A photo-thermal combined catalyst and a preparation method and application thereof
By mixing photocatalytic materials with binders and attaching them to photothermal materials to form a photothermal co-catalyst, the problem of low utilization rate of the full spectrum of sunlight in existing technologies is solved, and efficient and low-cost photocatalytic hydrogen production is achieved.
Patent Information
- Application Number
- CN202311416020.2
- Authority / Receiving Office
- CN · China
- Patent Type
- Patents(China)
- Current Assignee / Owner
- Filing Date
- 2023-10-30
- Publication Date
- 2025-12-09
- Estimated Expiration
- 2043-10-30
AI Technical Summary
Existing photocatalysts cannot effectively utilize the full spectrum of sunlight, especially visible and infrared light beyond ultraviolet light, resulting in low solar energy utilization and high hydrogen production costs.
Photocatalytic materials are mixed with binders and mechanically attached to lightweight photothermal materials to form a photothermal co-catalyst. The photothermal conversion effect of the photothermal materials provides a heat source for the photocatalytic materials, improves carrier mobility and energy transfer rate, and makes full use of photons in all bands of sunlight.
It achieves efficient utilization of solar energy, reduces hydrogen production costs, and improves hydrogen production efficiency, especially exhibiting higher hydrogen production performance under visible and infrared light conditions.
Smart Images
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Abstract
Description
TECHNICAL FIELD
[0001] The application belongs to the technical field of hydrogen production catalysts, and particularly relates to a light-heat combined catalyst and a preparation method and application thereof. BACKGROUND
[0002] The photocatalytic decomposition of water to produce hydrogen using solar energy is an effective way to solve the global energy crisis and environmental pollution problems. Under the background of the "double carbon target", the development and convenient application of green hydrogen energy are even more urgent. Although great progress has been made in the research of photocatalytic hydrogen production in recent decades, it still cannot meet the requirements of industrial application. The biggest obstacle is the low utilization rate of solar energy and high cost of hydrogen production. Most photocatalysts can only be excited by ultraviolet or part of visible light. Because of the low photon energy, the infrared light which accounts for the largest proportion cannot excite the electrons on the valence band of the catalyst, and has been ignored in the field of photocatalysis for a long time, resulting in low utilization rate of sunlight. Moreover, most catalysts need to use LED light sources or xenon lamp light sources for excitation, which increases energy consumption and cost. In addition, the unreasonable design of hydrogen production system and the lack of precision work of optical glass also lead to a large number of incident photons being scattered and transmitted, which is also a major reason for the low utilization rate of sunlight. Therefore, the main challenge for the practical application of solar water splitting to produce hydrogen is to maximize the use of solar energy and make each waveband of light photon play its maximum advantage.
[0003] The combination of photocatalysis and photothermal effect can effectively utilize the full spectrum of sunlight, improve the photothermal synergistic effect of low-energy visible light and infrared photons which are insufficient to directly drive photocatalytic reactions, and improve the photocatalytic efficiency, so as to realize the efficient utilization of solar energy. The current research of photothermal synergistic system is mostly embedding plasmonic metal particles on the surface of the catalyst, or combining the catalyst with carbon materials to form a core-shell structure with carbon as the core. Although the plasmonic resonance effect of metal particles and the photothermal effect of carbon materials can effectively convert low-energy photons into heat to promote photocatalytic reactions, the metal particles on the surface of the catalyst will hinder the catalyst from receiving incident photons, and the carbon materials in the center have the problem of low photothermal conversion efficiency. SUMMARY
[0004] In view of the above shortcomings of the prior art, the application provides a light-heat combined catalyst and a preparation method and application thereof.
[0005] To achieve the above purpose, the technical scheme adopted by the application is as follows: a preparation method of a light-heat combined catalyst, comprising the following steps:
[0006] Disperse the photocatalytic material and the binder in the solvent to obtain a mixture A; immerse one side of the photothermal material in the mixture A, and then take out the photothermal material to sequentially perform drying and solidification, to obtain the light-heat combined catalyst; the photothermal material is carbon cloth, nickel foam or carbon foam.
