CN111229318A - Super-hydrophobic copper-based in-situ composite catalyst and preparation method and application thereof - Google Patents
Super-hydrophobic copper-based in-situ composite catalyst and preparation method and application thereof Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 30
- 238000011065 in-situ storage Methods 0.000 title claims abstract description 29
- 239000003054 catalyst Substances 0.000 title claims abstract description 24
- 239000010949 copper Substances 0.000 title claims abstract description 20
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- 230000003075 superhydrophobic effect Effects 0.000 title claims abstract description 15
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 title claims abstract description 12
- 229910052802 copper Inorganic materials 0.000 title claims abstract description 12
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 37
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 32
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 31
- PUZPDOWCWNUUKD-UHFFFAOYSA-M sodium fluoride Chemical compound [F-].[Na+] PUZPDOWCWNUUKD-UHFFFAOYSA-M 0.000 claims abstract description 30
- 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 claims abstract description 30
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims abstract description 26
- 239000004810 polytetrafluoroethylene Substances 0.000 claims abstract description 26
- 238000003756 stirring Methods 0.000 claims abstract description 17
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims abstract description 15
- 235000013024 sodium fluoride Nutrition 0.000 claims abstract description 15
- 239000011775 sodium fluoride Substances 0.000 claims abstract description 15
- -1 polytetrafluoroethylene Polymers 0.000 claims abstract description 12
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 11
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 claims abstract description 11
- 239000008103 glucose Substances 0.000 claims abstract description 11
- 239000010936 titanium Substances 0.000 claims abstract description 11
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims abstract description 9
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims abstract description 9
- 239000002105 nanoparticle Substances 0.000 claims abstract description 7
- 229910052719 titanium Inorganic materials 0.000 claims abstract description 7
- 239000010411 electrocatalyst Substances 0.000 claims abstract description 6
- 238000005516 engineering process Methods 0.000 claims abstract description 6
- 238000010438 heat treatment Methods 0.000 claims abstract description 5
- UQZIWOQVLUASCR-UHFFFAOYSA-N alumane;titanium Chemical compound [AlH3].[Ti] UQZIWOQVLUASCR-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 51
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 claims description 32
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 16
- 229910021529 ammonia Inorganic materials 0.000 claims description 16
- 230000015572 biosynthetic process Effects 0.000 claims description 14
- 238000003786 synthesis reaction Methods 0.000 claims description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 12
- 239000000839 emulsion Substances 0.000 claims description 11
- 229910009818 Ti3AlC2 Inorganic materials 0.000 claims description 9
- 239000002904 solvent Substances 0.000 claims description 8
- 239000008367 deionised water Substances 0.000 claims description 7
- 229910021641 deionized water Inorganic materials 0.000 claims description 7
- 238000004108 freeze drying Methods 0.000 claims description 7
- 150000002500 ions Chemical class 0.000 claims description 7
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- 239000006185 dispersion Substances 0.000 claims description 5
- 238000004519 manufacturing process Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910009819 Ti3C2 Inorganic materials 0.000 claims description 4
- 229910052799 carbon Inorganic materials 0.000 claims description 4
- 229920000557 Nafion® Polymers 0.000 claims description 3
- 235000019441 ethanol Nutrition 0.000 claims description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 238000013329 compounding Methods 0.000 claims description 2
- 238000005530 etching Methods 0.000 claims description 2
- 238000011049 filling Methods 0.000 claims description 2
- IXCSERBJSXMMFS-UHFFFAOYSA-N hcl hcl Chemical compound Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims description 2
- 238000009210 therapy by ultrasound Methods 0.000 claims description 2
- 238000002604 ultrasonography Methods 0.000 claims description 2
- 239000000243 solution Substances 0.000 claims 9
- 239000007864 aqueous solution Substances 0.000 claims 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 abstract description 16
- 239000000463 material Substances 0.000 abstract description 10
- 229910052757 nitrogen Inorganic materials 0.000 abstract description 8
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 238000003889 chemical engineering Methods 0.000 abstract 1
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- 239000012847 fine chemical Substances 0.000 abstract 1
- 239000000523 sample Substances 0.000 description 12
- 239000013078 crystal Substances 0.000 description 6
- 238000011160 research Methods 0.000 description 5
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- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 238000009620 Haber process Methods 0.000 description 2
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- 238000002474 experimental method Methods 0.000 description 2
- 239000005431 greenhouse gas Substances 0.000 description 2
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 2
- 239000010410 layer Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 230000008569 process Effects 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
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000012496 blank sample Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
