Electrocatalyst based on electric furnace dust as well as preparation method and application of electrocatalyst
By directly using electric furnace dust to prepare ZnO/ZnFe2O4 electrocatalysts, the high cost of precious metal catalysts and complex traditional treatments are solved, and efficient production of hydrogen peroxide is achieved, simplified the process flow and reduced environmental pollution.
Patent Information
- Application Number
- CN202510875848.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-06-27
- Publication Date
- 2025-09-02
AI Technical Summary
The existing precious metal catalysts are expensive, and the traditional methods of treating electric furnace dust are complex and seriously polluted, making it difficult to efficiently use electric furnace dust to prepare high-efficiency electrocatalysts for the production of hydrogen peroxide.
Using electric furnace dust as raw material, ZnO/ZnFe2O4 electrocatalyst was prepared by mixing it with perfluorosulfonic acid polymer and isopropanol solution and loading it on Toray carbon paper, and used to produce hydrogen peroxide for electrochemical oxygen reduction reaction.
The preparation process is simplified, heavy metal pollution is avoided, hydrogen peroxide is produced efficiently, transportation and treatment costs are reduced, and it has good environmental and economic benefits.
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Figure CN120575232A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the field of electrocatalysis technology, and in particular to an electrocatalyst based on electric furnace dust, and a preparation method and application thereof. Background Art
[0002] Hydrogen peroxide (H2O2) is an environmentally friendly oxidant and is widely used in wastewater treatment, papermaking, pharmaceuticals and other fields. The traditional anthraquinone production process is complex, energy-intensive and produces harmful by-products, and green alternative technologies are urgently needed. The electrochemical two-electron oxygen reduction reaction (2e - ORR) can directly synthesize H2O2 from water and oxygen, but existing precious metal catalysts are expensive. Therefore, transition metal oxides (TMOs) have received significant attention due to their wide availability, low cost and great stability. Although research on transition metal oxides has made progress, the current focus is on improving the two-electron reduction performance of metal oxides by introducing heteroatoms and studying the synergistic effect of supports; however, the synthesis methods of these catalysts are still complex and there is room for improvement in the selectivity for hydrogen peroxide; in contrast, the synthesis of pure metal oxides is simpler and easier to obtain in large quantities; pure metal oxides show significant potential in the production of hydrogen peroxide by two-electron oxygen reduction reaction; as the number of empty 3d orbitals in transition metal oxides decreases, the adsorption of *OOH, a key intermediate in the two-electron oxygen reduction reaction pathway, may be weakened, thereby improving the catalytic performance.
[0003] Existing studies have demonstrated the effectiveness of various transition metal oxides in driving the two-electron oxygen reduction reaction to produce H2O2; among them, the advantage of Zn-based transition metal oxides is that the 3d orbital of Zn is fully filled, which can hinder the formation of high oxidation states and facilitate the two-electron oxygen reduction reaction; however, the synthesis method of Zn-based electrocatalysts is still complicated, and the selectivity for hydrogen peroxide still needs to be improved.
[0004] Electric Arc Furnace Dust (EAFD) is a typical solid waste generated during the electric furnace steelmaking process in the steel industry. It mainly comes from the smelting of galvanized scrap steel or zinc-iron paragenetic minerals, where metal elements such as zinc and iron volatilize at high temperatures and condense with the flue gas to form fine particles. Its chemical composition is complex, and it is usually rich in zinc and iron oxides (such as ZnO, ZnFe2O4, Fe3O4, etc.), and contains heavy metals such as lead and cadmium and a small amount of alkaline substances (such as CaO, KCl). If not properly handled, it will cause serious environmental and resource waste problems.
[0005] Traditional landfilling not only consumes land resources, but also causes environmental problems such as soil and water pollution due to the leakage of heavy metals (such as zinc and lead), and cannot recover valuable metals. Pyrometallurgical reduction using rotary kilns or rotary hearth furnaces at high temperatures of 1200-1300°C requires large amounts of coke, high energy consumption, and CO2 emissions. In addition, the spinel structure of zinc ferrite (ZnFe2O4) is stable and requires excessive reducing agents to decompose, increasing costs. Hydrometallurgical methods such as sulfuric acid leaching can extract zinc and iron, but they require high acid concentrations and high temperatures, as well as the neutralization of wastewater and the treatment of heavy metal-containing sludge. The process is lengthy and has secondary pollution. Calcification roasting can reduce carbon consumption, but requires subsequent magnetic separation, which is a complex process.
[0006] Therefore, directly selecting electric furnace dust solid waste resources for direct utilization, so that the catalyst does not require a complicated preparation process, does not require excessive preparation costs, and has a simple operation process, has become an idea for the preparation of electrocatalysts. Summary of the Invention
[0007] The purpose of the present invention is to provide an electrocatalyst based on electric furnace dust, a preparation method and application thereof, and to use electric furnace dust to prepare a high-efficiency electrocatalyst for the efficient production of hydrogen peroxide through an electrochemical oxygen reduction reaction.