[0007] As a preferred embodiment of the present application, the photocatalytic material is a CuSA / TiO2 material, a Cu / ZnS material or a C3N4 / CdZnS material.
[0008] The CuSA / TiO2 material is a composite of monatomic Cu and TiO2, the Cu / ZnS material is a composite of elemental Cu and ZnS, and the C3N4 / CdZnS material is a composite of C3N4 and CdZnS.
[0009] As a preferred embodiment of the present application, the binder is at least one of polyethylene glycol diacrylate, polyoxymethylene diacrylate diglycol ester, oxidized alginic acid methacrylate, gelatin methyl acrylate, and hyaluronic acid methacrylate.
[0010] As a preferred embodiment of the present application, the mass ratio of the photocatalytic material to the binder is 1:(0.2-20).
[0011] As a preferred embodiment of the present application, the solvent is at least one of water, methanol, ethanol, dichloromethane, and cyclohexane.
[0012] As a preferred embodiment of the present application, the ratio of the volume of the solvent to the total mass of the photocatalytic material and the photothermal material is (1-500) mL:(1-1000) g.
[0013] As a preferred embodiment of the present application, the curing method is UV baking or heat treatment; the time of UV baking is 30-120 min; the temperature of heat treatment is 50-500℃, the time is 20-100 min, and the atmosphere of heat treatment is one or a mixture of two of air, nitrogen, argon, and hydrogen.
[0014] The present application also claims the photothermal combined catalyst prepared by the preparation method of the photothermal combined catalyst.
[0015] The photothermal combined catalyst is a photocatalytic material thin film attached to one side of a photothermal material.
[0016] The planar size of the photothermal material is (0.01-1 m)*(0.01-1 m), the thickness is 0.5-20 mm, the planar size of the photocatalytic material thin film is equal to that of the photothermal material, so that the photocatalytic material thin film can completely cover the planar size of the photothermal material, and the thickness of the photocatalytic material thin film is 10-2000 μm.
[0017] The present application also claims the application of the photothermal combined catalyst in photocatalytic hydrogen production, comprising the following steps:
[0018] The photothermal combined catalyst is placed in a reaction solution, and the photocatalytic material thin film of the photothermal combined catalyst faces the light source to produce hydrogen.
[0019] The light source can emit ultraviolet light, or visible light to infrared light band or full band light.
[0020] The reaction liquid is water and a hole sacrificial agent, and the volume ratio of the water and the hole sacrificial agent is 1:(0.1-0.8); and the size of the light-heat combined catalyst is determined according to the reaction container and the reaction scene.
[0021] The hole sacrificial agent is selected according to the type of the photocatalytic material, and includes methanol, triethanolamine, sodium sulfite, sodium sulfide or ascorbic acid.
[0022] Compared with the prior art, the present application has the beneficial effects that: the photocatalytic material is mechanically attached to one side of the light-heat material, and the synergistic effect of the photocatalytic material and the light-heat material is utilized, the light-heat conversion effect of the light-heat material provides a heat source for the photocatalytic material, thereby reducing the activation energy, improving the carrier mobility, and improving the energy quality transmission rate, realizing efficient solar energy capture and conversion, obtaining high-efficiency and low-cost full-spectrum response light-heat catalytic technology, and the light-heat material supplies water to the photocatalytic material, and both of them fully utilize the photons in each band of sunlight, especially the visible light and infrared light with lower energy, under the same light intensity, higher hydrogen production efficiency is obtained and the hydrogen production cost is reduced. Moreover, the size of the light-heat combined catalyst can be selected according to actual application, and it is easy to expand and mass produce, and it is closer to industrialization. DETAILED DESCRIPTION
[0023] In order to better illustrate the purpose, technical scheme and advantages of the present application, the present application will be further described below in combination with specific examples.
