Method for producing hydrogen by loading modified polyethylene foam on composite photo-thermal catalyst

Abstract

The invention relates to the technical field of photocatalytic material and hydrogen energy preparation, and discloses a composite photothermal catalyst supported modified polyethylene foam hydrogen production method, which comprises: carrying out surface modification treatment on waste polyethylene foam to obtain a water transmission support layer; preparing a cobaltosic oxide and indium zinc sulfide composite photo-thermal catalyst containing cobaltosic oxide and indium zinc sulfide; polypyrrole is adopted as an adhesive, a cobaltosic oxide and indium zinc sulfide composite photo-thermal catalyst is adhered to a water transmission supporting layer to form a photo-thermal absorption catalytic layer, and the photo-thermal absorption catalytic layer and the water transmission supporting layer jointly form an interface photo-thermal-photocatalytic evaporation hydrogen production system; under the illumination condition, the interface photo-thermal-photocatalytic evaporation hydrogen production system is used for catalyzing decomposition of water vapor to produce hydrogen. Economical, efficient and stable environment-friendly hydrogen production is realized through an interface photo-thermal-photocatalytic evaporation hydrogen production system by virtue of the synergistic advantages of a cheap substrate, an efficient catalyst and photo-thermal.

Description

Technical Field

[0001] The present invention relates to the technical field of photocatalytic materials and hydrogen energy preparation, and in particular to a method for producing hydrogen by using a composite photothermal catalyst-loaded modified polyethylene foam. Background Art

[0002] Global energy and environmental issues are becoming increasingly prominent, and the development of clean energy has become a consensus. Hydrogen, due to its clean and efficient properties, is considered a highly promising future energy source. Using solar photocatalytic water decomposition to produce hydrogen directly converts solar energy into hydrogen energy, making it a key technological path to achieving green hydrogen production and attracting widespread attention in the scientific research community.

[0003] In practical applications, traditional powdered photocatalysts often face limitations such as difficulty in catalyst recovery, easy recombination of photogenerated charges, and the usual requirement for pure water reaction. To address these problems, researchers have drawn on the principle of natural evaporation to develop an interfacial photothermal-photocatalytic water evaporation synergistic hydrogen production technology. This technology constructs special interface materials and uses the photothermal effect to convert liquid water into water vapor, which is then catalyzed by a photothermal catalyst to decompose the water vapor to produce hydrogen. This method is expected to improve energy utilization efficiency, broaden the range of available water quality, and simplify catalyst fixation and recovery. Currently, studies have attempted to use carbon-based materials, modified biomass, hydrogels, etc. as interface materials to construct such hydrogen production systems.

[0004] Although interfacial photothermal-photocatalytic technology shows good prospects, there are still some key issues that need to be optimized in the existing system before it can be promoted and applied. First, some reported interfacial materials, such as specially treated carbon materials or functional gels, have relatively complex preparation processes or high raw material costs, which to a certain extent limits the large-scale economic application of the technology. Secondly, the overall solar energy to hydrogen energy conversion efficiency of the current system still has room for improvement, which involves the coordination and optimization of multiple links such as photothermal conversion, water vapor transport, and the catalytic activity and charge separation efficiency of the photocatalyst itself. The comprehensive performance of some systems in this regard is not ideal. In addition, the long-term stability and anti-deactivation ability of the photocatalyst loaded on the interfacial material, as well as the structural durability and ease of operation of the entire hydrogen production system in actual water environment are also important factors affecting its practical application value.

[0005] Therefore, the present invention proposes a method for producing hydrogen by using a composite photothermal catalyst-loaded modified polyethylene foam to address the deficiencies of the prior art. Summary of the Invention

[0006] In response to the shortcomings of the existing technology, the present invention provides a method for producing hydrogen by composite photothermal catalyst-loaded modified polyethylene foam, which solves the bottleneck problem of the current interfacial photothermal-photocatalytic water evaporation hydrogen production technology in achieving an effective combination of low cost, high efficiency, high stability and convenient operation.

