CN113151859A - Preparation method and application of copper-indium composite catalyst - Google Patents
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Abstract
本发明公开一种铜铟复合催化剂的制备方法与应用，属于材料制备和电催化技术领域；所述复合氧化亚铜与氢氧化铟电催化剂是以二水合氯化铜CuCl2·2H2O、无水氯化铟InCl3、浓氨水、氢氧化钠、联氨溶液N2H4为原料，通过分批次投料，常温条件下共沉淀，将In基材料引入纯氧化亚铜Cu2O材料中，首次开发出高性能的电催化还原二氧化碳用复合氧化亚铜与氢氧化铟电催化剂。本发明制备的电催化剂具有比表面积大，电催化性能良好的优点。本发明的制备过程简单方便，能耗低，成本低，有较大的应用潜力。
The invention discloses a preparation method and application of a copper - indium composite catalyst, belonging to the technical field of material preparation and electrocatalysis ; Anhydrous indium chloride InCl 3 , concentrated ammonia water, sodium hydroxide, hydrazine solution N 2 H 4 are used as raw materials, and the In-based material is introduced into pure cuprous oxide Cu 2 O material by batch feeding and co-precipitation under normal temperature conditions In , for the first time, a high-performance composite cuprous oxide and indium hydroxide electrocatalyst for electrocatalytic reduction of carbon dioxide was developed. The electrocatalyst prepared by the invention has the advantages of large specific surface area and good electrocatalytic performance. The preparation process of the invention is simple and convenient, low in energy consumption, low in cost, and has great application potential.
Description
Technical Field
The invention belongs to the technical field of material preparation and electrocatalysis, and particularly relates to a preparation method and application of a copper-indium composite catalyst.
Background
In recent years, large-scale development has begun with fossil fuelsProblems with excessive carbon dioxide emissions also begin to arise with consumption. The excessive carbon dioxide emissions are a disruption to the carbon cycle and will lead to ecological problems, and therefore, reducing carbon dioxide emissions is one of the most important scientific challenges today. CO in the atmosphere2Rich resources, can be catalytically converted into industrially renewable chemicals and fuels, and therefore, the emitted CO2Alternatively, it can be considered as a valuable resource, CO2The recovery and conversion can solve two problems of environment and energy.
The current means in industry can be to introduce CO2Fixing the container in the sea, oil and gas field, deep coal seam and other places by geological sealing method; or reacting CO by chemical reaction2Synthesized into high value-added products, however, CO is industrially used2The amount of (C) is far from sufficient in comparison with the industrial discharge amount, and therefore, researchers have developed other means for converting and reducing CO2There are mainly the following ways: (1) a biological method, which utilizes the catalytic reduction of microorganisms or enzymes to realize the conversion of carbon dioxide resources; (2) a photocatalysis method, which simulates photosynthesis and directly utilizes light energy to realize the recycling of CO 2; (3) electrocatalytic processes, by applying a small bias, use renewable energy power to convert CO2 into new clean energy. In which the CO is reduced electrocatalytically2The method has the advantages that the selectivity of the reaction to the product can be regulated and controlled by controlling different reduction potentials or reduction currents; the reaction can be carried out under mild conditions (normal temperature and normal pressure), the electro-catalytic reaction has lower requirements on experimental devices, and the reaction system is simple; the power supply can be a carbon-free power supply (such as wind energy, solar energy, hydroelectric power and the like), and has a large development space; electrocatalytic reduction of CO2The problems of low catalyst efficiency, low stability, low selectivity, high energy consumption and the like exist, so the design of the high-efficiency catalyst is that the catalyst is used for the electro-catalytic reduction of CO2One of the important points of (1).
