Preparation method of Fe:CuO / PANI / Pt photocathode and application in photoelectrochemical water splitting
By using Fe-doped and Pt-loaded Fe:CuO/PANI/Pt photocathode films, the problems of high electron-hole recombination rate and weak charge transport capability of CuO photocathode materials were solved, and the high efficiency of photoelectrochemical water splitting performance and hydrogen production capability were improved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- LIAONING UNIVERSITY
- Filing Date
- 2026-03-09
- Publication Date
- 2026-06-09
AI Technical Summary
Existing CuO photocathode materials suffer from problems such as high recombination rate of photogenerated electrons and holes, weak charge transport capacity, insufficient surface catalytic activity, and poor stability, which affect the efficiency of photoelectrochemical water splitting.
The Fe:CuO/PANI/Pt photocathode was prepared by Fe doping and Pt loading to improve the CuO photocathode. The preparation process included electrodeposition and annealing, combined with the deposition of PANI, to form a Fe:CuO/PANI/Pt photocathode thin film.
It improves charge separation efficiency, enhances photoelectrochemical performance and water splitting capability, increases hydrogen production rate to 1.94 times that of CuO, and has low material cost and simple operation.
Smart Images
Figure CN122169154A_ABST
Abstract
Description
Technical Field
[0001] This invention belongs to the field of photoelectrochemical technology, specifically relating to a method for preparing a Fe:CuO / PANI / Pt photocathode and its application in photoelectrochemical water splitting. Background Technology
[0002] Photoelectrochemical water splitting for hydrogen production is considered one of the ideal "zero-carbon" energy pathways because it can directly convert solar energy into high-energy-density hydrogen energy. As the core component of the PEC system, the performance of the photocathode directly determines the energy conversion efficiency; therefore, developing efficient, stable, and low-cost photocathode materials is a key research challenge.
[0003] Currently, metal oxide semiconductors (such as CuO, Fe2O3, and BiVO4) are widely used as photocathode materials due to their suitable band structure, good light absorption performance, and abundance on Earth. Among them, CuO, as a p-type semiconductor, has been theoretically predicted to have a maximum photocurrent density of -35 mA·cm⁻¹ in its photocathode. -2 Copper oxide (CuO) is a low-cost semiconductor that can be obtained from abundant copper in the Earth's crust and from electronic waste containing large amounts of copper wire. However, pure CuO suffers from problems such as high photogenerated electron-hole recombination rate, weak charge transport capacity, insufficient surface catalytic activity, and poor stability. Summary of the Invention
[0004] In view of the shortcomings of existing technologies, this invention proposes a method for preparing Fe:CuO / PANI / Pt photocathodes and their application in photoelectrochemical water splitting. This method has the advantages of simple preparation, convenient operation, and easy control of experimental conditions.
[0005] To achieve the above objectives, the technical solution adopted by the present invention is as follows:
[0006] A method for preparing an Fe:CuO / PANI / Pt photocathode includes the following steps:
[0007] 1) Dissolve CuCl2·2H2O and KCl in deionized water and stir to obtain CuO electrodeposition solution;
[0008] 2) Add FeCl3·6H2O to the CuO electrodeposition solution and stir to obtain an Fe-containing electrodeposition solution;
[0009] 3) Fe-containing electrodeposition solution was placed in a three-electrode electrolytic cell. The working electrode was cleaned FTO conductive glass, the counter electrode was a platinum sheet electrode, and the reference electrode was an Ag / AgCl electrode. Fe-doped Cu nanoparticles were electrodeposited on the FTO conductive glass. Then, the nanoparticles were washed with deionized water and dried in air. The dried Fe-doped Cu nanoparticles were annealed in a muffle furnace to obtain Fe:CuO photocathode film.
[0010] 4) The PANI deposition solution was placed in a three-electrode electrolytic cell. The working electrode was a Fe:CuO photocathode, the counter electrode was a platinum sheet electrode, and the reference electrode was an Ag / AgCl electrode. Electrodeposition was performed on the Fe:CuO photocathode film, followed by drying at room temperature to obtain the Fe:CuO / PANI photocathode film.
[0011] 5) The diluted chloroplatinic acid solution was dropped onto the Fe:CuO / PANI photocathode film placed on the heating stage to load Pt onto the film and obtain the Fe:CuO / PANI / Pt photocathode film.
[0012] Furthermore, in the above-mentioned method for preparing a Fe:CuO / PANI / Pt photocathode, in step 1), according to the ratio of ion molar concentrations, Cu... 2+ :K + =1.25:1.00.
[0013] Furthermore, in the above-mentioned method for preparing a Fe:CuO / PANI / Pt photocathode, in step 2), the molar concentration of FeCl3·6H2O in the CuO electrodeposition solution is 0.006 mol / L.
