Preparation of Ru / Fe3O4-Fe3C heterostructured nanosheets / nitrogen-doped carbon and their electrocatalytic applications
By preparing Ru/Fe3O4-Fe3C heterostructured nanosheets/nitrogen-doped carbon, the problem of poor conductivity of Fe-based materials was solved, and a highly efficient electrocatalytic hydrogen evolution reaction was achieved, promoting the green development of the water electrolysis industry.
Patent Information
- Application Number
- CN202211673271.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2022-12-26
- Publication Date
- 2026-02-10
- Estimated Expiration
- 2042-12-26
AI Technical Summary
Existing Fe-based materials exhibit poor conductivity in electrocatalytic water reduction reactions, limiting their application in electrocatalytic hydrogen evolution reactions. Furthermore, the production of hydrogen from traditional fossil fuels hinders the development of green chemistry.
Ru/Fe3O4-Fe3C heterostructured nanosheets/nitrogen-doped carbon were prepared by heating a mixture of Fe2O3, dopamine, melamine and RuCl3 in an Ar atmosphere to form Ru/Fe3O4-Fe3C heterostructured nanosheets/nitrogen-doped carbon. Ru was loaded on the nitrogen-doped carbon to enhance the tolerance of alkaline electrolyte.
A current density of 10 mA/cm² was achieved during the electrocatalytic hydrogen evolution reaction in 0.5 mol/L H₂SO₄ electrolyte, reducing the overpotential and promoting the development of the water electrolysis industry.
Smart Images
Figure HDA0004017032760000011
Abstract
Description
Technical Field
[0001] This invention relates to the preparation of Ru / Fe3O4-Fe3C heterostructure nanosheets / nitrogen-doped carbon and their electrocatalytic applications, belonging to the field of materials preparation and application. Background Technology
[0002] The extensive use of fossil fuels has exacerbated the emission of harmful gases, causing serious environmental problems. The utilization of clean and renewable energy sources has attracted widespread attention. Among these efforts, the production of hydrogen through water splitting has become a hot topic. Hydrogen is an excellent energy carrier, and the electrolysis of water to produce hydrogen can effectively improve energy efficiency. The current research focus is on finding catalysts for the electrocatalytic reduction of water to produce hydrogen, ensuring their high activity and stability in achieving the hydrogen evolution reaction.
[0003] Among various substances, Fe-based materials are abundant in the Earth's crust and have low cost, but their poor conductivity limits their widespread application in electrocatalytic water reduction reactions. Researchers are using various methods to construct Fe-based materials with faster electron transport, thereby achieving highly active electrocatalytic reactions. For example, Zai et al. synthesized Fe3C / PG nanoparticles using a template method with FeCl3·6H2O, CH3OH, oleic acid, etc., and applied them to the electrocatalytic oxygen evolution reaction, achieving 10 mA / cm² at 299 mV. 2 (Chemical Communications, 2018, 54, 3158). Lei et al. combined FeCl2·4H2O, CO(NH2)2, and C6H... 12 O6, C 18 H 29 NaO3S and foamed Ni were mixed and hydrothermally heated at 120℃ for 12 h to obtain Fe3C / NF. The Fe3C / NF was then subjected to an electrocatalytic oxygen evolution reaction in 1M KOH, achieving a voltage of 262mV and a current of 10mA / cm. 2 (International Journal of Hydrogen Energy, 2019, 44, 16507-16515). Tsiakaras et al. used resorcinol, formaldehyde, (NH4)2CO3, and FeCl3, hydrothermally treated at 100℃ for 24 h, and then calcined the product at 910℃ for 3 h in an inert atmosphere to obtain Fe3O4-300@HPNC, which exhibited Pt-like activity in the electrocatalytic oxygen reduction reaction (Electrochimica Acta, 2018, 260, 264-273). Rojas et al. mixed isophthalonitrile, ZnCl2, and ferric acetate, treated at 400℃ for 46 h in an inert atmosphere, and then treated at 900℃ for 30 min in an NH3 / N2 atmosphere to obtain a Fe / N / C catalyst, which exhibited excellent electrocatalytic oxygen reduction performance (Journal of Power Sources, 2021, 490, 229487).
