A catalyst based on biomass-based nitrogen and oxygen co-doped carbon material and a preparation method and use thereof
By leveraging the synergistic effect of biomass-based nitrogen-oxygen dual-doped carbon materials and platinum-based bimetallic components, a low-cost, highly active catalyst was prepared, solving the problem of high cost of existing catalysts. This catalyst is suitable for SO2 depolarization electrolysis reactions, improving hydrogen production efficiency and stability.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- INSTITUTE OF PROCESS ENGINEERING CHINESE ACADEMY OF SCIENCES
- Filing Date
- 2022-01-25
- Publication Date
- 2026-07-03
AI Technical Summary
The existing catalysts for SO2 depolarization electrolysis are mainly platinum-carbon catalysts, which require a high amount of heavy metals and are expensive, thus limiting their industrial application. In addition, existing precious metal catalysts such as iridium catalysts are expensive and have limited catalytic activity.
A catalyst using biomass-based nitrogen-oxygen dual-doped carbon material and platinum-based bimetallic active components is developed. Porous carbon materials are prepared from biomass materials and loaded with Pt and second metal elements Cr, Pd, Cu, Rh or Ir to form nitrogen-oxygen dual-doped carbon materials, thereby improving catalytic activity and stability.
It provides a highly active and stable catalyst for SO2 depolarization electrolysis reaction, which is low in cost, has excellent electrochemical catalytic activity, and is suitable for mixed sulfur cycle hydrogen production process, realizing comprehensive resource utilization and green environmental protection.
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Figure CN116536675B_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of catalysts, specifically to a catalyst based on biomass-based nitrogen-oxygen dual-doped carbon material, its preparation method, and its applications. Background Technology
[0002] Energy is the most fundamental material guarantee for human survival and social development. As the world transitions to a low-carbon energy system, hydrogen plays an increasingly important role. The mixed sulfur cycle (HyS) is one of the most promising technologies for large-scale hydrogen production, utilizing nuclear energy for this purpose. The SO2 depolarization electrolysis reaction is the core step in this process, and its process conditions significantly impact the efficiency of hydrogen production in the mixed sulfur cycle. Current research focuses on materials with excellent catalytic activity and chemical stability for the SO2 depolarization electrolysis reaction. These include noble metals such as Pt, Au, and Pd, as well as some transition metals and carbon materials. Among these, Pt-based catalysts have received widespread attention due to their excellent electrochemical activity and stability.
[0003] Biomass, as a renewable energy source, plays a vital role in achieving sustainable economic and ecological development. Preparing carbon materials from biomass is a simple and low-cost method for utilizing biomass. Carbon materials, due to their high specific surface area, high stability, and controllable pore size, are widely used in lithium-ion batteries, supercapacitors, and catalyst supports. Heteroatom doping can effectively regulate the electronic properties of carbon, optimizing its charge carrier concentration and providing numerous catalytically active sites, significantly enhancing the electrochemical activity of the original carbon and thus improving catalyst support performance, demonstrating promising development prospects.
[0004] Currently, the main catalyst for SO2 depolarization electrolysis is platinum-carbon catalyst, but the high amount of heavy metals required and the high cost limit its industrial application.
[0005] CN112481635A discloses a noble metal iridium hydrogen evolution electrocatalyst and its application. The catalyst uses iridium wire as raw material and has excellent electrocatalytic performance, but its high cost limits its large-scale promotion.
[0006] CN110227485A discloses a ruthenium-doped iron-nickel alloy catalyst for hydrogen production via water electrolysis and its preparation method. The catalyst has a limited catalytic effect and low catalytic activity, as it involves coating an iron-nickel-ruthenium alloy onto a layer of nickel foam.
[0007] Therefore, it is of great significance to develop a catalyst product that is simple to prepare and has high activity and high stability for the electrolytic hydrogen production reaction. Summary of the Invention
[0008] To address the above problems, the present invention aims to provide a catalyst based on biomass-based nitrogen-oxygen dual-doped carbon materials, its preparation method, and its applications. Compared with existing technologies, the catalyst provided by the present invention, through the synergistic effect of the biomass-based nitrogen-oxygen dual-doped carbon materials and platinum-based bimetallic active components, can be used in SO2 depolarization electrolysis reactions and exhibits high catalytic activity and electrical performance. The preparation method provided by the present invention is simple to operate, low in cost, and environmentally friendly.
[0009] To achieve this objective, the present invention adopts the following technical solution:
[0010] In a first aspect, the present invention provides a catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material, the catalyst comprising a biomass-based support and a platinum-based bimetallic active component supported on the biomass-based support; the biomass-based support comprises a porous carbon material; the porous carbon material contains nitrogen and oxygen elements; the platinum-based bimetallic active component contains Pt and a second metal element; the second metal element comprises any one or a combination of at least two of Cr, Pd, Cu, Rh, or Ir.
[0011] The catalyst provided by this invention comprises a porous carbon material containing nitrogen and oxygen elements and a platinum-based bimetallic active component. The porous carbon material containing nitrogen and oxygen elements in this invention is a nitrogen-oxygen dual-doped carbon material, obtained from biomass as raw material, with abundant N and O element doping. The carbon atoms in the carbon skeleton are replaced by nitrogen and oxygen heteroatoms, or the carbon material surface is doped with oxygen and nitrogen heteroatoms. The electronegativity and atomic size of nitrogen and oxygen in the nitrogen-oxygen dual-doped carbon material differ from those of carbon atoms, which promotes the rearrangement of the electron cloud of the carbon skeleton and changes the charge distribution in the matrix. Nitrogen and oxygen atoms are electron donors, which can provide additional charge carriers and effectively reduce the band gap. Nitrogen atoms can increase the number of electron holes and improve the overall conductivity of the carbon material. Further, by combining the platinum-based bimetallic active component and controlling the second metal element to include any one or at least two of Cr, Pd, Cu, Rh or Ir, the electrochemical performance and catalytic activity of the catalyst can be further improved, especially for the SO2 depolarization electrolysis reaction, which has excellent conductivity, electrochemical catalytic activity and stability.
[0012] The second metallic element includes any one or a combination of at least two of Cr, Pd, Cu, Rh or Ir, wherein typical but non-limiting combinations include combinations of Cr and Pd, combinations of Pd and Cu, or combinations of Rh and Ir, etc.
