Hydrogen and oxygen evolution bifunctional catalytic electrode based on foamed nickel in-situ growth FeMOF spontaneous oxidation reduction deposition Pt nano particles and preparation and application of hydrogen and oxygen evolution bifunctional catalytic electrode
The spontaneous redox deposition of Pt nanoparticles by growing crystalline FeMOF in situ in foam nickel, and the development of dual-function catalytic electrodes solves the problem that precious metal-based catalysts cannot simultaneously improve the efficiency of HER and OER in the prior art, and achieves low-cost and efficient hydrogen evolution and oxygen evolution catalytic performance, which is suitable for industrial water electrolysis.
Patent Information
- Application Number
- CN202510660428.7
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-21
- Publication Date
- 2025-08-15
AI Technical Summary
The existing precious metal-based catalysts can only promote HER or OER alone in the process of electrolyzing hydrogen production, and cannot improve the efficiency of both reactions at the same time. They are costly and scarce, which hinders large-scale application.
Pt nanoparticles were deposited by spontaneous redox growth of crystalline FeMOF in situ. Through the synergistic action of FeMOF and Pt, a dual-function catalytic electrode was developed to simplify the preparation process, avoid the use of additional reducing agents, and the platinum load was low.
It has achieved excellent bifunctional catalytic performance and good stability under alkaline conditions, suitable for industrial water electrolysis, and has broad application prospects.
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Abstract
Description
Technical Field
[0001] The present invention belongs to the field of preparation and application of electrocatalytic electrodes, and particularly relates to the preparation of a dual-function catalytic electrode for hydrogen and oxygen evolution by in-situ growth of FeMOF on nickel foam and spontaneous redox deposition of Pt nanoparticles, and the application of the electrode in electrocatalytic hydrogen evolution, oxygen evolution and water electrolysis. Background Art
[0002] Water electrolysis hydrogen production technology is widely regarded as the greenest hydrogen production technology with the greatest development potential in future hydrogen production technologies. Hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) are two key half-reactions in the water electrolysis hydrogen production process. Their kinetic hysteresis problems (manifested as high activation energy and slow charge transfer rate) hinder the overall water electrolysis efficiency. The key to developing efficient and large-scale industrial water electrolysis hydrogen production lies in the development of efficient and stable electrocatalytic electrodes. So far, precious metal-based materials (Ir, Ru, Pt) are still the most widely used OER and HER electrocatalysts in commercial applications. However, the high cost and scarcity of these materials seriously hinder their large-scale application. Moreover, these precious metal-based catalysts can only promote the separate HER or OER process in the water electrolysis hydrogen production process, but cannot improve the efficiency of both reactions at the same time.
[196] In order to simplify the structure of water electrolyzers and reduce the overall cost of electrode and electrolyzer manufacturing, the research and development of bifunctional electrocatalytic electrodes with both high performance and cost-effectiveness are crucial to achieve large-scale green hydrogen production.
