CN113046781B - Electrocatalytic carbon dioxide reduction material and preparation method and application thereof - Google Patents
Electrocatalytic carbon dioxide reduction material and preparation method and application thereof Download PDFInfo
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Abstract
The invention discloses an electrocatalytic oxidationThe carbon reduction material and the preparation method and the application thereof, wherein the preparation method comprises the following steps: (1) mixing the gelator, cobalt salt and water, and then adjusting the pH value to be neutral or alkalescent to obtain a gel precursor; (2) will modify C3N4Or adding the modified multi-walled carbon nanotube into the gel precursor obtained in the step (1), and uniformly mixing by ultrasonic stirring to obtain a mixed solution; (3) and (3) carrying out hydrothermal reaction on the mixed solution obtained in the step (2), washing and drying a product obtained after the hydrothermal reaction, and calcining the dried product to obtain the electrocatalytic carbon dioxide reduction material. The electrocatalytic carbon dioxide reduction material has the advantages of good electrocatalytic carbon dioxide reduction effect, high product utilization value, low cost, greenness, safety, and simple and convenient preparation process.
Description
Technical Field
The invention relates to the technical field of electrocatalysis carbon dioxide reduction, in particular to an electrocatalysis carbon dioxide reduction material based on a gel precursor, and a preparation method and application thereof.
Background
With the increasing influence of the greenhouse effect and the accumulation of carbon dioxide concentration, the reduction of carbon dioxide into valuable additional substances is urgently needed in the current society. The recycling value of the catalyst is realized by catalyzing the reduction of carbon dioxide into fuels and useful chemicals, such as carbon monoxide, formic acid, methane, ethylene and the like, and simultaneously, the fuel and environmental problems are solved. Electrocatalytic carbon dioxide reduction is therefore of great practical significance for this.
Since the 70 s of the 20 th century, organic homogeneous catalysts have attracted much attention in the field of electrocatalytic carbon dioxide due to their unique active centers, but gradually replaced inorganic heterogeneous catalysts due to their own toxicity, complicated separation and the like. By virtue of the advantages of environmental friendliness, high efficiency, simple and convenient synthesis and the like, the inorganic heterogeneous catalyst is still widely applied in the field of carbon dioxide reduction. But the existing electrocatalytic carbon dioxide reduction catalyst still has a larger promotion space in the aspects of catalytic efficiency, additional products, environmental protection and process operation. The development of electrocatalytic carbon dioxide reducing materials that simultaneously have high catalytic efficiency, high additional products, are environmentally friendly and can be used for industrial mass production is the direction of development in the current field.
Disclosure of Invention
The invention mainly aims to provide an electrocatalytic carbon dioxide reduction material, and a preparation method and application thereof.
In order to accomplish the above object, according to one aspect of the present invention, there is provided a method for preparing an electrocatalytic carbon dioxide reducing material, comprising the steps of:
(1) mixing the gelator, cobalt salt and water, and then adjusting the pH value to be neutral or alkalescent to obtain a gel precursor;
(2) will modify C3N4Or adding the modified multi-walled carbon nanotube into the gel precursor obtained in the step (1), and uniformly mixing by ultrasonic stirring to obtain a mixed solution;
(3) and (3) carrying out hydrothermal reaction on the mixed solution obtained in the step (2), then washing and drying a product after the hydrothermal reaction, and calcining the dried product to obtain the electrocatalytic carbon dioxide reduction material.
After being prepared, the single metal gel has insufficient active sites relative to electrocatalytic carbon dioxide reduction, does not have enough reduction capability and has ordinary conductivity. The invention modifies C by introducing3N4Or modifying the gel precursor by the modified multi-walled carbon nano tube, and obtaining the electrocatalytic carbon dioxide reduction material after hydrothermal reaction and high-temperature calcination. Modification C3N4Or the modified multi-walled carbon nanotube has good conductivity, and the conductivity of the material can be effectively improved by adding the modified multi-walled carbon nanotube into a gel precursor, and meanwhile, a good nitrogen source and a good carbon source can be provided for the precursor; the modification C3N4Or modified multi-wall carbon nano-tube cogel precursorThe three-dimensional network structure of the composite material has synergistic effect, and the activity of the composite material is further improved. The invention introduces modification C into gel precursor3N4Or the modified multi-walled carbon nano-tube effectively improves the conductivity of the electrocatalytic carbon dioxide reduction material and the activity of carbon dioxide reaction sites, thereby improving the electrocatalytic carbon dioxide reduction performance of the material.
