技术领域Technical field
本发明涉及水解产氢技术领域，具体涉及一种利用吸湿性材料与多孔体结合的大气补水光解水产氢方法及装置。The invention relates to the technical field of hydrogen production through hydrolysis, and specifically relates to a method and device for photolyzing water to produce hydrogen through atmospheric water replenishment by combining a hygroscopic material with a porous body.
背景技术Background technique
随着世界人口的逐渐增加和工业化的飞速发展，人们对能源的需求量也越来越大。而传统的化石燃料的大量使用会使环境污染愈发严重，加之化石燃料所具有的不可再生性，开发绿色、清洁的可再生能源迫在眉睫。氢能作为一种清洁高效的新能源，具有低能耗、无污染、热值高、燃烧性能好、应用广泛等突出优点，正在成为未来能源的新星。With the gradual increase in the world's population and the rapid development of industrialization, people's demand for energy is also increasing. The extensive use of traditional fossil fuels will make environmental pollution more serious. Coupled with the non-renewability of fossil fuels, it is urgent to develop green, clean renewable energy. As a clean and efficient new energy, hydrogen energy has outstanding advantages such as low energy consumption, no pollution, high calorific value, good combustion performance, and wide application. It is becoming a new star of future energy.
光催化分解水产氢在热力学上是Gibbs自由能增大的过程，因此又被称为人工光合作用。光催化分解水产氢的本质是半导体材料的光电效应。当入射光的能量大于等于半导体的能带时，光能被吸收，价带电子跃迁到导带，产生光生电子和空穴。电子和空穴迁移到材料表面，与水发生氧化还原反应，产生氧气和氢气。水作为光催化产氢的原料是反应过程中必不可少的，目前光催化产氢过程主要有两种方式：一种是将催化剂分散在液态水域当中；另一种是将液态水相变蒸发为气态水与催化剂接触制氢。然而这两种方式均无法兼具高制氢效率及低成本，且需要提供水源作为原料，不适用于干旱地区以及偏远海岛地区。因此，开发低成本、高效制氢装置对能源结构转型和发展具有重大意义。Photocatalytic decomposition of water to produce hydrogen is thermodynamically a process of increasing Gibbs free energy, so it is also called artificial photosynthesis. The essence of photocatalytic water decomposition to produce hydrogen is the photoelectric effect of semiconductor materials. When the energy of the incident light is greater than or equal to the energy band of the semiconductor, the light energy is absorbed, and the valence band electrons transition to the conduction band, generating photogenerated electrons and holes. Electrons and holes migrate to the surface of the material and undergo a redox reaction with water to produce oxygen and hydrogen. Water, as a raw material for photocatalytic hydrogen production, is essential in the reaction process. Currently, there are two main methods for photocatalytic hydrogen production: one is to disperse the catalyst in liquid water; the other is to evaporate the liquid water through phase change. Hydrogen is produced by contacting gaseous water with a catalyst. However, neither of these two methods can combine high hydrogen production efficiency and low cost, and need to provide water sources as raw materials, making them unsuitable for arid areas and remote island areas. Therefore, the development of low-cost and efficient hydrogen production devices is of great significance to the transformation and development of the energy structure.
发明内容Contents of the invention
本发明所要解决的技术问题是提供了一种利用吸湿性材料与多孔体结合的光解水产氢方法及装置，主要解决了现目前水解产氢成本高、操作复杂且难以在干旱地区实施的技术问题。The technical problem to be solved by the present invention is to provide a method and device for photolyzing water to produce hydrogen by combining hygroscopic materials and porous bodies, which mainly solves the current technology of high cost, complex operation and difficulty in implementing hydrogen production in arid areas. question.