[0013] The present invention preferably controls the second metal element to include any one or at least two of Cr, Pd, Cu, Rh or Ir, because the second metal element and Pt will produce electronic effects, stress effects and synergistic effects, which can further enhance the activity of the catalyst.
[0014] Preferably, the specific surface area of the porous carbon material is 460-550 m². 2 / g, for example, could be 460m 2 / g、470m 2 / g、480m 2 / g、490m 2 / g、500m 2 / g、510m 2 / g、520m 2 / g、530m 2 / g、540m 2 / g or 550m 2 / g, but not limited to the listed values, other unlisted values within the range also apply.
[0015] Preferably, the average pore size of the porous carbon material is 3.9-5.7 nm, for example, it can be 3.9 nm, 4.0 nm, 4.1 nm, 4.2 nm, 4.3 nm, 4.4 nm, 4.5 nm, 4.6 nm, 4.7 nm, 4.8 nm, 4.9 nm, 5.0 nm, 5.5 nm or 5.7 nm, but is not limited to the listed values, and other unlisted values within the range are also applicable.
[0016] Preferably, the pore volume of the porous carbon material is 0.50-0.65 cm³. 3 / g, for example, could be 0.50cm 3 / g, 0.52cm 3 / g, 0.54cm 3 / g, 0.56cm 3 / g, 0.58cm 3 / g, 0.60cm 3 / g, 0.62cm 3 / g, 0.64cm 3 / g or 0.65cm 3 / g, but not limited to the listed values, other unlisted values within the range also apply.
[0017] Preferably, the average particle size of the porous carbon material is 4.8-6.0 nm, for example, it can be 4.8 nm, 5.0 nm, 5.2 nm, 5.4 nm, 5.6 nm, 5.8 nm or 6.0 nm, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0018] Preferably, the average particle size of the catalyst is 3.1-3.9 nm, for example, it can be 3.1 nm, 3.2 nm, 3.3 nm, 3.4 nm, 3.5 nm, 3.6 nm, 3.7 nm, 3.8 nm or 3.9 nm, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0019] Preferably, the mass percentage of Pt in the catalyst is 29-47%, for example, it can be 29%, 30%, 32%, 34%, 36%, 40%, 42%, 44%, 46% or 47%, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0020] The present invention preferably controls the mass percentage of Pt in the catalyst within a specific range, which can ensure that the catalyst has excellent electrochemical activity and stability.
[0021] Preferably, the mass percentage of the second metal element in the catalyst is 12-29%, for example, it can be 12%, 14%, 16%, 18%, 20%, 22%, 24%, 26%, 28% or 29%, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0022] The present invention preferably controls the mass percentage of the second metal element in the catalyst within a specific range, which can reduce costs and improve the catalytic activity of the catalyst.
[0023] Preferably, the biomass-based support in the catalyst has a mass percentage content of 24-59%, for example, it can be 24%, 30%, 38%, 40%, 44%, 45%, 46%, 47%, 48%, 49%, 50%, 51%, 52%, 53%, 54%, 55%, 56%, 57%, 58% or 59%, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0024] The present invention preferably controls the mass percentage of the biomass-based support in the catalyst within a specific range, which can load active components, reduce catalyst costs, and improve catalyst activity and stability.
[0025] Preferably, the mass ratio of Pt to the second metal element in the catalyst is (1.0-3.8):1, for example, it can be 1.0:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2.0:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1, 3.0:1, 3.2:1, 3.4:1, 3.6:1 or 3.8:1, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0026] Secondly, the present invention provides a method for preparing a catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material as described in the first aspect of the present invention, the preparation method comprising the following steps:
[0027] (1) Mix biomass materials and activator solution, then stir and dry them sequentially to obtain a solid product;
[0028] (2) The solid product obtained in step (1) is carbonized, washed and ground in sequence to obtain porous carbon material;
[0029] (3) The porous carbon material obtained in step (2) is mixed with a metal element precursor solution, wherein the metal element precursor solution includes a Pt-containing precursor solution and a precursor solution containing a second metal element; the precursor solution containing the second metal element includes any one or a combination of at least two of CrN3O9 solution, PdCl2 solution, CuCl2 solution, RhCl3 solution or H2IrCl6 solution; then the mixture is stirred and dried sequentially to obtain the precursor.
[0030] (4) The precursor obtained in step (3) is mixed with a reducing agent, and then stirred, separated into solid and liquid and dried in sequence to obtain the catalyst.
[0031] This invention prepares porous carbon materials by mixing and activating biomass materials with an activator, followed by carbonization. Further, by mixing and loading Pt and a second metal element, a catalyst is obtained. The catalyst provided by this invention exhibits excellent electrochemical catalytic activity and stability for SO2 depolarization electrolysis. The preparation method provided by this invention uses biomass materials as raw materials, which are inexpensive, widely available, and lower in cost than traditional carbon material preparation methods. It enables the reuse of agricultural and forestry biomass, and is green, environmentally friendly, and pollution-free.
[0032] The present invention does not specifically limit the method of solid-liquid separation, and it can be any method for solid-liquid separation known to those skilled in the art, such as filtration or centrifugation.
[0033] The precursor solution containing the second metal element includes any one or a combination of at least two of the following: CrN3O9 solution, PdCl2 solution, CuCl2 solution, RhCl3 solution, or H2IrCl6 solution. Typical but non-limiting combinations include combinations of CrN3O9 solution and PdCl2 solution, combinations of PdCl2 solution and RhCl3 solution, or combinations of RhCl3 solution and H2IrCl6 solution.
[0034] Preferably, the biomass material in step (1) includes any one or a combination of at least two of corn stalks, lignin, cellulose or holocellulose, wherein typical but non-limiting combinations include combinations of corn stalks and lignin, combinations of lignin and cellulose or combinations of cellulose and holocellulose, etc., preferably corn stalks.
[0035] The preferred biomass material for this invention is corn stalk because corn stalk is widely available, has low pretreatment costs, and has excellent carrier performance, resulting in higher catalyst activity.