[0003] Platinum-based catalysts are currently the most advanced precious metal-based HER electrocatalysts, but their high cost and scarcity, as well as lack of OER activity, have seriously hindered their large-scale application. Therefore, optimizing the mass loading of Pt and improving the catalytic activity of Pt are extremely important for promoting the widespread application of platinum-based catalysts in the field of hydrogen production by total water splitting. Metal-organic frameworks (MOFs), as a class of coordination compounds with high crystallinity and long-range order, are interconnected by the coordination of metal ions / clusters and organic ligands. They have rich active centers, fast mass transfer, adjustable and rich pores, and good metal nodes / organic ligands, and have stood out in the development of electrocatalysts. Moreover, the self-supporting nickel foam material of in situ grown MOF can be directly used as a catalytic electrode. It has the characteristics of uniform dispersion of catalytic active sites, improved electron conduction, stable structure, and avoidance of binder use. It has received widespread attention in OER catalysis research, but most of them show very poor HER activity. Therefore, the use of Fe in iron metal organic framework (FeMOF) is the key to the development of electrocatalysts. 2+ Based on the spontaneous redox reaction between FeMOF and Pt precursor under mild conditions, we designed the spontaneous redox deposition of Pt nanoparticles by in situ growth of FeMOF on nickel foam. Based on the synergistic effect of FeMOF and Pt, we developed a bifunctional catalytic electrode that simultaneously catalyzes the HER and OER processes and applied it to alkaline water electrolysis. Summary of the Invention
[0004] The present invention provides a dual-functional catalytic electrode for hydrogen and oxygen evolution based on the spontaneous redox deposition of Pt nanoparticles by in-situ growth of crystalline FeMOF on nickel foam, as well as its preparation and application. The catalytic electrode preparation method is simple, the reduction deposition of Pt nanoparticles does not require the use of an additional reducing agent, the platinum loading is low, and it has excellent electrocatalytic performance for hydrogen and oxygen evolution, showing great application prospects in industrial water electrolysis. The present invention is mainly implemented by the following technical solutions:
[0005] A method for preparing a hydrogen and oxygen evolution dual-function catalytic electrode based on in-situ growth of crystalline FeMOF and spontaneous redox deposition of Pt nanoparticles on nickel foam (NF), characterized by comprising the following steps:
[0006] 1) Pretreatment of nickel foam: ultrasonically clean the nickel foam in 1 M hydrochloric acid solution, acetone solution, ethanol, and deionized water for 5 to 10 minutes, and collect the resulting nickel foam for later use;
[0007] 2) Preparation of FeMOF / NF: Dissolve ferric nitrate nonahydrate in DMF, ultrapure water, and ethanol in a volume ratio of 4:1:1 (Solution A). Dissolve terephthalic acid in the same volume of DMF (Solution B). Add Solution B dropwise to Solution A at room temperature with continuous stirring for 30-60 minutes. Transfer the NF and the mixture to a reactor, control the temperature at 120-180°C, and react for 2-12 hours. After the reaction is complete, rinse the NF with ethanol and ultrapure water, respectively, to prepare an in situ grown crystalline iron metal organic framework (FeMOF / NF) on nickel foam, and vacuum dry it for later use.
[0008] 3) Pt x Preparation of FeMOF / NF: FeMOF / NF was placed in a certain concentration of chloroplatinic acid aqueous solution at room temperature to undergo spontaneous redox reaction for 20 to 60 minutes. The NF was then rinsed with ethanol and ultrapure water in turn. Finally, it was dried in vacuum at 60°C to obtain a dual-functional catalytic electrode for hydrogen and oxygen evolution based on in-situ growth of crystalline FeMOF on nickel foam and uniformly loaded with Pt nanoparticles (Pt x -FeMOF / NF, x represents the concentration of chloroplatinic acid solution is x mg / 10 mL).
[0009] Preferably, in step 2), the concentrations of ferric nitrate and terephthalic acid are 0.01 to 0.05 mol / L.
[0010] Preferably, in step 2), stirring is continued at room temperature for 30 to 60 minutes.
[0011] Preferably, in step 2), the temperature is controlled at 120-180° C. and the reaction is carried out for 2-12 hours.
[0012] Preferably, in step 3), the concentration of the chloroplatinic acid aqueous solution is 1 to 20 mg / 10 mL.
[0013] Preferably, in step 3), the FeMOF / NF is placed in a chloroplatinic acid aqueous solution at room temperature to undergo a spontaneous redox reaction.
[0014] Preferably, in step 3), the reaction time at room temperature is 20 to 60 minutes.
[0015] The present invention provides a hydrogen and oxygen evolution dual-function catalytic electrode prepared by the above-mentioned preparation method, which is based on the spontaneous redox deposition of Pt nanoparticles by in-situ growth of crystalline FeMOF grown on nickel foam.
[0016] The present invention provides a hydrogen and oxygen evolution dual-function catalytic electrode based on spontaneous redox deposition of Pt nanoparticles by crystalline FeMOF grown in situ on nickel foam, and its application in electrocatalytic hydrogen evolution, oxygen evolution and water electrolysis.
