High-performance IT / PANI / CoPi photoelectrode film and preparation method and application thereof
By constructing IT/PANI/CoPi photoelectrode films, the problems of poor stability and low photogenerated carrier transmission efficiency of existing TiO2 photocatalytic materials are solved, and more efficient photoelectrochemical performance and water decomposition ability are achieved.
Patent Information
- Application Number
- CN202510188224.8
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-02-20
- Publication Date
- 2025-05-23
AI Technical Summary
The existing TiO2 photocatalytic materials have poor stability, large bandwidth of band-discharge, and serious photogenerated electron hole pair recombination, resulting in low photocatalytic efficiency.
Using the preparation method of IT/PANI/CoPi photoelectrode film, an IT nanoarray was formed through hydrothermal reaction, and then a PANI hole transport layer was constructed, and a CoPi cocatalyst was loaded on its surface to achieve the preparation of the film by electrodeposition.
The transmission efficiency of photogenerated carriers is improved, the recombination of electron-hole pairs is inhibited, the surface OER reaction is accelerated, the photoelectrochemical performance and water decomposition ability are significantly improved, and the hydrogen production rate is increased by 2.5 times.
Smart Images
Figure CN120026370A_ABST
Abstract
Description
Technical Field
[0001] The present invention belongs to the field of photoelectrochemical technology, and specifically relates to a high-performance IT / PANI / CoPi photoelectrode film and a preparation method and application thereof. Background Art
[0002] The decline of fossil fuel reserves and the release of carbon dioxide and other greenhouse gases have exacerbated global warming, driving the growing demand for clean and sustainable energy and exploring alternative ways to reduce carbon footprints. Solar energy is currently the largest energy source on Earth, but its decentralized and intermittent nature remains a huge challenge to energy demand.
[0003] Due to its natural high stability, non-toxicity, abundance and strong oxidizing ability, TiO 2 The photoelectrocatalytic performance of TiO 2 There are three main phases: anatase (Eg = 3.2 eV), rutile (Eg = 3 eV) and brookite. Theoretically, TiO 2 The theoretical photocurrent at 1.23 V (vs. RHE) is 12.6 mA / cm 2 , a high solar-to-hydrogen conversion efficiency of 15.5% can be achieved. Due to its large bandgap, serious photogenerated electron-hole pairing, poor stability and other shortcomings, pure TiO 2 The photoelectrocatalytic efficiency is still quite small. Summary of the invention
[0004] In view of the shortcomings of the prior art, the present invention proposes a method for preparing a high-performance IT / PANI / CoPi photoelectrode film and its application. The method has the advantages of simple preparation method, convenient operation, and easy control of experimental conditions.
[0005] To achieve the above object, the present invention adopts the following technical solution: A method for preparing a high-performance IT / PANI / CoPi photoelectrode film, comprising the following steps:
[0006] 1) dissolving tetrabutyl titanate in a mixed solution of deionized water and hydrochloric acid, and stirring thoroughly until dissolved to obtain a precursor A solution;
[0007] 2) dissolving indium trichloride in deionized water, stirring to obtain an indium trichloride solution, adding the indium trichloride solution to the precursor A solution in step 1), stirring to obtain an indium-containing precursor B solution;
[0008] 3) placing the cleaned FTO conductive glass in a reactor with the conductive surface facing upward, adding the indium-containing precursor B solution in step 2) into the reactor, and forming an IT nanoarray on the conductive surface of the FTO conductive glass through a hydrothermal reaction; washing and drying the IT nanoarray, and calcining at a high temperature under air conditions to obtain an IT photoelectrode film;
[0009] 4) dissolving aniline in deionized water and adjusting the solution pH to 3 using concentrated hydrochloric acid to obtain a PANI electrodeposition solution C, and electrodepositing the IT photoelectrode obtained in step 3) in the electrodeposition solution C to obtain an IT / PANI photoelectrode; washing the IT / PANI with water and drying it to obtain an IT / PANI photoelectrode film;
[0010] 5) Dissolve dipotassium hydrogen phosphate, potassium dihydrogen phosphate and cobalt nitrate hexahydrate in deionized water to obtain CoPi electrodeposition solution D, and electrodeposit the IT / PANI photoelectrode obtained in step 4) in the electrodeposition solution D. After electrodeposition, rinse and dry the sample to obtain an IT / PANI / CoPi photoelectrode film.
[0011] Preferably, in the above-mentioned high-performance IT / PANI / CoPi photoelectrode film, in step 1), the volume ratio of deionized water: hydrochloric acid is 1:1.
[0012] Preferably, in the above-mentioned high-performance IT / PANI / CoPi photoelectrode film, in step 2), the solubility of the indium trichloride solution is 0.008 mol / L.