[0036] Preferably, the particle size of the biomass material is 0.07-0.15 mm, for example, it can be 0.07 mm, 0.08 mm, 0.09 mm, 0.10 mm, 0.11 mm, 0.12 mm, 0.13 mm, 0.14 mm or 0.15 mm, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0037] Preferably, the activator solution comprises a calcium chloride solution.
[0038] The present invention preferably uses calcium chloride solution as the activator solution. Compared with traditional alkaline activators, the present invention uses calcium chloride as the activator, which results in a catalyst with better electrochemical catalytic performance and stability, lower cost, less demanding equipment requirements, and avoids secondary pollution.
[0039] The biomass material described in this invention is washed multiple times with ethanol and water, then dried before proceeding to step (1).
[0040] Preferably, the mass ratio of the biomass material to the calcium chloride solution is 1:(1-4), for example, it can be 1:1, 1:1.2, 1:1.4, 1:1.6, 1:1.8, 1:2, 1:2.2, 1:2.4, 1:2.6, 1:2.8, 1:3, 1:3.2, 1:3.6, 1:3.8 or 1:4, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0041] Preferably, the drying temperature in step (1) is 100-120℃, for example, it can be 100℃, 102℃, 104℃, 106℃, 108℃, 110℃, 112℃, 114℃, 116℃, 118℃ or 120℃, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0042] Preferably, the drying time in step (1) is 3-5 hours, for example, it can be 3 hours, 3.2 hours, 3.4 hours, 3.6 hours, 3.8 hours, 4 hours, 4.2 hours, 4.4 hours, 4.6 hours, 4.8 hours or 5 hours, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0043] Preferably, the carbonization temperature in step (2) is 600-800℃, for example, it can be 600℃, 620℃, 640℃, 660℃, 680℃, 700℃, 720℃, 740℃, 760℃, 780℃ or 800℃, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0044] The present invention preferably controls the carbonization temperature within a specific range, which is conducive to complete carbonization and obtaining carbon materials with a nitrogen-oxygen dual-doped structure.
[0045] The carbonization described in this invention is carried out under a nitrogen atmosphere to avoid introducing other impurities.
[0046] Preferably, the carbonization time is 1-2.5 hours, for example, it can be 1 hour, 1.1 hours, 1.2 hours, 1.3 hours, 1.4 hours, 1.5 hours, 1.6 hours, 1.7 hours, 1.8 hours, 1.9 hours, 2 hours, 2.1 hours, 2.2 hours, 2.3 hours, 2.4 hours or 2.5 hours, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0047] Preferably, the washing includes acid washing and water washing.
[0048] Preferably, the acid solution used for pickling includes a hydrochloric acid solution.
[0049] Preferably, the concentration of the acid solution is 1-4 mol / L, for example, it can be 1 mol / L, 1.2 mol / L, 1.4 mol / L, 1.6 mol / L, 1.8 mol / L, 2 mol / L, 2.2 mol / L, 2.4 mol / L, 2.6 mol / L, 2.8 mol / L, 3 mol / L, 3.2 mol / L, 3.4 mol / L, 3.6 mol / L, 3.8 mol / L or 4 mol / L, but is not limited to the listed values, and other unlisted values within the range are also applicable.
[0050] Preferably, the percentage of the mass of Pt element in the Pt-containing precursor solution to the mass of metal element in the metal element precursor solution in step (3) is 50.0%-79.0%, for example, it can be 50.0%, 52.0%, 54.0%, 56.0%, 58.0%, 60.0%, 62.0%, 64.0%, 66.0%, 68.0%, 70.0%, 72.0%, 74.0%, 76.0%, 78.0% or 79.0%, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0051] The metal precursor solution described in this invention is obtained by dissolving a Pt-containing precursor and a precursor containing a second metal element in isopropanol.
[0052] Preferably, the percentage of the mass of the second metal element in the precursor solution containing the second metal to the mass of the metal element in the precursor solution is 21.0%-50.0%, for example, it can be 21.0%, 22.0%, 25.0%, 28.0%, 30.0%, 32.0%, 35.0%, 38.0%, 40.0%, 42.0%, 45.0%, 48.0%, or 50.0%, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0053] Preferably, the mass ratio of the metal element contained in the metal element precursor solution to the porous carbon material in step (3) is (0.67-1.50):1, for example, it can be 0.67:1, 0.70:1, 0.80:1, 0.90:1, 1.00:1, 1.20:1, 1.40:1 or 1.50:1, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0054] Preferably, the stirring time in step (3) is 12-24h, for example, it can be 12h, 13h, 14h, 15h, 16h, 17h, 18h, 19h, 20h, 21h, 22h, 23h or 24h, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0055] Preferably, the drying in step (3) includes freeze drying.
[0056] The preferred drying method of this invention is freeze drying, which can prevent the active metal particles from agglomerating due to heat and is conducive to forming a higher electrochemical active surface area.
[0057] Preferably, the reducing agent in step (4) includes a NaBH4 solution.
[0058] Preferably, the molar amount of the reducing agent is 20-30 times the molar amount of the metal element in the metal element precursor solution, for example, it can be 20 times, 21 times, 22 times, 23 times, 24 times, 25 times, 26 times, 27 times, 28 times, 29 times or 30 times, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0059] Preferably, the stirring time in step (4) is 20-40 min, for example, it can be 20 min, 22 min, 24 min, 26 min, 28 min, 30 min, 32 min, 34 min, 36 min, 38 min or 40 min, but is not limited to the listed values. Other unlisted values within the range are also applicable.
[0060] Preferably, the drying in step (4) includes freeze drying.
[0061] As a preferred embodiment of the second aspect of the present invention, the preparation method includes the following steps:
[0062] (1) Mix biomass material and calcium chloride solution, wherein the mass ratio of biomass material to calcium chloride solution is 1:(1-4), wherein the biomass material includes any one or a combination of at least two of corn stalks, lignin, cellulose or holocellulose, wherein the particle size of the biomass material is 0.07-0.15 mm, and then dry at 100-120℃ for 3-5 h to obtain a solid product;
[0063] (2) The solid product obtained in step (1) is carbonized at 600-800℃ for 1-2.5h, then acid-washed with 1-4mol / L hydrochloric acid, then washed with water until neutral, and then ground to obtain porous carbon material.