In early studies on catalysts for reducing carbon dioxide, the transition metal In was thought to be In the reaction of CO2Has potential in reducing to formic acid. Recent studies have also shown faradaic efficiency>In 80% aqueous electrolyte, the In-based catalyst can easily react CO2Reducing into formate. Copper-based metal oxides are basic in nature, CO2And also has acidic (Lewis acid) properties, so that the use of copper oxide as an electrocatalyst may enhance CO2The adsorption of (2) makes it possible to design a composite cuprous oxide and indium hydroxide catalyst for efficiently electro-catalytically reducing carbon dioxide. Copper-based catalysts have excellent catalytic capabilities and can produce a variety of carbon dioxide reduction products, including carbon monoxide, formate, ethanol, and ethylene. However, copper-based catalysts still suffer from a number of problems, such as: (1) high electrical overpotentials lead to low energy efficiency; (2) the electron transfer kinetics are slow; (3) the product is complex in type, poor in selectivity to a specific product and difficult to separate; (4) the poor stability of the catalyst, which generally deactivates within a few hours, severely limits the commercial use of copper-based catalysts.
Disclosure of Invention
In order to solve the problems in the prior art, the invention provides a preparation method of a copper-indium composite catalyst, which is prepared by using copper chloride dihydrate CuCl2·2H2O, anhydrous indium chloride InCl3Concentrated ammonia water, sodium hydroxide and hydrazine solution N2H4The raw materials are fed In batches and coprecipitated at normal temperature, and In-based materials are introduced into pure cuprous oxide Cu2In O materials, a high-performance copper-indium composite catalyst for electrocatalytic reduction of carbon dioxide is developed for the first time.
The technical scheme of the invention is as follows:
the invention discloses a preparation method of a copper-indium composite catalyst, which takes copper chloride dihydrate, anhydrous indium chloride, concentrated ammonia water, sodium hydroxide and hydrazine solution as raw materials and compounds cuprous oxide and an indium hydroxide catalyst by feeding the copper-indium composite catalyst in batches.
Further, the preparation method of the copper-indium composite catalyst specifically comprises the following steps:
(1) weighing raw materials of anhydrous indium chloride and copper chloride dihydrate, placing the raw materials in a container, adding deionized water, stirring for 3-4 min at normal temperature, and dissolving to obtain a mixed solution;
(2) adding 14M concentrated ammonia water into the mixed solution in the step (1), stirring for 2-3 min at normal temperature, and uniformly mixing;
(3) continuously dropwise adding a 1M sodium hydroxide solution into the mixed solution, and stirring at normal temperature for 10-15 min;
(4) finally, dropwise adding a hydrazine solution into the mixed solution, and stirring at normal temperature for 8-10 min to obtain Cu (OH)2Fully reduced to Cu2O, rapidly filtering the mixture;
(5) and (3) respectively cleaning and filtering the obtained material by using water and ethanol, and finally, transferring the material into a vacuum oven to dry for 24-30 h at the temperature of 60-70 ℃ to obtain the copper-indium composite catalyst.
Furthermore, the molar ratio of the anhydrous indium chloride to the copper chloride dihydrate in the step (1) is 1: 5-20.
Further, the volume ratio of the concentrated ammonia water added in the step (2) to the mixed solution is 1: 40.
Further, the volume ratio of the sodium hydroxide added in the step (3) to the mixed solution is 1: 10.
Further, the volume ratio of the hydrazine solution to the mixed solution added in the step (4) is 1: 100.
The invention also discloses the copper-indium composite catalyst prepared by the preparation method of the copper-indium composite catalyst.
The invention also discloses an application of the copper-indium composite catalyst in electrochemical reduction of carbon dioxide.
Further, the copper-indium composite catalyst is applied to electrochemical reduction of carbon dioxide, and the copper-indium composite catalyst is made into a working electrode.
Further, the method for manufacturing the copper-indium composite catalyst into the working electrode comprises the following steps:
s1, weighing the copper-indium composite catalyst, and dispersing the copper-indium composite catalyst in a dispersion liquid consisting of 20 mu Lnafion, 240 mu L water and 240 mu L ethanol;
s2, ultrasonically dispersing the slurry prepared in the step S1 for at least 1 hour;
and S3, dispersing the slurry prepared in the step S2 on carbon paper, drying the carbon paper at the temperature of 60-70 ℃ to prepare a working electrode, and then carrying out electrocatalytic reduction reaction on carbon dioxide by using a traditional three-electrode system.