本发明解决上述技术问题的技术方案如下：The technical solutions of the present invention to solve the above technical problems are as follows:
第一方面，本发明提供了一种利用吸湿性材料与多孔体结合的大气补水光解水产氢方法，包括如下步骤：S1、采用光催化剂分散液滴涂在多孔体骨架，进行干燥，得到负载光催化剂多孔体；S2、将所述负载光催化剂多孔体设置于热敏解吸附型吸湿性材料的上表面后，得到大气补水光解水产氢模块；S3、所述大气补水光解水产氢模块处于光照时，所述负载光催化剂多孔体吸光发热使得所述热敏解吸附型吸湿性材料释放水蒸气，水蒸气扩散通过所述负载光催化剂多孔体并在光照和光催化剂的作用下发生产氢反应，即完成光解水产氢；S4、所述大气补水光解水产氢模块不处于光照时，所述热敏解吸附型吸湿性材料从大气中吸附水分子，完成大气补水。In the first aspect, the present invention provides a method for atmospheric water replenishment and photolysis of water to produce hydrogen by combining a hygroscopic material with a porous body, which includes the following steps: S1. Use photocatalyst dispersion droplets to coat the porous body skeleton, dry it, and obtain a load. Photocatalyst porous body; S2. After arranging the loaded photocatalyst porous body on the upper surface of a thermosensitive desorption hygroscopic material, an atmospheric water replenishment photolysis water hydrogen production module is obtained; S3. The atmospheric water replenishment photolysis water hydrogen production module When exposed to light, the photocatalyst-loaded porous body absorbs light and generates heat, causing the thermosensitive desorption hygroscopic material to release water vapor. The water vapor diffuses through the photocatalyst-loaded porous body and generates hydrogen under the action of light and photocatalyst. The reaction is to complete the photolysis of water to produce hydrogen; S4. When the atmospheric water replenishment photolysis water hydrogen production module is not in the light, the heat-sensitive desorption hygroscopic material absorbs water molecules from the atmosphere to complete the atmospheric water replenishment.
本发明的有益效果是：本发明利用热敏解吸附型吸湿性材料的热力学特性，解决了传统光催化产氢过程中水源短缺的问题。相较于传统的液态大水域光催化制氢方案，巧妙地将光催化剂与多孔骨架进行复合，大大提高了小规模制氢的便捷性，同时降低了光催化产氢的成本。The beneficial effects of the present invention are: the present invention utilizes the thermodynamic properties of the heat-sensitive desorption hygroscopic material to solve the problem of water shortage in the traditional photocatalytic hydrogen production process. Compared with the traditional solution for photocatalytic hydrogen production in liquid large water areas, the clever combination of photocatalysts and porous frameworks greatly improves the convenience of small-scale hydrogen production and reduces the cost of photocatalytic hydrogen production.
进一步，上述多孔体骨架为多孔二氧化硅、多孔氧化铝、多孔氧化镍或多孔纤维，所述多孔体骨架的孔径为1-1000μm，所述多孔体骨架的孔隙率为20％-90％。Furthermore, the above-mentioned porous body skeleton is porous silica, porous alumina, porous nickel oxide or porous fiber, the pore diameter of the porous body skeleton is 1-1000 μm, and the porosity of the porous body skeleton is 20%-90%.
进一步，上述光催化剂分散液包括固体光催化剂、牺牲剂和分散剂。Furthermore, the above-mentioned photocatalyst dispersion liquid includes a solid photocatalyst, a sacrificial agent and a dispersant.
其中分散剂主要作为固体光催化剂和牺牲剂的溶剂。The dispersant is mainly used as a solvent for solid photocatalysts and sacrificial agents.
本发明上述进一步有益效果是：通过分散剂将固体光催化剂与牺牲剂分散后滴涂渗透至多孔体骨架孔隙内，然后烘干分散剂，使固体光催化剂和牺牲剂物理负载于多孔体骨架上，制得负载光催化剂的多孔体。The above-mentioned further beneficial effects of the present invention are: dispersing the solid photocatalyst and the sacrificial agent through the dispersant, then drop-coating and penetrating into the pores of the porous body skeleton, and then drying the dispersant, so that the solid photocatalyst and the sacrificial agent are physically loaded on the porous body skeleton. , to prepare a porous body supporting photocatalyst.