[0064] (3) The porous carbon material obtained in step (2) is mixed with a metal element precursor solution, wherein the metal element precursor solution includes a Pt-containing precursor solution and a precursor solution containing a second metal element; the precursor solution containing the second metal element includes any one or a combination of at least two of CrN3O9 solution, PdCl2 solution, CuCl2 solution, RhCl3 solution or H2IrCl6 solution, wherein the mass percentage of Pt element in the Pt-containing precursor solution is 50.0-79.0% of the mass of metal element in the metal element precursor solution, and the mass percentage of the second metal element in the second metal element precursor solution is 21.0-50.0% of the mass of metal element in the metal element precursor solution to the porous carbon material obtained in step (3) is (0.67-1.50):1, and then stirred for 12-24 hours, followed by freeze drying to obtain the precursor;
[0065] (4) The precursor obtained in step (3) is mixed with NaBH4 solution, wherein the molar amount of NaBH4 is 20-30 times the molar amount of metal element in the metal element precursor solution, and then stirred for 20-40 min. After solid-liquid separation, the mixture is freeze-dried to obtain the catalyst.
[0066] Thirdly, the present invention provides the use of a catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material as described in the first aspect of the present invention, said catalyst being used in an SO2 depolarization electrolysis reaction.
[0067] The catalyst provided by this invention exhibits excellent electrochemical catalytic activity and stability in SO2 depolarization electrolysis reactions. Compared with traditional Pt / C catalysts, it is lower in cost, more environmentally friendly, and enables comprehensive utilization of resources.
[0068] Compared with the prior art, the present invention has the following beneficial effects:
[0069] (1) The catalyst based on biomass-based nitrogen and oxygen dual-doped carbon material provided by this invention has low cost and excellent catalytic performance, and is suitable for SO2 depolarization electrolysis reaction. When the polarization curve analysis of the catalyst is performed, the maximum current density that can be achieved at a potential voltage of 1V is 440mA / cm. 2 The above achieves 500 mA / cm under optimal conditions. 2 The above-mentioned substances exhibit excellent electrochemical catalytic activity; during cyclic voltammetry analysis, the oxidation peak reaches above 0.55V, and under optimal conditions, it reaches above 0.58V, demonstrating good stability.
[0070] (2) The preparation method of the catalyst based on biomass-based nitrogen-oxygen dual-doped carbon material provided by the present invention is simple, uses biomass materials as raw materials, is low in cost and widely available, can solve the pollution problem of agricultural and forestry biomass, and realize the comprehensive utilization of resources. Attached Figure Description
[0071] Figure 1 These are the XRD patterns of the porous carbon materials described in Examples 1-3 of this invention.
[0072] Figure 2 These are polarization curves of the catalysts described in Examples 1-3 of this invention.
[0073] Figure 3 This is a graph showing the cyclic voltammetry test results of the catalyst described in Example 1 of this invention.
[0074] Figure 4 This is a graph showing the cyclic voltammetry test results of the catalyst described in Example 2 of this invention.
[0075] Figure 5This is a graph showing the cyclic voltammetry test results of the catalyst described in Example 3 of this invention.
[0076] Figure 6 This is the C1s analysis diagram of XPS in Embodiment 3 of the present invention. Detailed Implementation
[0077] The technical solution of the present invention will be further illustrated below through specific embodiments. Those skilled in the art should understand that the embodiments described are merely illustrative of the present invention and should not be construed as limiting the invention in any way.
[0078] Example 1
[0079] This embodiment provides a method for preparing a catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material, the preparation method comprising the following steps:
[0080] (1) Mix corn stalks with a calcium chloride solution with a concentration of 0.1 g / mL, wherein the mass ratio of corn stalks to calcium chloride in the calcium chloride solution is 1:1, and the particle size of the corn stalks is 0.07 mm. Then dry at 110 °C for 4 h to obtain a solid product.
[0081] (2) The solid product obtained in step (1) is carbonized at 700°C for 2 hours, then acid-washed with 2 mol / L hydrochloric acid, then washed with water until neutral, and then ground to obtain porous carbon material.
[0082] (3) The porous carbon material obtained in step (2) is mixed with a metal element precursor solution, wherein the metal element precursor solution includes H2PtCl6 solution and Cr(NO3)3 solution; the mass percentage of Pt element in the H2PtCl6 solution is 78.96% of the mass of metal element in the metal element precursor solution, the mass percentage of Cr element in the Cr(NO3)3 solution is 21.04% of the mass of metal element in the metal element precursor solution, and the mass ratio of the metal element in the metal element precursor solution to the porous carbon material obtained in step (3) is 1.50:1. The mixture is then stirred for 20 hours and then freeze-dried to obtain the precursor.
[0083] (4) The precursor obtained in step (3) is mixed with NaBH4 solution, wherein the molar amount of NaBH4 is 30 times the molar amount of metal element in the metal element precursor solution, and then stirred for 30 min, filtered, and then freeze-dried to obtain the catalyst.
[0084] This embodiment also provides a catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material obtained by the above preparation method. The catalyst comprises a porous carbon material containing N and O elements and a platinum-based bimetallic active component supported on the porous carbon material. The platinum-based bimetallic active component contains Pt and Cr; the mass ratio of Pt to Cr is 3.75:1; the average particle size of the catalyst is 3.25 nm; the mass percentage of Pt in the catalyst is 46.8%; the mass percentage of Cr in the catalyst is 12.4%; and the mass percentage of the porous carbon material is 40.8%.
[0085] XRD tests were performed on the porous carbon material described in Example 1, and the results are as follows: Figure 1 As shown, the porous carbon material has a strong peak at 23° and a weak peak at 43°, which correspond to the (002) and (100) crystal planes of the graphite structure, respectively. Therefore, the prepared porous carbon material is a partially graphitized porous carbon.
[0086] BET testing of the porous carbon material described in Example 1 showed that the porous carbon material has a wide pore size distribution and possesses a hierarchical porous structure including micropores, mesopores, and macropores, which is beneficial for the transport of electrolyte ions and the accumulation of charge; the specific surface area of the porous carbon material is 474 m². 2 / g; average pore size 4.53nm; pore volume 0.54cm³ 3 / g.