[0004] Traditional methods of hydrogen production from fossil fuels have hindered the development of green chemistry. By constructing Ru / Fe3O4-Fe3C heterostructured nanosheets / nitrogen-doped carbon through electrocatalytic water splitting, the tolerance of alkaline electrolytes is enhanced, effectively reducing overpotential and thus promoting the development of the water electrolysis industry. Summary of the Invention:
[0005] This invention aims to provide the preparation of Ru / Fe3O4-Fe3C heterostructure nanosheets / nitrogen-doped carbon and their electrocatalytic applications.
[0006] Based on the above objectives, the technical solution involved in this invention is as follows:
[0007] (1) Preparation of Ru / Fe3O4-Fe3C heterostructure nanosheets / nitrogen-doped carbon: 29mg-39mg of Fe2O3 nanosheets (JCPDS#36-0664) with a particle size of 21-44nm, 142-156mg of tris(hydroxymethyl)aminomethane, and 49-69mg of dopamine hydrochloride were dispersed in 40mL of ethanol and 40mL of water. After drying, it was mixed with 146-198mg of melamine and 11-23mg of RuCl3 and heated at 470-560℃ for 1-4h in an Ar atmosphere to obtain Ru / Fe3O4-Fe3C heterostructure nanosheets / nitrogen-doped carbon. In the above preparation method, the Ru / Fe3O4-Fe3C heterostructure nanosheets / nitrogen-doped carbon nanosheets encapsulate the Fe3O4-Fe3C heterostructure nanosheets, with Ru loaded on the nitrogen-doped carbon. The Fe3O4 crystal phase belongs to standard card JCPDS#19-0629, and the Fe3C crystal phase belongs to standard card JCPDS#35-0772.
[0008] (2) Application of Ru / Fe3O4-Fe3C heterostructured nanosheets / nitrogen-doped carbon prepared by the above preparation method in electrocatalytic reactions; in 0.5 mol / L H2SO4 electrolyte, the current density of the electrocatalytic hydrogen evolution reaction at 130-160 mV is 10 mA / cm². 2 .
[0009] The present invention has the following advantages:
[0010] 1) A new synthetic route for Ru / Fe3O4-Fe3C heterostructure nanosheets / nitrogen-doped carbon is provided.
[0011] 2) Ru / Fe3O4-Fe3C heterostructure nanosheets / nitrogen-doped carbon can effectively electrocatalyze hydrogen evolution. Attached image description:
[0012] Figure 1The results are XRD (a), electron microscopy (bg), and elemental distributions of Ru (h), Fe (i), C (j), N (k), and O (l) for Ru / Fe3O4-Fe3C heterostructure nanosheets / nitrogen-doped carbon. Detailed Implementation
[0013] The following examples are used to further illustrate the present invention, but are not intended to limit the invention.
[0014] Example 1
[0015] Preparation of Ru / Fe3O4-Fe3C heterostructured nanosheets / nitrogen-doped carbon and its electrocatalytic application: 29 mg of Fe2O3 nanosheets (JCPDS#36-0664) with a particle size of 21-44 nm, 142 mg of tris(hydroxymethyl)aminomethane, and 49 mg of dopamine hydrochloride were dispersed in 40 mL of ethanol and 40 mL of water. After drying, the mixture was mixed with 146 mg of melamine and 11 mg of RuCl3 and heated at 470 °C for 1 h in an Ar atmosphere to obtain Ru / Fe3O4-Fe3C heterostructured nanosheets / nitrogen-doped carbon. The above preparation method involves encapsulating Fe3O4-Fe3C heterostructured nanosheets / nitrogen-doped carbon nanosheets with nitrogen-doped carbon nanosheets. Ru is loaded onto the nitrogen-doped carbon. The Fe3O4 crystal phase is classified under standard card JCPDS#19-0629, and the Fe3C crystal phase is classified under standard card JCPDS#35-0772. The application of Ru / Fe3O4-Fe3C heterostructured nanosheets / nitrogen-doped carbon in electrocatalytic reactions is also discussed. In a 0.5 mol / L H2SO4 electrolyte, the current density for the electrocatalytic hydrogen evolution reaction at 130 mV is 10 mA / cm². 2 .
