CN114438515A - Co(OH)2Modified NiAl-LDH/alpha-Fe2O3Composite light anode and preparation method thereof - Google Patents
Co(OH)2Modified NiAl-LDH/alpha-Fe2O3Composite light anode and preparation method thereof Download PDFInfo
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Abstract
The invention belongs to the technical field of photocatalysis and material chemistry, and particularly relates to Co (OH)2Modified NiAl-LDH/alpha-Fe2O3A composite light anode and a preparation method thereof. Method for preparing alpha-Fe with visible light response by hydrothermal method2O3Powder deposited on fluorine doped SnO2Preparing alpha-Fe on the conductive glass2O3And a photo-anode. Soaking alpha-Fe by using mixed aqueous solution containing nickel nitrate, cobalt nitrate and aluminum nitrate2O3Photoanode, after hydrothermal reactionObtaining Co (OH)2Modified NiAl-LDH/alpha-Fe2O3And (4) a composite light anode. The invention has low raw material price and simple process, and simultaneously loads the multi-element hydrotalcite-like compound on the alpha-Fe2O3On the photo-anode, the prepared composite material has a regular cross-linked network structure, can effectively promote the migration and separation of photo-generated electron holes, and greatly improves the photoelectrochemical activity of the hematite-based photo-anode.
Description
Technical Field
The invention belongs to the technical field of photocatalysis and material chemistry, and particularly relates to Co (OH)2Modified NiAl-LDH/alpha-Fe2O3A composite light anode and a preparation method thereof.
Background
With the rapid development of society, people's demand for energy is increasing day by day. However, the problems of atmospheric and environmental pollution caused by fossil energy have brought great challenges to the sustainable development of human society, so that the development of clean and pollution-free renewable energy is urgently needed. Hydrogen is one of the most potential clean energy sources because of its abundant earth reserves and large combustion heat value. In the existing hydrogen production mode, the advantages of hydrogen production by decomposing water with sunlight are that the device is simple, the operation is simple and convenient, the product purity is high, and the separation is easy, so how to effectively develop and utilize solar energy resources and safely and efficiently convert the solar energy into hydrogen energy becomes a research hotspot in the world.
Since 1972, Fujishima and Honda first reported that titanium dioxide (TiO) was exposed to sunlight2) The electrodes are capable of catalytically decomposing water to produce hydrogen. Since then, hydrogen production by solar hydrolysis of water using semiconductor materials has been widely studied. However, in the process of photoelectrochemical water decomposition, the disadvantages of slow oxidation kinetics, high overpotential and poor stability of anode water seriously affect the improvement of the energy conversion efficiency of the system. Therefore, the development of the anode photoelectric material with low price, high activity and good stability is of great significance.
The current research discovers that BiVO4，WO3，Ta3N5And alpha-Fe2O3The photoelectric anode materials have the function of decomposing water by photocatalysis. Wherein, alpha-Fe2O3The photoanode has the advantages of low band gap value (1.9-2.1 eV), high utilization rate of visible light, abundant reserves, light corrosion resistance, good thermodynamic stability under strong alkaline conditions and the like, and thus the photoanode is widely concerned. At 1.5 standard solar raysIn the presence of alpha-Fe2O3The photocurrent density of the photoanode at 1.23V vs. RHE (relative to standard hydrogen level) can theoretically reach 12.6mA/cm2. However, due to α -Fe2O3The conductivity is poor, the recombination rate of photo-generated electron holes is high, the oxidation reaction speed of water is slow and the like, so that the migration of photo-generated carriers is greatly inhibited, and the lower photoelectrocatalysis activity is caused.
Disclosure of Invention
To solve the technical problems pointed out in the background section, the invention provides Co (OH)2Modified NiAl-LDH/alpha-Fe2O3The composite photoanode is prepared by hydrothermal method of mixing Ni-Al hydrotalcite and Co (OH)2Loaded in alpha-Fe2O3And constructing a novel efficient composite photo-anode material on the photo-anode.
The technical scheme adopted by the invention for solving the technical problems is as follows: co (OH)2Modified NiAl-LDH/alpha-Fe2O3The one-step synthesis method of the composite light anode comprises the following steps:
(1) ultrasonic cleaning FTO glass 1 × 2cm in acetone, anhydrous ethanol and deionized water for 30min, and drying at 80 deg.C for 1 h.