[0087] The porous carbon material obtained in Example 1 was tested using an elemental analyzer (Vario EL III, German Elemental Analysis Systems GmbH). The nitrogen and oxygen contents of the porous carbon material were 1.83% and 2.18%, respectively, indicating that the porous carbon material successfully achieved nitrogen and oxygen dual doping and verifying the presence of N and O.
[0088] Example 2
[0089] This embodiment provides a method for preparing a catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material, the preparation method comprising the following steps:
[0090] (1) Mix corn stalks with a calcium chloride solution with a concentration of 0.3 g / mL, wherein the mass ratio of corn stalks to calcium chloride in the calcium chloride solution is 1:3, and the particle size of the corn stalks is 0.07 mm. Then dry at 110 °C for 4 h to obtain a solid product.
[0091] (2) The solid product obtained in step (1) is carbonized at 750°C for 2 hours, then acid-washed with 2 mol / L hydrochloric acid, then washed with water until neutral, and then ground to obtain porous carbon material.
[0092] (3) The porous carbon material obtained in step (2) is mixed with a metal element precursor solution, wherein the metal element precursor solution includes H2PtCl6 solution and Cr(NO3)3 solution; the mass percentage of Pt element in the H2PtCl6 solution is 78.96% of the mass of metal element in the metal element precursor solution, the mass percentage of Cr element in the Cr(NO3)3 solution is 21.04% of the mass of metal element in the metal element precursor solution, and the mass ratio of the metal element in the metal element precursor solution to the porous carbon material obtained in step (3) is 1.50:1. The mixture is then stirred for 20 hours and then freeze-dried to obtain the precursor.
[0093] (4) The precursor obtained in step (3) is mixed with NaBH4 solution, wherein the molar amount of NaBH4 is 30 times the molar amount of metal element in the metal element precursor solution, and then stirred for 30 min, filtered, and then freeze-dried to obtain the catalyst.
[0094] This embodiment also provides a catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material obtained by the above preparation method. The catalyst comprises a porous carbon material containing N and O elements and a platinum-based bimetallic active component supported on the porous carbon material. The platinum-based bimetallic active component contains Pt and Cr. The mass ratio of Pt to Cr is 3.75:1. The average particle size of the catalyst is 3.17 nm. The mass percentage of Pt in the catalyst is 46.8%. The mass percentage of Cr in the catalyst is 12.4%. The mass percentage of the porous carbon material in the catalyst is 40.8%.
[0095] XRD tests were performed on the porous carbon material described in Example 2, and the results are as follows: Figure 1 As shown, the porous carbon material has a strong peak at 23° and a weak peak at 43°, which correspond to the (002) and (100) crystal planes of the graphite structure, respectively. Therefore, the prepared porous carbon material is a partially graphitized porous carbon.
[0096] BET testing of the porous carbon material described in Example 2 showed that it has a wide pore size distribution and possesses a hierarchical porous structure including micropores, mesopores, and macropores, which is beneficial for electrolyte ion transport and charge accumulation. The specific surface area of the porous carbon material is 492 m². 2 / g; average pore size 4.2nm; pore volume 0.52cm³ 3 / g.
[0097] Example 3
[0098] This embodiment provides a method for preparing a catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material, the preparation method comprising the following steps:
[0099] (1) Mix corn stalks with a calcium chloride solution with a concentration of 0.3 g / mL, wherein the mass ratio of corn stalks to calcium chloride in the calcium chloride solution is 1:3, and the particle size of the corn stalks is 0.07 mm. Then dry at 110 °C for 4 h to obtain a solid product.
[0100] (2) The solid product obtained in step (1) is carbonized at 700°C for 1.5 h, then acid-washed with 2 mol / L hydrochloric acid, then washed with water until neutral, and then ground to obtain porous carbon material.
[0101] (3) The porous carbon material obtained in step (2) is mixed with a metal element precursor solution, wherein the metal element precursor solution includes H2PtCl6 solution and Cr(NO3)3 solution; the mass percentage of Pt element in the H2PtCl6 solution is 78.96% of the mass of metal element in the metal element precursor solution, the mass percentage of Cr element in the Cr(NO3)3 solution is 21.04% of the mass of metal element in the metal element precursor solution, and the mass ratio of the metal element in the metal element precursor solution to the porous carbon material obtained in step (3) is 1.50:1. The mixture is then stirred for 20 hours and then freeze-dried to obtain the precursor.
[0102] (4) The precursor obtained in step (3) is mixed with NaBH4 solution, wherein the molar amount of NaBH4 is 30 times the molar amount of metal element in the metal element precursor solution, and then stirred for 30 min, filtered, and then freeze-dried to obtain the catalyst.
[0103] This embodiment also provides a catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material obtained by the above preparation method. The catalyst comprises a porous carbon material containing N and O elements and a platinum-based bimetallic active component supported on the porous carbon material. The platinum-based bimetallic active component contains Pt and Cr. The mass ratio of Pt to Cr is 3.75:1. The average particle size of the catalyst is 3.20 nm. The mass percentage of Pt in the catalyst is 46.8%. The mass percentage of Cr in the catalyst is 12.4%. The mass percentage of the porous carbon material in the catalyst is 40.8%.
[0104] XRD tests were performed on the porous carbon material described in Example 3, and the results are as follows: Figure 1 As shown, the porous carbon material has a strong peak at 23° and a weak peak at 43°, which correspond to the (002) and (100) crystal planes of the graphite structure, respectively. Therefore, the prepared porous carbon material is a partially graphitized porous carbon.
[0105] BET testing of the porous carbon material described in Example 3 showed that the porous carbon material has a wide pore size distribution and possesses a hierarchical porous structure including micropores, mesopores, and macropores, which is beneficial for the transport of electrolyte ions and the accumulation of charge; the specific surface area of the porous carbon material is 502 m². 2 / g; average pore size 5.64nm; pore volume 0.65cm³ 3 / g.
[0106] XPS analysis of the catalyst obtained in Example 3 yielded the following results: Figure 6 As shown, the binding energies of C=C, CO, and C=O groups are 284.5 eV, 286.2 eV, and 288.1 eV, respectively, confirming the presence of oxygen-containing functional groups.