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- 125000000524 functional group Chemical group 0.000 description 1
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 1
- 230000002209 hydrophobic effect Effects 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 238000009830 intercalation Methods 0.000 description 1
- 230000002687 intercalation Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
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- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- 239000004332 silver Substances 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
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- 229910000314 transition metal oxide 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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/06—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing polymers
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/72—Copper
-
- 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
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- B01J35/23—
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- 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
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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
- C25B11/091—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
- C25B11/095—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 at least one of the compounds being organic
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- 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 super-hydrophobic copper-based in-situ composite catalyst, and a preparation method and application thereof, and belongs to the technical fields of material preparation, electrocatalysis and fine chemical engineering. The electrocatalyst is prepared by using sodium fluoride, hydrochloric acid, commercial titanium aluminum carbide, N-methyl pyrrolidone, polytetrafluoroethylene, glucose and copper acetate as raw materials, feeding in batches, heating and stirring under mild conditions, and simultaneously loading cuprous oxide nanoparticles on titanium carbide by using an in-situ growth technology, so that a high-performance titanium carbide-cuprous oxide in-situ composite electrocatalyst for electrocatalysis nitrogen fixation is successfully developed. 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 great application potential.
Description
Technical Field
The invention belongs to the technical field of material preparation and electrocatalysis, and particularly relates to a super-hydrophobic copper-based in-situ composite catalyst, and a preparation method and application thereof.
Background of the inventioncurrently, the world's synthetic ammonia technology is an important part of the chemical synthesis field, and ammonia is involved in the practical applications in many fields, such as food supply, clean energy, fuel cells, energy transportation, etc. Therefore, how to realize efficient, stable, sustainable, green and safe production of synthetic ammonia is a current research hotspot. The production of ammonia in modern society relies primarily on the industrial high temperature, high pressure Haber-Bosch process. The Haber-Bosch process has many limitations, such as harsh reaction conditions and greenhouse gas emission. The method has great application prospect in finding an alternative environment-friendly ammonia synthesis process with mild conditions to replace the traditional process. The electrochemical synthesis of ammonia is a current research hotspot, and can utilize solvent water directly as a hydrogen proton source instead of hydrogen, so that the emission of greenhouse gases is reduced, the indexes of environmental protection are met, and meanwhile, the electrochemical synthesis of ammonia can be realized at normal temperature and normal pressure. However, there are severe hydrogen evolution reactions in the electrochemical synthesis of ammonia, which limit the electron utilization, resulting in a low overall reaction rate. Until now, the faradaic efficiency of aqueous reactions under ambient conditions has not substantially exceeded 10%.
Titanium carbide as a novel two-dimensional layered material has excellent electrochemical properties such as abundant surface functional groups, good electronic conductivity and hydrophilic properties, and meanwhile, the titanium carbide structure is highly ordered due to the layered structureThe titanium carbide catalyst has larger internal surface area, 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 an effective catalyst for fixing nitrogen by electroreduction, and the previous research results also prove that the titanium carbide catalyst has the advantages of high activity, high stability and high stability. Cuprous oxide (Cu)2O) is one of the binary transition metal oxide crystals that have been most intensively studied in the past decades as a typical p-type semiconductor. In addition to well-known advantages, including low cost, non-toxicity, abundance and ease of synthesis, Cu2The customized structure of O crystals has led to extensive research because of their physicochemical properties enabling various functions. Especially in the fields of energy conversion, catalysts and chemical templates, breakthrough progress has been made, the key being the synthesis of structures with controlled size, shape, area, defects, doping and heterostructures. Polyhedral Cu2O structure is an ideal model for studying crystal plane-related properties, and some specific structure-oriented properties have been found. In particular, various Cu having polyhedral structural units2O nanoparticles have found good application in photoelectrochemical and photovoltaic solar energy conversion. However, novel polyhedral Cu surrounded by highly active faces2The synthesis of O crystals remains an interesting and challenging topic for basic research and potential applications.