(2) Impregnating the FTO glass obtained in the step (1) in FeCl3·6H2O and NaNO3Carrying out hydrothermal reaction at 80-120 ℃ for 4-8 h in the deionized water solution, drying at 80 ℃ for 1h, roasting at 500-550 ℃ for 3-7 h, annealing at 750 ℃ for 15-60 min, and naturally cooling to room temperature to obtain orange red alpha-Fe2O3And a photo-anode.
Wherein FeCl3·6H2O and NaNO3The feeding molar ratio of (1-3: 1) and the addition amount of deionized water is 35-45 mL.
(3) A certain amount of Ni (NO)3)2·6H2O、Co(NO3)2·6H2O、Al(NO3)3·9H2O、CO(NH)2And NH4F is dissolved in deionized water, ultrasonic oscillation is carried out for 15min, and the alpha-Fe obtained in the step (2) is added2O3The photoanode is dipped in the mixed solution of 80 to cHydrothermal reaction at 100 ℃ for 2-6 h, drying at 80 ℃ for 12h to obtain Co (OH)2Modified NiAl-LDH/alpha-Fe2O3And (4) a composite light anode.
Wherein, Co (NO)3)2·6H2O，Ni(NO3)2·6H2O and Al (NO)3)3·9H2The feeding molar ratio of O is 0.5-6: 3:1, the adding amount of deionized water is 25-45 mL.
The invention has the beneficial effects that:
(1) the raw materials adopted by the invention are cheap and easy to obtain, and the alpha-Fe is prepared by adopting a simple hydrothermal auxiliary roasting method2O3And a photo-anode. Cobalt nitrate, nickel nitrate and aluminum nitrate are selected as precursors of the photo-anode material, different feeding amounts of the cobalt nitrate, the nickel nitrate and the aluminum nitrate are adjusted, and a one-step hydrothermal method is utilized to obtain Co (OH)2Modified NiAl-LDH in-situ supported alpha-Fe2O3A photo anode surface.
(2) The NiAl-LDH is beneficial to the exposure of surface active sites due to the unique layered structure, thereby promoting the penetration of hydroxyl and the precipitation of oxygen in the process of photoelectric water decomposition. Co (OH)2The existence of the compound light anode plays roles in enhancing charge density and accelerating charge transmission, can further improve the photoelectric oxidation performance of the compound light anode, and promotes the kinetic rate of the anode oxygen evolution reaction to be accelerated.
(3)Co(OH)2Modified NiAl-LDH/alpha-Fe2O3The surface of the composite photo-anode has a cross-linked network structure. The structure effectively improves the specific surface area of the material, is beneficial to increasing the photoelectrocatalysis active sites, and also accelerates the migration rate of photoproduction electron holes, thereby being beneficial to improving the photoelectrochemical activity of the photoanode.
(4) The invention provides a Co (OH)2Modified NiAl-LDH/alpha-Fe2O3The preparation method of the composite photo-anode aims at improving alpha-Fe2O3The existing defect of the method is that the multi-element hydrotalcite with more interface occupation ratio is simultaneously loaded on alpha-Fe2O3The composite photo-anode has good photoelectrochemical properties and high stability, and can be usedHydrogen is produced by photoelectric decomposition of water.
Description of the drawings:
FIG. 1 is a view of alpha-Fe2O3Photoanode and NiAl-LDH/alpha-Fe with different Ni and Al molar ratios2O3An X-ray diffraction pattern of the composite photo-anode and a corresponding real object pattern thereof.
FIG. 2 is a view of alpha-Fe2O3Photoanode and Co (OH) with different molar ratios of Ni, Co and Al2/Ni3Al-LDH/α-Fe2O3An X-ray diffraction pattern of the composite photo-anode and a corresponding real object pattern thereof.
FIG. 3(a) is a-Fe2O3Scanning electron micrographs of photoanode(s), (b) and (c) are Ni3Al-LDH/α-Fe2O3Scanning electron micrographs of the composite photoanode, (d), (e) and (f) are [ Co (OH)2]1/Ni3Al-LDH/α-Fe2O3Scanning electron microscopy of the composite photoanode.
