Preparation and application of In-Cu2O catalyst with electro-catalytic property
By preparing the In-Cu2O catalyst, the problem of poor selectivity of catalyst products in the prior art was solved, efficient catalytic carbon dioxide reduction was achieved, formic acid production performance was significantly improved, and the catalyst had good stability and low toxicity.
Patent Information
- Application Number
- CN202411327871.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-09-23
- Publication Date
- 2025-04-25
AI Technical Summary
In the prior art, during the catalytic carbon dioxide reduction (ECO2RR), the product selectivity of the catalyst is poor, resulting in low yields of each product, making it difficult to effectively solve energy and environmental problems.
Using the In-Cu2O catalyst, NaOH solution was formed by adding NaOH particles and deionized water to a round bottom flask, followed by adding CuCl2, In(NO3)3 and glucose, stirring and heat treatment were performed to obtain an In-Cu2O catalyst with electrocatalytic properties.
It has achieved good electrocatalytic reduction of carbon dioxide under -1.0V vs.RHE, and its formic acid production performance is as high as 80%. It also has the characteristics of stable structure, strong adsorption capacity, low dosage, and non-toxicity.
Smart Images
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Abstract
Description
Technical Field
[0001] The present invention belongs to the technical field related to electrocatalysis, and in particular relates to an In-Cu2O catalyst with electrocatalytic performance, and a preparation method and application thereof. Background Art
[0002] The energy crisis is a complex issue, behind which lies the contradiction between the growing global energy demand and resource shortage and environmental pollution. At the same time, with the gradual depletion of oil resources, countries around the world are looking for alternative energy sources. In addition, the use of alternative energy may also bring new environmental pollution problems, such as air pollution, water pollution and soil pollution. In view of energy and climate issues, in addition to focusing on energy conservation and emission reduction, strengthening energy conservation, increasing environmental protection and improving energy structure, the development of new carbon capture, storage, utilization and conversion technologies is also of great strategic significance.
[0003] Since the Industrial Revolution, the combustion and use of fossil energy has produced a large amount of carbon dioxide (CO2), which has enhanced the "greenhouse effect" and caused many adverse consequences such as rainwater acidification and sea level rise, which has been troubling countries around the world. In this context, my country has made requirements for long-term CO2 management in my country. Therefore, electrocatalytic carbon dioxide reduction (ECO2RR) technology has received widespread attention.
[0004] Using electrochemical catalytic reduction of CO2 technology to reduce greenhouse gas CO2 into chemicals or fuels, such as CO, formic acid, ethanol, methane, ethane, etc., can provide raw materials for the production of chemical products while alleviating environmental pressure. In addition, with the increasing global energy shortage and the continuous growth of energy demand, research on ECO2RR has attracted more and more attention.
[0005] Cu has a more suitable binding ability to the *CO intermediate, so it is easier for Cu to form *COH or *CHO intermediates through further reaction and promote CC coupling, so that subsequent reactions can proceed smoothly, and it is also easier to generate multi-electron transfer products. Because of Cu's unique ability to catalyze the production of multiple products, Cu-based catalysts are now widely used in the field of ECO2RR. However, In has a weak binding ability to the *COOH intermediate and has a good effect on the catalysis of formic acid. Combining In with Cu can combine the advantages of the two metals and optimize the performance of catalyzing formic acid.
[0006] Copper chloride and indium chloride are both important metal salts with good electrical and chemical properties, and have good electrocatalytic reduction performance for CO2 under electrocatalytic conditions. Although copper itself can produce a variety of products, the product selectivity is poor, making the yield of each product not very high. It is necessary to introduce other elements to transform it in order to improve its catalytic performance for CO2 and its selectivity for products. This is also the current research focus. Summary of the invention
[0007] The purpose of the embodiments of the present invention is to provide an In-Cu2O catalyst with electrocatalytic performance and a preparation method and application thereof, in order to solve the problems existing in the prior art pointed out in the background technology.
[0008] The embodiment of the present invention is implemented as follows: a method for preparing an In-Cu2O catalyst with electrocatalytic performance comprises the following steps: adding NaOH particles and deionized water to a round-bottom flask to form a NaOH solution. Subsequently, a certain amount of CuCl2, In(NO3)3 and glucose are added to a sample bottle in sequence. After continuous stirring for 5 minutes, the sample bottle is placed in a 70°C oil bath and vigorously stirred for 4 minutes. The precipitate obtained by centrifugation is rinsed with deionized water and vacuum dried at room temperature to obtain an In-Cu2O catalyst with electrocatalytic performance.
[0009] As another preferred embodiment of the present invention, the mass ratio of cupric chloride dihydrate to indium chloride is 85:(11-44).