Further, the multi-walled carbon nanotube is a graphitized carboxylated multi-walled carbon nanotube (abbreviated as CNT (20-30)) having an inner diameter of 5nm to 10nm, an outer diameter of 20nm to 30nm, and a length of 10 μm to 30 μm, or a graphitized carboxylated multi-walled carbon nanotube (abbreviated as CNT (> 50)) having an inner diameter of 5nm to 10nm, an outer diameter of > 50nm, and a length of 10 μm to 20 μm. More preferably, the graphitized carboxylated multi-wall carbon nanotubes employ CNTs (20-30).
Further, modification C3N4The preparation method comprises the following steps: adding potassium hydroxide into ultrapure water, fully and uniformly stirring, adding urea into the uniformly mixed solution, uniformly stirring, heating for evaporation, calcining the evaporated product in air atmosphere, washing with water and drying to obtain modified C3N4。
Specifically, modification C3N4Is g-C3N4-0.005 and g-C3N4-0.01. More preferably, modification C3N4With g-C3N4-0.01。
The specific preparation method comprises the following steps:
(1) adding 0.005g or 0.01g of potassium hydroxide into 30.0g of ultrapure water, and fully stirring and uniformly mixing;
(2) adding 15g of urea into the solution, uniformly stirring, and evaporating at 80 ℃ for 10 h;
(3) calcining the evaporated product at 550 deg.C in air atmosphere for 4h, washing with water, and drying to obtain g-C3N4-0.005 (prepared from 0.005g potassium hydroxide), g-C3N40.01 (prepared from 0.01g of potassium hydroxide).
Further, in the step (1), the mass percent of the gel factor in the gel precursor is 60-75%, and the mass percent of the cobalt salt is 25-33%. The gelator, cobalt salt and water together form a hydrogel system.
Further, in the step (1), the gelator is one or two of gelator L-PT and gelator D-PT. More preferably, the gelator is gelator L-PT.
Specifically, the preparation methods of the gelator L-PT and the gelator D-PT are as follows:
(1) adding L-tryptophan or D-tryptophan and KOH into ultrapure water, and fully stirring and uniformly mixing to obtain a solution I;
(2) adding 4-pyridylaldehyde into methanol, fully stirring and dissolving, slowly adding the solution I, and stirring at room temperature for reaction to obtain a solution II;
(3) cooling the solution II in an ice-water bath, slowly adding sodium borohydride, and stirring for reaction to obtain a solution III;
(4) adding glacial acetic acid into the reacted solution III, adjusting the pH value to 4.0-5.0, and stirring for reaction to obtain a solution IV;
(5) and filtering the solution IV after the reaction, performing suction filtration on the product by using methanol and water, and drying to obtain the gelator L-PT or gelator D-PT (the specific product type is determined by the configuration of tryptophan).
Further, in the step (1), the cobalt salt is one or more of cobalt acetate, cobalt chloride, cobalt sulfate and cobalt nitrate. More preferably, cobalt acetate is used as the cobalt salt.
Further, in the step (1), the adjustment of pH to neutral or weakly alkaline means specifically the adjustment of pH to 7 to 8.
Further, in the step (2), the time of ultrasonic stirring is 15min-30 min.
Further, in the step (3), the hydrothermal reaction is carried out in a constant-temperature oven, the temperature of the hydrothermal reaction is 150-180 ℃, and the time of the hydrothermal reaction is 6-12 h.