FIGS. 4(a) and (b) are NiAl-LDH/alpha-Fe with different molar ratios of Ni and Al2O3A linear voltammetric scan of the composite anodic water oxidation.
FIGS. 5(a) and (b) are Co (OH) having different molar ratios of Ni, Co and Al2/NiAl-LDH/α-Fe2O3A linear voltammetric scan of the composite anodic water oxidation.
FIG. 6 is a view of α -Fe2O3，Ni3Al-LDH/α-Fe2O3And [ Co (OH)2]1/Ni3Al-LDH/α-Fe2O3Transient photocurrent curve of the photoanode.
FIG. 7 is a view of α -Fe2O3，Ni3Al-LDH/α-Fe2O3And [ Co (OH)2]1/Ni3Al-LDH/α-Fe2O3Photoelectrochemical stability test curve of photoanode.
Detailed Description
The present invention is further illustrated by the following examples, but the scope of the present invention is not limited to the following examples.
Example 1
And ultrasonically cleaning 1X 2cm of FTO glass in acetone, absolute ethyl alcohol and deionized water for 30min, and drying at 80 ℃ for 1 h.
0.95g FeCl was weighed out separately3·6H2O and 0.30g NaNO3Dissolving the mixture in 35mL of deionized water, mechanically stirring the mixture for 30min, and transferring the mixture to a 50mL high-pressure reaction kettle. And (3) soaking the FTO glass in the solution, carrying out hydrothermal reaction at 100 ℃ for 4h, cooling to room temperature, washing with deionized water and absolute ethyl alcohol for 3 times respectively, and drying at 80 ℃ for 1h to obtain the FTO conductive glass attached with the faint yellow beta-FeOOH membrane. Placing the product in a muffle furnace, roasting at 500 ℃ for 3h, annealing at 750 ℃ for 15min, and cooling to room temperature to obtain orange red alpha-Fe2O3And (4) a photo-anode for standby.
0.36g of Co (NO)3)2·6H2O，2.19g Ni(NO3)2·6H2O，0.94g Al(NO3)3·9H2O，0.30g CO(NH)2And 0.74g NH4And F is dissolved in 25mL of deionized water, and the homogeneous mixed solution is obtained after ultrasonic oscillation for 15 min. Mixing the above-mentioned alpha-Fe2O3Immersing the photoanode in the solution, carrying out hydrothermal reaction at 100 ℃ for 2h, cooling to room temperature, washing with deionized water and absolute ethyl alcohol respectively for three times, and vacuum drying at 80 ℃ for 12h to obtain [ Co (OH) ]2]0.5/Ni3Al-LDH/α-Fe2O3And (4) a composite light anode.
Example 2
0.73g of Co (NO)3)2·6H2O，2.19g Ni(NO3)2·6H2O，0.94g Al(NO3)3·9H2O、0.30g CO(NH)2And 0.74g of NH4F in 25mL of deionized water, and obtaining a homogeneous mixed solution after ultrasonic oscillation for 15 min. alpha-Fe prepared in example 12O3Immersing the photoanode in the solution, carrying out hydrothermal reaction at 100 ℃ for 2h, cooling to room temperature, washing with deionized water and absolute ethyl alcohol respectively for three times, and vacuum drying at 80 ℃ for 12h to obtain [ Co (OH) ]2]1/Ni3Al-LDH/α-Fe2O3And (4) a composite light anode.
Example 3
1.46g of Co (NO)3)2·6H2O，2.19g Ni(NO3)2·6H2O，0.94g Al(NO3)3·9H2O、0.30g CO(NH)2And 0.74g NH4And F is dissolved in 25mL of deionized water, and the homogeneous mixed solution is obtained after ultrasonic oscillation for 15 min. alpha-Fe prepared in example 12O3Immersing the photoanode in the solution, carrying out hydrothermal reaction at 100 ℃ for 2h, cooling to room temperature, washing with deionized water and absolute ethyl alcohol respectively for three times, and vacuum drying at 80 ℃ for 12h to obtain [ Co (OH) ]2]2/Ni3Al-LDH/α-Fe2O3And (4) a composite light anode.