[0017] Description of the drawings
[0018] Figure 1 Schematic diagram of the preparation process of the hydrogen and oxygen evolution dual-functional catalytic electrode based on the spontaneous redox deposition of Pt nanoparticles by in-situ growth of crystalline FeMOF on nickel foam.
[0019] Figure 2 The present invention is based on the in-situ growth of nickel foam crystalline FeMOF spontaneous redox deposition of Pt nanoparticles hydrogen evolution and oxygen evolution dual-function catalytic electrode Pt x -LSV polarization curves of hydrogen and oxygen evolution of FeMOF / NF in 1 M KOH.
[0020] Figure 3 The Pt prepared by the present invention 10 -LSV polarization curves of hydrogen evolution of the FeMOF / NF bifunctional catalytic electrode in 1 M KOH solution before and after 1000 CV cycles.
[0021] Figure 4 The Pt prepared by the present invention 10 -FeMOF / NF bifunctional catalytic electrode in 1M KOH solution, oxygen evolution LSV polarization curves before and after 1000 CV cycles.
[0022] Figure 5 Pt 10 -FeMOF / NF was used as cathode and anode for water electrolysis stability test (1.0M KOH solution, current density 10mAcm -2 ). DETAILED DESCRIPTION
[0023] The present invention is described in more detail below with reference to examples, but the scope of protection of the claims of the present invention is not limited thereto.
[0024] Example 1
[0025] 1) Pretreatment of nickel foam: Place a suitable size (3×2 cm in this example) 2 ) were ultrasonically cleaned in 1 M hydrochloric acid solution, acetone solution, ethanol and deionized water for 10 min respectively, and the obtained nickel foams were collected for later use.
[0026] 2) Preparation of FeMOF / NF: Dissolve 1 mmol of Fe(NO₃)₃·9H₂O in 10 mL of DMF, 2.5 mL of ultrapure water, and 2.5 mL of ethanol (Solution A). Dissolve 1 mmol of terephthalic acid in 10 mL of DMF (Solution B). Add Solution B dropwise to Solution A at room temperature with continuous stirring for 30 minutes. NFs were placed in a reactor and heat-treated at 120°C for 6 hours. After the reaction, the NFs were rinsed with ethanol and ultrapure water, respectively. Finally, vacuum drying was performed at 60°C for 4 hours to obtain FeMOF / NFs.
[0027] 3) Preparation of Pt1-FeMOF / NF: 1 mg of H2PtCl6·6H2O was dissolved in 10 mL of ultrapure water, and then FeMOF / NF was placed in the solution and reacted at room temperature for 30 min. After the reaction, the NF was rinsed with ethanol and ultrapure water in sequence. Finally, the NF was dried under vacuum at 60°C for 4 h to obtain Pt1-FeMOF / NF. 10 -FeMOF / NF.
[0028] Example 2
[0029] 1) Pretreatment of nickel foam: Place a suitable size (3×2 cm in this example) 2 ) were ultrasonically cleaned in 1 M hydrochloric acid solution, acetone solution, ethanol and deionized water for 10 minutes respectively, and the obtained nickel foams were collected for later use.
[0030] 2) FeMOF / NF Preparation: Dissolve 1 mmol of Fe(NO₃)₃·9H₂O in 10 mL of DMF, 2.5 mL of ultrapure water, and 2.5 mL of ethanol (Solution A). Dissolve 1 mmol of terephthalic acid in 10 mL of DMF (Solution B). Add Solution B dropwise to Solution A at room temperature with continuous stirring for 30 minutes. NFs were placed in a reactor and heat-treated at 150°C for 9 hours. After the reaction, the NFs were rinsed with ethanol and ultrapure water, respectively. Finally, vacuum drying was performed at 60°C for 4 hours to obtain FeMOF / NFs.
[0031] 3) Preparation of Pt5-FeMOF / NF: 5 mg of H2PtCl6·6H2O was dissolved in 10 mL of ultrapure water, and then FeMOF / NF was placed in the solution to react at room temperature for 30 min. After the reaction, the NF was rinsed with ethanol and ultrapure water in sequence. Finally, the NF was dried under vacuum at 60°C for 4 h to obtain Pt5-FeMOF / NF. 10 -FeMOF / NF.