进一步，在上述光催化剂分散液中，所述固体光催化剂的浓度为0.01-1g/mL，所述牺牲剂的浓度为0.01-1g/mL。Further, in the above photocatalyst dispersion liquid, the concentration of the solid photocatalyst is 0.01-1g/mL, and the concentration of the sacrificial agent is 0.01-1g/mL.
本发明上述进一步有益效果是：上述固体光催化剂的浓度和牺牲剂的浓度在该范围区间时能够保证光催化剂分散液能够与多孔体骨架有效结合，从而得到The above-mentioned further beneficial effects of the present invention are: when the concentration of the above-mentioned solid photocatalyst and the concentration of the sacrificial agent are within this range, it can ensure that the photocatalyst dispersion can be effectively combined with the porous body skeleton, thereby obtaining
进一步，上述固体光催化剂为Pt/TiO2、WS2/CdS或Cu2O/C3N4等；所述牺牲剂为乙二醇、聚乙二醇或三乙醇胺等；所述分散剂为纯水或乙醇溶液等易挥发液体。Further, the above-mentioned solid photocatalyst is Pt/TiO2 , WS2 /CdS or Cu2 O/C3 N4 , etc.; the sacrificial agent is ethylene glycol, polyethylene glycol or triethanolamine, etc.; the dispersant is Volatile liquids such as pure water or ethanol solution.
其中牺牲剂除开选择上述原料等还可以选择其他具有还原性但不易挥发的液体。In addition to the above-mentioned raw materials, the sacrificial agent can also be selected from other reducing but non-volatile liquids.
进一步，上述热敏解吸附型吸湿性材料为加入吸湿性盐的水凝胶、乙二醇溶液或MOF等。Furthermore, the above-mentioned thermosensitive desorption type hygroscopic material is a hydrogel, ethylene glycol solution, MOF, etc. added with hygroscopic salt.
第二方面，本发明还提供了一种利用吸湿性材料与多孔体结合的大气补水光解水产氢装置，包括排气抽样结构、大气补水结构、多孔催化结构、气体收集结构；所述气体收集结构包括法兰底板和上腔体，所述法兰底板的中心开设有凹槽，所述大气补水结构包括热敏解吸附型吸湿性材料层，所述热敏解吸附型吸湿性材料层设置于所述凹槽内；所述多孔催化结构包括负载光催化剂的多孔体层，所述负载光催化剂的多孔体层紧贴于所述热敏解吸附型吸湿性材料层上表面；所述排气抽样结构设置于所述上腔体的外壁。In a second aspect, the present invention also provides an atmospheric water replenishment photohydrogen production device that combines hygroscopic materials with porous bodies, including an exhaust sampling structure, an atmospheric water replenishment structure, a porous catalytic structure, and a gas collection structure; the gas collection structure The structure includes a flange bottom plate and an upper cavity. A groove is provided in the center of the flange bottom plate. The atmospheric water replenishing structure includes a thermal desorption type hygroscopic material layer. The thermal desorption type hygroscopic material layer is provided In the groove; the porous catalytic structure includes a photocatalyst-loaded porous body layer, and the photocatalyst-loaded porous body layer is close to the upper surface of the thermosensitive desorption hygroscopic material layer; the exhaust The gas sampling structure is arranged on the outer wall of the upper cavity.