Example 4
2.18g of Co (NO)3)2·6H2O，2.19g Ni(NO3)2·6H2O，0.94g Al(NO3)3·9H2O，0.30g CO(NH)2And 0.74g NH4And F is dissolved in 25mL of deionized water, and the homogeneous mixed solution is obtained after ultrasonic oscillation for 15 min. alpha-Fe prepared in example 12O3Immersing the photoanode in the solution, carrying out hydrothermal reaction at 100 ℃ for 2h, cooling to room temperature, washing with deionized water and absolute ethyl alcohol respectively for three times, and vacuum drying at 80 ℃ for 12h to obtain [ Co (OH) ]2]3/Ni3Al-LDH/α-Fe2O3And (4) a composite light anode.
Example 5
2.92g of Co (NO)3)2·6H2O，2.19g Ni(NO3)2·6H2O，0.94g Al(NO3)3·9H2O、0.30g CO(NH)2And 0.74g NH4And F is dissolved in 25mL of deionized water, and the homogeneous mixed solution is obtained after ultrasonic oscillation for 15 min. alpha-Fe prepared in example 12O3Immersing the photoanode in the solution, carrying out hydrothermal reaction at 100 ℃ for 2h, cooling to room temperature, washing with deionized water and absolute ethyl alcohol respectively for three times, and vacuum drying at 80 ℃ for 12h to obtain [ Co (OH) ]2]4/Ni3Al-LDH/α-Fe2O3And (4) a composite light anode.
Comparative example 1
0.36g of Ni (NO)3)2·6H2O，0.94g Al(NO3)3·9H2O，0.30g CO(NH)2And 0.74g NH4And F is dissolved in 25mL of deionized water, and the homogeneous mixed solution is obtained after ultrasonic oscillation for 15 min. alpha-Fe prepared in example 12O3Immersing a photo-anode in the solution, carrying out hydrothermal reaction at 100 ℃ for 2h, cooling to room temperature, washing with deionized water and absolute ethyl alcohol respectively for three times, and vacuum drying at 80 ℃ for 12h to obtain Ni0.5Al-LDH/α-Fe2O3。
Comparative example 2
0.73g of Ni (NO)3)2·6H2O，0.94g Al(NO3)3·9H2O，0.30g CO(NH)2And 0.74g of NH4And F is dissolved in 25mL of deionized water, and the homogeneous mixed solution is obtained after ultrasonic oscillation for 15 min. alpha-Fe prepared in example 12O3Immersing a photo-anode in the solution, carrying out hydrothermal reaction at 100 ℃ for 2h, cooling to room temperature, washing with deionized water and absolute ethyl alcohol respectively for three times, and vacuum drying at 80 ℃ for 12h to obtain Ni1Al-LDH/α-Fe2O3。
Comparative example 3
1.46g of Ni (NO)3)2·6H2O，0.94g Al(NO3)3·9H2O，0.30g CO(NH)2And 0.74g of NH4And F is dissolved in 25mL of deionized water, and the solution is subjected to ultrasonic oscillation for 15min to obtain a homogeneous mixed solution. alpha-Fe prepared in example 12O3Immersing a photo-anode in the solution, carrying out hydrothermal reaction at 100 ℃ for 2h, cooling to room temperature, washing with deionized water and absolute ethyl alcohol respectively for three times, and vacuum drying at 80 ℃ for 12h to obtain Ni2Al-LDH/α-Fe2O3。
Comparative example 4
2.19g of Ni (NO)3)2·6H2O，0.94g Al(NO3)3·9H2O，0.30g CO(NH)2And 0.74g of NH4And F is dissolved in 25mL of deionized water, and the homogeneous mixed solution is obtained after ultrasonic oscillation for 15 min. alpha-Fe prepared in example 12O3Immersing a photo-anode in the solution, carrying out hydrothermal reaction at 100 ℃ for 2h, cooling to room temperature, washing with deionized water and absolute ethyl alcohol respectively for three times, and vacuum drying at 80 ℃ for 12h to obtain Ni3Al-LDH/α-Fe2O3。
Comparative example 5
2.91g of Ni (NO)3)2·6H2O，0.94g Al(NO3)3·9H2O，0.30g CO(NH)2And 0.74g of NH4And F is dissolved in 25mL of deionized water, and the homogeneous mixed solution is obtained after ultrasonic oscillation for 15 min. alpha-Fe prepared in example 12O3Immersing a photo-anode in the solution, carrying out hydrothermal reaction at 100 ℃ for 2h, cooling to room temperature, washing with deionized water and absolute ethyl alcohol respectively for three times, and vacuum drying at 80 ℃ for 12h to obtain Ni4Al-LDH/α-Fe2O3。
Application examples
The photoelectrochemical tests were carried out on an electrochemical workstation model CHI730E under 1.5 standard exposures of sunlight simulated by a 500W xenon lamp. In the testing process, a 1mol/L KOH solution is used as an electrolyte, the prepared photo-anode is used as a working electrode, a Pt sheet is used as a counter electrode, and Ag/AgCl is used as a reference electrode. Wherein the area of the working electrode immersed in the electrolyte is fixed to 1cm2The linear voltammetry scanning (LSV) test interval is 0.4-1.6V vs RHE, and the scanning rate is 0.1V/s.