[0008] The present invention provides a method for preparing an electrocatalyst, comprising the following steps:
[0009] S1: Electric furnace dust (EAFD), perfluorosulfonic acid polymer solution (Nafion solution) and isopropanol solution are mixed in proportion to obtain a suspension;
[0010] S2: The suspension is loaded onto Toray carbon paper and dried to obtain an electrocatalyst.
[0011] Preferably, the mass ratio of the electric furnace dust (EAFD): perfluorosulfonic acid polymer solution (Nafion solution): isopropanol solution is 1:5:95.
[0012] Preferably, in S1, the uniform mixing is achieved by ultrasonic mixing, wherein the ultrasonic frequency is 40 to 59 kHz, the output power is 30 to 100 W, and the ultrasonic mixing time is 10 to 40 minutes.
[0013] Preferably, in S2, the drying temperature is 60-80°C; and the drying time is 5-12 hours.
[0014] Preferably, the catalyst loading amount on the Dongli carbon paper in S2 is 0.02 mg / cm² to 0.5 mg / cm²; the area of the Dongli carbon paper is 1×3 cm², and the catalyst loading area is 1 cm².
[0015] An application of the electrocatalyst in producing hydrogen peroxide.
[0016] Preferably, the electrocatalyst obtained in S2 is placed as a cathode electrode in the cathode chamber of an H-type electrolytic cell, a constant potential is input into the H-type electrolytic cell, and oxygen is introduced to produce hydrogen peroxide.
[0017] The present invention produces hydrogen peroxide at the gas-liquid-solid three-phase interface through an electrochemical oxygen reduction reaction. Specifically, oxygen (O2) is first adsorbed on the catalyst surface and reacts with OH in the alkaline electrolyte. - Combined, a two-electron oxygen reduction reaction occurs at the active site of the catalyst to generate the intermediate HO2 - (O2+H2O+2e⁻→HO2⁻+OH⁻); the catalyst suppresses the four-electron pathway by regulating the adsorption energy of the OOH* intermediate and selectively promotes the production of H2O2.
[0018] Preferably, the constant potential is -0.1 to 0.4 V vs. RHE; the oxygen aeration rate is 0 ml / min to 80 ml / min; the electrolyte in the H-type electrolytic cell is 0.1 mol / L KOH with a pH of 13, 0.1 mol / L PBS with a pH of 7, or 0.5 mol / L H2SO4 with a pH of 0.
[0019] When the aeration rate of the present invention is 0, since the system is open, part of the dissolved oxygen in the solution comes from the air.
[0020] Preferably, the ZnO or ZnFe2O4 electrocatalyst is prepared by the method for preparing the electrocatalyst based on electric furnace dust.
[0021] The present invention discloses the following technical effects: The present invention provides an electrocatalyst based on electric furnace dust and its preparation method and application:
[0022] (1) The present invention directly utilizes electric furnace dust as the raw material of ZnO / ZnFe2O4 electrocatalyst, avoiding the pollution risks such as heavy metal leaching and waste acid discharge in traditional treatment, and does not require complex pretreatment or metal extraction steps, thereby realizing the resource utilization of solid waste and simplifying the solid waste resource utilization process. Traditional methods require multiple steps to recover metals, while the present invention only requires a simple electrode preparation step. Solid waste electric furnace dust is used to prepare ZnO / ZnFe2O4 electrocatalyst as a cathode electrode for electrochemical production of hydrogen peroxide, which can make high-value-added utilization of solid waste (electric furnace dust) that should be landfilled, reducing problems such as waste space occupation and environmental pollution. The prepared ZnO / ZnFe2O4 electrocatalyst can be used for in-situ electrosynthesis of H2O2, replacing the traditional anthraquinone method, avoiding toxic by-products, facilitating decentralized production, and saving transportation costs.
[0023] (2) The prepared ZnO / ZnFe2O4 electrocatalyst has a good hydrogen peroxide yield in the range of 835.9-1023.7 mmol / g·h, which is in line with the current decentralized and efficient production of hydrogen peroxide and avoids the transportation costs and risks after large-scale industrial production. It has good application prospects in the field of environmental purification.
[0024] (3) The prepared cathode does not require a complicated preparation process, does not require excessive preparation costs, and has a simple operation process. BRIEF DESCRIPTION OF THE DRAWINGS
[0025] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.