本发明的有益效果为：本发明提供的该装置可吸收95％以上的太阳光辐射，在实际应用过程中，提高了太阳光吸收率，进而提高了光催化产氢效率。大气补水结构采用热敏解吸附型吸湿性材料。在夜间装置处于待机状态时打开上腔体，大气补水结构即可从周围大气环境中吸附水蒸气作为光催化的水源，相较于传统的光催化制氢装置，无需额外水源，且装料槽具有良好的透气性，在吸湿性材料夜间进行大气补水过程中，无需拆下装料槽即可完成自动补水，大大提高了装置整体的便捷性与可操作性，且法兰底板与上腔体之间形成密封空间，可储存光催化过程中产生的氢气；且该装置结构简单，操作容易，适用于有充足光照的内陆和沿海地区，具有潜在的实用价值与应用前景。The beneficial effects of the present invention are: the device provided by the present invention can absorb more than 95% of solar radiation, and during practical application, the solar light absorption rate is increased, thereby improving the photocatalytic hydrogen production efficiency. The atmospheric water replenishing structure adopts heat-sensitive desorption hygroscopic material. When the device is in standby mode at night, the upper chamber is opened, and the atmospheric water replenishment structure can absorb water vapor from the surrounding atmosphere as a water source for photocatalysis. Compared with traditional photocatalytic hydrogen production devices, no additional water source is needed, and the charging tank It has good air permeability. During the atmospheric water replenishment of hygroscopic materials at night, automatic water replenishment can be completed without removing the loading tank, which greatly improves the overall convenience and operability of the device, and the flange bottom plate and upper cavity A sealed space is formed between them, which can store hydrogen generated during the photocatalytic process; and the device has a simple structure and is easy to operate. It is suitable for inland and coastal areas with sufficient light, and has potential practical value and application prospects.
进一步，上述排气抽样结构包括进气阀、排气阀、橡胶塞，所述进气阀、排气阀、橡胶塞均设置于所述上腔体的外壁并与所述上腔体的内部连通。Furthermore, the above-mentioned exhaust sampling structure includes an air intake valve, an exhaust valve, and a rubber plug. The air intake valve, exhaust valve, and rubber plug are all arranged on the outer wall of the upper cavity and connected with the inside of the upper cavity. Connected.
本发明上述进一步有益效果是：在装置工作前将进气阀与惰性保护气体N2进气管连接，排气阀与保护气体排气管连接，使装置内充满保护气体，避免空气中杂质气体污染光催化剂，有利于提高光催化产氢效率和氢气纯度。同时，进气阀和排气阀也可用作氢气导出阀。在装置工作过程中，将取样针贯穿插入橡胶塞可对产生氢气进行检查，确保装置安全性。The above-mentioned further beneficial effects of the present invention are: before the device is operated, the air inlet valve is connected to the inert protective gasN2 inlet pipe, and the exhaust valve is connected to the protective gas exhaust pipe, so that the device is filled with protective gas and avoids contamination by impurity gases in the air. Photocatalyst is conducive to improving photocatalytic hydrogen production efficiency and hydrogen purity. At the same time, the intake and exhaust valves can also be used as hydrogen derivation valves. During the operation of the device, insert the sampling needle through the rubber stopper to check the hydrogen generated and ensure the safety of the device.
进一步，在上述法兰底板与所述上腔体之间的连接处设置有密封垫圈，所述法兰底板与所述上腔体之间通过多个螺栓密封连接。Further, a sealing gasket is provided at the connection between the flange bottom plate and the upper cavity, and the flange bottom plate and the upper cavity are sealingly connected through a plurality of bolts.
本发明上述进一步有益效果是：通过密封垫圈提高了上腔体与法兰底板的密封性，而螺栓则进一步稳固了装置整体的密封性能。The above-mentioned further beneficial effects of the present invention are: the sealing performance of the upper cavity and the flange bottom plate is improved through the sealing gasket, and the bolts further stabilize the sealing performance of the entire device.
附图说明Description of the drawings
图1为本发明实例中装置整体的结构示意图；Figure 1 is a schematic structural diagram of the entire device in an example of the present invention;
图2为本发明实例中装置的结构爆炸图；Figure 2 is an exploded view of the structure of the device in an example of the present invention;
图3为本发明实例中提供的方法原理示意图；Figure 3 is a schematic diagram of the method principle provided in the example of the present invention;
图4为本发明实例中提供的户外实验测试结果。Figure 4 shows the outdoor experimental test results provided in the example of the present invention.
图标：1-排气抽样结构；101-进气阀；102-排气阀；103-橡胶塞；2-多孔催化结构；201-负载光催化剂多孔体层；3-大气补水结构；301-热敏解吸附型吸湿性材料层；4-气体收集结构；401-螺栓；402-上腔体；403-密封垫圈；404-环形凹槽；405-凹槽；406-法兰底板；407-螺母。Icon: 1-exhaust sampling structure; 101-inlet valve; 102-exhaust valve; 103-rubber plug; 2-porous catalytic structure; 201-loaded photocatalyst porous body layer; 3-atmospheric water supply structure; 301-heat Sensitive desorption type hygroscopic material layer; 4-gas collection structure; 401-bolt; 402-upper cavity; 403-sealing gasket; 404-annular groove; 405-groove; 406-flange bottom plate; 407-nut .