[0013] Preferably, in the above-mentioned high-performance IT / PANI / CoPi photoelectrode film, in step 2), the indium-containing precursor B solution has a molar ratio of indium to titanium of 0.002:1.
[0014] Preferably, in the above-mentioned high-performance IT / PANI / CoPi photoelectrode film, in step 3), the hydrothermal reaction has a temperature of 160-180° C. and a time of 3-5 h.
[0015] Preferably, in the above-mentioned high-performance IT / PANI / CoPi photoelectrode film, in step 3), during the high-temperature calcination, calcination is performed at 350-550°C for 2-4h, and the heating rate is 1-10°C / min.
[0016] Preferably, in the above-mentioned high-performance IT / PANI / CoPi photoelectrode film, in step 4), the concentration of the PANI electrodeposition solution C is 0.1 mol / L.
[0017] Preferably, in the above-mentioned high-performance IT / PANI / CoPi photoelectrode film, in step 4), the electrodeposition process is first performed at 100 mW / cm 2 Deposition under light, voltage is 0.5-0.7V vs.Ag / AgCl, time is 30-60s. Then deposition under lightless conditions, voltage is 0.8-1.2V vs.Ag / AgCl, time is 45-90s.
[0018] Preferably, in the above-mentioned high-performance IT / PANI / CoPi photoelectrode film, in step 4), during the drying process, the drying temperature is 60-80° C. and the drying time is 30-60 min.
[0019] Preferably, in the above-mentioned high-performance IT / PANI / CoPi photoelectrode film, in step 5), the molar ratio of dipotassium hydrogen phosphate: potassium dihydrogen phosphate: cobalt nitrate hexahydrate is 1:1:0.005.
[0020] Preferably, in the above-mentioned high-performance IT / PANI / CoPi photoelectrode film, in step 5), the electrodeposition process is carried out at 100 mW / cm 2 Deposition was performed under light conditions with a voltage of 0.2-0.5 V vs. Ag / AgCl and a time of 250-350 s.
[0021] Preferably, in the above-mentioned high-performance IT / PANI / CoPi photoelectrode film, in step 5), during the drying process, the drying temperature is 60-80° C. and the drying time is 30-60 min.
[0022] The high-performance IT / PANI / CoPi photoelectrode film provided by the present invention is used in photoelectrochemical water decomposition.
[0023] The beneficial effects of the present invention are:
[0024] 1. The IT / PANI / CoPi photoelectrode film provided by the present invention improves the transmission efficiency of internal photogenerated carriers and inhibits the recombination of electron-hole pairs by constructing the PANI hole transport layer. At the same time, the loading of the CoPi co-catalyst further accelerates the surface OER reaction, which can effectively improve the photoelectrochemical performance and water decomposition ability.
[0025] 2. The IT / PANI / CoPi photoelectrode film provided by the present invention has a preparation method with cheap and readily available raw materials, simple and convenient operation, provides a new catalytic material for water decomposition, alleviates the current energy shortage situation, and has good application prospects.
[0026] 3. The IT / PANI / CoPi photoelectrode film provided by the present invention has a hydrogen production rate under visible light that is about 2.5 times that of IT.
[0027] 4. The present invention uses an electrodeposition method to construct a PANI hole transport layer on the outer layer of the IT film. Through the construction of the hole transport layer, the serious problem of electron-hole pair recombination on the surface is improved, and the transmission of internal photogenerated carriers is accelerated. At the same time, the loading of CoPi co-catalyst on the surface further solves the serious recombination problem on the surface. The synergistic effect of the two improves the problem of too many defects on the surface of the photoelectrode and slow carrier transmission.
[0028] 5. In the IT / PANI / CoPi photoelectrode film provided by the present invention, PANI improves the transmission efficiency of IT photogenerated carriers and improves the problem of surface electron-hole pair recombination. The presence of CoPi co-catalyst can further accelerate the surface OER reaction. IT / PANI / CoPi photoelectrode film is a promising material for photoelectrochemical water splitting. BRIEF DESCRIPTION OF THE DRAWINGS
[0029] Figure 1 XRD patterns of IT, IT / PANI and IT / PANI / CoPi photoelectrode films prepared in Example 1.
[0030] Figure 2 This is a comparison chart of the LSV of IT, IT / PANI and IT / PANI / CoPi photoelectrode films prepared in Example 1.
[0031] Figure 3 η of the IT, IT / PANI and IT / PANI / CoPi photoelectrode films prepared in Example 1 bulk Comparison chart.
[0032] Figure 4 η of the IT, IT / PANI and IT / PANI / CoPi photoelectrode films prepared in Example 1 surface Comparison chart.