[0014] Furthermore, in the above-mentioned method for preparing a Fe:CuO / PANI / Pt photocathode, in step 3), the specific operation of cleaning the FTO conductive glass is as follows: first, ultrasonically clean the FTO conductive glass in deionized water for 10-30 min, then ultrasonically clean it in ethanol for 10-30 min; then repeat the above operation 3-5 times, and blow it dry.
[0015] Furthermore, in the above-mentioned method for preparing a Fe:CuO / PANI / Pt photocathode, in step 3), the electrodeposition is performed at a voltage of -2 to -4 V for 1 to 6 minutes.
[0016] Furthermore, in the above-mentioned method for preparing a Fe:CuO / PANI / Pt photocathode, in step 3), annealing is carried out in a muffle furnace under an air atmosphere at 300 ℃~450 ℃ for 2~4 h, with a heating rate of 5 ℃ / min.
[0017] Furthermore, in the above-mentioned method for preparing Fe:CuO / PANI / Pt photocathode, in step 4), the preparation method of the PANI electrodeposition solution is as follows: 0.93g of aniline is added to 100mL of water and 0.82mL of concentrated hydrochloric acid is added, and the mixture is stirred and sonicated to disperse it evenly.
[0018] Furthermore, in step 4) of the above-mentioned method for preparing a Fe:CuO / PANI / Pt photocathode, the electrodeposition is performed at a voltage of -0.1 to -0.3 V for 5 to 60 s.
[0019] Furthermore, in step 5) of the above-mentioned method for preparing a Fe:CuO / PANI / Pt photocathode, the diluted chloroplatinic acid solution is: a 1 g / 100 mL chloroplatinic acid solution diluted five times; the amount of the diluted chloroplatinic acid solution added is 0.02 mL.
[0020] The application of the Fe:CuO / PANI / Pt photocathode described in any of the above items in photoelectrochemical water splitting.
[0021] Furthermore, the above application method is as follows: using Fe:CuO / PANI / Pt photocathode film as the working electrode, platinum sheet as the counter electrode, Ag / AgCl as the reference electrode, 0.5 M sodium sulfate as the electrolyte, a 300 W xenon lamp as the light source, and a bias voltage of 0 V vs. RHE, water decomposition to produce hydrogen is carried out.
[0022] The beneficial effects of this invention are:
[0023] 1. The Fe:CuO / PANI / Pt photocathode thin film provided by this invention improves the efficiency of charge separation, which can effectively enhance photoelectrochemical performance and water splitting ability.
[0024] 2. The Fe:CuO / PANI / Pt photocathode thin film provided by this invention uses inexpensive and readily available raw materials, and is simple and convenient to operate. It provides a new catalytic material for water splitting and has a promising application prospect.
[0025] 3. The Fe:CuO / PANI / Pt photocathode film provided by this invention has a hydrogen production rate under visible light that is about 1.94 times that of CuO. Attached Figure Description
[0026] Figure 1 The images show XRD patterns of the CuO, Fe:CuO, Fe:CuO / PANI, and Fe:CuO / PANI / Pt photocathode films prepared in Example 1.
[0027] Figure 2The image shows a comparison of linear scanning voltammetry results for the CuO, Fe:CuO, Fe:CuO / PANI, and Fe:CuO / PANI / Pt photocathode films prepared in Example 1.
[0028] Figure 3 The graph shows a comparison of the carrier separation efficiencies of the CuO, Fe:CuO, Fe:CuO / PANI, and Fe:CuO / PANI / Pt photocathode films prepared in Example 1.
[0029] Figure 4 The graph shows a comparison of the carrier injection efficiencies of the CuO, Fe:CuO, Fe:CuO / PANI, and Fe:CuO / PANI / Pt photocathode films prepared in Example 1.
[0030] Figure 5 The graph shows a comparison of the water decomposition rates of CuO and Fe:CuO / PANI / Pt photocathode films prepared in Example 1. Detailed Implementation
[0031] Example 1: High-performance Fe:CuO / PANI / Pt photocathode thin film
[0032] (I) Preparation method
[0033] 1) Preparation of CuO electrodeposition solution
[0034] CuCl2·2H2O (0.86 g) and KCl (0.3 g) were dissolved in 100 mL of deionized water, with molar concentrations of 0.005 mol and 0.004 mol, respectively. After magnetic stirring for 15 min, CuO electrodeposition solution was obtained.
[0035] 2) Preparation of Fe-containing electrodeposition solution
[0036] FeCl3·6H2O (0.0162 g) was dissolved in CuO electrodeposition solution to obtain a Fe-containing electrodeposition solution with a molar concentration of 0.006 mol / L. The solution was stirred for 15 min.