The construction of a functionally oriented heterostructure can bring unexpected properties to improve the potential applications of the crystal. Obviously, for different types of Ti3C2The study of the synthesis strategy and formation mechanism of the hybrid-based materials will be to understand the fundamental principles of the interface in heterostructures to improve their electrocatalytic properties. Therefore, Cu is synthesized by hydrothermal synthesis2O is loaded on the surface of the titanium carbide two-dimensional nano material and Cu is utilized2O unique surface property and excellent photoelectrocatalysis performance to improve the electrocatalytic reduction N of the titanium carbide material2Performance becomes possible.
Disclosure of Invention
The invention aims to provide a super-hydrophobic copper-based in-situ composite catalyst, and a preparation method and application thereof.
In order to achieve the purpose, the invention adopts the following technical scheme:
a super-hydrophobic copper-based in-situ composite catalyst is prepared from NaF, HCl and Ti3AlC2N-methylpyrrolidone NMP, polytetrafluoroethylene PTFE, glucose C6H12O6Copper acetate Cu (CH)3COO)2The raw materials are fed in batches, a heating and stirring method is carried out under mild conditions, cuprous oxide nano particles are loaded on titanium carbide by utilizing an in-situ growth technology, and polytetrafluoroethylene emulsion is introduced; and preparing the super-hydrophobic copper-based in-situ composite electrocatalyst.
Further, the method specifically comprises the following steps:
step S1, etching and dissolving out an Al layer in the aluminum titanium carbide by using sodium fluoride and hydrochloric acid;
step S2, filling Al layer space with N-methyl pyrrolidone at a certain temperature to form layered titanium carbide Ti3C2；
Step S3 is carried out by dissolving titanium carbide, glucose and copper acetate into water solution and reacting at certain temperature;
and step S4, adding the polytetrafluoroethylene emulsion to enable the polytetrafluoroethylene and the catalyst to form tight compounding, and finally obtaining the super-hydrophobic titanium carbide-cuprous oxide in-situ composite catalyst.
Further, the method more specifically comprises the following steps:
1) taking 1 g of Ti3AlC2And 50 mL of NMP solution containing NaF and HCl are put into a plastic reactor and stirred and heated; taking out the reaction solution and placing the reaction solution in an ultrasonic machine for ultrasonic treatment; centrifuging the obtained suspension until the pH value is equal to 7, and then performing vacuum drying;
2) 200 mg of the solid powder of step (1) was dissolved in 100 mL of ultrapure water, and glucose and copper acetate (molar ratio 1: 1) continuously stirring and reacting for 5 hours at 90 ℃ and 1000 r/min, then adding 50-100 mu L of 40wt% polytetrafluoroethylene emulsion, and continuously stirring and reacting for 1 hour;
3) and centrifuging the reaction solution in a centrifugal machine of 3500 r/min to remove the solvent, washing with absolute ethyl alcohol and deionized water respectively until the total ion concentration in the solution is lower than 10 ppm, and finally transferring into a freeze dryer for freeze drying to obtain a sample.
Further, the concentration of the NaF solution in the step (1) is 6 mol/L, and the concentration of the HCl solution is 6 mol/L.
Further, the stirring and heating in the step (1) are carried out at the temperature of 60-100 ℃, the rotating speed is 1000 r/min, and the reaction time is 12 h.
Further, the ultrasound in the step (1) is specifically ultrasonic reaction for 1h under the frequency of 40 kHz and the power of 100W.
The application of the super-hydrophobic copper-based in-situ composite catalyst obtained by the preparation method in the electrocatalytic synthesis of ammonia specifically comprises the following steps: dispersing a 2 mg composite catalyst sample 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 to drop 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 is simple in preparation conditions, the in-situ growth technology is utilized for the first time to load the cuprous oxide on the titanium carbide material, and the prepared material has better electrochemical performance compared with the titanium carbide material which is not compounded. Due to the synergistic effect of the titanium carbide and the cuprous oxide and the existence of the cuprous oxide nano particles, the oxidation of titanium atoms is prevented, the atomic ratio of active titanium atoms is increased, and more reactive 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 cuprous oxide coating is creatively formed by using an in-situ growth technology, a strong composite structure of titanium carbide-cuprous oxide-polytetrafluoroethylene is formed, and the novel super-hydrophobic titanium carbide-cuprous oxide in-situ composite electrocatalyst is prepared for the first time.