具体实施方式Detailed ways
以下对本发明的原理和特征进行描述，所举实例只用于解释本发明，并非用于限定本发明的范围。实施例中未注明具体技术或条件者，按照本领域内的文献所描述的技术或条件，或者按照产品说明书进行。所用试剂或仪器未注明生产厂商者，均为可通过正规渠道商购得的常规产品。The principles and features of the present invention are described below. The examples cited are only used to explain the present invention and are not intended to limit the scope of the present invention. If specific techniques or conditions are not specified in the examples, the techniques or conditions described in literature in the field shall be followed, or the product instructions shall be followed. If the manufacturer of the reagents or instruments used is not indicated, they are all conventional products that can be purchased through regular channels.
在本发明的以下实施例中，所用的多孔体骨架、光催化剂分散液和热敏解吸附性吸湿性材料制备所用的原材料均购自于欣申试化工电商。In the following examples of the present invention, the porous body skeleton, photocatalyst dispersion liquid and raw materials used for the preparation of thermally sensitive desorption hygroscopic materials were all purchased from Xinshenshi Chemical e-commerce.
实施例1Example 1
请参照图1-2，图1所示为本发明实例中装置整体的结构示意图；图2所示为本发明实例中装置的结构爆炸图。Please refer to Figures 1-2. Figure 1 shows a schematic structural diagram of the entire device in an example of the present invention; Figure 2 shows an exploded view of the structure of the device in an example of the present invention.
本实施例涉及一种利用吸湿性材料与多孔体结合的光解水产氢方法，包括如下步骤：This embodiment relates to a method for photolyzing water to produce hydrogen by combining a hygroscopic material with a porous body, which includes the following steps:
将5g直径为200μm的二氧化硅颗粒与浓度为2％的海藻酸钠水溶液均匀混合后，倒入尺寸为50mm×50mm×1.5mm的模具中，随后在其表面均匀喷涂0.24mol/L的CaCl2水溶液以制备多孔前驱体。静置5分钟后，将多孔前驱体放入预设温度为70℃的烘箱中烘干2h以形成二氧化硅多孔体骨架。After uniformly mixing 5g of silica particles with a diameter of 200 μm and a sodium alginate aqueous solution with a concentration of 2%, pour it into a mold with a size of 50mm×50mm×1.5mm, and then evenly spray 0.24mol/L CaCl on the surface.2 aqueous solution to prepare porous precursors. After standing for 5 minutes, the porous precursor was placed in an oven with a preset temperature of 70°C and dried for 2 hours to form a porous silica skeleton.
光催化剂分散液由光催化剂、牺牲剂、分散剂组成。光催化剂选择Pt/TiO2，牺牲剂选择乙二醇(EG)，分散剂选择乙醇(EtOH)。制作流程如下：The photocatalyst dispersion liquid consists of a photocatalyst, a sacrificial agent, and a dispersant. The photocatalyst is Pt/TiO2 , the sacrificial agent is ethylene glycol (EG), and the dispersant is ethanol (EtOH). The production process is as follows:
取20mg Pt/TiO2固体，加入0.4g乙二醇溶液与10mL乙醇溶液，用超声振动仪使溶液混合均匀，制得光催化液。Take 20 mg Pt/TiO2 solid, add 0.4 g ethylene glycol solution and 10 mL ethanol solution, and mix the solution evenly with an ultrasonic vibrator to prepare a photocatalytic liquid.