[0007] To achieve the above objectives, the present invention is implemented through the following technical solutions: A method for producing hydrogen by composite photothermal catalyst-loaded modified polyethylene foam, comprising the following steps:

[0008] S1. Surface modification of waste polyethylene foam to obtain a water transmission support layer;

[0009] S2. Preparing a cobalt trioxide and indium zinc sulfide composite photothermal catalyst comprising cobalt trioxide and indium zinc sulfide;

[0010] S3. Using polypyrrole as an adhesive, the cobalt trioxide and indium zinc sulfide composite photothermal catalyst is bonded to the water transport support layer to form a photothermal absorption catalyst layer. The photothermal absorption catalyst layer and the water transport support layer together constitute an interfacial photothermal-photocatalytic evaporation hydrogen production system;

[0011] S4. Under light conditions, the interfacial photothermal-photocatalytic evaporation hydrogen production system is used to catalyze the decomposition of water vapor to produce hydrogen.

[0012] Preferably, the surface modification treatment in step S1 includes:

[0013] S11, grinding the waste polyethylene foam;

[0014] S12, dissolving 1 mg / ml to 3 mg / ml of dopamine hydrochloride in 8 mM to 10 M Tris-HCl at a pH of 8.0 to 9.0, and sonicating for 25 to 35 minutes to dissolve the dopamine hydrochloride to prepare a first mixed solution;

[0015] S13, soaking the polished waste polyethylene foam in the mixed solution 1, and stirring for 20 to 28 hours;

[0016] S14, taking out the soaked waste polyethylene foam, rinsing it thoroughly with deionized water, and then drying it;

[0017] S15. Repeat steps S13 and S14 2 to 4 times.

[0018] Preferably, the cobalt oxide of the cobalt oxide indium zinc sulfide composite photothermal catalyst in step S2 is prepared by the following method:

[0019] 4 mmol to 8 mmol of cobalt nitrate and 22 mmol to 26 mmol of dimethylimidazole were added to 90 ml to 110 ml of methanol solvent and stirred for 25 min to 35 min, then mixed and stirred for 25 min to 35 min, and then allowed to stand for 22 hours to 26 hours to precipitate to obtain an intermediate;

[0020] The intermediate is centrifuged and washed multiple times, and dried at a temperature of 50° C. to 70° C. for 24 to 36 hours to obtain ZIF-67 nanoparticles;

[0021] The ZIF-67 nanoparticles are vacuum calcined at a temperature of 500° C. to 600° C. for 1 to 3 hours to obtain cobalt trioxide nanoparticles.

[0022] Preferably, the indium zinc sulfide in the cobalt trioxide indium zinc sulfide composite photothermal catalyst in step S2 is prepared by the following method:

[0023] 133 mg to 139 mg of zinc chloride, 290 mg to 296 mg of indium chloride tetrahydrate, and 290 mg to 296 mg of thioacetamide are added to distilled water adjusted to a pH of 2.0 to 3.0 by 20 ml to 30 ml of glycerol and 90 ml to 110 ml of a 2.5 mol / L to 3.5 mol / L HCl solution, and dissolved by ultrasonic treatment for 25 minutes to 35 minutes to obtain a second mixed solution;

[0024] The mixed solution 2 is reacted in an oil bath at 70° C. to 90° C. for 1.5 to 2.5 hours to obtain a precipitated product 1;

[0025] The precipitated product is washed with deionized water and ethanol for multiple times, and dried at a temperature of 50° C. to 70° C. for 22 to 36 hours to obtain indium zinc sulfide.

[0026] Preferably, the method for preparing the cobalt trioxide indium zinc sulfide composite photothermal catalyst in step S2 comprises:

[0027] 7.5 mg to 9.5 mg of cobalt trioxide nanoparticles, 540 mg to 550 mg of zinc chloride, 1160 mg to 1180 mg of indium chloride tetrahydrate, and 580 mg to 620 mg of thioacetamide are added to distilled water adjusted to a pH of 2.0 to 3.0 by 20 ml to 30 ml of glycerol and 90 ml to 102 ml of a 2.5 mol / L to 3.5 mol / L HCl solution, and ultrasonically treated for 25 min to 35 min to obtain a mixed solution three;

[0028] The mixed solution 5 is reacted in an oil bath at 75° C. to 85° C. for 1.5 to 2.5 hours to obtain a precipitated product 2;

[0029] The precipitated product is washed by centrifugation multiple times with deionized water and ethanol, and dried at a temperature of 55° C. to 65° C. for 22 to 26 hours to obtain a composite photothermal catalyst of cobalt trioxide and indium zinc sulfide.

[0030] Preferably, the cobalt trioxide indium zinc sulfide composite photothermal catalyst in step S2 is a core-shell pn heterostructure.