Drawings
Fig. 1 is an X-ray powder diffraction pattern (XRD) of the cuprous oxide/titanium carbide in-situ composite catalyst obtained in examples 1 to 5.
FIG. 2 is a scanning electron microscope image of the cuprous oxide/titanium carbide in-situ composite catalyst obtained in example 3.
FIG. 3 is a graph comparing the ammonia content in the solution after electrochemical nitrogen fixation of a blank sample and the cuprous oxide/titanium carbide in-situ composite catalyst obtained in example 3 with bias voltage and no bias voltage.
Fig. 4 is a hydrophilicity and hydrophobicity test of the cuprous oxide/titanium carbide in-situ composite 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
Taking 1 g of Ti3AlC2And 50 mL of NMP solution containing 6 mol/L NaF and 6 mol/LHCl 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 12 h. The reaction solution was taken out and placed in an ultrasonic wave machine (frequency 40 kHz, power 100W) for ultrasonic reaction for 1 hour. And then centrifuging the reaction solution again until the pH value of the solution is equal to 7, performing vacuum drying, dissolving 200 mg of centrifugally dried solid powder in 100 mL of ultrapure water, and adding glucose and copper acetate in a molar ratio of 1: 1, the load amount is calculated according to 0wt% of the load amount of the cuprous oxide after the reaction, the stirring reaction is continued for 5 hours at 90 ℃ and 1000 r/min, then 50-100 mu L of PTFE emulsion (the content is 40 wt%) is added, and the stirring reaction is continued for 1 hour. And finally, taking out the reaction solution, centrifuging in a centrifugal machine of 3500 r/min to remove the solvent, and washing with absolute ethyl alcohol and deionized water respectively until the ion solubility in the solution is lower than 10 ppm. Finally, the sample is transferred into a freeze drier for freeze drying to obtain a sample Ti3C2/PTFE。
Example 2
Taking 1 g of Ti3AlC2And 50 mL of NMP solution containing 6 mol/L NaF and 6 mol/LHCl 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 12 h. The reaction solution was taken out and placed in an ultrasonic wave machine (frequency 40 kHz, power 100W) for ultrasonic reaction for 1 hour. And then centrifuging the reaction solution again until the pH value of the solution is equal to 7, performing vacuum drying, dissolving 200 mg of centrifugally dried solid powder in 100 mL of ultrapure water, and adding glucose and copper acetate in a molar ratio of 1: 1, the load amount is calculated according to 5wt% of the load amount of the cuprous oxide after the reaction, the stirring reaction is continued for 5 hours at 90 ℃ and 1000 r/min, then 50-100 mu L of PTFE emulsion (the content is 40 wt%) is added, and the stirring reaction is continued for 1 hour. And finally, taking out the reaction solution, centrifuging in a centrifugal machine of 3500 r/min to remove the solvent, and washing with absolute ethyl alcohol and deionized water respectively until the ion solubility in the solution is lower than 10 ppm. Finally, the sample is transferred into a freeze drier for freeze drying to obtain a sample Ti3C2-5wt% Cu2O/PTFE。
Example 3
Taking 1 g of Ti3AlC2And 50 mL of NMP solution containing 6 mol/L NaF and 6 mol/LHCl 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 12 h. The reaction solution was taken out and placed in an ultrasonic wave machine (frequency 40 kHz, power 100W) for ultrasonic reaction for 1 hour. And then centrifuging the reaction solution again until the pH value of the solution is equal to 7, performing vacuum drying, dissolving 200 mg of centrifugally dried solid powder in 100 mL of ultrapure water, and adding glucose and copper acetate in a molar ratio of 1: 1, the load amount is calculated according to the load amount of the reacted cuprous oxide being 10wt%, the reaction is continuously stirred for 5 hours at 90 ℃ and 1000 r/min, then 50-100 mu L of PTFE emulsion (the content is 40 wt%) is added, and the reaction is continuously stirred for 1 hour. And finally, taking out the reaction solution, centrifuging in a centrifugal machine of 3500 r/min to remove the solvent, and washing with absolute ethyl alcohol and deionized water respectively until the ion solubility in the solution is lower than 10 ppm. Finally, the sample is transferred into a freeze drier for freeze drying to obtain a sample Ti3C2-10wt% Cu2O/PTFE。