将光催化剂分散液分4次均匀地滴涂在二氧化硅多孔体骨架表面，并在每次滴涂后放入预设温度为70℃的烘箱中烘干5分钟，使光催化剂均匀地附着在多孔体骨架的孔隙内，以形成负载光催化剂多孔体。Apply the photocatalyst dispersion evenly on the surface of the silica porous body skeleton in 4 drops, and place it in an oven with a preset temperature of 70°C to dry for 5 minutes after each drop to make the photocatalyst evenly adhere. in the pores of the porous body skeleton to form a photocatalyst-loaded porous body.
大气补水结构选择质量分数为35％的LiCl-聚丙烯酰胺水凝胶作为热敏解吸附型吸湿性材料，具体制作流程如下：分别称取4.264g丙烯酰胺和0.027g亚甲基双丙烯酰胺，加入30ml去离子水和19.139g无水氯化锂后搅拌均匀，随后加入0.079g过硫酸铵并搅拌均匀。将配置好的溶液倒入尺寸为50mm×50mm×3mm模具，随后把模具放入透明的封闭容器中用紫外灯照射，并通入氮气作为保护气体，30min后即可成胶。For the atmospheric water replenishing structure, LiCl-polyacrylamide hydrogel with a mass fraction of 35% is selected as the thermally sensitive desorption hygroscopic material. The specific production process is as follows: weigh 4.264g acrylamide and 0.027g methylene bisacrylamide respectively. Add 30 ml of deionized water and 19.139 g of anhydrous lithium chloride and stir evenly. Then add 0.079 g of ammonium persulfate and stir evenly. Pour the prepared solution into a mold with a size of 50mm × 50mm × 3mm, and then put the mold into a transparent closed container and illuminate it with an ultraviolet lamp, and add nitrogen as a protective gas. The gel can be formed in 30 minutes.
首先将大气补水结构(3)置于法兰底板(406)中心的凹槽(405)内并将负载光催化剂多孔体覆于热敏解吸附型吸湿性材料上表面，随后将上腔体(40)2通过螺栓(401)与法兰底板(406)进行连接、密封。将进气阀(101)和排气阀(102)分别与N2进气管、排气管连接，排净装置内空气后，将装置置于户外太阳光下照射，大气补水结构(3)中的水分在太阳光照射下，在大气补水结构(3)在与多孔光催化剂交界面处解吸附产生水蒸气，与附着在SiO2多孔骨架上的光催化剂接触，在光照下发生催化裂解反应，产生氢气。First, place the atmospheric water replenishing structure (3) in the groove (405) in the center of the flange bottom plate (406) and cover the upper surface of the thermally sensitive desorption hygroscopic material with the photocatalyst-loaded porous body, and then place the upper cavity ( 40)2 is connected and sealed with the flange bottom plate (406) through bolts (401). Connect the air inlet valve (101) and exhaust valve (102) to the N2 air inlet pipe and exhaust pipe respectively. After draining the air in the device, place the device under outdoor sunlight and in the atmospheric water supply structure (3) Under the irradiation of sunlight, the moisture in the atmospheric water replenishing structure (3) is desorbed at the interface with the porous photocatalyst to generate water vapor, which contacts the photocatalyst attached to the SiO2 porous skeleton and undergoes a catalytic cracking reaction under the light. Hydrogen gas is produced.
实施例2Example 2
请参照图1-2，图1所示为本发明实例中装置整体的结构示意图；图2所示为本发明实例中装置的结构爆炸图。Please refer to Figures 1-2. Figure 1 shows a schematic structural diagram of the entire device in an example of the present invention; Figure 2 shows an exploded view of the structure of the device in an example of the present invention.