[0024] The preparation method of the CuSA / TiO2 material used in Examples 1-2, 6-8 and Comparative Examples 1-4 includes the following steps: 0.5g of titanium-based metal organic framework MIL-125 is taken as a precursor, is placed in a 40mL, 1.25mmol / L CuCl2 solution to adsorb Cu ions, and then is dried and heat treated at 450℃ for 4 hours to obtain CuSA / TiO2 powder.
[0025] The preparation method of the Cu / ZnS material used in Examples 3-4 is to prepare Cu / ZnS powder by using 0.2mmol of zinc nitrate, 0.2mmol of sodium sulfate and 0.005mmol of copper sulfate as raw materials by a co-precipitation method.
[0026] The preparation method of the C3N4 / CdZnS material used in Example 5 is as follows: 10 g of urea is calcined at 550 DEG C for 3 hours to obtain C3N4, and then 0.37 mmol of zinc acetate, 0.37 mmol of cadmium acetate and 0.015 mol of thiourea are dissolved in a suspension of 300 mg of C3N4, and a C3N4 / CdZnS powder is prepared by hydrothermal reaction at 200 DEG C for 24 hours.
[0027] Example 1
[0028] A preparation method of a photo-thermal combined catalyst, comprising the following steps:
[0029] 10 g of CuSA / TiO2 material and 10 g of oxidized alginate methacrylate are dispersed in 50 mL of ethanol, and a mixture A is obtained by fully stirring to a uniform viscous state; one side of carbon foam is immersed in the mixture A, and the carbon foam is taken out after 45 min, and then is sequentially subjected to drying and UV baking for 60 min to obtain a CuSA / TiO2 / carbon foam photo-thermal combined catalyst; the planar size of the CuSA / TiO2 film is 10 cm*10 cm, and the thickness is 10 μm; the planar size of the carbon foam is 10 cm*10 cm, and the thickness is 0.5 mm.
[0030] Example 2
[0031] A preparation method of a photo-thermal combined catalyst, comprising the following steps:
[0032] 10 g of CuSA / TiO2 material and 10 g of oxidized alginate methacrylate and 5 g of polyoxymethylene diacrylate diethylene glycol are dispersed in 50 mL of ethanol, and a mixture A is obtained by fully stirring to a uniform viscous state; one side of carbon foam is immersed in the mixture A, and the carbon foam is taken out after 45 min, and then is sequentially subjected to drying and UV baking for 30 min to obtain a CuSA / TiO2 / carbon foam photo-thermal combined catalyst; the planar size of the CuSA / TiO2 film is 10 cm*10 cm, and the thickness is 10 μm; the planar size of the carbon foam is 10 cm*10 cm, and the thickness is 0.5 mm.
[0033] Example 3
[0034] A preparation method of a photo-thermal combined catalyst, comprising the following steps:
[0035] 20g Cu / ZnS material and 25g gelatin methyl acrylate are dispersed in 50mL mixed solvent of ethanol and cyclohexane, and fully stirred to obtain a mixture A in uniform viscous state; one side of the nickel foam is immersed in the mixture A, and the nickel foam is taken out after 30min, and then is sequentially dried and heat treated at 200℃ for 30min to obtain a Cu / ZnS / nickel foam photo-thermal combined catalyst; the plane size of the Cu / ZnS film is 1m*1m, and the thickness is 2000μm; the plane size of the nickel foam is 1m*1m, and the thickness is 20mm.
[0036] Example 4
[0037] A preparation method of a photo-thermal combined catalyst, comprising the following steps:
[0038] 20g Cu / ZnS material and 25g gelatin methyl acrylate are dispersed in 50mL mixed solvent of ethanol and cyclohexane, and fully stirred to obtain a mixture A in uniform viscous state; one side of the carbon cloth is immersed in the mixture A, and the carbon cloth is taken out after 50min, and then is sequentially dried and heat treated at 200℃ under argon protection atmosphere for 30min to obtain a Cu / ZnS / carbon cloth photo-thermal combined catalyst; the plane size of the Cu / ZnS film is 1m*1m, and the thickness is 2000μm; the plane size of the nickel foam is 1m*1m, and the thickness is 20mm.