[0031] Preferably, the step S3 uses polypyrrole as an adhesive to bond the cobalt trioxide indium zinc sulfide composite photothermal catalyst to the water transmission support layer to form a photothermal absorption catalyst layer. The photothermal absorption catalyst layer and the water transmission support layer together constitute the interfacial photothermal-photocatalytic evaporation hydrogen production system. The steps include:

[0032] Spin-coating the dissolved polypyrrole on the surface of the water transport support layer to form a first polypyrrole coating;

[0033] Uniformly coating the cobalt trioxide indium zinc sulfide composite photothermal catalyst on the first polypyrrole coating, and applying polypyrrole to coat the surface of the cobalt trioxide indium zinc sulfide composite photothermal catalyst to obtain a modified polyethylene foam loaded with the photothermal catalyst;

[0034] The modified polyethylene foam loaded with the photothermal catalyst is dried at 55° C. to 65° C. for 25 to 35 minutes to obtain an interfacial photothermal-photocatalytic evaporation hydrogen production system.

[0035] Preferably, in step S4, the step of utilizing the interfacial photothermal-photocatalytic evaporation hydrogen production system to catalyze the decomposition of water vapor to produce hydrogen under light conditions comprises:

[0036] The interfacial photothermal-photocatalytic evaporation hydrogen production system is placed under light, so that the photothermal absorption catalytic layer of the system and the water transport support layer connected thereto absorb light energy and convert it into heat energy, and the local temperature is increased by utilizing the photothermal effect to promote the evaporation of liquid water in contact with the water transport support layer to form water vapor;

[0037] The water vapor is transported to the surface of the photothermal absorption catalytic layer, and under the synergistic catalysis of the continuous action of the light and the resulting photothermal effect, the photothermal absorption catalytic layer is used to decompose the water vapor contacting its surface to produce hydrogen.

[0038] The present invention provides a method for producing hydrogen by using a composite photothermal catalyst-loaded modified polyethylene foam. This method has the following beneficial effects:

[0039] 1. This invention utilizes widely available and inexpensive waste polyethylene foam as a base material and constructs a support layer with excellent water transport properties through a simple surface modification method. This innovative design not only significantly reduces the raw material cost of the photothermal catalytic hydrogen production system, significantly lowering the high-priced substrate materials used in traditional photocatalytic systems, but also enables the effective reuse of waste, in line with the green environmental protection concept of "waste treatment with waste," and provides a new technical approach to alleviating environmental pressures, promoting a circular economy, and sustainable development.

[0040] 2. The cobalt oxide-indium zinc sulfide composite photothermal catalyst prepared by this invention features a core-shell pn heterojunction structure that significantly enhances the separation efficiency of photogenerated electron-hole pairs and the interfacial charge transport capacity. Compared to single-component catalysts, this composite exhibits superior photocatalytic activity, enabling more efficient decomposition of water vapor to produce hydrogen under illumination, significantly improving the overall solar-to-hydrogen conversion efficiency.

[0041] 3. The interfacial photothermal-photocatalytic evaporation hydrogen production system formed by the modified polyethylene foam loaded with the composite photothermal catalyst cobalt tetroxide and indium zinc sulfide prepared in this invention exhibits stronger UV-visible light absorption and a wider UV-visible light absorption range than the composite photothermal catalyst cobalt tetroxide and indium zinc sulfide. This advantage significantly improves interfacial evaporation efficiency, more effectively converts absorbed light energy (especially solar energy) into heat energy, reduces energy loss, and promotes the decomposition of water vapor by the photothermal catalyst, making it a key to achieving efficient solar-driven water splitting for hydrogen production.

[0042] 4. This invention utilizes a polymer binder to in-situ load and fix the composite photothermal catalyst to the surface of a modified polyethylene foam, creating a stable interfacial photothermal catalytic water evaporation hydrogen production system. This design effectively avoids the agglomeration and loss of the powdered catalyst during the reaction, as well as the resulting light scattering, ensuring long-term catalyst stability and high utilization. Furthermore, the entire hydrogen production system is easily separated and recovered from the water after the reaction, allowing for simple processing and reuse, demonstrating excellent cyclic stability. The preparation process is simple, enabling ease of operation and scale-up.