Compared with the prior art, the invention has the beneficial effects that:
(1) the preparation method of the copper-indium composite catalyst provided by the invention adopts a coprecipitation method for the first time, firstly, a complex containing copper and indium is precipitated into hydroxide, and then, copper hydroxide is further reduced into cuprous oxide, and finally, the novel copper-indium composite catalyst is prepared; the method is carried out at normal temperature, and has the advantages of simple preparation conditions, low energy consumption, low cost and great application potential;
(2) in the copper-indium composite catalyst prepared by the invention, indium hydroxide in (OH) is utilized3The copper-based catalyst is doped, so that the specific surface area of the copper-indium composite catalyst is obviously improved compared with that of pure cuprous oxide, and the method is more favorable for CO2The adsorption of molecules on the surface of the composite material can provide more reactive sites; in another aspect, the catalyst prepared from the present invention is doped with indium hydroxide in (OH)3Then, compared with pure cuprous oxide, the catalyst has an inhibiting effect on hydrogen evolution in the electrocatalytic reduction reaction of carbon dioxide;
(3) the preparation method limits the anhydrous indium chloride InCl3With copper chloride dihydrate CuCl2.2H2The molar ratio of O is 1: 5-20, and the use of N is limited2H4The reduction reaction time is 8-10 min, and anhydrous indium chloride InCl can be avoided3With copper chloride dihydrate CuCl2.2H2The molar ratio of O is too large or too small, which causes the problem of poor product selectivity and simultaneously avoids using N2H4The cuprous oxide is easy to be reduced into a Cu simple substance if the reduction reaction time is too long, and the reduction of the material is incomplete if the reaction time is too short.
Drawings
Fig. 1 is an X-ray powder diffraction pattern (XRD) of pure cuprous oxide catalysts, copper indium composite catalyst samples 1 to 5, respectively prepared according to the methods of examples 1 to 4 of the present invention and comparative example 1;
fig. 2 is a tafel plot of pure cuprous oxide and copper indium composite catalyst prepared according to example 2 of the present invention and sample 5 prepared according to comparative example 1.
Detailed Description
In order to facilitate understanding of the present invention, the technical solutions of the present invention will be further described with reference to the following detailed description and the accompanying drawings, but the present invention is not limited thereto.
Example 1
A preparation method of a copper-indium composite catalyst specifically comprises the following steps:
(1) weighing anhydrous indium chloride and copper chloride dihydrate with the raw material molar ratio of 1:5, wherein the anhydrous indium chloride InCl30.221 g of CuCl, copper chloride dihydrate2·2H2O0.852 g, placing the mixture into a container, adding 100mL of deionized water, stirring the mixture for 3min at the rotation speed of 400r/min under the normal temperature condition, and dissolving the mixture to obtain a mixed solution;
(2) adding 2.5mL of concentrated ammonia water with the concentration of 14M into the mixed solution in the step (1), stirring for 2min at the normal temperature at the rotating speed of 800r/min, and uniformly mixing;
(3) continuously dropwise adding 10mL of 1M sodium hydroxide solution into the mixed solution, and stirring at normal temperature at the rotating speed of 800r/min for 10 min;
(4) finally, 1mL of hydrazine solution is dripped into the mixed solution, and the mixed solution is stirred for 8min at the normal temperature at the rotating speed of 800r/min, so that Cu (OH)2Fully reduced to Cu2O, rapidly filtering the mixture;
(5) the materials obtained by washing and filtering with water and ethanol respectively are finally transferred into a vacuum oven to be dried for 24 hours at the temperature of 60 ℃, and the copper-indium composite catalyst is obtained and is taken as a sample 1.
Example 2
A preparation method of a copper-indium composite catalyst specifically comprises the following steps:
(1) weighing anhydrous indium chloride and copper chloride dihydrate with the raw material molar ratio of 1:10, wherein the anhydrous indium chloride InCl30.111 g of CuCl, copper chloride dihydrate2·2H2O0.852 g, placing in a container, adding 100mL of deionized water, stirring at the rotation speed of 400r/min for 4min at normal temperature, dissolving, and mixingA solution;
(2) adding 2.5mL of concentrated ammonia water with the concentration of 14M into the mixed solution in the step (1), stirring for 3min at the normal temperature at the rotating speed of 800r/min, and uniformly mixing;
(3) continuously dropwise adding 10mL of 1M sodium hydroxide solution into the mixed solution, and stirring at normal temperature at the rotating speed of 800r/min for 15 min;
(4) finally, 1mL of hydrazine solution is dripped into the mixed solution, and the mixed solution is stirred for 10min at the normal temperature at the rotating speed of 800r/min, so that Cu (OH)2Fully reduced to Cu2O, rapidly filtering the mixture;
(5) the materials obtained by filtering were washed with water and ethanol, respectively, and finally transferred to a vacuum oven to be dried for 30 hours at 70 ℃ to obtain a copper-indium composite catalyst, which is sample 2.