[0037] 3) Preparation of CuO photocathode films and Fe:CuO photocathode films
[0038] The prepared CuO electrodeposition solution and Fe-containing electrodeposition solution were placed in a three-electrode electrolytic cell. In the three-electrode electrolytic cell, the working electrode (WE) was cleaned FTO conductive glass (specifically, the FTO conductive glass was ultrasonically cleaned in deionized water for 30 min, then ultrasonically cleaned in ethanol for 30 min; this process was repeated 3 times, and finally dried). The counter electrode (CE) was a platinum sheet electrode, and the reference electrode (RE) was an Ag / AgCl electrode. The applied voltage was -3 V vs. Ag / AgCl. Electrodeposition was performed on the FTO conductive glass for 6 minutes to obtain Cu nanoparticles and Fe-doped Cu nanoparticles, respectively. These were then cleaned with deionized water and dried in air. The dried Cu nanoparticles and Fe-doped Cu nanoparticles were annealed in a muffle furnace under air atmosphere at 450 °C for 2 hours at a heating rate of 5 °C / min to obtain CuO photocathode films and Fe:CuO photocathode films, respectively.
[0039] 4) Preparation of Fe:CuO / PANI photocathode films and Fe:CuO / PANI / Pt photocathode films
[0040] 0.93 g of aniline was added to 100 mL of deionized water to prepare a solution. The solution was stirred and sonicated for 30 min each time to improve its solubility in water. Then, 0.82 mL of concentrated hydrochloric acid was added and stirred again for 30 min to obtain a PANI deposition solution. The PANI deposition solution was placed in a three-electrode electrolytic cell. In the three-electrode electrolytic cell, the working electrode (WE) was a Fe:CuO photocathode, the counter electrode (CE) was a platinum sheet electrode, and the reference electrode (RE) was an Ag / AgCl electrode. The applied voltage was -0.2 V vs. Ag / AgCl. Deposition was performed on the Fe:CuO photocathode film for 10 s, followed by drying at room temperature to obtain a Fe:CuO / PANI photocathode film. A 1 g / 100 mL chloroplatinic acid solution was diluted five times and set aside. 0.02 mL of the diluted chloroplatinic acid solution was dropped onto the Fe:CuO / PANI photocathode film placed on a heating stage. After drying, a Fe:CuO / PANI / Pt photocathode film was obtained.
[0041] (II) Testing
[0042] Figure 1 XRD patterns of the prepared CuO, Fe:CuO, Fe:CuO / PANI, and Fe:CuO / PANI / Pt photocathode films. Figure 1As can be seen, the CuO sample corresponds to the diffraction peaks of FTO (PDF#46-1088) and CuO (PDF#48-1548). However, for Fe:CuO / PANI / Pt, due to the lower Fe doping content and the lower loading of PANI and Pt, the XRD diffraction peaks do not show significant changes.
[0043] Example 2 Application
[0044] The prepared CuO photocathode films, Fe:CuO photocathode films, Fe:CuO / PANI photocathode films, and Fe:CuO / PANI / Pt photocathode films were subjected to performance tests such as linear scanning voltammetry, carrier separation and injection efficiency, and water splitting efficiency.
[0045] All electrochemical experiments were conducted on a three-electrode electrochemical workstation (Princeton Applied Research 2273). CuO and Fe:CuO / PANI / Pt photocathode films were used as working electrodes, respectively, with platinum sheets as counter electrodes and Ag / AgCl as reference electrodes. The electrolyte was 0.5 M sodium sulfate, and the electrolyte for charge separation efficiency was a mixture of 0.5 M sodium sulfate and 0.5 M sodium sulfite. The sample irradiation area was 1 cm². 2 The water splitting test used a GC-1690 to detect the hydrogen production over each time period.
[0046] Linear scanning voltammetry test: The light source was a 300 W xenon lamp, and the results were as follows. Figure 2 As shown, the results indicate that the photocurrent density of the Fe:CuO / PANI / Pt photocathode film is much greater than that of the CuO photocathode film, and the performance of the Fe:CuO / PANI / Pt photocathode film is 2.06 times better than that of the CuO photocathode film at 0 V.
[0047] Carrier separation efficiency test: The light source was a 300 W xenon lamp, and the test results are as follows. Figure 3 As shown in the results, the separation efficiency of the Fe:CuO / PANI / Pt photocathode film is higher than that of the CuO photocathode film. This indicates that Fe doping and the Fe:CuO / PANI / Pt photocathode films loaded with PANI and Pt can accelerate the separation and transport of charge carriers within them, thereby improving the performance of the PEC.