[0043] 5. By utilizing inexpensive and readily available raw materials and a simple preparation process, combined with its efficient hydrogen production performance and excellent recyclability, this present invention possesses excellent economic potential and practical application value. This floatable interfacial photothermal catalytic water evaporation hydrogen production system can directly utilize evaporated water vapor from the surface of natural water bodies for solar-driven hydrogen production. This feature makes it suitable not only for conventional environments but also for clean energy production using seawater evaporation in coastal areas or limited water resources in arid and semi-arid regions. BRIEF DESCRIPTION OF THE DRAWINGS

[0044] Figure 1 X-ray diffraction patterns of cobalt oxide (Co3O4) prepared in Example 1, indium zinc sulfide (ZnIn2S4) prepared in Example 2, and cobalt oxide indium zinc sulfide composite photothermal catalyst (Co3O4@ZIS) prepared in Example 3;

[0045] Figure 2UV-visible absorption spectra of the cobalt oxide (Co3O4) prepared in Example 1, the indium zinc sulfide (ZnIn2S4) prepared in Example 2, the cobalt oxide and indium zinc sulfide composite photothermal catalyst (Co3O4@ZIS) prepared in Example 3, the modified polyethylene foam (M-EPE) prepared in Example 5, and the water evaporation hydrogen production system (Co3O4@ZIS / M-EPE) with an interface-loaded photothermal catalyst content of 1.0% Co3O4@ZIS;

[0046] Figure 3 This is a bar graph of the hydrogen production-time of the products obtained from the cobalt trioxide (Co3O4) prepared in Example 1, the indium zinc sulfide (ZnIn2S4) prepared in Example 2, and the cobalt trioxide indium zinc sulfide composite photothermal catalyst (Co3O4@ZIS) prepared in Example 3 in a pure water environment under standard sunlight;

[0047] Figure 4 Schematic diagram and scanning electron microscope image of the interfacial photothermal catalytic water evaporation hydrogen production system prepared in Example 5;

[0048] Figure 5 The bar graph is a graph showing the hydrogen production amount versus time for the products obtained in Examples 4-6 in a pure water environment under standard sunlight;

[0049] Figure 6 This is a cyclic experimental diagram of hydrogen production-time of the product obtained in Example 5 in a pure water environment under standard sunlight;

[0050] Figure 7 This is a bar graph of hydrogen production versus time for the product obtained in Example 5 under standard sunlight in a non-pure water environment;

[0051] Figure 8 Schematic diagram of hydrogen production by evaporation in a floatable photothermal-photocatalytic system. DETAILED DESCRIPTION

[0052] The following will clearly and completely describe the technical solutions in the embodiments of the present invention in conjunction with the drawings in the present specification. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without making creative efforts are within the scope of protection of the present invention.

[0053] In order to better understand the present invention, the above contents are described in detail below in conjunction with specific embodiments.

[0054] Please see the attached Figure 1 -Attached Figure 8 The present invention provides a method for producing hydrogen by using a composite photothermal catalyst loaded modified polyethylene foam.

[0055] The floatable photothermal-photocatalytic system based on waste polymer-based photothermal materials is loaded with photothermal catalysts to realize the evaporation of water into hydrogen through the heat exchange layer, converting the traditional three-phase hydrogen production system into a solid-gas two-phase hydrogen production system, reducing the energy barrier of the reduction hydrogen production reaction, and accelerating the hydrogen generation rate.

[0056] Through simple modification and rational structural design, a high-level reuse of discarded polyethylene foam (EPE) is achieved. This not only reduces the cost of photothermal materials but also provides a platform for photocatalytic hydrogen production. This not only allows for waste reuse and protects the environment, but also overcomes the limitation of traditional photocatalytic hydrogen production on pure water, thus aligning with the concept of sustainable development. Furthermore, it can fully utilize solar energy resources in arid regions, avoiding the waste of renewable energy.

[0057] At the same time, a simple “adhesive method” was used to load the photothermal catalyst Co3O4@ZIS onto the modified polyethylene foam (named M-EPE), constructing an integrated structure of interfacial photothermal-photocatalytic evaporation hydrogen production Co3O4@ZIS / M-EPE. While retaining the strong mechanical properties and high thermal insulation capabilities of EPE, it also has good hydrophilicity, wide spectrum absorption capacity and low thermal conductivity, which maximizes the photothermal synergistic effect and greatly enhances the efficiency of solar-hydrogen energy conversion. The polyethylene material itself is durable and can achieve cyclic stability of hydrogen production efficiency in water bodies, which can break the dependence on high-energy-consuming materials. Floating photothermal-photocatalytic evaporation hydrogen production system such as Figure 8 shown.