[0016] Example 2
[0017] Preparation of Ru / Fe3O4-Fe3C heterostructured nanosheets / nitrogen-doped carbon and its electrocatalytic application: 39 mg of Fe2O3 nanosheets (JCPDS#36-0664) with a particle size of 21-44 nm, 156 mg of tris(hydroxymethyl)aminomethane, and 69 mg of dopamine hydrochloride were dispersed in 40 mL of ethanol and 40 mL of water. After drying, the mixture was mixed with 198 mg of melamine and 23 mg of RuCl3 and heated at 560 °C for 4 h in an Ar atmosphere to obtain Ru / Fe3O4-Fe3C heterostructured nanosheets / nitrogen-doped carbon. The above preparation method involves encapsulating Fe3O4-Fe3C heterostructured nanosheets / nitrogen-doped carbon nanosheets with nitrogen-doped carbon nanosheets. Ru is loaded onto the nitrogen-doped carbon. The Fe3O4 crystal phase is classified under standard card JCPDS#19-0629, and the Fe3C crystal phase is classified under standard card JCPDS#35-0772. The application of Ru / Fe3O4-Fe3C heterostructured nanosheets / nitrogen-doped carbon in electrocatalytic reactions is also discussed. In a 0.5 mol / L H2SO4 electrolyte, the current density for the electrocatalytic hydrogen evolution reaction at 160 mV is 10 mA / cm². 2 .
[0018] Example 3
[0019] Preparation of Ru / Fe3O4-Fe3C heterostructured nanosheets / nitrogen-doped carbon and their electrocatalytic application: 29 mg of Fe2O3 nanosheets (JCPDS#36-0664) with a particle size of 21-44 nm, 156 mg of tris(hydroxymethyl)aminomethane, and 69 mg of dopamine hydrochloride were dispersed in 40 mL of ethanol and 40 mL of water. After drying, the mixture was mixed with 146 mg of melamine and 23 mg of RuCl3 and heated at 500 °C for 2 h in an Ar atmosphere to obtain Ru / Fe3O4-Fe3C heterostructured nanosheets / nitrogen-doped carbon. The above preparation method involves encapsulating Fe3O4-Fe3C heterostructured nanosheets with nitrogen-doped carbon nanosheets in the Ru / Fe3O4-Fe3C heterostructured nanosheets / nitrogen-doped carbon structure. Ru is loaded onto the nitrogen-doped carbon. The Fe3O4 crystal phase is classified under standard card JCPDS#19-0629, and the Fe3C crystal phase is classified under standard card JCPDS#35-0772. The application of Ru / Fe3O4-Fe3C heterostructured nanosheets / nitrogen-doped carbon in electrocatalytic reactions is also discussed. In a 0.5 mol / L H2SO4 electrolyte, the current density for the electrocatalytic hydrogen evolution reaction at 140 mV is 10 mA / cm². 2 .
Claims
1. A method for preparing Ru / Fe3O4-Fe3C heterostructured nanosheets / nitrogen-doped carbon, characterized in that, Includes the following steps: 29-39 mg of Fe₂O₃ nanosheets, 142-156 mg of tris(hydroxymethyl)aminomethane, and 49-69 mg of dopamine hydrochloride were dispersed in 40 mL of ethanol and 40 mL of water. After drying, the mixture was combined with 146-198 mg of melamine and 11-23 mg of RuCl₃ and heated at 470-560 °C for 1-4 h in an Ar atmosphere to obtain Ru / Fe₃O₄-Fe₃C heterostructured nanosheets / nitrogen-doped carbon; the Fe₂O₃ nanosheets had a particle size of 21-44 mm. nm, the Fe2O3 nanosheet crystal phase belongs to standard card JCPDS#36-0664; the obtained Ru / Fe3O4-Fe3C heterostructure nanosheet / nitrogen-doped carbon nanosheets encapsulating Fe3O4-Fe3C heterostructure nanosheets, Ru is loaded on nitrogen-doped carbon, the Fe3O4 crystal phase belongs to standard card JCPDS#19-0629, and the Fe3C crystal phase belongs to standard card JCPDS#35-0772.
2. The application of Ru / Fe3O4-Fe3C heterostructured nanosheets / nitrogen-doped carbon prepared by the method described in claim 1 in electrocatalytic reactions; in 0.5 mol / L H2SO4 electrolyte, the current density for the electrocatalytic hydrogen evolution reaction at 130-160 mV is 10 mA / cm². 2 .