Further, in the step (3), a high-temperature calcination reaction is carried out in a high-temperature tube furnace, the calcination temperature is 600-800 ℃, the calcination reaction time is 2.5-3.5 h, the carrier gas of the calcination reaction is argon or a hydrogen-argon mixed gas, and the temperature rise rate of the calcination reaction is 5-10 ℃/min.
According to another aspect of the present invention, there is provided an electrocatalytic carbon dioxide reduction material prepared by the above-described preparation method.
According to another aspect of the invention, the application of the electrocatalytic carbon dioxide reduction material prepared by the preparation method is provided, and the electrocatalytic carbon dioxide reduction material is used as a carbon dioxide reduction electrocatalyst in an electrocatalytic carbon dioxide reduction reaction.
Specifically, the electrocatalytic carbon dioxide reduction material ink is coated on carbon cloth, is clamped by a glassy carbon electrode clamp after being dried to serve as a working electrode, forms a three-electrode system together with a saturated silver chloride reference electrode and a platinum sheet, and is subjected to electrocatalytic carbon dioxide reduction reaction in an H-shaped electrolytic cell.
Compared with the prior art, the invention has the beneficial effects that:
(1) the electrocatalytic carbon dioxide reduction material has good electrocatalytic carbon dioxide reduction effect, and the gel precursor is wide in application and strong in universality.
(2) Modification C introduced in the invention3N4Or the graphitized carboxylated multi-walled carbon nano-tube has a better graphitized structure, thereby not only improving the conductivity of the reducing material, but also enhancing the carbon dioxide reaction activity of the reducing material and increasing the reaction active sites of the material.
(3) The electrocatalytic carbon dioxide reduction material provided by the invention is low in price, green and safe, and simple and convenient in manufacturing process, and has important significance for industrial application of electrocatalytic carbon dioxide reduction.
Drawings
FIG. 1 is a diagram showing faradic efficiencies of carbon dioxide reduction at-1.2V and different times for the electrocatalytic carbon dioxide reduction material obtained in example 3 of the present invention.
FIG. 2 is a graph of faradaic efficiency of carbon dioxide reduction at-1.2V and different times for the electrocatalytic carbon dioxide reduction material obtained in example 4 of the present invention.
Detailed Description
In order to facilitate an understanding of the present invention, the present invention will be described more fully and in detail with reference to the preferred embodiments, but the scope of the present invention is not limited to the specific embodiments described below.
Unless otherwise defined, all terms of art used hereinafter have the same meaning as commonly understood by one of ordinary skill in the art. The terminology used herein is for the purpose of describing particular embodiments only and is not intended to limit the scope of the present invention.
Unless otherwise specifically indicated, various raw materials, reagents, instruments, equipment and the like used in the present invention are commercially available or can be prepared by existing methods.
In the present invention, the gelator (including L-PT and D-PT) is named by the inventor, and the preparation method of the gelator is as follows:
(1) adding 1g L-tryptophan or D-tryptophan and 0.28g KOH into 10.0g ultrapure water, and fully stirring and uniformly mixing;
(2) adding 0.54g of 4-pyridylaldehyde into 5ml of methanol, fully stirring and dissolving, slowly adding the solution, and stirring at room temperature for 2 hours;
(3) cooling the mixed solution in an ice-water bath, slowly adding 0.23g of sodium borohydride, and stirring for 3 hours;
(4) adding 50% glacial acetic acid into the mixed solution after reaction, adjusting the pH value to 4.0-5.0, and stirring for 2 h;
(5) filtering the reacted mixed solution, filtering and washing the product with methanol and water, and drying at 50 deg.c to obtain L-PT (prepared from L-tryptophan) or D-PT (prepared from D-tryptophan).
g-C used in the invention3N4(including g-C)3N4-0.005 and g-C3N4-0.01) the preparation method is as follows:
(1) adding 0.005g or 0.01g of potassium hydroxide into 30.0g of ultrapure water, and fully stirring and uniformly mixing;
(2) adding 15g of urea into the solution, uniformly stirring, and evaporating at 80 ℃ for 10 h;
(3) subjecting the evaporated product to air at 550 deg.CCalcining at high temperature for 4h in atmosphere, washing with water and drying to obtain g-C3N4-0.005 (prepared from 0.005g potassium hydroxide), g-C3N40.01 (prepared from 0.01g of potassium hydroxide).