[0058] The interface photo-thermal-photo-catalytic hydrogen production system has a double-layer structure. The upper layer is formed by the photo-thermal catalyst Co3O4@ZIS and polypyrrole (PPy) which has good ultraviolet-visible light absorption capacity. The lower layer is a support layer which is formed by the EPE modified by the polydopamine (PDA) polymer with strong adhesion and good photo-thermal conversion performance. The EPE has a large pore structure, and the M-EPE has good water transmission capacity due to the hydrophilic property. Under light irradiation, the water evaporation efficiency can be improved. The photo-thermal catalyst Co3O4@ZIS does not directly contact with water, and is supported by the substrate with a distance of about 1 mm from the water surface. Under solar irradiation, the catalyst generates electron-hole pairs, and the photo-thermal effect causes the temperature of the catalyst and the surrounding environment to rise, resulting in the evaporation of the water surface below, and the water vapor rises to the catalyst surface. Under the joint action of photo-catalysis and thermal catalysis, the water vapor is decomposed into H2 and O2. From the perspective of the phase interface, the floatable photo-thermal-photo-catalytic system presents a water vapor / photo-thermal catalyst two-phase interface. The photo-thermal catalyst is fixed on the polymer substrate. Under standard solar spectrum irradiation, the Co3O4@ZIS composite structure can widen the light absorption range, accelerate the separation efficiency of the carriers, and improve the photo-catalytic activity. The photo-thermal catalyst Co3O4@ZIS and the water vapor decomposed by the photo-thermal effect undergo a reduction reaction to generate hydrogen. Compared with the traditional solid-liquid-gas three-phase hydrogen production, the solid-gas two-phase hydrogen production can reduce the reaction barrier of hydrogen.

[0059] Example 1

[0060] Step one, respectively take 6mmol of cobalt nitrate, 24mmol of dimethyl imidazole, and respectively add 100ml of methanol solvent, respectively stir for 30min, then mix and stir for 30min, stand for 24h to precipitate, get dark purple precipitate A1 (intermediate);

[0061] Step two, the material A1 (intermediate) obtained in step one is washed and dried by methanol and ethanol for several times, and dried in a 60℃ oven for 24h to obtain purple ZIF-67, marked as B1;

[0062] Step three, put the material B2 obtained in step two into a porcelain week, heat at a rate of 1℃ / min in a tube furnace, keep at 550℃ for 2h to obtain black Co3O4, marked as C1.

[0063] Example 2

[0064] Step one, respectively take 136.3mg of zinc chloride, 293.24mg of thioacetamide and 293.24mg of indium chloride tetrahydrate, take 24ml of glycerol, add 96ml of distilled water adjusted to pH=2.5 with HCl solution (3mol / L), and ultrasonic for 30min to dissolve, get material A2 (mixed liquid two);

[0065] Step 2: Add the A2 (mixed solution 2) obtained in step 1 into a 250 ml single-necked flask and incubate in an oil bath at 80°C for 2 h to obtain a light yellow precipitate B2 (precipitation product 1);

[0066] Step 3: The material B2 (precipitation product 1) obtained in step 2 is centrifugally washed and dried with deionized water and ethanol for multiple times, and then dried in an oven at 60° C. for 24 h to obtain indium zinc sulfide C2.

[0067] Example 3:

[0068] Step 1: Weigh 545 mg of zinc chloride, 601 mg of thioacetamide, 1173 mg of indium chloride tetrahydrate, and 8.5 mg of cobalt tetroxide, respectively, add 24 ml of glycerol, add 96 ml of distilled water adjusted to pH 2.5 with HCl solution (3 mol / L), and sonicate for 30 minutes to dissolve, to obtain material A3 (mixed solution 3);

[0069] Step 2: Add the material A3 (mixed solution 3) obtained in step 1 into a 250 ml single-necked flask and place it in an oil bath at 80°C for 2 hours to obtain a light gray precipitate B3 (precipitation product 2);

[0070] Step 3: The B3 (precipitation product 2) material obtained in step 2 is centrifugally washed and dried with deionized water and ethanol multiple times, and then dried in an oven at 60° C. for 24 h to obtain a 1% cobalt trioxide indium zinc sulfide composite photothermal catalyst C3.