[0107] The porous carbon material obtained in Example 3 was tested using an elemental analyzer (Vario EL III elemental analyzer, German Elemental Analysis Systems GmbH). The nitrogen content and oxygen content of the obtained porous carbon material were 1.83% and 2.18%, respectively, indicating that the porous carbon material successfully achieved nitrogen and oxygen dual doping, verifying the presence of N and O.
[0108] Example 4
[0109] This embodiment provides a method for preparing a catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material, the preparation method comprising the following steps:
[0110] (1) Mix cellulose and calcium chloride solution with a concentration of 0.4 g / mL, wherein the mass ratio of cellulose to calcium chloride in the calcium chloride solution is 1:4, and the particle size of the cellulose is 0.15 mm. Then dry at 100 °C for 5 h to obtain a solid product.
[0111] (2) The solid product obtained in step (1) is carbonized at 600°C for 2.5 h, then acid-washed with 1 mol / L hydrochloric acid, then washed with water until neutral, and then ground to obtain porous carbon material.
[0112] (3) The porous carbon material obtained in step (2) is mixed with a metal element precursor solution, wherein the metal element precursor solution includes H2PtCl6 solution and PdCl2 solution; the mass percentage of Pt element in the H2PtCl6 solution is 55% of the mass of metal element in the metal element precursor solution, the mass percentage of Pd element in the PdCl2 solution is 45% of the mass of metal element in the metal element precursor solution, and the mass ratio of the metal element in the metal element precursor solution to the porous carbon material obtained in step (3) is 1.2:1. The mixture is then stirred for 12 hours and then freeze-dried to obtain the precursor.
[0113] (4) The precursor obtained in step (3) is mixed with NaBH4 solution, wherein the molar amount of NaBH4 is 20 times the molar amount of metal element in the metal element precursor solution, and then stirred for 40 min, filtered, and then freeze-dried to obtain the catalyst.
[0114] This embodiment also provides a catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material obtained by the above preparation method. The catalyst comprises a porous carbon material containing N and O elements and a platinum-based bimetallic active component supported on the porous carbon material. The platinum-based bimetallic active component contains Pt and Pd. The mass ratio of Pt to Pd is 1.2:1. The average particle size of the catalyst is 3.3 nm. The mass percentage of Pt in the catalyst is 30%. The mass percentage of Pd in the catalyst is 25%. The mass percentage of the porous carbon material in the catalyst is 45%.
[0115] The porous carbon material described in Example 4 was subjected to a BET test, and the specific surface area of the porous carbon material was 544.67 m². 2 / g; the average pore size of the porous carbon material is 4.55nm; the pore volume of the porous carbon material is 0.62cm³. 3 / g.
[0116] Example 5
[0117] This embodiment provides a method for preparing a catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material, the preparation method comprising the following steps:
[0118] (1) Mix cellulose and a calcium chloride solution with a concentration of 0.2 g / mL, wherein the mass ratio of cellulose to calcium chloride in the calcium chloride solution is 1:2, and the particle size of the cellulose is 0.11 mm. Then dry at 120 °C for 3 h to obtain a solid product.
[0119] (2) The solid product obtained in step (1) is carbonized at 800°C for 1 hour, then acid-washed with 4 mol / L hydrochloric acid, then washed with water until neutral, and then ground to obtain porous carbon material.
[0120] (3) The porous carbon material obtained in step (2) is mixed with a metal element precursor solution, wherein the metal element precursor solution includes H2PtCl6 solution and PdCl2 solution; the mass percentage of Pt element in the H2PtCl6 solution is 71% of the mass of metal element in the metal element precursor solution, the mass percentage of Pd element in the PdCl2 solution is 29% of the mass of metal element in the metal element precursor solution, and the mass ratio of the metal element in the metal element precursor solution to the porous carbon material obtained in step (3) is 0.67:1. The mixture is then stirred for 12 hours and then freeze-dried to obtain the precursor.
[0121] (4) The precursor obtained in step (3) is mixed with NaBH4 solution, wherein the molar amount of NaBH4 is 25 times the molar amount of metal element in the metal element precursor solution, and then stirred for 30 min, then filtered, and then freeze-dried to obtain the catalyst.
[0122] This embodiment also provides a catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material obtained by the above preparation method. The catalyst comprises a porous carbon material containing N and O elements and a platinum-based bimetallic active component supported on the porous carbon material. The platinum-based bimetallic active component contains Pt and Pd. The mass ratio of Pt to Pd is 2.4:1. The average particle size of the catalyst is 3.44 nm. The mass percentage of Pt in the catalyst is 29%. The mass percentage of Pd in the catalyst is 12%. The mass percentage of the porous carbon material in the catalyst is 59%.
[0123] The porous carbon material described in Example 5 was subjected to a BET test, and the specific surface area of the porous carbon material was 491.54 m². 2 / g; the average pore size of the porous carbon material is 4.2nm; the pore volume of the porous carbon material is 0.52cm³. 3 / g.
[0124] Example 6
[0125] This embodiment provides a method for preparing a catalyst based on biomass-based nitrogen-oxygen dual-doped carbon material. The only difference from Example 1 is that corn stalks are replaced with lignin.
[0126] Example 7
[0127] This embodiment provides a method for preparing a catalyst based on biomass-based nitrogen-oxygen dual-doped carbon material. The only difference from Example 1 is that the calcium chloride solution is replaced with a potassium hydroxide solution.
[0128] Comparative Example 1
[0129] This comparative example provides a method for preparing a catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material. The only difference from Example 1 is that the porous carbon material is replaced with carbon black.
[0130] Comparative Example 2
[0131] This comparative example provides a method for preparing a catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material. The only difference from Example 1 is that the Cr(NO3)3 solution is replaced with a RuCl3 solution.
[0132] Polarization curves of the catalysts obtained in Examples 1-7 and Comparative Examples 1-2 were analyzed using the galvanostatic method, with the initial current density set to 80 mA / cm². 2 The current density increment was set to 20 mA / cm². 2 Under these conditions, the various voltages required by the electrochemical workstation to achieve the set current density were tested. Taking Examples 1-3 as examples, the polarization curves obtained are as follows: Figure 2 As shown. From Figure 2 It can be seen that, at a potential voltage of 1V, the maximum current density in Examples 1-3 is 560mA / cm², respectively. 2 520mA / cm 2 and 540mA / cm 2 Furthermore, the obtained polarization curve shows a stable upward trend, indicating good electrolysis performance.