[0010] As another preferred embodiment of the present invention, the stirring time for preparing the In-Cu2O catalyst with electrocatalytic performance is 2 to 10 minutes, and the oil bath time for preparing the In-Cu2O catalyst with electrocatalytic performance is 2 to 6 minutes.
[0011] As another preferred embodiment of the present invention, during the centrifugation process, the sample is placed in a centrifuge, the speed is controlled to rise to 6000-8000 rpm at a rate of 10 rpm / s, and centrifuged at 6000-8000 rpm for 5-10 minutes.
[0012] As another preferred solution of the embodiment of the present invention, during the drying process, the product is placed in a vacuum drying oven at 60-80° C. for 6-8 hours.
[0013] As another preferred embodiment of the present invention, the molar ratio of copper chloride dihydrate to indium chloride is 10:(1-4).
[0014] Another object of an embodiment of the present invention is to provide an In-Cu2O catalyst having electrocatalytic performance prepared by the above method.
[0015] As another preferred embodiment of the present invention, the diameter of the In-Cu2O catalyst is 1 μm to 2 μm, and it is a nanoparticle with stable structure, good dispersion performance and uniform particle size, and has good performance of electrocatalytic reduction of carbon dioxide.
[0016] Another object of an embodiment of the present invention is to provide an application of an In-Cu2O catalyst having electrocatalytic performance prepared by the above method in reducing carbon dioxide.
[0017] The In-Cu2O catalyst of the present invention has the characteristics of stable structure and strong adsorption capacity, which is conducive to the transmission of electrons; the preparation method of the present invention is simple, low in cost, and high in electrocatalytic efficiency. The prepared In-Cu2O catalyst has good electrocatalytic reduction performance of carbon dioxide at -1.0V vs.RHE, and the formic acid production performance is as high as 80%. In addition, the In-Cu2O catalyst with electrocatalytic performance of the present invention also has the characteristics of small dosage and non-toxicity. BRIEF DESCRIPTION OF THE DRAWINGS
[0018] Figure 1 is the XRD spectrum of In-Cu2O catalyst;
[0019] Figure 2 is the SEM image of In-Cu2O catalyst;
[0020] Figure 3 TEM and EDX images of In-Cu2O catalyst;
[0021] Figure 4 This is the electrochemical test diagram of In-Cu2O catalyst. DETAILED DESCRIPTION
[0022] In order to make the purpose, technical solution and advantages of the present invention more clearly understood, the present invention is further described in detail below in conjunction with the embodiments. It should be understood that the specific embodiments described herein are only used to explain the present invention and are not used to limit the present invention.
[0023] The specific implementation of the present invention is described in detail below in conjunction with specific embodiments.
[0024] Example 1
[0025] This embodiment provides an In-Cu2O catalyst having the performance of electrocatalytic reduction of carbon dioxide, and a preparation method thereof, comprising the following steps:
[0026] (1) While stirring 10 ml of 0.6 M NaOH solution, add 10 ml of 0.1 M copper chloride solution, 10 ml of 0.02 M indium chloride solution, and 10 ml of 0.07 M glucose solution. The solution changes from transparent to light blue. Stir continuously for 5 min.
[0027] (2) Place the thoroughly stirred solution in a 70°C oil bath and stir vigorously for 4 min. The solution changes from light blue to orange.
[0028] (3) The obtained solution was centrifuged three times with deionized water, and the centrifuge parameters were set to 6000 rpm. After centrifugation, the solution was placed in a 60° C. vacuum oven and dried for 6 h to obtain an In-Cu2O catalyst with electrocatalytic reduction performance of carbon dioxide.
[0029] Example 2
[0030] This embodiment provides an In-Cu2O catalyst having the performance of electrocatalytic reduction of carbon dioxide, and a preparation method thereof, comprising the following steps:
[0031] (1) While stirring 10 ml of 0.6 M NaOH solution, add 10 ml of 0.1 M copper chloride solution, 10 ml of 0.01 M indium chloride solution, and 10 ml of 0.07 M glucose solution. The solution changes from transparent to light blue and is stirred for 4 min.
[0032] (2) Place the thoroughly stirred solution in a 70°C oil bath and stir vigorously for 4 min. The solution changes from light blue to orange.
[0033] (3) The obtained solution was centrifuged three times with deionized water, and the centrifuge parameters were set to 6000 rpm. After centrifugation, the solution was placed in a vacuum oven at 80° C. and dried for 7 h, thereby obtaining an In-Cu2O catalyst with electrocatalytic reduction performance of carbon dioxide.