As shown in FIG. 1, except for α -Fe2O3Outside the X-ray characteristic diffraction peak of (2), Ni3Al-LDH/α-Fe2O3The X-ray characteristic diffraction peaks of the composite photo-anode at 2 theta (19.7 degrees) and 53.5 degrees respectively correspond to NiAl-NO3the-LDH, NiAl-LDH crystalline phase, indicating that NiAl-LDH/α -Fe2O3The composite photo-anode is successfully prepared and has high purity.
As shown in fig. 2, except for α -Fe2O3When 2 θ is 19.0 °, 32.7 ° and 53.5 °, the diffraction pattern of (A) is expressed in [ Co (OH) ]2]1/Ni3Al-LDH/α-Fe2O3Co (OH) appears in the composite light anode respectively2And the X-ray characteristics of NiAl-LDHDiffraction peaks, description of Co (OH)2Modified NiAl-LDH/alpha-Fe2O3The composite photo-anode is successfully prepared and has high purity.
As shown in FIG. 3(a), α -Fe2O3Is in a nano rod-shaped structure and is uniformly dispersed on the surface of the FTO glass. FIG. 3(b) shows Ni3Al-LDH/α-Fe2O3The surface appearance of the composite photoanode is a cross-linked reticular structure with loose texture, which indicates that the NiAl-LDH is uniformly covered on the alpha-Fe2O3The NiAl-LDH on the surface and in partial area is in a flower-like microsphere structure formed by aggregating disordered nano sheets, and the diameter of the NiAl-LDH is about 1-4 mu m. As shown in FIGS. 3(c, d and e), [ Co (OH ]2]1/Ni3Al-LDH/α-Fe2O3The composite photo-anode maintains the cross-linked reticular morphology structure, but part of the area is in a spherical flower cluster structure. FIG. 3(f) is a cross-sectional view showing [ Co (OH) ]2]1/Ni3Al-LDH/α-Fe2O3The composite light anode has obvious layered structure of FTO and alpha-Fe2O3And Co (OH)2The NiAl-LDH has a sandwich-like structure, in which [ Co (OH)2]1/Ni3Al-LDH and alpha-Fe2O3Are about 250 and 222.2nm, respectively.
As shown in FIG. 4(a), under dark state conditions, oxidation current of water occurred for all samples when the applied bias was greater than 1.35V vs RHE. As shown in FIG. 4(b), Ni was present under light irradiation3Al-LDH/α-Fe2O3Photocurrent ratio pure alpha-Fe of composite photo-anode2O3The photo-anode is improved by 2.6 times.
As shown in FIG. 5(a), under dark state conditions, oxidation current of water occurred for all samples when the applied bias was greater than 1.30V vs RHE. As shown in FIG. 5(b), under light irradiation, [ Co (OH) ]2]1/Ni3Al-LDH/α-Fe2O3The photocurrent density of the composite photo-anode is 2.03mA/cm2Relatively pure alpha-Fe2O3The improvement is 5 times.
As shown in FIG. 6, pure α -Fe is compared2O3And Ni3Al-LDH/α-Fe2O3Photoanode, [ Co (OH) ]2]1/Ni3Al-LDH/α-Fe2O3The composite light anode has higher transient light current value, which shows that Co (OH)2Modified NiAl-LDH/alpha-Fe2O3The composite photo-anode shows excellent conductivity.