[0026] Figure 1 This is a comparison chart of hydrogen peroxide yields of the electric furnace dust of the present invention and single-component ZnO and ZnFe2O4;
[0027] Figure 2 This is the XRD diagram of the phase composition of the electric furnace dust of the present invention;
[0028] Figure 3 This is a graph showing the hydrogen peroxide yield of the electrocatalyst of the present invention at different loading amounts;
[0029] Figure 4 Graph showing hydrogen peroxide yields of the electrocatalyst of the present invention at different potentials;
[0030] Figure 5 This is a graph showing the hydrogen peroxide production of the electrocatalyst of the present invention under different oxygen aeration rates;
[0031] Figure 6 : is a graph showing the hydrogen peroxide production of the electrocatalyst of the present invention under different electrolytes. DETAILED DESCRIPTION
[0032] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the accompanying drawings. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.
[0033] In order to make the above-mentioned objects, features and advantages of the present invention more obvious and easy to understand, the present invention is further described in detail below with reference to the accompanying drawings and specific embodiments.
[0034] Example 1:
[0035] The present invention provides a method for producing hydrogen peroxide by preparing an electrocatalyst using solid waste electric furnace dust, comprising the following steps:
[0036] Among them, the main phase components of electric furnace dust include ZnO and ZnFe2O4, and a small amount of KCl components, of which Zn accounts for 48.2%, Fn accounts for 29.8%, and K accounts for 2%. Figure 2 shown.
[0037] Specifically, 10 mg of electric furnace dust, 50 μL of Nafion solution and 950 μL of isopropanol were ultrasonically mixed at an ultrasonic frequency of 40 kHz, an output power of 100 W, and a time of ultrasonic mixing of 20 minutes to obtain a catalyst suspension; the obtained suspension was loaded on Toray carbon paper TGP-H-060, the catalyst loading amount on the Toray carbon paper was 0.04 mg / cm², the area of the Toray carbon paper was 1×3 cm², and the catalyst loading area was 1 cm². The suspension was dried indoors to obtain an electrocatalyst loaded with EAFD on the Toray carbon paper.
[0038] The prepared ZnO / ZnFe2O4 electrocatalyst has efficient electrocatalytic performance. Specifically, the specific process of producing hydrogen peroxide using the ZnO / ZnFe2O4 electrocatalyst as a cathode electrode is as follows:
[0039] Example 1
[0040] (1) Build an H-type electrolytic cell. There are 50 ml of 0.1 M KOH electrolyte with a pH of 13 in the cathode chamber and 50 ml in the anode chamber respectively. Set a Nafion117 proton exchange membrane in the middle of the H-type electrolytic cell. Load the cathode on the platinum electrode clamp in the cathode chamber, and place a Hg / HgO reference electrode and an oxygen aeration pipe to introduce 80 ml / min of oxygen. Connect a graphite rod electrode as the anode in the anode chamber.
[0041] (2) Input a constant potential of 0 V vs. RHE through the electrochemical workstation, take a sample every 15 minutes, for a total of 5 times, take 0.1 ml of the sample, add 0.9 ml of KOH, and then add 3 ml of 0.5 mM Ce(SO4)2·4H2O. Determine the hydrogen peroxide concentration by spectrophotometer at 318 nm, and calculate the hydrogen peroxide yield.
[0042] Example 2
[0043] (1) An H-type electrolytic cell was constructed. 50 ml of 0.1 mol / L PBS electrolyte with a pH of 7 was placed in the cathode chamber and 50 ml of PBS electrolyte with a pH of 7 was placed in the anode chamber. A Nafion 117 proton exchange membrane was placed in the middle of the H-type electrolytic cell. A cathode was placed on the platinum electrode clamp in the cathode chamber, and an Ag / AgCl reference electrode and an oxygen aeration tube were placed to introduce 80 ml / min of oxygen. A graphite rod electrode was connected to the anode chamber as the anode.
[0044] (2) Input a constant potential of 0 V vs. RHE through the electrochemical workstation, take a sample every 15 minutes, for a total of 5 times, take 0.1 ml of the sample, add 0.9 ml of KOH, and then add 3 ml of 0.5 mM Ce(SO4)2·4H2O. Determine the hydrogen peroxide concentration by spectrophotometer at 318 nm, and calculate the hydrogen peroxide yield.
[0045] Example 3
[0046] (1) Build an H-type electrolytic cell. There are 50 ml of 0.5 mol / L H2SO4 electrolyte with a pH of 0 in the cathode chamber and 50 ml of 0.5 mol / L H2SO4 electrolyte in the anode chamber. Set a Nafion117 proton exchange membrane in the middle of the H-type electrolytic cell. Load the cathode on the platinum electrode clamp in the cathode chamber, and place an Ag / AgCl reference electrode and an oxygen aeration pipe to introduce 80 ml / min of oxygen. Connect a graphite rod electrode as the anode in the anode chamber.