[0039] Example 5
[0040] A preparation method of a photo-thermal combined catalyst, comprising the following steps:
[0041] 15g C3N4 / CdZnS material and 20g hyaluronic acid methyl methacrylate are dispersed in 40mL methanol, and fully stirred to obtain a mixture A in uniform viscous state; one side of the carbon cloth is immersed in the mixture A, and the carbon cloth is taken out after 50min, and then is sequentially dried and heat treated at 150℃ under argon protection atmosphere for 60min to obtain a C3N4 / CdZnS / carbon cloth photo-thermal combined catalyst; the plane size of the C3N4 / CdZnS film is 1m*1m, and the thickness is 2000μm; the plane size of the carbon cloth is 1m*1m, and the thickness is 20mm.
[0042] Example 6
[0043] A preparation method of a photo-thermal combined catalyst, comprising the following steps:
[0044] 10g CuSA / TiO2 material and 5g polyethylene glycol diacrylate are dispersed in 50mL ethanol, fully stirred to obtain a uniform viscous mixture A; one side of the carbon foam is immersed in mixture A, and after 200min, the carbon foam is taken out and sequentially dried, UV baked for 120min to obtain a CuSA / TiO2 / carbon foam light-heat combined catalyst; the planar size of the CuSA / TiO2 film is 10cm*10cm, and the thickness is 20μm; the planar size of the carbon foam is 10cm*10cm, and the thickness is 0.5mm.
[0045] Example 7
[0046] A preparation method of a light-heat combined catalyst, comprising the following steps:
[0047] 10g CuSA / TiO2 material and 200g polyethylene glycol diacrylate are dispersed in 50mL ethanol, fully stirred to obtain a uniform viscous mixture A; one side of the carbon foam is immersed in mixture A, and after 10min, the carbon foam is taken out and sequentially dried, heat treated at 500℃ under argon protection atmosphere for 20min to obtain a CuSA / TiO2 / carbon foam light-heat combined catalyst; the planar size of the CuSA / TiO2 film is 10cm*10cm, and the thickness is 10μm; the planar size of the carbon foam is 10cm*10cm, and the thickness is 0.5mm.
[0048] Example 8
[0049] A preparation method of a light-heat combined catalyst, comprising the following steps:
[0050] 10g CuSA / TiO2 material and 20g polyethylene glycol diacrylate are dispersed in 50mL ethanol, fully stirred to obtain a uniform viscous mixture A; one side of the carbon foam is immersed in mixture A, and after 50min, the carbon foam is taken out and sequentially dried, heat treated at 50℃ under argon protection atmosphere for 100min to obtain a CuSA / TiO2 / carbon foam light-heat combined catalyst; the planar size of the CuSA / TiO2 film is 10cm*10cm, and the thickness is 10μm; the planar size of the carbon foam is 10cm*10cm, and the thickness is 0.5mm.
[0051] Comparative Example 1
[0052] A preparation method of a light-heat combined catalyst, comprising the following steps:
[0053] 10g CuSA / TiO2 material and 10g oxidized alginate methacrylate adhesive were dispersed in 50mL ethanol to obtain a mixture A in uniform viscous state by fully stirring; the carbon foam was fully immersed in the mixture A, and after 45min, the carbon foam was taken out and sequentially dried and UV-baked for 60min to obtain a CuSA / TiO2 / carbon foam light-heat combined catalyst; the CuSA / TiO2 film had a planar size of 10cm*10cm and a thickness of 10μm, and the carbon foam had a planar size of 10cm*10cm and a thickness of 0.5mm.