[0034] Example 3
[0035] This embodiment provides an In-Cu2O catalyst having the performance of electrocatalytic reduction of carbon dioxide, and a preparation method thereof, comprising the following steps:
[0036] (1) While stirring 10 ml of 0.6 M NaOH solution, add 10 ml of 0.1 M copper chloride solution, 10 ml of 0.03 M indium chloride solution, and 10 ml of 0.07 M glucose solution. The solution changes from transparent to light blue. Stir continuously for 10 min.
[0037] (2) Place the thoroughly stirred solution in a 70°C oil bath and stir vigorously for 2 min. The solution changes from light blue to orange.
[0038] (3) The resulting solution was centrifuged three times with deionized water, with the centrifuge parameter set to 8000 rpm. After centrifugation, the solution was placed in a vacuum oven at 70° C. and dried for 6 h, thereby obtaining an In-Cu2O catalyst having the performance of electrocatalytic reduction of carbon dioxide.
[0039] Example 4
[0040] This embodiment provides an In-Cu2O catalyst having the performance of electrocatalytic reduction of carbon dioxide, and a preparation method thereof, comprising the following steps:
[0041] (1) While stirring 10 ml of 0.6 M NaOH solution, add 10 ml of 0.1 M copper chloride solution, 10 ml of 0.04 M indium chloride solution, and 10 ml of 0.07 M glucose solution. The solution changes from transparent to light blue. Stir continuously for 2 min.
[0042] (2) Place the thoroughly stirred solution in a 70°C oil bath and stir vigorously for 6 min. The solution changes from light blue to orange.
[0043] (3) The obtained solution was centrifuged three times with deionized water, and the centrifuge parameters were set to 8000 rpm. After centrifugation, the solution was placed in a vacuum oven at 60° C. and dried for 8 h, thereby obtaining an In-Cu2O catalyst with electrocatalytic reduction performance of carbon dioxide.
[0044] Example 5
[0045] This embodiment provides an In-Cu2O catalyst having the performance of electrocatalytic reduction of carbon dioxide, and a preparation method thereof, comprising the following steps:
[0046] (1) While stirring 10 ml of 0.6 M NaOH solution, add 10 ml of 0.1 M copper chloride solution, 10 ml of 0.02 M indium chloride solution, and 10 ml of 0.07 M glucose solution. The solution changes from transparent to light blue and is stirred for 8 min.
[0047] (2) Place the thoroughly stirred solution in a 70°C oil bath and stir vigorously for 3 min. The solution changes from light blue to orange.
[0048] (3) The obtained solution was centrifuged three times with deionized water, and the centrifuge parameters were set to 7000 rpm. After centrifugation, the solution was placed in a 60° C. vacuum oven and dried for 7 h, and then an In-Cu2O catalyst with electrocatalytic reduction of carbon dioxide was obtained.
[0049] Example 6
[0050] This embodiment provides an In-Cu2O catalyst having the performance of electrocatalytic reduction of carbon dioxide, and a preparation method thereof, comprising the following steps:
[0051] (1) While stirring 10 ml of 0.6 M NaOH solution, add 10 ml of 0.1 M copper chloride solution, 10 ml of 0.04 M indium chloride solution, and 10 ml of 0.07 M glucose solution. The solution changes from transparent to light blue and is stirred for 8 min.
[0052] (2) Place the thoroughly stirred solution in a 70°C oil bath and stir vigorously for 6 min. The solution changes from light blue to orange.
[0053] (3) The resulting solution was centrifuged three times with deionized water, with the centrifuge parameter set to 8000 rpm. After centrifugation, the solution was placed in a 60° C. vacuum oven and dried for 7 h, thereby obtaining an In-Cu2O catalyst having the performance of electrocatalytic reduction of carbon dioxide.
[0054] Example 7
[0055] This embodiment provides an In-Cu2O catalyst having the performance of electrocatalytic reduction of carbon dioxide, and a preparation method thereof, comprising the following steps:
[0056] (1) While stirring 10 ml of 0.6 M NaOH solution, add 10 ml of 0.1 M copper chloride solution, 10 ml of 0.01 M indium chloride solution, and 10 ml of 0.07 M glucose solution. The solution changes from transparent to light blue and is stirred for 9 min.
[0057] (2) Place the thoroughly stirred solution in a 70°C oil bath and stir vigorously for 5 min. The solution changes from light blue to orange.
[0058] (3) The obtained solution was centrifuged three times with deionized water, and the centrifuge parameters were set to 6000 rpm. After centrifugation, the solution was placed in a 60° C. vacuum oven and dried for 6 h to obtain an In-Cu2O catalyst with electrocatalytic reduction performance of carbon dioxide.
[0059] Example 8
[0060] This embodiment provides an In-Cu2O catalyst having the performance of electrocatalytic reduction of carbon dioxide, and a preparation method thereof, comprising the following steps:
[0061] (1) While stirring 10 ml of 0.6 M NaOH solution, add 10 ml of 0.1 M copper chloride solution, 10 ml of 0.03 M indium chloride solution, and 10 ml of 0.07 M glucose solution. The solution changes from transparent to light blue and is stirred for 5 min.