Example 3
A preparation method of a copper-indium composite catalyst specifically comprises the following steps:
(1) weighing anhydrous indium chloride and copper chloride dihydrate with the raw material molar ratio of 1:20, wherein the anhydrous indium chloride InCl30.055 g of CuCl, copper chloride dihydrate2·2H2O0.852 g, placing the mixture into a container, adding 100mL of deionized water, stirring the mixture for 3min at the rotation speed of 400r/min under the normal temperature condition, and dissolving the mixture to obtain a mixed solution;
(2) adding 2.5mL of concentrated ammonia water with the concentration of 14M into the mixed solution in the step (1), stirring for 3min at the normal temperature at the rotating speed of 800r/min, and uniformly mixing;
(3) continuously dropwise adding 12mL of 1M sodium hydroxide solution into the mixed solution, and stirring at normal temperature at the rotating speed of 800r/min for 15 min;
(4) finally, 1mL of hydrazine solution is dripped into the mixed solution, and the mixed solution is stirred for 9min at the normal temperature at the rotating speed of 800r/min, so that Cu (OH)2Fully reduced to Cu2O, rapidly filtering the mixture;
(5) the materials obtained by washing and filtering with water and ethanol respectively are finally transferred into a vacuum oven to be dried for 26 hours at 65 ℃, and the copper-indium composite catalyst is obtained and is a sample 3.
Example 4
A preparation method of a copper-indium composite catalyst specifically comprises the following steps:
(1) weighing anhydrous indium chloride and copper chloride dihydrate with the raw material molar ratio of 1:5, wherein the anhydrous indium chloride InCl30.221 g of CuCl, copper chloride dihydrate2·2H2O0.852 g, placing the mixture into a container, adding 100mL of deionized water, stirring the mixture for 4min at the rotation speed of 400r/min under the normal temperature condition, and dissolving the mixture to obtain a mixed solution;
(2) adding 2.5mL of concentrated ammonia water with the concentration of 14M into the mixed solution in the step (1), stirring for 2min at the normal temperature at the rotating speed of 800r/min, and uniformly mixing;
(3) continuously dropwise adding 12mL of 1M sodium hydroxide solution into the mixed solution, and stirring for 14min at normal temperature at the rotating speed of 800 r/min;
(4) finally, 1mL of hydrazine solution is dripped into the mixed solution, and the mixed solution is stirred for 8min at the normal temperature at the rotating speed of 800r/min, so that Cu (OH)2Fully reduced to Cu2O, rapidly filtering the mixture;
(5) the materials obtained by washing and filtering with water and ethanol respectively are finally transferred into a vacuum oven to be dried for 24 hours at the temperature of 60 ℃, and the copper-indium composite catalyst is obtained and is a sample 4.
Example 5
The copper-indium composite catalyst prepared by the method of any one of embodiments 1 to 4 is applied to electrochemical reduction of carbon dioxide, and the prepared copper-indium composite catalyst is prepared into a working electrode, wherein the preparation method of the working electrode comprises the following steps:
s1, weighing and dispersing 5mg of the copper-indium composite catalyst prepared in the embodiments 1 to 4 in 500 mu L of dispersion liquid to form slurry, wherein the dispersion liquid is composed of 20 mu L of nafion, 240 mu L of water and 240 mu L of ethanol;
s2, ultrasonically dispersing the slurry prepared in the step S1 for at least 1 hour;
s3, taking 80 mu L of the slurry prepared in the step S2 and dispersing in 1 x 1.5cm2Drying the carbon paper at 60 ℃ to prepare the working electrode.
Comparative example 1
The samples in this comparative example were prepared as in example 1, but without the addition of InCl3Thus, sample 5 was obtained.
Comparative example 2
This comparative example is a comparative example to example 5, in which a blank carbon paper was used as the working electrode.