Example 4
Taking 1 g of Ti3AlC2And 50 mL of NMP solution containing 6 mol/L NaF and 6 mol/LHCl 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 12 h. The reaction solution was taken out and placed in an ultrasonic wave machine (frequency 40 kHz, power 100W) for ultrasonic reaction for 1 hour. And then centrifuging the reaction solution again until the pH value of the solution is equal to 7, performing vacuum drying, dissolving 200 mg of centrifugally dried solid powder in 100 mL of ultrapure water, and adding glucose and copper acetate in a molar ratio of 1: 1, the load amount is calculated according to 20wt% of the load amount of the cuprous oxide after the reaction, the stirring reaction is continued for 5 hours at 90 ℃ and 1000 r/min, then 50-100 mu L of PTFE emulsion (the content is 40 wt%) is added, and the stirring reaction is continued for 1 hour. And finally, taking out the reaction solution, centrifuging in a centrifugal machine of 3500 r/min to remove the solvent, and washing with absolute ethyl alcohol and deionized water respectively until the ion solubility in the solution is lower than 10 ppm. Finally, the sample is transferred into a freeze drier for freeze drying to obtain a sample Ti3C2-20wt% Cu2O/PTFE。
Example 5
Taking 1 g of Ti3AlC2And 50 mL of NMP solution containing 6 mol/L NaF and 6 mol/LHCl 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 12 h. The reaction solution was taken out and placed in an ultrasonic wave machine (frequency 40 kHz, power 100W) for ultrasonic reaction for 1 hour. And then centrifuging the reaction solution again until the pH value of the solution is equal to 7, performing vacuum drying, dissolving 200 mg of centrifugally dried solid powder in 100 mL of ultrapure water, and adding glucose and copper acetate in a molar ratio of 1: 1, the load amount is calculated according to 100wt% of the load amount of the cuprous oxide after the reaction, the stirring reaction is continued for 5 hours at 90 ℃ and 1000 r/min, then 50-100 mu L of PTFE emulsion (the content is 40 wt%) is added, and the stirring reaction is continued for 1 hour. And finally, taking out the reaction solution, centrifuging in a centrifugal machine of 3500 r/min to remove the solvent, and washing with absolute ethyl alcohol and deionized water respectively until the ion solubility in the solution is lower than 10 ppm. Finally, the sample is transferred into a freeze dryer for freeze drying to obtain a sampleTi3C2-Cu2O(1:1)/PTFE。
Application example 1
Dispersing a 2 mg sample 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. Then the traditional three-electrode system is used for electrocatalytic synthesis of ammonia.
Fig. 1 is an X-ray powder diffraction pattern of the cuprous oxide/titanium carbide in-situ composite catalyst obtained in examples 1 to 5, and it can be seen from fig. 1 that, in the titanium carbide after being loaded with cuprous oxide, a characteristic peak belonging to titanium carbide and a characteristic peak belonging to cuprous oxide exist on XRD of the titanium carbide-cuprous oxide composite material, and the crystal form is obvious, which indicates that the two materials are well compounded together.
Fig. 2 is a comparison of scanning electron micrographs of cuprous oxide nanoparticles and cuprous oxide/titanium carbide in situ composite prepared in example 3. As can be seen from the figure, the cuprous oxide is nanoparticulate (fig. 2 left). The titanium carbide-cuprous oxide composite material prepared by the method can clearly see that cuprous oxide nanoparticles are uniformly loaded on the surface of the titanium carbide in a scanning electron microscope (right in figure 2).
FIG. 3 shows the cuprous oxide/titanium carbide in-situ composite material (Ti) prepared in example 33C2-10wt%Cu2O/PTFE) is prepared into an electrocatalytic working electrode, a three-electrode system is adopted, a bias voltage of-0.5V is applied and no bias voltage is applied, a blank experiment is carried out under an argon atmosphere, and the blank experiment directly uses 1 cm x 1 cm without dripping any solution-2The carbon paper of (2) was used as a blank and the ammonia yield after the nitrogen fixation reaction was compared. 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. It can be seen that the composite material has excellent electrochemical nitrogen fixation performance.