[0054] Comparative Example 2
[0055] A preparation method of a light-heat combined catalyst, comprising the following steps:
[0056] 10g CuSA / TiO2 material was dispersed in 50mL ethanol to obtain a mixture; one side of the carbon foam was immersed in the mixture, and the carbon foam was taken out and sequentially dried and UV-baked for 60min to obtain a CuSA / TiO2 / carbon foam light-heat combined catalyst; the carbon foam had a planar size of 10cm*10cm and a thickness of 0.5mm, and the amount of CuSA / TiO2 material loaded on the carbon foam was the same as that in Example 1.
[0057] Comparative Example 3
[0058] A preparation method of a light-heat combined catalyst, comprising the following steps:
[0059] 10g CuSA / TiO2 material and 10g P123 were dispersed in 50mL ethanol to obtain a mixture A in uniform viscous state by fully stirring; one side of the carbon foam was immersed in the mixture A, and after 45min, the carbon foam was taken out and sequentially dried and UV-baked for 60min to obtain a CuSA / TiO2 / carbon foam light-heat combined catalyst; the CuSA / TiO2 film had a planar size of 10cm*10cm and a thickness of 10μm, and the carbon foam had a planar size of 10cm*10cm and a thickness of 0.5mm.
[0060] Comparative Example 4
[0061] A preparation method of a light-heat combined catalyst, comprising the following steps:
[0062] 10 g CuSA / TiO2 film and 10 g oxidized alginate methacrylate adhesive were dispersed in 50 mL ethanol to obtain a mixture A in uniform viscous state by sufficient stirring; one side of the carbon foam was coated with the same amount of mixture A as in Example 1, and then was sequentially subjected to drying and UV baking for 60 min to obtain a CuSA / TiO2 / carbon foam light-heat combined catalyst; the CuSA / TiO2 film had a planar size of 10 cm*10 cm and a thickness of 10 μm, and the carbon foam had a planar size of 10 cm*10 cm and a thickness of 0.5 mm.
[0063] Effect Example
[0064] This effect example is to test the hydrogen production effect of the test samples under ultraviolet light (365 nm), visible-infrared light (>400 nm) or full-band light (350-750 nm), and the quantum yield under 365 nm and 420 nm light.
[0065] Test samples: Examples 1-8 and Comparative Examples 1-4, the same carbon foam as in Example 1, the same CuSA / TiO2 film as in Example 1, the same C3N4 / CdZnS film as in Example 5, the same Cu / ZnS film as in Example 3, the same carbon cloth as in Example 5, and the same nickel foam as in Example 3.
[0066] An application of a light-heat combined catalyst in photocatalytic hydrogen production, comprising the following steps:
[0067] The test sample was placed in a reaction solution, and the photocatalyst film in the test sample was placed facing the light source, and hydrogen was produced under ultraviolet light (365 nm), visible-infrared light (>400 nm) or full-band light (350-750 nm), respectively, and the test results are shown in Table 1; the reaction solution was composed of water and methanol, and the volume ratio of water to methanol was 1:0.5.
[0068] Table 1
[0069]
[0070]
[0071] According to the performance comparison of Examples 1-8 and Comparative Examples 1-4, carbon foam, carbon cloth, nickel foam and C3N4 / CdZnS film and Cu / ZnS film in Table 1, the material prepared in the examples has high hydrogen production rate and high quantum yield.
[0072] According to the comparison between the embodiment 1 and the comparative example 1, it can be seen that in the comparative example 1, the carbon foam is entirely immersed in the mixture A, and the carbon foam is entirely covered by the photocatalytic film, which hinders the progress of the photothermal process, and thus the hydrogen production effect of the material under the visible-infrared light and the full wave band is significantly reduced, and the quantum yield under the light of 420 nm is also reduced.