[0033] Figure 5 This is a comparison chart of the hydrogen production rates from water decomposition of IT, IT / PANI and IT / PANI / CoPi photoelectrode films prepared in Example 1. DETAILED DESCRIPTION
[0034] Example 1 High-performance IT / PANI / CoPi photoelectrode film
[0035] (I) Preparation method
[0036] 1. Preparation of IT photoelectrode film
[0037] First, tetrabutyl titanate (0.48 mL, 0.4704 mol) was dissolved in a mixed solution of 15 mL deionized water and 15 mL hydrochloric acid, and the precursor A solution was obtained after magnetic stirring for 15 min. Indium trichloride (0.044236 g, 0.2 μmol) was dissolved in 25 ml deionized water, and the indium trichloride solution was prepared by magnetic stirring for 15 min. Then, 0.515 ml of the indium trichloride solution was put into the precursor A solution, and the precursor B solution was obtained by magnetic stirring for 10 min. The precursor B solution and the cleaned FTO conductive glass were placed in a 50 mL hydrothermal reactor, and the hydrothermal reaction was carried out at 180 ° C for 3.5 h. The precursor IT was grown on the FTO conductive glass to obtain the precursor IT photoelectrode film; the precursor IT photoelectrode film was calcined at 500 ° C for 3 h under air conditions to obtain the IT photoelectrode film.
[0038] 2. Preparation of IT / PANI photoelectrode film
[0039] First, 0.1 M aniline (AR grade) was dissolved in 100 mL of deionized water and magnetically stirred for 30 min, followed by 30 min of ultrasonic dispersion to ensure a uniform solution. The pH of the solution was adjusted to 3 using hydrochloric acid. In a three-electrode system, an IT photoanode was used as the working electrode, a saturated Ag / AgCl electrode was used as the reference electrode, and Pt was used as the counter electrode (CE). The IT photoanode was then heated to 100 mW / cm 2 The resulting IT / PANI photoanode was exposed to 0.6 V vs. Ag / AgCl for 30 s in the absence of light and then treated at 1.0 V vs. Ag / AgCl for 60 s in the absence of light, all in the same solution. The resulting IT / PANI photoanode was thoroughly rinsed with deionized water and dried at 80 °C.
[0040] 3. Preparation of IT / PANI / CoPi photoelectrode films
[0041] Potassium dihydrogen phosphate (1.7417 g), potassium dihydrogen phosphate (1.3608 g) and cobalt nitrate hexahydrate (0.0146 g) were dissolved in 100 ml of deionized water to obtain a CoPi electrodeposition solution, and the IT / PANI film was immersed in the CoPi electrodeposition solution. A 1.5G filter was used as a light source to provide simulated sunlight, and the power intensity was calibrated to 100 mW / cm 2 Then light-assisted electrodeposition was performed at 0.4 V vs. Ag / AgCl for 300 s.
[0042] (II) Testing
[0043] Figure 1 XRD patterns of the prepared IT, IT / PANI and IT / PANI / CoPi photoelectrode films. Figure 1 It can be seen that IT corresponds to SnO 2(FTO), TiO 2 The diffraction peaks of PANI and CoPi are not shown because the PANI and CoPi layers are too thin to be detected.
[0044] Example 2 Application
[0045] The prepared IT, IT / PANI and IT / PANI / CoPi photoelectrode films were subjected to LSV, η bulk , η surface And performance tests such as decomposing water to produce hydrogen.
[0046] All electrochemical experimental tests were conducted in a three-electrode electrochemical workstation (Princeton Applied Research 2273). The sample film was used as the working electrode, the platinum sheet was used as the counter electrode, the Ag / AgCl was used as the reference electrode, the electrolyte was 0.5 M sodium sulfate, and the sample light irradiation area was 1 cm 2 The water decomposition hydrogen production test uses GC-1690 to detect the hydrogen production in each period of time.
[0047] LSV test: The light source is a 300W xenon lamp, and the test results are as follows Figure 2 As shown in the figure, the photocurrent density of IT / PANI and IT / PANI / CoPi photoelectrode films is much greater than that of IT photoelectrode films, among which the photocurrent density of IT / PANI / CoPi photoelectrode is the highest. This shows that the synergistic effect of the hole transport layer PANI and the co-catalyst CoPi improves the photoelectrochemical performance of IT films.
[0048] η bulk Test: The light source is a 300W xenon lamp, and the test results are as follows Figure 3 As shown in the figure, the charge separation efficiency of IT / PANI / CoPi photoelectrode film is much higher than that of IT, indicating that the construction of the hole transport layer PANI improves the transmission of internal carriers and enables holes to be effectively transmitted to the surface. The loading of the co-catalyst CoPi further accelerates the separation efficiency of internal photogenerated carriers, thereby improving the performance of IT / PANI / CoPi photoelectrode film.