本实施例涉及一种利用吸湿性材料与多孔体结合的光解水产氢方法，包括如下步骤：选择尺寸为50mm×50mm×1.5mm的多孔氧化铝作为多孔体骨架。光催化剂分散液由光催化剂、牺牲剂、分散剂组成。光催化剂选择WS2/CdS，牺牲剂选择聚乙二醇，分散剂选择纯水。制作流程如下：This embodiment relates to a method for photolyzing water to produce hydrogen by combining a hygroscopic material with a porous body, which includes the following steps: selecting porous alumina with a size of 50 mm × 50 mm × 1.5 mm as the porous body skeleton. The photocatalyst dispersion liquid consists of a photocatalyst, a sacrificial agent, and a dispersant. The photocatalyst is WS2 /CdS, the sacrificial agent is polyethylene glycol, and the dispersant is pure water. The production process is as follows:
取20mg WS2/CdS固体，加入0.4g聚乙二醇溶液与10mL纯水，用超声振动仪使溶液混合均匀，制得光催化剂分散液。Take 20 mg of WS2 /CdS solid, add 0.4 g of polyethylene glycol solution and 10 mL of pure water, and mix the solution evenly with an ultrasonic vibrator to prepare a photocatalyst dispersion.
将光催化溶液分5次均匀地滴涂在亲水性多孔体骨架表面，并在每次滴涂后放入预设温度为90℃的烘箱中烘干3分钟，使光催化剂均匀地附着在多孔体骨架孔隙内，以形成负载光催化剂的多孔体。The photocatalytic solution was evenly dropped on the surface of the hydrophilic porous body skeleton in 5 times, and after each drop coating, it was placed in an oven with a preset temperature of 90°C to dry for 3 minutes, so that the photocatalyst could evenly adhere to the surface of the hydrophilic porous body. within the skeleton pores of the porous body to form a porous body supporting the photocatalyst.
大气补水结构选择质量分数为40％的乙二醇水溶液作为热敏解吸附型吸湿性材料，此时，大气补水结构为液态乙二醇水溶液。The atmospheric water replenishing structure selects an ethylene glycol aqueous solution with a mass fraction of 40% as the heat-sensitive desorption hygroscopic material. At this time, the atmospheric water replenishing structure is a liquid ethylene glycol aqueous solution.
首先将大气补水结构(3)(7.5mL 40％乙二醇水溶液)置于法兰底板(406)中心的凹槽(405)内并将负载光催化剂多孔体覆于热敏解吸附型吸湿性材料上表面，随后将上腔体(40)2通过螺栓(401)与法兰底板(406)进行连接、密封。将进气阀(101)和排气阀(102)分别与N2进气管、排气管连接，排净装置内空气后，将装置置于户外太阳光下照射，大气补水结构(3)中的水分在太阳光照射下，在大气补水结构(3)在与多孔光催化剂交界面处解吸附产生水蒸气，与附着在SiO2多孔骨架上的光催化剂接触，在光照下发生催化裂解反应，产生氢气。First, place the atmospheric water replenishing structure (3) (7.5mL 40% ethylene glycol aqueous solution) in the groove (405) in the center of the flange bottom plate (406), and cover the photocatalyst-loaded porous body on the thermally sensitive desorption type hygroscopic material. The upper surface of the material is then connected and sealed with the upper cavity (40) 2 and the flange bottom plate (406) through bolts (401). Connect the air inlet valve (101) and exhaust valve (102) to the N2 air inlet pipe and exhaust pipe respectively. After draining the air in the device, place the device under outdoor sunlight and in the atmospheric water supply structure (3) Under the irradiation of sunlight, the moisture in the atmospheric water replenishing structure (3) is desorbed at the interface with the porous photocatalyst to generate water vapor, which contacts the photocatalyst attached to the SiO2 porous skeleton and undergoes a catalytic cracking reaction under the light. Hydrogen gas is produced.
实施例3Example 3
请参照图1-2，图1所示为本发明实例中装置整体的结构示意图；图2所示为本发明实例中装置的结构爆炸图。Please refer to Figures 1-2. Figure 1 shows a schematic structural diagram of the entire device in an example of the present invention; Figure 2 shows an exploded view of the structure of the device in an example of the present invention.