[0048] Carrier injection efficiency test: The light source was a 300 W xenon lamp, and the test results are as follows. Figure 4 As shown in the results, the implantation efficiency of the Fe:CuO / PANI / Pt photocathode film is higher than that of the CuO photocathode film. This indicates that the Fe:CuO / PANI / Pt photocathode film can alter the surface water oxidation reaction, achieving better catalytic performance.
[0049] Hydrogen production test from water splitting: A 300 W xenon lamp was selected as the light source, with a bias voltage of 0 V vs. RHE. The results are as follows. Figure 5 As shown, the hydrogen production rate of the Fe:CuO / PANI / Pt photocathode film is greater than that of CuO, indicating that the Fe:CuO / PANI / Pt photocathode film effectively improves the hydrogen production efficiency of CuO. The hydrogen production efficiency is 1.94 times higher than that of CuO film, proving that the Fe:CuO / PANI / Pt photocathode film has a more effective driving force for water oxidation.
Claims
1. A Fe:CuO / PANI / Pt photocathode, characterized in that, Its preparation method includes the following steps: 1) Dissolve CuCl2·2H2O and KCl in deionized water and stir to obtain CuO electrodeposition solution; 2) Add FeCl3·6H2O to the CuO electrodeposition solution and stir to obtain an Fe-containing electrodeposition solution; 3) Fe-containing electrodeposition solution was placed in a three-electrode electrolytic cell. The working electrode was cleaned FTO conductive glass, the counter electrode was a platinum sheet electrode, and the reference electrode was an Ag / AgCl electrode. Fe-doped Cu nanoparticles were electrodeposited on the FTO conductive glass. Then, the nanoparticles were washed with deionized water and dried in air. The dried Fe-doped Cu nanoparticles were annealed in a muffle furnace to obtain Fe:CuO photocathode film. 4) The PANI deposition solution was placed in a three-electrode electrolytic cell. The working electrode was a Fe:CuO photocathode, the counter electrode was a platinum sheet electrode, and the reference electrode was an Ag / AgCl electrode. Electrodeposition was performed on the Fe:CuO photocathode film, followed by drying at room temperature to obtain the Fe:CuO / PANI photocathode film. 5) The diluted chloroplatinic acid solution was dropped onto the Fe:CuO / PANI photocathode film placed on the heating stage to load Pt onto the film and obtain the Fe:CuO / PANI / Pt photocathode film.
2. The Fe:CuO / PANI / Pt photocathode as described in claim 1, characterized in that, In step 1), according to the ratio of ion molar concentrations, Cu 2+ :K + =1.25:1.
00.
3. The Fe:CuO / PANI / Pt photocathode as described in claim 1, characterized in that, In step 2), the molar concentration of FeCl3·6H2O in the CuO electrodeposition solution is 0.006 mol / L.
4. The Fe:CuO / PANI / Pt photocathode as described in claim 1, characterized in that, In step 3), the specific operation of cleaning the FTO conductive glass is as follows: first, ultrasonically clean the FTO conductive glass in deionized water for 10-30 minutes, then ultrasonically clean it in ethanol for 10-30 minutes; then repeat the above operation 3-5 times and blow it dry.
5. The Fe:CuO / PANI / Pt photocathode as described in claim 1, characterized in that, In step 3), the electrodeposition is carried out at a voltage of -2 to -4 V for 1 to 6 min; and annealing is performed in an air atmosphere in a muffle furnace at 300 ℃ to 450 ℃ for 2 to 4 h, with a heating rate of 5 ℃ / min.
6. The Fe:CuO / PANI / Pt photocathode as described in claim 1, characterized in that, In step 4), the preparation method of the PANI electrodeposition solution is as follows: 0.93g of aniline is added to 100mL of water and 0.82mL of concentrated hydrochloric acid is added, and the mixture is stirred and sonicated to disperse it evenly.
7. The Fe:CuO / PANI / Pt photocathode as described in claim 1, characterized in that, In step 4), the electrodeposition is performed at a voltage of -0.1 to -0.3 V for 5 to 60 seconds.
8. The Fe:CuO / PANI / Pt photocathode as described in claim 1, characterized in that, In step 5), the diluted chloroplatinic acid solution is: a 1 g / 100 mL chloroplatinic acid solution diluted five times; the amount of the diluted chloroplatinic acid solution added is 0.02 mL.
9. The application of the Fe:CuO / PANI / Pt photocathode according to any one of claims 1 to 8 in photoelectrochemical water splitting.
10. The application according to claim 9, characterized in that, The application method is as follows: Fe:CuO / PANI / Pt photocathode film is used as the working electrode, platinum sheet is used as the counter electrode, Ag / AgCl is used as the reference electrode, 0.5 M sodium sulfate is used as the electrolyte, 300 W xenon lamp is used as the light source, and the bias voltage is 0 V vs. RHE to produce hydrogen from water.