[0032] Example 3
[0033] 1) Pretreatment of nickel foam: Place a suitable size (3×2 cm in this example) 2 ) were ultrasonically cleaned in 1 M hydrochloric acid solution, acetone solution, ethanol and deionized water for 10 minutes respectively, and the obtained nickel foams were collected for later use.
[0034] 2) FeMOF / NF Preparation: Dissolve 1 mmol of Fe(NO₃)₃·9H₂O in 10 mL of DMF, 2.5 mL of ultrapure water, and 2.5 mL of ethanol (Solution A). Dissolve 1 mmol of terephthalic acid in 10 mL of DMF (Solution B). Add Solution B dropwise to Solution A at room temperature with continuous stirring for 60 minutes. NFs were placed in a reactor and heat-treated at 180°C for 2 hours. After the reaction, the NFs were rinsed with ethanol and ultrapure water, respectively. Finally, vacuum drying was performed at 60°C for 4 hours to obtain FeMOF / NFs.
[0035] 3) Pt 10 -FeMOF / NF preparation: 10 mg of H2PtCl6·6H2O was dissolved in 10 mL of ultrapure water, and then FeMOF / NF was placed in the solution and reacted at room temperature for 40 min. After the reaction, the NF was rinsed with ethanol and ultrapure water in turn. Finally, it was dried in vacuum at 60°C for 4 h to obtain Pt 10 -FeMOF / NF.
[0036] Example 4
[0037] 1) Pretreatment of nickel foam: Place a suitable size (3×2 cm in this example) 2 ) were ultrasonically cleaned in 1 M hydrochloric acid solution, acetone solution, ethanol and deionized water for 10 minutes respectively, and the obtained nickel foams were collected for later use.
[0038] 2) FeMOF / NF Preparation: Dissolve 1 mmol of Fe(NO₃)₃·9H₂O in 10 mL of DMF, 2.5 mL of ultrapure water, and 2.5 mL of ethanol (Solution A). Dissolve 1 mmol of terephthalic acid in 10 mL of DMF (Solution B). Add Solution B dropwise to Solution A at room temperature with continuous stirring for 30 minutes. NFs were placed in a reactor and heat-treated at 160°C for 6 hours. After the reaction, the NFs were rinsed with ethanol and ultrapure water, respectively. Finally, vacuum drying was performed at 60°C for 4 hours to obtain FeMOF / NFs.
[0039] 3) Pt 15 -FeMOF / NF preparation: 15 mg of H2PtCl6·6H2O was dissolved in 10 mL of ultrapure water, and then FeMOF / NF was placed in the solution and reacted at room temperature for 60 min. After the reaction, the NF was rinsed with ethanol and ultrapure water in turn. Finally, it was dried in vacuum at 60 ° C for 4 h to obtain Pt 15 -FeMOF / NF.
[0040] Example 5
[0041] 1) Pretreatment of nickel foam: Place a suitable size (3×2 cm in this example) 2 ) were ultrasonically cleaned in 1 M hydrochloric acid solution, acetone solution, ethanol and deionized water for 10 minutes respectively, and the obtained nickel foams were collected for later use.
[0042] 2) FeMOF / NF Preparation: Dissolve 1 mmol of Fe(NO₃)₃·9H₂O in 10 mL of DMF, 2.5 mL of ultrapure water, and 2.5 mL of ethanol (Solution A). Dissolve 1 mmol of terephthalic acid in 10 mL of DMF (Solution B). Add Solution B dropwise to Solution A at room temperature with continuous stirring for 30 minutes. NFs were placed in a reactor and heat-treated at 150°C for 9 hours. After the reaction, the NFs were rinsed with ethanol and ultrapure water, respectively. Finally, vacuum drying was performed at 60°C for 4 hours to obtain FeMOF / NFs.