[0071] Example 4:

[0072] Step 1: Weigh 2 mg / ml of dopamine hydrochloride and dissolve it in 10 mM Tris-HCl (pH = 8.5). Ultrasonicate for 30 minutes to dissolve it to obtain material A4 (mixture 1);

[0073] Step 2: Sandpaper-polished waste polyethylene foam with a diameter of 3.5 cm and a thickness of 0.2 cm was immersed in material A4 and stirred continuously for 24 hours. After removal, it was rinsed with deionized water and dried. This process was repeated for 3 days to obtain dark gray modified polyethylene foam B4.

[0074] Step 3: Spin-coat the dissolved polypyrrole on the surface of material B4, then weigh 0.5 mg of cobalt trioxide indium zinc sulfide composite photothermal catalyst and spin-coat it evenly, and finally coat it with polypyrrole to obtain modified polyethylene foam C4 loaded with photothermal catalyst;

[0075] Step 4: drying the material C4 obtained in step 3 in an oven at 60° C. for 30 minutes to obtain a water evaporation hydrogen production system with an interface-loaded photothermal catalyst content of 0.5% Co 3 O 4 @ ZIS;

[0076] Embodiment 5:

[0077] Step 1: Weigh 2 mg / ml of dopamine hydrochloride and dissolve it in 10 mM Tris-HCl (pH = 8.5). Ultrasonicate for 30 minutes to dissolve it to obtain material A5 (mixture 1);

[0078] Step 2: Sandpaper-polished waste polyethylene foam with a diameter of 3.5 cm and a thickness of 0.2 cm was immersed in material A4 and stirred continuously for 24 hours. After removal, it was rinsed with deionized water and dried. This process was repeated for 3 days to obtain dark gray modified polyethylene foam B5.

[0079] Step 3: Spin-coat the dissolved polypyrrole on the surface of material B5, then weigh 10 mg of cobalt trioxide indium zinc sulfide composite photothermal catalyst and spin-coat it evenly, and finally coat it with polypyrrole to obtain modified polyethylene foam C5 loaded with photothermal catalyst;

[0080] Step 4: Dry the material C5 obtained in step 3 in an oven at 60° C. for 30 minutes to obtain a water evaporation hydrogen production system with an interface-loaded photothermal catalyst content of 1.0% Co 3 O 4 @ ZIS;

[0081] Example 6:

[0082] Step 1: Weigh 2 mg / ml of dopamine hydrochloride and dissolve it in 10 mM Tris-HCl (pH = 8.5). Ultrasonicate for 30 minutes to dissolve it to obtain material A6 (mixture 1);

[0083] Step 2: Sandpaper-polished waste polyethylene foam with a diameter of 3.5 cm and a thickness of 0.2 cm was immersed in material A6 and stirred continuously for 24 hours. After removal, it was rinsed with deionized water and dried. This process was repeated for 3 days to obtain dark gray modified polyethylene foam B6.

[0084] Step 3: Spin-coat the dissolved polypyrrole on the surface of material B6, then spin-coat 20 mg of cobalt trioxide indium zinc sulfide composite photothermal catalyst evenly, and finally coat it with polypyrrole to obtain modified polyethylene foam C6 loaded with photothermal catalyst;

[0085] Step 4: Dry the material C6 obtained in step 3 in an oven at 60° C. for 30 minutes to obtain a water evaporation hydrogen production system with an interface-loaded photothermal catalyst content of 2.0% Co 3 O 4 @ ZIS;

[0086] Application Example 1:

[0087] The blank cobalt tetroxide obtained in Example 1, the blank indium zinc sulfide obtained in Example 2, and the 1.0% Co3O4@ZIS semiconductor powder obtained in Example 3 were used as photothermal catalysts. In a nitrogen atmosphere, triethanolamine was used as a hole sacrificial agent, and a pure water environment was used to carry out visible light photocatalytic water decomposition to produce hydrogen. The effect of cobalt tetroxide itself on the photocatalytic decomposition of water to produce hydrogen was investigated (see Appendix). Figure 3 ), and found that cobalt tetroxide itself cannot photocatalytically decompose water to produce hydrogen under visible light when triethanolamine is used as a sacrificial agent, but can only serve as a co-catalyst to improve the hydrogen production performance of the semiconductor.