Example 1:
the preparation method of the electrocatalytic carbon dioxide reduction material comprises the following steps:
(1) adding 29.5mg of the gel factor L-PT into 1.0g of water, stirring uniformly and fully dissolving to obtain 0.1 mol/L-PT mother liquor;
(2) 24.908mg of cobalt acetate is added into 1.0g of water, and the cobalt acetate is stirred uniformly and fully dissolved to obtain 0.1mol/L of cobalt acetate mother liquor;
(3) adding 0.6ml of gelator L-PT mother liquor and 0.3ml of cobalt acetate mother liquor into 2.1ml of water, fully mixing, and dropwise adding an ammonia water solution to adjust the pH value to about 7.0-8.0 to obtain a gel precursor;
(4) 8mg of g-C3N4-0.005 is added into the gel precursor, ultrasonic stirring is continued for 30min, and the mixture is uniformly mixed;
(5) putting the mixed solution into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a constant-temperature oven for hydrothermal reaction at 180 ℃ for 12 hours, and washing and drying a product after the hydrothermal reaction;
(6) and (3) putting the dried product into a porcelain boat, putting the porcelain boat into a high-temperature tube furnace, and reacting for 3 hours at the temperature rise rate of 10 ℃/min under the atmosphere of hydrogen-argon mixed gas to obtain the electrocatalytic carbon dioxide reduction material.
Example 2:
the preparation method of the electrocatalytic carbon dioxide reduction material comprises the following steps:
(1) adding 29.5mg of gelator L-PT into 1.0g of water, stirring uniformly and fully dissolving to obtain 0.1mol/L gelator L-PT mother liquor;
(2) 24.908mg of cobalt acetate is added into 1.0g of water, and the mixture is stirred uniformly and fully dissolved to obtain 0.1mol/L of cobalt acetate mother liquor;
(3) adding 0.6ml of gelator L-PT mother liquor and 0.3ml of cobalt acetate mother liquor into 2.1ml of water, fully mixing, and dropwise adding an ammonia water solution to adjust the pH value to about 7.0-8.0 to obtain a gel precursor;
(4) adding 8mg of graphitized carboxylated multi-wall carbon nano-tube (CNT (> 50)) into the gel precursor, continuing ultrasonic stirring for 30min, and uniformly mixing;
(5) putting the mixed solution into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a constant-temperature oven for hydrothermal reaction at 180 ℃ for 12 hours, and washing and drying a product after the hydrothermal reaction;
(6) and (3) putting the dried product into a porcelain boat, putting the porcelain boat into a high-temperature tube furnace, and reacting for 3 hours at the temperature rise rate of 10 ℃/min under the atmosphere of hydrogen-argon mixed gas to obtain the electrocatalytic carbon dioxide reduction material.
Example 3:
the preparation method of the electrocatalytic carbon dioxide reduction material comprises the following steps:
(1) adding 29.5mg of gelator L-PT into 1.0g of water, stirring uniformly and fully dissolving to obtain 0.1mol/L gelator L-PT mother liquor;
(2) 24.908mg of cobalt acetate is added into 1.0g of water, and the mixture is stirred uniformly and fully dissolved to obtain 0.1mol/L of cobalt acetate mother liquor;
(3) adding 0.6ml of gelator L-PT mother liquor and 0.3ml of cobalt acetate mother liquor into 2.1ml of water, fully mixing, and dropwise adding an ammonia water solution to adjust the pH value to about 7.0-8.0 to obtain a gel precursor;
(4) 8mg of g-C3N4Adding 0.01 percent of the mixture into the gel precursor, continuing to stir for 30min by ultrasonic waves, and uniformly mixing;
(5) putting the mixed solution into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a constant-temperature oven for hydrothermal reaction at 180 ℃ for 12 hours, and washing and drying a product after the hydrothermal reaction;
(6) and (3) putting the dried product into a porcelain boat, putting the porcelain boat into a high-temperature tube furnace, and reacting for 3 hours at the temperature rise rate of 10 ℃/min under the atmosphere of hydrogen-argon mixed gas to obtain the electrocatalytic carbon dioxide reduction material.