[0043] 3) Pt 20 -FeMOF / NF preparation: 20 mg of H2PtCl6·6H2O was dissolved in 10 mL of ultrapure water, and then FeMOF / NF was placed in the solution and reacted at room temperature for 60 min. After the reaction, the NF was rinsed with ethanol and ultrapure water in turn. Finally, it was dried in vacuum at 60 ° C for 4 h to obtain Pt 20 -FeMOF / NF.
[0044] Comparative Example
[0045] FeMOF grown on nickel foam was prepared by following the same steps and conditions as those for nickel foam pretreatment and FeMOF / NF in Example 1, and labeled as FeMOF / NF.
[0046] The catalytic performance of the catalytic electrodes prepared in Examples 1-5 and the comparative examples for hydrogen and oxygen evolution was evaluated using a CHI 660B electrochemical test system (Shanghai Chenhua) using a graphite rod and a saturated calomel electrode (SCE) as the auxiliary electrode and the reference electrode, respectively. 2 The test electrolyte was 1 M KOH aqueous solution at room temperature. Linear sweep voltammetry (LSV) was performed at a scan rate of 5 mV / s. The potentials of all measured electrocatalysts were converted to overpotentials relative to the reversible hydrogen electrode (RHE): E(RHE) = E(SCE) + (0.059 × pH) + 0.241. All LSV curves were not iR-corrected.
[0047] Figure 2 a is the LSV polarization curve of hydrogen evolution in 1 M KOH of the catalytic electrodes prepared in Examples 1-5 and the comparative example. Figure 2 b is the LSV polarization curve of the nickel foam self-supporting electrode prepared in Examples 1-5 and Comparative Example in 1M KOH for oxygen evolution. Figure 2 a and Figure 2 As shown in b, Pt x -FeMOF / NF have good catalytic activity for hydrogen and oxygen evolution. In 1M KOH solution, Pt1-FeMOF / NF, Pt5-FeMOF / NF, Pt 10 -FeMOF / NF, Pt 15 -FeMOF / NF and Pt 20 -FeMOF / NF electrode hydrogen evolution overpotential η 10 are 85, 49, 21, 40, 38 and 280 mV respectively, and the oxygen evolution overpotential η 20 are 353, 341, 319, 340, 368 and 352 mV respectively. 10 -FeMOF / NF has the best catalytic performance for hydrogen and oxygen evolution, and its performance is even better than most of the bifunctional hydrogen and oxygen evolution catalytic materials reported so far.
[0048] At the same time, the voltage was applied to the 1 M KOH solution at 100 mV s -1 The CV cycles were performed for 1000 times at a scanning rate of 1000, and the LSV polarization curves before and after the cycles were measured and compared to evaluate the stability of the electrode. Figure 3 Pt prepared in Example 3 10 -LSV polarization curves of hydrogen evolution of FeMOF / NF before and after 1000 CV cycles. Figure 4 Pt prepared in Example 3 10-FeMOF / NF oxygen evolution LSV polarization curves before and after 1000 CV cycles. Figure 3 and Figure 4 The test results show that the dual-functional catalytic electrode for hydrogen and oxygen evolution based on spontaneous redox deposition of Pt nanoparticles by crystalline FeMOF grown in situ on nickel foam proposed in the present invention has excellent stability in catalyzing hydrogen and oxygen evolution in 1M KOH solution.
[0049] Test Example 3 prepared Pt 10 -FeMOF / NF full hydrolysis performance, and investigate its potential industrial applications. 10 -FeMOF / NF was used as both cathode and anode for full water splitting in a 1M KOH electrolytic cell. 10 -FeMOF / NF exhibits excellent full water splitting performance, driving 10 mA cm at a low voltage of 1.50 V. -2 current density. Figure 5 Pt 10 -FeMOF / NF / / Pt 10 -FeMOF / NF electrolysis device at 10mAcm -2 The long-term stability test curve is carried out under the current density of Figure 5 As shown, Pt 10 -FeMOF / NF / / Pt 10 The FeMOF / NF electrolysis device showed almost no current density decay during continuous operation for up to 30 h, showing stable long-term durability, indicating that the proposed Pt-based electrolysis device at room temperature is 4+ with Fe 2+ The spontaneous redox reaction between the prepared nickel foam in situ grown crystalline FeMOF and uniformly loaded Pt nanoparticles has a very excellent durability and has a good industrial application prospect.