[0088] Application Example 2:

[0089] The interfacial photothermal catalytic water evaporation hydrogen production system supported by the cobalt trioxide indium zinc sulfide composite material obtained in Examples 4-6 was compared with the corresponding powdered cobalt trioxide indium zinc sulfide composite catalyst. In a nitrogen atmosphere, triethanolamine was used as a hole sacrificial agent in a pure water environment to carry out solid-gas two-phase interfacial water evaporation hydrogen production to investigate the effect of different photothermal catalyst Co3O4@ZIS loading amounts on the interfacial photothermal catalytic water evaporation hydrogen production system (see Appendix Figure 5 ), with the increase of Co3O4@ZIS loading, the interfacial photothermal catalytic water evaporation hydrogen production rate first increased and then decreased. When the Co3O4@ZIS loading reached 1.0%, the interfacial photothermal catalytic water evaporation hydrogen production effect was optimal.

[0090] Application Example 3:

[0091] The interfacial photothermal catalytic water evaporation hydrogen production system with a loading of 1.0% Co3O4@ZIS obtained in Example 5 was used to conduct a cycle experiment of water evaporation hydrogen production at a solid-gas two-phase interface in a nitrogen atmosphere with triethanolamine as a hole sacrificial agent in a pure water environment to investigate the stability of the interfacial photothermal catalytic system loaded with Co3O4@ZIS photothermal catalyst in the photocatalytic decomposition of water vapor to produce hydrogen (see Appendix). Figure 6 ), after 3 cycles, the hydrogen production from interfacial photothermal catalytic water decomposition decreased by 4%, and the stability was good.

[0092] Application Example 4:

[0093] The interfacial photothermal catalytic water evaporation hydrogen production system with a loading of 1.0% Co3O4@ZIS obtained in Example 5 was used to investigate the hydrogen production capacity of the interfacial photothermal catalytic water decomposition hydrogen production system in a non-pure water environment with triethanolamine as a hole sacrificial agent and tap water as a solvent in a nitrogen atmosphere (see Appendix). Figure 7 ), and found that the interfacial photothermal catalytic water evaporation hydrogen production system with a loading of 1.0% Co3O4@ZIS produced hydrogen in impure water conditions at a rate basically the same as that in pure water conditions, reflecting the potential of the interfacial photothermal catalytic water evaporation system in industrial applications.

[0094] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for producing hydrogen by composite photothermal catalyst-loaded modified polyethylene foam, characterized in that: The following steps are involved: S1. Surface modification of waste polyethylene foam to obtain a water transmission support layer; S2. Preparing a cobalt trioxide and indium zinc sulfide composite photothermal catalyst comprising cobalt trioxide and indium zinc sulfide; S3. Using polypyrrole as an adhesive, the cobalt trioxide and indium zinc sulfide composite photothermal catalyst is bonded to the water transport support layer to form a photothermal absorption catalyst layer. The photothermal absorption catalyst layer and the water transport support layer together constitute an interfacial photothermal-photocatalytic evaporation hydrogen production system; S4. Under light conditions, the interfacial photothermal-photocatalytic evaporation hydrogen production system is used to catalyze the decomposition of water vapor to produce hydrogen.

2. The method for producing hydrogen by composite photothermal catalyst-loaded modified polyethylene foam according to claim 1, characterized in that: The surface modification treatment in step S1 includes: S11, grinding the waste polyethylene foam; S12, dissolving 1 mg / ml to 3 mg / ml of dopamine hydrochloride in 8 mM to 10 M Tris-HCl at a pH of 8.0 to 9.0, and sonicating for 25 to 35 minutes to dissolve the dopamine hydrochloride to prepare a first mixed solution; S13, soaking the polished waste polyethylene foam in the mixed solution 1, and stirring for 20 to 28 hours; S14, taking out the soaked waste polyethylene foam, rinsing it thoroughly with deionized water, and then drying it; S15. Repeat steps S13 and S14 2 to 4 times.

3. The method for producing hydrogen by composite photothermal catalyst-loaded modified polyethylene foam according to claim 1, characterized in that: The cobalt oxide of the cobalt oxide indium zinc sulfide composite photothermal catalyst in step S2 is prepared by the following method: 4 mmol to 8 mmol of cobalt nitrate and 22 mmol to 26 mmol of dimethylimidazole were added to 90 ml to 110 ml of methanol solvent and stirred for 25 min to 35 min, then mixed and stirred for 25 min to 35 min, and then allowed to stand for 22 hours to 26 hours to precipitate to obtain an intermediate; The intermediate is centrifuged and washed multiple times, and dried at a temperature of 50° C. to 70° C. for 24 to 36 hours to obtain ZIF-67 nanoparticles; The ZIF-67 nanoparticles are vacuum calcined at a temperature of 500° C. to 600° C. for 1 to 3 hours to obtain cobalt trioxide nanoparticles.