As shown in FIG. 7, pure α -Fe is compared2O3And Ni3Al-LDH/α-Fe2O3Photoanode, [ Co (OH) ]2]1/Ni3Al-LDH/α-Fe2O3After the photoelectric reaction for 2h, the composite photo-anode still has higher photocurrent density, which indicates that Co (OH)2Modified NiAl-LDH/alpha-Fe2O3The composite photo-anode has higher photoelectrochemical stability.
Claims (6)
1. Co (OH)2Modified NiAl-LDH/alpha-Fe2O3The composite light anode is characterized in that nickel-aluminum hydrotalcite and Co (OH)2Loaded in alpha-Fe2O3And constructing the high-efficiency composite photo-anode material on the photo-anode material.
2. Co (OH)2Modified NiAl-LDH/alpha-Fe2O3The preparation method of the composite photo-anode is characterized by comprising the following steps:
(1) ultrasonically cleaning FTO glass of 1 × 2cm in acetone, absolute ethyl alcohol and deionized water for 30min, and drying at 80 deg.C for 1 h;
(2) impregnating the FTO glass obtained in the step (1) in FeCl3·6H2O and NaNO3After hydrothermal reaction in the deionized water solution, drying at 80 ℃ for 1h, roasting, annealing at 750 ℃ for 15-60 min, and naturally cooling to room temperature to obtain orange red alpha-Fe2O3A photo-anode;
(3) mixing Ni (NO)3)2·6H2O、Co(NO3)2·6H2O、Al(NO3)3·9H2O、CO(NH)2And NH4F is dissolved in the deionized water, and then,ultrasonic oscillating for 15min, and mixing the alpha-Fe obtained in the step (2)2O3Immersing the photoanode in the mixed solution for hydrothermal reaction, drying at 80 ℃ for 12h to obtain Co (OH)2Modified NiAl-LDH/alpha-Fe2O3And (4) a composite light anode.
3. The Co (OH) of claim 22Modified NiAl-LDH/alpha-Fe2O3The preparation method of the composite photoanode is characterized in that the FeCl in the step (2)3·6H2O and NaNO3The molar ratio of (A) to (B) is 1-3: 1, and the addition amount of deionized water is 35-45 mL.
4. The Co (OH) of claim 22Modified NiAl-LDH/alpha-Fe2O3The preparation method of the composite photoanode is characterized in that the hydrothermal reaction temperature in the step (2) is 80-120 ℃, and the hydrothermal reaction time is 4-8 hours; the roasting temperature is 500-550 ℃, and the roasting time is 3-7 h.
5. The Co (OH) of claim 22Modified NiAl-LDH/alpha-Fe2O3The preparation method of the composite photoanode is characterized in that the Co (NO) in the step (3)3)2·6H2O，Ni(NO3)2·6H2O and Al (NO)3)3·9H2The molar ratio of O is 0.5-6: 3: 1; the adding amount of the deionized water is 25-45 mL.
6. Co (OH) according to claim 22Modified NiAl-LDH/alpha-Fe2O3The preparation method of the composite photo-anode is characterized by comprising the following steps: and (3) carrying out hydrothermal reaction at the temperature of 80-100 ℃ for 2-6 h.
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| CN115233254A (en) * | 2022-06-20 | 2022-10-25 | 厦门大学 | Core-shell structure of TiO 2 Composite electrode of/NiCoAl-LDH nanorod array and preparation method and application thereof |
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| CN109453777A (en) * | 2018-11-26 | 2019-03-12 | 中国华能集团清洁能源技术研究院有限公司 | α-Fe is improved based on ternary layered double-metal hydroxide2O3The method of photoelectrocatalysis hydrogen production by water decomposition performance |
| CN110760872A (en) * | 2019-06-17 | 2020-02-07 | 常州大学 | α -Fe modified by metal boride2O3Preparation method of base photo-anode |
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| CN109453777A (en) * | 2018-11-26 | 2019-03-12 | 中国华能集团清洁能源技术研究院有限公司 | α-Fe is improved based on ternary layered double-metal hydroxide2O3The method of photoelectrocatalysis hydrogen production by water decomposition performance |
| CN110760872A (en) * | 2019-06-17 | 2020-02-07 | 常州大学 | α -Fe modified by metal boride2O3Preparation method of base photo-anode |
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