[0073] According to the comparison between the embodiment 1 and the comparative example 2, it can be seen that the CuSA / TiO2 particles are easy to fall off due to the poor adhesion between the CuSA / TiO2 particles and the carbon foam, and the granular photocatalyst is easy to enter the pores of the carbon foam, and the adhesion agent is lacking, and the heat conduction effect is weakened, thus the hydrogen production performance of the material under the ultraviolet light, the visible-infrared light and the full wave band is significantly reduced, and the quantum yield under the light of 365 nm and 420 nm is also reduced.
[0074] According to the comparison between the embodiment 1 and the comparative example 3, it can be seen that the P123 adhesion agent used in the comparative example 3 can adhere the photocatalytic material film to the carbon foam, but since the P123 has almost no photodegradability, the photon utilization of the photocatalyst is affected, and compared with the P123, the adhesion agent of the present application has the effect of heat conduction, and can improve the hydrogen production performance of the material under the ultraviolet light, the visible-infrared light and the full wave band.
[0075] According to the comparison between the embodiment 1 and the comparative example 4, it can be seen that the coating method can reduce the film uniformity of the photocatalytic material on the carbon foam, and thus the hydrogen production performance of the material is reduced.
[0076] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present application, and are not intended to limit the protection scope of the present application. Although the present application has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that the technical solutions of the present application can be modified or replaced by equivalents without departing from the spirit and scope of the technical solutions of the present application.
Claims
1. A method for preparing a photocatalyst, characterized by, It comprises the following steps: The photocatalytic material and the adhesive are dispersed in a solvent to obtain a mixture A by sufficient stirring; one side of the photo-thermal material is immersed in the mixture A, and then the photo-thermal material is taken out and sequentially dried and solidified to obtain the photo-thermal combined catalyst; the photo-thermal material is carbon cloth, nickel foam or carbon foam; The adhesive is at least one of polyethylene glycol diacrylate, polyoxymethylene diacrylate diethylene glycol, oxidized alginate methacrylate, gelatin methyl acrylate and hyaluronic acid methacrylate.
2. The preparation method of the photothermal co-catalyst as described in claim 1, characterized in that, The photocatalytic material is CuSA / TiO2 material, Cu / ZnS material or C3N4 / CdZnS material; the mass ratio of the photocatalytic material to the adhesive is 1:(0.2-20); and the mass ratio of the photocatalytic material to the photo-thermal material is 1:(0.5-80).
3. The method for preparing the photothermal co-catalyst as described in claim 1, characterized in that, The solvent is at least one of water, methanol, ethanol, dichloromethane and cyclohexane.
4. The method for preparing the photothermal co-catalyst as described in claim 1, characterized in that, The ratio of the volume of the solvent to the total mass of the photocatalytic material and the photo-thermal material is (1-500) mL:(1-1000) g.
5. The method for preparing the photothermal co-catalyst as described in claim 1, characterized in that, The solidification mode is UV baking or heat treatment; the UV baking time is 30-120 min; the heat treatment temperature is 50-500℃, the heat treatment time is 20-100 min, and the heat treatment atmosphere is one or a mixture of two of air, nitrogen, argon and hydrogen.
6. The photo-thermal combined catalyst prepared by the preparation method of the photo-thermal combined catalyst according to any one of claims 1-5.
7. The combined photo-thermal catalyst of claim 6, wherein, The photocatalytic material is attached to the upper surface of the photo-thermal material as a thin film to form the photo-thermal combined catalyst.
8. The combined photo-thermal catalyst of claim 7, wherein, The planar size of the photo-thermal material is (0.01-1 m)*(0.01-1 m), and the thickness is 0.5-20 mm; the planar size of the photocatalytic material thin film is the same as that of the photo-thermal material, and the thickness is 10-2000 μm.
9. Use of a photocatalyst according to claim 8 for the photocatalytic production of hydrogen, characterized in that, It comprises the following steps: The photo-thermal combined catalyst is placed in a reaction liquid, and the photocatalytic material thin film in the photo-thermal combined catalyst faces the light source to produce hydrogen.