4. The method for producing hydrogen by composite photothermal catalyst-loaded modified polyethylene foam according to claim 1, characterized in that: Indium zinc sulfide in the cobalt trioxide indium zinc sulfide composite photothermal catalyst in step S2 is prepared by the following method: 133 mg to 139 mg of zinc chloride, 290 mg to 296 mg of indium chloride tetrahydrate, and 290 mg to 296 mg of thioacetamide are added to distilled water adjusted to a pH of 2.0 to 3.0 by 20 ml to 30 ml of glycerol and 90 ml to 110 ml of a 2.5 mol / L to 3.5 mol / L HCl solution, and dissolved by ultrasonic treatment for 25 minutes to 35 minutes to obtain a second mixed solution; The mixed solution 2 is reacted in an oil bath at 70° C. to 90° C. for 1.5 to 2.5 hours to obtain a precipitated product 1; The precipitated product is washed with deionized water and ethanol for multiple times, and dried at a temperature of 50° C. to 70° C. for 22 to 36 hours to obtain indium zinc sulfide.

5. The method for producing hydrogen by composite photothermal catalyst-loaded modified polyethylene foam according to claim 1, characterized in that: The preparation method of the cobalt trioxide indium zinc sulfide composite photothermal catalyst in step S2 includes: 7.5 mg to 9.5 mg of cobalt trioxide nanoparticles, 540 mg to 550 mg of zinc chloride, 1160 mg to 1180 mg of indium chloride tetrahydrate, and 580 mg to 620 mg of thioacetamide are added to distilled water adjusted to a pH of 2.0 to 3.0 by 20 ml to 30 ml of glycerol and 90 ml to 102 ml of a 2.5 mol / L to 3.5 mol / L HCl solution, and ultrasonically treated for 25 min to 35 min to obtain a mixed solution three; The mixed solution 5 is reacted in an oil bath at 75° C. to 85° C. for 1.5 to 2.5 hours to obtain a precipitated product 2; The precipitated product is washed by centrifugation multiple times with deionized water and ethanol, and dried at a temperature of 55° C. to 65° C. for 22 to 26 hours to obtain a composite photothermal catalyst of cobalt trioxide and indium zinc sulfide.

6. The method for producing hydrogen by composite photothermal catalyst-loaded modified polyethylene foam according to claim 5, characterized in that: The cobalt trioxide indium zinc sulfide composite photothermal catalyst in step S2 is a core-shell pn heterostructure.

7. The method for producing hydrogen by composite photothermal catalyst-loaded modified polyethylene foam according to claim 1, characterized in that: The step S3 uses polypyrrole as an adhesive to bond the cobalt trioxide indium zinc sulfide composite photothermal catalyst to the water transmission support layer to form a photothermal absorption catalyst layer. The photothermal absorption catalyst layer and the water transmission support layer together constitute an interfacial photothermal-photocatalytic evaporation hydrogen production system. The steps include: Spin-coating the dissolved polypyrrole on the surface of the water transport support layer to form a first polypyrrole coating; Uniformly coating the cobalt trioxide indium zinc sulfide composite photothermal catalyst on the first polypyrrole coating, and applying polypyrrole to coat the surface of the cobalt trioxide indium zinc sulfide composite photothermal catalyst to obtain a modified polyethylene foam loaded with the photothermal catalyst; The modified polyethylene foam loaded with the photothermal catalyst is dried at 55° C. to 65° C. for 25 to 35 minutes to obtain an interfacial photothermal-photocatalytic evaporation hydrogen production system.

8. The method for producing hydrogen by composite photothermal catalyst-loaded modified polyethylene foam according to claim 1, characterized in that: In step S4, under light conditions, the step of utilizing the interfacial photothermal-photocatalytic evaporation hydrogen production system to catalyze the decomposition of water vapor to produce hydrogen includes: The interfacial photothermal-photocatalytic evaporation hydrogen production system is placed under light, so that the photothermal absorption catalytic layer of the system and the water transport support layer connected thereto absorb light energy and convert it into heat energy, and the local temperature is increased by utilizing the photothermal effect to promote the evaporation of liquid water in contact with the water transport support layer to form water vapor; The water vapor is transported to the surface of the photothermal absorption catalytic layer, and under the synergistic catalysis of the continuous action of the light and the resulting photothermal effect, the photothermal absorption catalytic layer is used to decompose the water vapor contacting its surface to produce hydrogen.

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