[0133] Polarization curve analysis was performed in Examples 1-7 and Comparative Examples 1-2, and the maximum current density achievable at 1V is shown in Table 1.
[0134] Cyclic voltammetry analysis was performed on the catalysts obtained in Examples 1-7 and Comparative Examples 1-2. The test method was as follows: the scan rate was set to 100 mV / s, and the scan voltage range was set to 0.1-1.2 V (SHE). During the test, the voltage was scanned from the anode potential to the cathode potential. Taking Examples 1-3 as an example, the cyclic voltammetry curves are shown below. Figure 3-5 As shown, from Figure 3-5 It can be seen that the oxidation peak positions in Examples 1-3 are 0.60V, 0.62V and 0.58V, respectively, indicating that the catalysts obtained in Examples 1-3 have excellent stability.
[0135] Cyclic voltammetry analysis was performed on the catalysts obtained in Examples 1-7 and Comparative Examples 1-2, and the oxidation peak positions are shown in Table 1.
[0136] Table 1
[0137]
[0138]
[0139] The following points can be observed from Table 1:
[0140] (1) As can be seen from the data of Examples 1-7, the catalysts obtained in Examples 1-7 can achieve a maximum current density of 440 mA / cm² when the potential voltage is 1 V during polarization curve analysis. 2 The above, under optimal conditions, achieves 500 mA / cm. 2 The above results show that the oxidation peak reached above 0.55V during cyclic voltammetry analysis, and above 0.58V under optimal conditions, indicating that the catalyst provided by this invention has excellent electrochemical catalytic activity and stability.
[0141] (2) A comprehensive comparison of the data from Example 6 and Example 1 shows that the only difference between Example 6 and Example 1 is that the corn stalks were replaced with lignin. The catalyst in Example 1 had a maximum current density of 560 mA / cm² at 1V. 2 The oxidation peak was at 0.60 V, while the maximum current density in Example 6 was only 440 mA / cm². 2 The oxidation peak was 0.55V, indicating that the preferred biomass material of this invention, corn stalks, can significantly improve the electrochemical catalytic activity and stability of the catalyst.
[0142] (3) A comprehensive comparison of the data from Example 7 and Example 1 shows that the only difference between Example 7 and Example 1 is that the calcium chloride solution is replaced with potassium hydroxide solution. The catalyst in Example 1 has a maximum current density of 560 mA / cm² at 1V. 2 The oxidation peak was at 0.60 V, while the maximum current density in Example 7 was only 480 mA / cm². 2 The oxidation peak position is 0.57V. In this invention, calcium chloride solution is preferred as the activator solution, which can significantly improve the electrochemical catalytic activity and stability of the catalyst.
[0143] (4) A comprehensive comparison of the data from Example 1 and Comparative Example 1 shows that the only difference between Comparative Example 1 and Example 1 is that the porous carbon material is replaced with carbon black. The catalyst in Example 1 has a maximum current density of 560 mA / cm² at 1V. 2 The oxidation peak was at 0.60 V, while the maximum current density in Comparative Example 1 was only 540 mA / cm². 2 The oxidation peak position is 0.48V. This invention uses porous carbon materials containing nitrogen and oxygen elements as a support, which can significantly improve the electrochemical catalytic activity and stability of the catalyst.
[0144] (5) A comprehensive comparison of the data from Example 1 and Comparative Example 2 shows that the only difference between Comparative Example 2 and Example 1 is that the Cr(NO3)3 solution is replaced with RuCl3 solution. The catalyst in Example 1 has a maximum current density of 560 mA / cm at 1V. 2 The oxidation peak was at 0.60 V, while the maximum current density in Comparative Example 2 was only 520 mA / cm². 2 The oxidation peak position is 0.42V. By selecting the second metal element, this invention can significantly improve the electrochemical catalytic activity and stability of the catalyst.
[0145] In summary, the preparation method of the catalyst based on biomass-based nitrogen-oxygen dual-doped carbon material provided by this invention is simple to operate and low in cost. When the polarization curve analysis of the obtained catalyst is performed, the maximum current density that can be achieved at a potential voltage of 1V is 440mA / cm. 2 The above, under optimal conditions, achieves 500 mA / cm. 2 The above-mentioned substances exhibit excellent electrochemical catalytic activity; during cyclic voltammetry analysis, the oxidation peak reaches above 0.55V, and under optimal conditions, it reaches above 0.58V, demonstrating good stability.
[0146] The applicant declares that the above description is only a specific embodiment of the present invention, but the protection scope of the present invention is not limited thereto. Those skilled in the art should understand that any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope disclosed in the present invention fall within the protection and disclosure scope of the present invention.
Claims
1. A catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material, characterized in that, The catalyst comprises a biomass-based support and a platinum-based bimetallic active component supported on the biomass-based support; The biomass-based carrier includes porous carbon materials; The porous carbon material contains N and O elements; The platinum-based bimetallic active component contains Pt and a second metallic element; The second metallic element includes any one or a combination of at least two of Cr, Pd, Cu, Rh, or Ir; The catalyst is obtained by the following preparation method: (1) Mix biomass material and activator solution, then stir and dry them sequentially to obtain a solid product; the biomass material is corn stalks; The activator solution is a calcium chloride solution; (2) The solid product obtained in step (1) is carbonized, washed and ground in sequence to obtain a porous carbon material; the carbonization temperature is 600-800℃; the carbonization time is 1-2.5h; The carbonization was carried out under a nitrogen atmosphere; (3) The porous carbon material obtained in step (2) is mixed with a metal element precursor solution, wherein the metal element precursor solution includes a Pt-containing precursor solution and a precursor solution containing a second metal element. The precursor solution containing the second metal element includes any one or a combination of at least two of the following: CrN3O9 solution, PdCl2 solution, CuCl2 solution, RhCl3 solution, or H2IrCl6 solution; then, the solution is stirred and dried sequentially to obtain the precursor. (4) The precursor obtained in step (3) is mixed with a reducing agent, and then stirred, separated into solid and liquid and dried in sequence to obtain the catalyst.