Fig. 4 is a hydrophilicity and hydrophobicity test of the cuprous oxide/titanium carbide in-situ composite material prepared in example 1. As can be seen from the figure, the contact angle of water reaches 142 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 (9)
1. A preparation method of a super-hydrophobic copper-based in-situ composite catalyst is characterized by comprising the following steps: sodium fluoride NaF, hydrochloric acid HCl and commercial titanium aluminum carbide Ti3AlC2N-methylpyrrolidone NMP, polytetrafluoroethylene PTFE, glucose C6H12O6Copper acetate Cu (CH)3COO)2The raw materials are fed in batches, a heating and stirring method is carried out under mild conditions, cuprous oxide nano particles are loaded on titanium carbide by utilizing an in-situ growth technology, and polytetrafluoroethylene emulsion is introduced; and preparing the super-hydrophobic copper-based in-situ composite electrocatalyst.
2. The method of claim 1, wherein: the method comprises the following specific steps:
(1) etching and dissolving out an Al layer in the titanium aluminum carbide by using sodium fluoride and hydrochloric acid;
(2) filling Al layer space with N-methyl pyrrolidone at a certain temperature to form layered titanium carbide Ti3C2；
(3) Dissolving titanium carbide, glucose and copper acetate in an aqueous solution and reacting at a certain temperature;
(4) then adding the polytetrafluoroethylene emulsion to enable the polytetrafluoroethylene and the catalyst to form tight compounding, and finally obtaining the super-hydrophobic titanium carbide-cuprous oxide in-situ composite catalyst.
3. The method of claim 2, wherein: the method specifically comprises the following steps:
1) taking 1 g of Ti3AlC2And 50 mL of NMP solution containing NaF and HCl are put into a plastic reactor and stirred and heated; taking out the reaction solution and placing the reaction solution in an ultrasonic machine for ultrasonic treatment; the obtained suspensionCentrifuging the turbid solution until the pH value is equal to 7, and then performing vacuum drying;
2) 200 mg of the solid powder of step (1) was dissolved in 100 mL of ultrapure water, and a solution of 1: 1, continuously stirring and reacting for 5 hours at 90 ℃ and 1000 r/min, then adding 50-100 mu L of 40wt% polytetrafluoroethylene emulsion, and continuously stirring and reacting for 1 hour;
3) and centrifuging the reaction solution in a centrifugal machine of 3500 r/min to remove the solvent, washing with absolute ethyl alcohol and deionized water respectively until the total ion concentration in the solution is lower than 10 ppm, and finally transferring into a freeze dryer for freeze drying to obtain a sample.
4. The production method according to claim 3, characterized in that: the concentration of the NaF solution in the step (1) is 6 mol/L, and the concentration of the HCl solution is 6 mol/L.
5. The production method according to claim 3, characterized in that: and (2) stirring and heating at the temperature of 60-100 ℃ in the step (1), wherein the rotating speed is 1000 r/min, and the reaction time is 12 h.
6. The production method according to claim 3, characterized in that: the ultrasound in the step (1) is specifically ultrasonic reaction for 1h under the frequency of 40 kHz and the power of 100W.
7. A super-hydrophobic copper-based in-situ composite catalyst obtained by the preparation method of any one of claims 1 to 5.
8. Application of the super-hydrophobic copper-based in-situ composite catalyst obtained by the preparation method of any one of claims 1 to 5 in electrocatalytic ammonia synthesis.