Claims
1. A method for preparing a hydrogen and oxygen evolution dual-functional catalytic electrode based on spontaneous redox deposition of Pt nanoparticles by crystalline FeMOF grown in situ on nickel foam (NF), characterized in that: The specific steps include: 1) Pretreatment of nickel foam: ultrasonically clean the nickel foam in 1 M hydrochloric acid solution, acetone solution, ethanol, and deionized water for 5 to 10 minutes, and collect the resulting nickel foam for later use; 2) Preparation of FeMOF / NF: Dissolve ferric nitrate nonahydrate in DMF, ultrapure water, and ethanol in a volume ratio of 4:1:1 (Solution A). Dissolve terephthalic acid in the same volume of DMF (Solution B). Add Solution B dropwise to Solution A at room temperature with continuous stirring for 30-60 minutes. Transfer the NF and the mixture to a reactor, control the temperature at 120-180°C, and react for 2-12 hours. After the reaction is complete, rinse the NF with ethanol and ultrapure water, respectively, to prepare an in situ grown crystalline iron metal organic framework (FeMOF / NF) on nickel foam, and vacuum dry it for later use. 3) Pt x Preparation of FeMOF / NF: FeMOF / NF was placed in a certain concentration of chloroplatinic acid aqueous solution at room temperature to undergo spontaneous redox reaction for 20 to 60 minutes. The NF was then rinsed with ethanol and ultrapure water in turn. Finally, it was dried in vacuum at 60°C to obtain a dual-functional catalytic electrode for hydrogen and oxygen evolution based on in-situ growth of crystalline FeMOF on nickel foam and uniformly loaded with Pt nanoparticles (Pt x -FeMOF / NF, x represents the concentration of chloroplatinic acid solution is x mg / 10 mL).
2. The method for preparing the bifunctional catalytic electrode for hydrogen and oxygen evolution according to claim 1, wherein: In the step 2), the concentrations of ferric nitrate and terephthalic acid are 0.01 to 0.05 mol / L.
3. The method for preparing the bifunctional catalytic electrode for hydrogen and oxygen evolution according to claim 1, wherein: In the step 2), stirring is continued at room temperature for 30 to 60 minutes.
4. The method for preparing the hydrogen and oxygen evolution dual-function catalytic electrode according to claim 1, wherein: In the step 2), the temperature is controlled at 120-180° C. and the reaction is carried out for 2-12 hours.
5. The method for preparing the bifunctional catalytic electrode for hydrogen and oxygen evolution according to claim 1, wherein: In the step 3), the concentration of the chloroplatinic acid aqueous solution is 1 to 20 mg / 10 mL.
6. The method for preparing the bifunctional catalytic electrode for hydrogen and oxygen evolution according to claim 1, wherein: In the step 3), the FeMOF / NF is placed in a chloroplatinic acid aqueous solution at room temperature to undergo a spontaneous redox reaction.
7. The method for preparing a bifunctional catalytic electrode for hydrogen and oxygen evolution according to claim 1, wherein: In the step 3), the reaction time at room temperature is 20 to 60 minutes.
8. A bifunctional catalytic electrode for hydrogen and oxygen evolution prepared by the method for preparing a bifunctional catalytic electrode for hydrogen and oxygen evolution based on spontaneous redox deposition of Pt nanoparticles by in-situ growth of crystalline FeMOF on nickel foam (NF) according to any one of claims 1 to 7, characterized in that The preparation method of the hydrogen and oxygen evolution dual-function catalytic electrode is simple, the reduction deposition of Pt nanoparticles does not require the use of an additional reducing agent, the platinum loading is low, and it has excellent hydrogen and oxygen evolution electrocatalytic performance and stability, and has good application prospects in actual industrial water electrolysis.