2. The catalyst according to claim 1, characterized in that, The porous carbon material has a specific surface area of 460-550 m². 2 / g.
3. The catalyst according to claim 1, characterized in that, The average pore size of the porous carbon material is 3.9-5.7 nm.
4. The catalyst according to claim 1, characterized in that, The porous carbon material has a pore volume of 0.50-0.65 cm³. 3 / g.
5. The catalyst according to claim 1, characterized in that, The average particle size of the porous carbon material is 4.8-6.0 nm.
6. The catalyst according to claim 1, characterized in that, The catalyst has an average particle size of 3.1-3.9 nm.
7. The catalyst according to claim 1, characterized in that, The catalyst contains 29-47% Pt by mass.
8. The catalyst according to claim 1, characterized in that, The catalyst contains 12-29% by mass of the second metallic element.
9. The catalyst according to claim 1, characterized in that, The biomass-based support in the catalyst has a mass percentage content of 24-59%.
10. The catalyst according to claim 1, characterized in that, The mass ratio of Pt to the second metal element in the catalyst is (1.0-3.8):
1.
11. A method for preparing a catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material as described in any one of claims 1-10, characterized in that, The preparation method includes the following steps: (1) Mix biomass material and activator solution, then stir and dry them sequentially to obtain a solid product; the biomass material is corn stalk; the activator solution is calcium chloride solution; (2) The solid product obtained in step (1) is carbonized, washed and ground in sequence to obtain porous carbon material; the carbonization temperature is 600-800℃; the carbonization time is 1-2.5h; the carbonization is carried out under a nitrogen atmosphere; (3) The porous carbon material obtained in step (2) is mixed with a metal element precursor solution, wherein the metal element precursor solution includes a Pt-containing precursor solution and a precursor solution containing a second metal element; the precursor solution containing the second metal element includes any one or a combination of at least two of CrN3O9 solution, PdCl2 solution, CuCl2 solution, RhCl3 solution or H2IrCl6 solution; then the mixture is stirred and dried sequentially to obtain the precursor. (4) The precursor obtained in step (3) is mixed with a reducing agent, and then stirred, separated into solid and liquid and dried in sequence to obtain the catalyst.
12. The preparation method according to claim 11, characterized in that, The particle size of the biomass material in step (1) is 0.07-0.15 mm.
13. The preparation method according to claim 11, characterized in that, The mass ratio of the biomass material to the calcium chloride solution is 1:(1-4).
14. The preparation method according to claim 11, characterized in that, The drying temperature in step (1) is 100-120℃.
15. The preparation method according to claim 11, characterized in that, The drying time in step (1) is 3-5 hours.
16. The preparation method according to claim 11, characterized in that, The washing process in step (2) includes acid washing and water washing.
17. The preparation method according to claim 16, characterized in that, The acid solution used for pickling includes hydrochloric acid solution.
18. The preparation method according to claim 17, characterized in that, The concentration of the acid solution is 1-4 mol / L.
19. The preparation method according to claim 11, characterized in that, In step (3), the mass percentage of Pt in the Pt-containing precursor solution is 50.0-79.0% of the mass of metal in the metal element precursor solution.
20. The preparation method according to claim 11, characterized in that, The mass percentage of the second metal element in the precursor solution containing the second metal is 21.0-50.0% of the mass of the metal element in the precursor solution containing the metal element.
21. The preparation method according to claim 11, characterized in that, The mass ratio of the metal element in the metal element precursor solution to the porous carbon material in step (3) is (0.67-1.50):
1.
22. The preparation method according to claim 11, characterized in that, The stirring time in step (3) is 12-24 hours.
23. The preparation method according to claim 11, characterized in that, The drying process in step (3) includes freeze drying.
24. The preparation method according to claim 11, characterized in that, The reducing agent in step (4) includes a NaBH4 solution.
25. The preparation method according to claim 11, characterized in that, The molar amount of the reducing agent is 20-30 times the molar amount of the metal element in the metal element precursor solution.
26. The preparation method according to claim 11, characterized in that, The stirring time in step (4) is 20-40 minutes.
27. The preparation method according to claim 11, characterized in that, The drying process in step (4) includes freeze drying.
28. The preparation method according to claim 11, characterized in that, The preparation method includes the following steps: (1) Mix biomass material and calcium chloride solution, wherein the mass ratio of biomass material to calcium chloride in calcium chloride solution is 1:(1-4), the particle size of biomass material is 0.07-0.15 mm, and then dry at 100-120℃ for 3-5 h to obtain solid product; wherein the biomass material is corn straw; (2) The solid product obtained in step (1) is carbonized at 600-800℃ for 1-2.5h, then acid-washed with 1-4mol / L hydrochloric acid, then washed with water until neutral, and then ground to obtain porous carbon material; the carbonization is carried out under nitrogen atmosphere; (3) The porous carbon material obtained in step (2) is mixed with a metal element precursor solution, wherein the metal element precursor solution includes a Pt-containing precursor solution and a precursor solution containing a second metal element; the precursor solution containing the second metal element includes any one or a combination of at least two of CrN3O9 solution, PdCl2 solution, CuCl2 solution, RhCl3 solution or H2IrCl6 solution, wherein the mass percentage of Pt element in the Pt-containing precursor solution is 50.0-79.0% of the mass of metal element in the metal element precursor solution, and the mass percentage of the second metal element in the second metal-containing precursor solution is 21.0-50.0% of the mass of metal element in the metal element precursor solution to the porous carbon material obtained in step (3) is (0.67-1.50):1, and then stirred for 12-24 hours, followed by freeze drying to obtain the precursor; (4) The precursor obtained in step (3) is mixed with NaBH4 solution, wherein the molar amount of NaBH4 is 20-30 times the molar amount of metal element in the metal element precursor solution, and then stirred for 20-40 min. After solid-liquid separation, the mixture is freeze-dried to obtain the catalyst.
29. The use of a catalyst based on a biomass-based nitrogen-oxygen dual-doped carbon material as described in any one of claims 1-10, characterized in that, The catalyst is used in the SO2 depolarization electrolysis reaction.