CN111229318B - 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 PDF

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CN111229318B
CN111229318B CN202010256783.5A CN202010256783A CN111229318B CN 111229318 B CN111229318 B CN 111229318B CN 202010256783 A CN202010256783 A CN 202010256783A CN 111229318 B CN111229318 B CN 111229318B
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江莉龙
詹辉
梁诗景
刘福建
曹彦宁
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Fuzhou University
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Abstract

The invention discloses a super-hydrophobic copper-based in-situ composite catalyst and a preparation method and application thereof, belonging 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

Super-hydrophobic copper-based in-situ composite catalyst and preparation method and application thereof
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 property, and meanwhile, the titanium carbide structure is highly ordered, and the layered structure has a larger internal surface area, and the distance between crystal planes of the titanium carbide after intercalation by N-methylpyrrolidone can be further increased, so that the internal surface area is further enlarged, and the interlayer space of the titanium carbide is beneficial to enrichment of nitrogen, so that the titanium carbide can become an effective catalyst for electroreduction and nitrogen fixation, and previous research results also prove that. Cuprous oxide (Cu) 2 O) 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, cu 2 The 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, the key point is that the synthesis has controllable size, shape, surface and defectTraps, dopings and heterostructures. Polyhedral Cu 2 O 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 elements 2 O nanoparticles have found great application in photoelectrochemical and photovoltaic solar energy conversion. However, novel polyhedral Cu surrounded by highly active faces 2 The 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 Ti 3 C 2 The 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 synthesis 2 O is loaded on the surface of the titanium carbide two-dimensional nano material and Cu is utilized 2 O unique surface property and excellent photoelectrocatalysis performance to improve the electrocatalytic reduction N of the titanium carbide material 2 Performance 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 realize the purpose, the invention adopts the following technical scheme:
a super-hydrophobic copper-based in-situ composite catalyst is prepared from NaF, HCl and Ti 3 AlC 2 N-methylpyrrolidone NMP, polytetrafluoroethylene PTFE, glucose C 6 H 12 O 6 Copper acetate Cu (CH) 3 COO) 2 The 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 titanium aluminum carbide by using sodium fluoride and hydrochloric acid;
s2, filling Al layer space with N-methylpyrrolidone at a certain temperature to form layered titanium carbide Ti 3 C 2 ；
S3, dissolving titanium carbide, glucose and copper acetate in an aqueous solution and reacting at a certain temperature;
and 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 Ti 3 AlC 2 And 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 carrying out 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 to 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: 2 mg of the composite catalystDispersing the 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 -2 The 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 remarkable advantages that:
(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 example 1 to example 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 Ti 3 AlC 2 And 50 mL of NMP solution containing 6 mol/L NaF and 6 mol/L HCL 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 at 3500 r/min to remove the solvent, and washing with absolute ethyl alcohol and deionized water respectively until the ionic 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 Ti 3 C 2 /PTFE。
Example 2
Taking 1 g of Ti 3 AlC 2 And 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 subjected to ultrasonic reaction in an ultrasonic wave machine (frequency 40 kHz, power 100W) 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 loading amount is calculated according to the 5wt% of the cuprous oxide loading amount after the reaction, 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. Finally, the reaction solution is taken out, centrifuged in a centrifugal machine of 3500 r/min to remove the solvent, and then absolute ethyl alcohol and deionized water are respectively usedThe solution is washed with water until the ionic solubility of the solution is less than 10 ppm. Finally, the sample is transferred into a freeze drier for freeze drying to obtain a sample Ti 3 C 2 -5wt% Cu 2 O/PTFE。
Example 3
Taking 1 g of Ti 3 AlC 2 And 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 Ti 3 C 2 -10wt% Cu 2 O/PTFE。
Example 4
Taking 1 g of Ti 3 AlC 2 And 50 mL of NMP solution containing 6 mol/L NaF and 6 mol/L HCL 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 subjected to ultrasonic reaction in an ultrasonic wave machine (frequency 40 kHz, power 100W) 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. Finally, the reaction solution is taken out, centrifuged in a centrifugal machine of 3500 r/min to remove the solvent, and then respectivelyWashing with absolute ethyl alcohol and deionized water until the ionic solubility in the solution is less than 10 ppm. Finally, the sample is transferred into a freeze drier for freeze drying to obtain a sample Ti 3 C 2 -20wt% Cu 2 O/PTFE。
Example 5
Taking 1 g of Ti 3 AlC 2 And 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 drier for freeze drying to obtain a sample Ti 3 C 2 -Cu 2 O(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 -2 The 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 (Ti) prepared in example 3 3 C 2 -10wt%Cu 2 O/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 is directly carried out by using 1 cm x 1 cm without dripping any solution -2 The 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 the equivalent changes and modifications made according to the claims of the present invention should be covered by the present invention.

Claims (7)

1. The application of the super-hydrophobic copper-based in-situ composite catalyst in the electrocatalytic synthesis of ammonia is characterized in that: sodium fluoride NaF, hydrochloric acid HCl and aluminum titanium carbide Ti 3 AlC 2 N-methylpyrrolidone NMP, polytetrafluoroethylene PTFE, glucose C 6 H 12 O 6 Copper acetate Cu (CH) 3 COO) 2 The raw materials are fed in batches, a heating and stirring method is adopted under mild conditions, cuprous oxide nanoparticles are loaded on titanium carbide by utilizing an in-situ growth technology, and polytetrafluoroethylene emulsion is introduced; preparing the super-hydrophobic copper protogenAn electrocatalyst is complexed.
2. Use according to claim 1, characterized in that: 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 Ti 3 C 2 ；
(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. Use according to claim 2, characterized in that: the method specifically comprises the following steps:
1) Taking 1 g of Ti 3 AlC 2 And 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 carrying out vacuum drying;
2) 200 mg of the solid powder of step 1) were dissolved in 100 mL of ultrapure water and, depending on the loading, a molar ratio 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 to a freeze dryer for freeze drying to obtain a sample.
4. Use 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. Use according to claim 3, characterized in that: 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.
6. Use according to claim 3, characterized in that: the ultrasonic wave in the step 1) is specifically ultrasonic reaction for 1h under the frequency of 40 kHz and the power of 100W.
7. Use according to claim 1, 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 after one hour of ultrasonic dispersion, taking 50 muL dispersed liquid to drop in 1 x 1 cm -2 The 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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