The electrocatalytic carbon dioxide reduction material prepared by the embodiment is applied to electrocatalytic reduction of carbon dioxide, and specifically comprises the following components: the reduced material ink prepared in the example was coated on carbon cloth, dried, and then clamped by a glassy carbon electrode clamp as a working electrode, and a three-electrode system was formed with a saturated silver chloride reference electrode and a platinum sheet, and tested in an H-type electrolytic cell. Carbon dioxide is reduced to carbon monoxide and hydrogen at-1.2V.
The faradaic efficiency graph of the electrocatalytic carbon dioxide reduction material of the present example shows the faradaic efficiency of carbon dioxide reduction at-1.2V and different times, as shown in fig. 1. As can be seen from FIG. 1, the reduced material obtained in this example electrocatalytically reduced carbon dioxide to carbon monoxide and hydrogen at-1.2V. Under the condition, the yield of hydrogen is 76.58% and the yield of carbon monoxide is 20.23% at the time of reaction for 150min, which shows that the reducing material has good electrocatalytic carbon dioxide reducing capability.
Example 4:
the preparation method of the electrocatalytic carbon dioxide reduction material comprises the following steps:
(1) adding 29.5mg of gelator L-PT into 1.0g of water, stirring uniformly and fully dissolving to obtain 0.1mol/L gelator L-PT mother liquor;
(2) 24.908mg of cobalt acetate is added into 1.0g of water, and the mixture is stirred uniformly and fully dissolved to obtain 0.1mol/L of cobalt acetate mother liquor;
(3) adding 0.6ml of gelator L-PT mother liquor and 0.3ml of cobalt acetate mother liquor into 2.1ml of water, fully mixing, and then dropwise adding an ammonia water solution to adjust the pH value to about 7.0-8.0 to obtain a gel precursor;
(4) adding 8mg of graphitized carboxylated multi-wall carbon nano-tube (CNT (20-30)) into the gel precursor, continuing ultrasonic stirring for 30min, and uniformly mixing;
(5) putting the mixed solution into a hydrothermal reaction kettle, putting the hydrothermal reaction kettle into a constant-temperature oven for hydrothermal reaction at 180 ℃ for 12 hours, and washing and drying a product after the hydrothermal reaction;
(6) and (3) putting the dried product into a porcelain boat, putting the porcelain boat into a high-temperature tube furnace, and reacting for 3 hours at the temperature rise rate of 10 ℃/min under the atmosphere of hydrogen-argon mixed gas to obtain the electrocatalytic carbon dioxide reduction material.
The electrocatalytic carbon dioxide reduction material prepared by the embodiment is applied to electrocatalytic reduction of carbon dioxide, and specifically comprises the following components: the reducing material ink prepared in the embodiment is coated on carbon cloth, is clamped by a glassy carbon electrode clamp after being dried to be used as a working electrode, and forms a three-electrode system together with a saturated silver chloride reference electrode and a platinum sheet, and the three-electrode system is tested in an H-type electrolytic cell. Carbon dioxide is reduced to carbon monoxide and hydrogen at-1.2V.