[0047] (2) Input a constant potential of 0 V vs. RHE through the electrochemical workstation, take a sample every 15 minutes, for a total of 5 times, take 0.1 ml of the sample, add 0.9 ml of KOH, and then add 3 ml of 0.5 mM Ce(SO4)2·4H2O. Determine the hydrogen peroxide concentration by spectrophotometer at 318 nm, and calculate the hydrogen peroxide yield.
[0048] Figure 1 It can be seen that under the same experimental conditions, the hydrogen peroxide yield of electric furnace dust is higher than that of single-component ZnO and ZnFe2O4.
[0049] Figure 2 It can be seen that the main components of electric furnace dust are ZnFe2O4 and ZnO.
[0050] Figure 3 It can be seen that the best effect is achieved when the loading amount is 0.04 mg / cm². Too much loading amount affects the contact between the catalyst and oxygen, and too little loading amount has no obvious optimization effect.
[0051] Figure 4 It can be seen that when the potential is 0 V vs. RHE (with Hg / HgO as the reference electrode), the yield of electrochemical production of hydrogen peroxide in the H-type electrolytic cell is the highest.
[0052] Figure 5It can be seen that the reactant of the two-electron oxygen reduction reaction participates in the reaction. In a nitrogen environment, the amount of hydrogen peroxide produced is significantly reduced due to the lack of oxygen.
[0053] Figure 6 It can be seen that the prepared ZnO / ZnFe2O4 electrocatalyst exhibits good hydrogen peroxide generation performance in an alkaline environment.
[0054] The various embodiments in this specification are described in a progressive manner, with each embodiment focusing on the differences from other embodiments. Reference can be made to the common and similar parts between the various embodiments. For the devices disclosed in the embodiments, since they correspond to the methods disclosed in the embodiments, the description is relatively simple, and the relevant parts can be referred to the method description.
[0055] The embodiments described above are merely descriptions of preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Without departing from the spirit of the present invention, various modifications and improvements made to the technical solutions of the present invention by persons skilled in the art should fall within the scope of protection defined by the claims of the present invention.
Claims
1. A method for preparing an electrocatalyst based on electric furnace dust, characterized in that: The following steps are involved: S1: The electric furnace dust, the perfluorosulfonic acid type polymer solution and the isopropyl alcohol solution are mixed uniformly in proportion to obtain a suspension; S2: The suspension is loaded onto Toray carbon paper and dried to obtain an electrocatalyst.
2. The method for preparing an electrocatalyst based on electric furnace dust according to claim 1, characterized in that: The mass ratio of the electric furnace dust: the perfluorosulfonic acid polymer solution: the isopropyl alcohol solution is 1:5:
95.
3. The method for preparing an electrocatalyst based on electric furnace dust according to claim 2, characterized in that: In said S1, said uniform mixing is carried out by ultrasonic mixing, wherein the ultrasonic frequency is 40 to 59 kHz, the output power is 30 to 100 W, and the ultrasonic mixing time is 10 to 40 minutes.
4. The method for preparing an electrocatalyst based on electric furnace dust according to claim 1, characterized in that: In S2, the drying temperature is 60-80°C; and the drying time is 5-12 hours.
5. The method for preparing an electrocatalyst based on electric furnace dust according to claim 1, characterized in that: The catalyst loading amount on the Toray carbon paper in S2 is 0.02 mg / cm² to 0.5 mg / cm²; the area of the Toray carbon paper is 1×3 cm², and the catalyst loading area is 1 cm².
6. Use of the electric furnace dust-based electrocatalyst according to any one of claims 1 to 5 in the production of hydrogen peroxide.
7. The use of an electrocatalyst based on electric furnace dust in the production of hydrogen peroxide according to claim 6, characterized in that: The electrocatalyst obtained in S2 is placed as a cathode electrode in the cathode chamber of an H-type electrolytic cell, and a constant potential is input into the H-type electrolytic cell, and oxygen is introduced to produce hydrogen peroxide.
8. The use of an electrocatalyst based on electric furnace dust in the production of hydrogen peroxide according to claim 7, characterized in that: The constant potential is -0.1 to 0.4 V vs. RHE; the oxygen aeration rate is 0 ml / min to 80 ml / min; the electrolyte in the H-type electrolytic cell is 0.1 mol / L KOH with a pH of 13, 0.1 mol / L PBS with a pH of 7, or 0.5 mol / L H2SO4 with a pH of 0.
9. An electrocatalyst based on electric furnace dust, characterized in that: The electrocatalyst is prepared by the method for preparing the electrocatalyst based on electric furnace dust according to any one of claims 1 to 5.
10. The electrocatalyst based on electric furnace dust according to claim 9, characterized in that: The electrocatalyst is ZnO or ZnFe2O4.