9. Use according to claim 8, characterized in that: dispersing a 2 mg composite catalyst sample in a dispersion liquid consisting of 225 muL ethanol, 225 muL water and 50 muL nafion, and dropping 50 muL dispersion liquid in the dispersion liquid after ultrasonic dispersion for one hour1*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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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112264062A (en) * | 2020-10-28 | 2021-01-26 | 兰州交通大学 | Preparation and application of monatomic platinum catalyst based on MXene quantum dots |
| CN113089001A (en) * | 2021-03-24 | 2021-07-09 | 福州大学 | Preparation method and application of super-hydrophobic molybdenum-based catalyst |
Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI20061263A1 (en) * | 2006-06-29 | 2007-12-30 | Solvay Solexis Spa | ASSEMBLED FOR ELECTROCHEMICAL DEVICES |
| CN101462076A (en) * | 2009-01-06 | 2009-06-24 | 上海汽车工业(集团)总公司 | Novel use of hydrophobing agent/conductive carbon material composite body |
| CN106589362A (en) * | 2016-12-22 | 2017-04-26 | 陕西科技大学 | Polyaniline nano particle/two-dimensional layered titanium carbide composite material and low-temperature preparation method of polyaniline nano particle/two-dimensional layered titanium carbide composite material |
| CN109167066A (en) * | 2018-09-03 | 2019-01-08 | 济南大学 | A kind of preparation method of few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material |
| CN110152699A (en) * | 2019-05-19 | 2019-08-23 | 北京化工大学 | A kind of application of the preparation method and its photocatalytic reduction of carbon oxide of cuprous oxide and two carbonization Tritanium/Trititanium heterojunction composites |
| CN110565112A (en) * | 2019-08-19 | 2019-12-13 | 天津大学 | method for changing cathode oxygen reduction activity by regulating hydrophilicity and hydrophobicity |
| CN110835765A (en) * | 2018-08-17 | 2020-02-25 | 中国科学院大连化学物理研究所 | Catalyst and device for preparing high-purity hydrogen through electrocatalysis water-vapor shift reaction |
| CN110841676A (en) * | 2019-11-22 | 2020-02-28 | 陕西科技大学 | Titanium carbide-cuprous oxide photocatalytic material and preparation method and application thereof |
-
2020
- 2020-04-02 CN CN202010256783.5A patent/CN111229318B/en active Active
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ITMI20061263A1 (en) * | 2006-06-29 | 2007-12-30 | Solvay Solexis Spa | ASSEMBLED FOR ELECTROCHEMICAL DEVICES |
| CN101462076A (en) * | 2009-01-06 | 2009-06-24 | 上海汽车工业(集团)总公司 | Novel use of hydrophobing agent/conductive carbon material composite body |
| CN106589362A (en) * | 2016-12-22 | 2017-04-26 | 陕西科技大学 | Polyaniline nano particle/two-dimensional layered titanium carbide composite material and low-temperature preparation method of polyaniline nano particle/two-dimensional layered titanium carbide composite material |
| CN110835765A (en) * | 2018-08-17 | 2020-02-25 | 中国科学院大连化学物理研究所 | Catalyst and device for preparing high-purity hydrogen through electrocatalysis water-vapor shift reaction |
| CN109167066A (en) * | 2018-09-03 | 2019-01-08 | 济南大学 | A kind of preparation method of few layer titanium carbide growth in situ nitrogen-doped carbon nanometer pipe three-dimensional composite material |
| CN110152699A (en) * | 2019-05-19 | 2019-08-23 | 北京化工大学 | A kind of application of the preparation method and its photocatalytic reduction of carbon oxide of cuprous oxide and two carbonization Tritanium/Trititanium heterojunction composites |
| CN110565112A (en) * | 2019-08-19 | 2019-12-13 | 天津大学 | method for changing cathode oxygen reduction activity by regulating hydrophilicity and hydrophobicity |
| CN110841676A (en) * | 2019-11-22 | 2020-02-28 | 陕西科技大学 | Titanium carbide-cuprous oxide photocatalytic material and preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| ZHANG, NQ ET.AL: "Polytetrafluoroethylene modifying: A low cost and easy way to improve the H2O resistance ability over MnOx for low-temperature NH3-SCR", 《JOURNAL OF ENVIRONMENTAL CHEMICAL ENGINEERING》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112264062A (en) * | 2020-10-28 | 2021-01-26 | 兰州交通大学 | Preparation and application of monatomic platinum catalyst based on MXene quantum dots |
| CN113089001A (en) * | 2021-03-24 | 2021-07-09 | 福州大学 | Preparation method and application of super-hydrophobic molybdenum-based catalyst |
| CN113089001B (en) * | 2021-03-24 | 2022-05-13 | 福州大学 | Preparation method and application of super-hydrophobic molybdenum-based catalyst |
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