The faradaic efficiency graph of the electrocatalytic carbon dioxide reduction material of this example shows the faradaic efficiency of carbon dioxide reduction at-1.2V and at different times, as shown in fig. 2. As can be seen from FIG. 2, the reduced material obtained in this example electrocatalytically reduced carbon dioxide to carbon monoxide and hydrogen at-1.2V. Under the condition, the yield of hydrogen is 74.18% and the yield of carbon monoxide is 21.99% when the reaction is carried out for 60min, and the reduction material has good electrocatalytic carbon dioxide reduction capability.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A preparation method of an electrocatalytic carbon dioxide reduction material is characterized by comprising the following steps:
(1) mixing the gel factor, cobalt salt and water, and then adjusting the pH value to be neutral or alkalescent to obtain a gel precursor;
(2) will modify C3N4Or adding the modified multi-walled carbon nanotube into the gel precursor obtained in the step (1), and uniformly mixing by ultrasonic stirring to obtain a mixed solution;
(3) carrying out hydrothermal reaction on the mixed solution obtained in the step (2), washing and drying a product obtained after the hydrothermal reaction, and calcining the dried product to obtain an electrocatalytic carbon dioxide reduction material;
the multi-wall carbon nano-tube is a graphitized carboxylated multi-wall carbon nano-tube with the inner diameter of 5nm-10nm, the outer diameter of 20nm-30nm and the length of 10 mu m-30 mu m, or the graphitized carboxylated multi-wall carbon nano-tube with the inner diameter of 5nm-10nm, the outer diameter of more than 50nm and the length of 10 mu m-20 mu m;
the modification C3N4The preparation method comprises the following steps: adding potassium hydroxide into ultrapure water, fully and uniformly stirring, adding urea into the uniformly mixed solution, uniformly stirring, heating for evaporation, calcining the evaporated product in air atmosphere, washing with water and drying to obtain modified C3N4；
In the step (1), the gelator is prepared by the following method: adding L-tryptophan or D-tryptophan and potassium hydroxide into ultrapure water, fully stirring and uniformly mixing to obtain a solution I; adding 4-pyridylaldehyde into methanol, fully stirring and dissolving, slowly adding the solution I, and stirring and reacting at room temperature to obtain a solution II; cooling the solution II in ice water bath, slowly adding sodium borohydride, and stirring for reaction to obtain a solution III; adding glacial acetic acid into the solution III to adjust the pH value to 4.0-5.0, and stirring for reaction to obtain a solution IV; and filtering the solution IV, performing suction filtration on the product by using methanol and water, and drying to obtain the gelator.
2. The method for preparing an electrocatalytic carbon dioxide reducing material according to claim 1, wherein in the step (1), the mass percentage of the gel factor in the gel precursor is 60-75%, and the mass percentage of the cobalt salt is 25-33%.
3. The method for preparing an electrocatalytic carbon dioxide reducing material according to claim 1, wherein in the step (1), the cobalt salt is one or more of cobalt acetate, cobalt chloride, cobalt sulfate and cobalt nitrate; adjusting the pH to neutral or weakly alkaline specifically means adjusting the pH to 7-8; in the step (2), the ultrasonic stirring time is 15min-30 min.
4. The method for preparing an electrocatalytic carbon dioxide reducing material according to claim 1, wherein the hydrothermal reaction temperature in step (3) is 150 ℃ to 180 ℃ and the hydrothermal reaction time is 6h to 12 h.
5. The method for preparing an electrocatalytic carbon dioxide reducing material as set forth in claim 1, wherein in the step (3), the calcination temperature is 600 ℃ to 800 ℃, the calcination reaction time is 2.5h to 3.5h, the carrier gas for the calcination reaction is argon gas or a hydrogen-argon mixture gas, and the temperature rise rate for the calcination reaction is 5 ℃/min to 10 ℃/min.
6. An electrocatalytic carbon dioxide reducing material produced by the production method according to any one of claims 1 to 5.
7. The application of the electrocatalytic carbon dioxide reduction material prepared by the preparation method according to any one of claims 1 to 5, wherein the electrocatalytic carbon dioxide reduction material ink is coated on carbon cloth, dried and used as a working electrode to form a three-electrode system together with a saturated silver chloride reference electrode and a platinum sheet, and an electrocatalytic carbon dioxide reduction reaction is carried out in an electrolytic cell.
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