting of 225 muL ethanol, 225 muL water and 50 muL nafion, and after one hour of ultrasonic dispersion, taking 50 muL dispersed liquid drops in 1 x 1 cm-2The working electrode is made on the carbon paper, and then the traditional three-electrode system is used for electrocatalytic synthesis of ammonia.
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