[0062] (2) Place the thoroughly stirred solution in a 70°C oil bath and stir vigorously for 7 min. The solution changes from light blue to orange.
[0063] (3) The obtained solution was centrifuged three times with deionized water, and the centrifuge parameters were set to 6000 rpm. After centrifugation, the solution was placed in a vacuum oven at 80° C. and dried for 7 h, thereby obtaining an In-Cu2O catalyst with electrocatalytic reduction performance of carbon dioxide.
[0064] Example 9
[0065] This embodiment provides an In-Cu2O catalyst having the performance of electrocatalytic reduction of carbon dioxide, and a preparation method thereof, comprising the following steps:
[0066] (1) While stirring 10 ml of 0.6 M NaOH solution, add 10 ml of 0.1 M copper chloride solution, 10 ml of 0.02 M indium chloride solution, and 10 ml of 0.07 M glucose solution. The solution changes from transparent to light blue. Stir continuously for 5 min.
[0067] (2) Place the thoroughly stirred solution in a 70°C oil bath and stir vigorously for 3 min. The solution changes from light blue to orange.
[0068] (3) The obtained solution was centrifuged three times with deionized water, and the centrifuge parameters were set to 7000 rpm. After centrifugation, the solution was placed in a vacuum oven at 70° C. and dried for 6 h, thereby obtaining an In-Cu2O catalyst with electrocatalytic reduction performance of carbon dioxide.
[0069] Example 10
[0070] This embodiment provides an In-Cu2O catalyst having the performance of electrocatalytic reduction of carbon dioxide, and a preparation method thereof, comprising the following steps:
[0071] (1) While stirring 10 ml of 0.6 M NaOH solution, add 10 ml of 0.1 M copper chloride solution, 10 ml of 0.02 M indium chloride solution, and 10 ml of 0.07 M glucose solution. The solution changes from transparent to light blue. Stir continuously for 5 min.
[0072] (2) Place the thoroughly stirred solution in a 70°C oil bath and stir vigorously for 4 min. The solution changes from light blue to orange.
[0073] (3) The obtained solution was centrifuged three times with deionized water, and the centrifuge parameters were set to 8000 rpm. After centrifugation, the solution was placed in a vacuum oven at 60° C. and dried for 8 h, thereby obtaining an In-Cu2O catalyst with electrocatalytic reduction performance of carbon dioxide.
Claims
1. A method for preparing an In-Cu2O catalyst having electrocatalytic performance, characterized in that: The following steps are involved: Copper chloride dihydrate, indium chloride and glucose are uniformly dispersed in a sodium hydroxide solution. After continuous stirring, the solution is placed in an oil bath, vigorously stirred, and then washed, centrifuged and dried to obtain the final In-Cu2O catalyst.
2. The method for preparing the In-Cu2O catalyst having electrocatalytic performance according to claim 1, characterized in that: The mass ratio of copper chloride dihydrate to indium chloride is 85:(11-44).
3. The method for preparing the In-Cu2O catalyst having electrocatalytic performance according to claim 1, characterized in that: The stirring time for preparing In-Cu2O is 2 to 10 minutes, and the oil bath time for preparing In-Cu2O is 2 to 6 minutes.
4. The method for preparing the In-Cu2O catalyst having electrocatalytic performance according to claim 1, characterized in that: During the centrifugal treatment, the sample is placed in a centrifuge, the speed is controlled to rise to 6000-8000 rpm at a rate of 10 rpm / s, and centrifuged at 6000-8000 rpm for 5-10 minutes.
5. The method for preparing the In-Cu2O catalyst having electrocatalytic performance according to claim 1, characterized in that: During the drying process, the mixture is placed in a vacuum drying oven at 60-80° C. for 6-8 hours.
6. The method for preparing the In-Cu2O catalyst having electrocatalytic performance according to claim 1, characterized in that: The molar ratio of copper chloride dihydrate to indium chloride is 10:(1-4).
7. The method for preparing the In-Cu2O catalyst having electrocatalytic performance according to claim 1, characterized in that: The copper chloride is copper chloride dihydrate.
8. An In-Cu2O catalyst having electrocatalytic performance prepared by the method according to any one of claims 1 to 7.
9. The In-Cu2O catalyst with electrocatalytic performance according to claim 8, characterized in that: The diameter of the In-Cu2O catalyst with electrocatalytic performance is 1 μm to 2 μm.
10. Use of the In-Cu2O catalyst with electrocatalytic performance as claimed in claim 8 or 9 in reducing carbon dioxide.