[0049] η surface Test: The light source is a 300W xenon lamp, and the test results are as follows Figure 4As shown in the figure, the surface injection efficiency of IT / PANI / CoPi photoelectrode film is much higher than that of IT, indicating that the construction of the hole transport layer PANI effectively improves the recombination problem of surface electrons and holes and improves the surface injection efficiency. After the CoPi co-catalyst is loaded, the surface recombination problem is further improved by improving the OER reaction and accelerating the surface injection efficiency. Thus, the performance of IT / PANI / CoPi photoelectrode film is improved.
[0050] Water decomposition hydrogen production test: The light source is selected as 300W xenon lamp, the bias voltage is 1.23V vs. RHE, and the test results are as follows Figure 5 As shown, the IT / PANI / CoPi photoelectrode film significantly improves the rate of hydrogen production by constructing a PANI hole transport layer and loading the co-catalyst CoPi, which increases the hydrogen production efficiency of the photoelectrode film by 2.5 times. This proves that the IT / PANI / CoPi photoelectrode film has a more effective driving force for water oxidation.
Claims
1. A high-performance IT / PANI / CoPi photoelectrode film, characterized in that: The preparation method comprises the following steps: 1) dissolving tetrabutyl titanate in a mixed solution of deionized water and hydrochloric acid, and stirring thoroughly until dissolved to obtain a precursor A solution; 2) dissolving indium trichloride in deionized water, stirring to obtain an indium trichloride solution, adding the indium trichloride solution to the precursor A solution in step 1), stirring to obtain an indium-containing precursor B solution; 3) placing the cleaned FTO conductive glass in a reactor with the conductive surface facing upward, adding the indium-containing precursor B solution in step 2) into the reactor, and forming an IT nanoarray on the conductive surface of the FTO conductive glass through a hydrothermal reaction; The IT nanoarray is washed with water, dried, and calcined at high temperature under air conditions to obtain an IT photoelectrode film; 4) dissolving aniline in deionized water and adjusting the solution pH to 3 using concentrated hydrochloric acid to obtain a PANI electrodeposition solution C, and electrodepositing the IT photoelectrode obtained in step 3) in the electrodeposition solution C to obtain an IT / PANI photoelectrode; washing the IT / PANI with water and drying it to obtain an IT / PANI photoelectrode film; 5) Dissolve dipotassium hydrogen phosphate, potassium dihydrogen phosphate and cobalt nitrate hexahydrate in deionized water to obtain CoPi electrodeposition solution D, and electrodeposit the IT / PANI photoelectrode obtained in step 4) in the electrodeposition solution D. After electrodeposition, rinse and dry the sample to obtain an IT / PANI / CoPi photoelectrode film.
2. A high-performance IT / PANI / CoPi photoelectrode film according to claim 1, characterized in that: In step 1), the volume ratio of deionized water to hydrochloric acid is 1:
1.
3. A high-performance IT / PANI / CoPi photoelectrode film according to claim 1, characterized in that: In step 2), the solubility of the indium trichloride solution is 0.008 mol / L; and the molar ratio of indium to titanium in the indium-containing precursor B solution is 0.002:
1.
4. A high performance IT / PANI / CoPi photoelectrode film according to claim 1, characterized in that: In step 3), the hydrothermal reaction is carried out at a temperature of 160-180° C. and a time of 3-5 h.
5. A high-performance IT / PANI / CoPi photoelectrode film according to claim 1, characterized in that: In step 3), during the high temperature calcination, the calcination is carried out at 350-550° C. for 2-4 hours, and the heating rate is 1-10° C. / min.
6. A high performance IT / PANI / CoPi photoelectrode film according to claim 1, characterized in that: In step 4), the concentration of the PANI electrodeposition solution C is 0.1 mol / L.
7. A high performance IT / PANI / CoPi photoelectrode film according to claim 1, characterized in that: In step 4), the electrodeposition process is first performed at 100 mW / cm 2 Deposition under light, voltage is 0.5-0.7V vs.Ag / AgCl, time is 30-60s. Then deposition under lightless conditions, voltage is 0.8-1.2V vs.Ag / AgCl, time is 45-90s.
8. A high performance IT / PANI / CoPi photoelectrode film according to claim 1, characterized in that: In step 5), the molar ratio of dipotassium hydrogen phosphate: potassium dihydrogen phosphate: cobalt nitrate hexahydrate is 1:1:0.
005.
9. A high performance IT / PANI / CoPi photoelectrode film according to claim 1, characterized in that: In step 5), the electrodeposition process is carried out at 100 mW / cm 2 Deposition was performed under light conditions with a voltage of 0.2-0.5 V vs. Ag / AgCl and a time of 250-350 s.
10. Application of the high performance IT / PANI / CoPi photoelectrode film prepared by the method according to any one of claims 1 to 9 in photoelectrochemical water splitting.