And (3) performance testing:
1. XRD measurement of samples 1 to 4 prepared according to examples 1 to 4 of the present invention and sample 5 prepared according to comparative example 1
Referring to FIG. 1, the diffraction pattern of the composite sample is shown with the exception of Cu2In addition to the characteristic diffraction peak of O, in (OH)3And in (OH)3The intensity of one distinct diffraction peak (22.3 ℃) of (a) increases with the increase of its content in the sample, and only Cu is observed in sample 52And the characteristic diffraction peak of O proves that the copper-indium composite catalyst is successfully prepared by using the method.
2. The pore volume, pore diameter and specific surface area of samples 1 to 4 prepared according to examples 1 to 4 of the present invention and sample 5 prepared according to comparative example 1 were measured, and the specific results are shown in the following table:
at the same time, the sample 5 was measured to obtain a pore volume of 0.07m3·g-1Average pore diameter of 24.42nm and specific surface area of 12.11m2·g-1From the data, it can be seen that the specific surface area and pore volume parameters of sample 5 are lower than those of samples 1-4, indicating that the sample is added with anhydrous indium chloride InCl3The specific surface area and the micropore volume of the post catalyst are improved, which is more beneficial to CO2The adsorption of molecules on the surface of the composite material can provide more reactive sites.
3. Electrocatalytic reduction of carbon dioxide by CO for samples 1 to 4 prepared according to examples 1 to 4 of the present invention and sample 5 prepared according to comparative example 12Activity assay
The activity test conditions in this experimental example were: using a three-electrode system with a platinum sheet as the counter electrode and Ag/AgCl as the reference electrode, anIn the working electrode prepared by the preparation method of the embodiment 5 of the invention, the electrolyte is KHCO with the concentration of 0.1M3Applying the same constant voltage of-0.8V to the solution;
the atmosphere in the reactor is CO2The gas phase product is detected by using gas chromatography, the liquid phase product is detected by using ion chromatography, and the test results are shown in the following table:
it can be seen that the yield of selectively producing CO of samples 1 to 4 prepared according to the invention under the same working electrode preparation conditions and activity test conditions is significantly greater than that of sample 5, and the yield of CO is significantly greater than that of H in the reaction2The generation plays a role in obvious inhibition, so the selectivity of the copper-indium composite catalyst prepared based on the invention is better than that of the catalyst in the comparative example.
4. Tafel plot determination of sample 2 prepared according to the invention, example 2, and sample 5 prepared according to comparative example 1
The curve test conditions are as follows: a three-electrode system is adopted, a platinum sheet is used as a counter electrode, and Ag/AgCl is used as a reference electrode; the electrolyte is KHCO with a concentration of 0.1M3A solution; the atmosphere in the reactor is CO2(ii) a The overpotential of the hydrogen evolution reaction of the system is corrected to obtain a figure 2, and as shown in the figure 2, the Tafel slope of a sample 5 (pure cuprous oxide) is smaller than that of a sample 2 (copper-indium composite catalyst), namely the copper-indium composite catalyst prepared based on the method is less prone to hydrogen evolution reaction.
5. CO for sample 2 prepared according to the invention example 2 to prepare a working electrode and the blank carbon paper of comparative example 2 to prepare a working electrode2And Ar electrocatalytic reduction Activity test
The activity of the catalyst is tested under the same test conditions, and CO is respectively adopted2Comparing the yields of the products after the carbon paper samples of 1cm x 1.5cm, to which the sample 2 was added and to which the sample was not added, participated in the reduction reaction of carbon dioxide under a bias of-0.8V in both atmospheres with argon atmosphere, the results were as follows:
as can be seen from the table, neither the working electrode to which the sample was added under argon atmosphere nor the blank working electrode had C-containing products, and CO was added2Under the atmosphere, when the working electrode is only carbon paper, almost no C product is generated, so that the detected product can be preliminarily determined to be derived from CO2Catalytic conversion of the gas.
The above description is only an embodiment of the present invention, and not intended to limit the scope of the present invention, and all modifications of equivalent structures and equivalent processes, which are made by the present specification, or directly or indirectly applied to other related technical fields, are included in the scope of the present invention.
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