本实施例涉及一种利用吸湿性材料与多孔体结合的光解水产氢方法，包括如下步骤：选择尺寸为50mm×50mm×1.5mm的多孔纤维作为多孔体骨架。光催化剂分散液由光催化剂、牺牲剂、分散剂组成。光催化剂选择Cu2O/C3N4，牺牲剂选择三乙醇胺，分散剂选择乙醇溶液。制作流程如下：This embodiment relates to a method for photolyzing water to produce hydrogen by combining a hygroscopic material with a porous body, which includes the following steps: selecting a porous fiber with a size of 50 mm × 50 mm × 1.5 mm as the porous body skeleton. The photocatalyst dispersion liquid consists of a photocatalyst, a sacrificial agent, and a dispersant. Cu2 O/C3 N4 was selected as the photocatalyst, triethanolamine was selected as the sacrificial agent, and ethanol solution was selected as the dispersing agent. The production process is as follows:
取20mg Cu2O/C3N4固体，加入0.4g三乙醇胺与10mL乙醇溶液，用超声振动仪使溶液混合均匀，制得光催化剂分散液。Take 20 mg of Cu2 O/C3 N4 solid, add 0.4 g of triethanolamine and 10 mL of ethanol solution, and mix the solution evenly with an ultrasonic vibrator to prepare a photocatalyst dispersion.
将光催化剂分散液分3次均匀地滴涂在纤维多孔体骨架表面，并在每次滴涂后放入预设温度为80℃的烘箱中烘干7分钟，使光催化溶液均匀地附着在多孔体骨架内，以形成负载光催化剂多孔体。The photocatalyst dispersion was evenly dropped on the surface of the fiber porous body skeleton in three times, and after each drop coating, it was placed in an oven with a preset temperature of 80°C to dry for 7 minutes, so that the photocatalytic solution could evenly adhere to the surface of the fiber porous body. within the porous body skeleton to form a photocatalyst-loaded porous body.
大气补水结构选择金属有机框架(MOF)作为热敏解吸附型吸湿性材料，具体制作流程如下：将MOF粉末倒入尺寸为50mm×50mm×3mm模具，成型。The metal organic framework (MOF) is selected as the heat-sensitive desorption hygroscopic material for the atmospheric water replenishing structure. The specific production process is as follows: Pour the MOF powder into a mold with a size of 50mm×50mm×3mm and form it.
首先将大气补水结构(3)置于法兰底板(406)中心的凹槽(405)内并将负载光催化剂多孔体覆于热敏解吸附型吸湿性材料上表面，随后将上腔体(40)2通过螺栓(401)与法兰底板(406)进行连接、密封。将进气阀(101)和排气阀(102)分别与N2进气管、排气管连接，排净装置内空气后，将装置置于户外太阳光下照射，大气补水结构(3)中的水分在太阳光照射下，在大气补水结构(3)在与多孔光催化剂交界面处解吸附产生水蒸气，与附着在SiO2多孔骨架上的光催化剂接触，在光照下发生催化裂解反应，产生氢气。First, place the atmospheric water replenishing structure (3) in the groove (405) in the center of the flange bottom plate (406) and cover the upper surface of the thermally sensitive desorption hygroscopic material with the photocatalyst-loaded porous body, and then place the upper cavity ( 40)2 is connected and sealed with the flange bottom plate (406) through bolts (401). Connect the air inlet valve (101) and exhaust valve (102) to the N2 air inlet pipe and exhaust pipe respectively. After draining the air in the device, place the device under outdoor sunlight and in the atmospheric water supply structure (3) Under the irradiation of sunlight, the moisture in the atmospheric water replenishing structure (3) is desorbed at the interface with the porous photocatalyst to generate water vapor, which contacts the photocatalyst attached to the SiO2 porous skeleton and undergoes a catalytic cracking reaction under the light. Hydrogen gas is produced.
实施例4Example 4
本实施例涉及一种利用吸湿性材料与多孔体结合的光解水产氢装置，包括排气抽样结构(1)、大气补水结构(3)、多孔催化结构(2)、气体收集结构(4)；所述气体收集结构(4)包括法兰底板(406)和上腔体(402)，所述法兰底板(406)的中心开设有凹槽(405)，所述大气补水结构(3)包括热敏解吸附型吸湿性材料层(301)，所述热敏解吸附型吸湿性材料层(301)设置于所述凹槽(405)内；所述多孔催化结构(2)包括负载光催化剂的多孔体层(201)，所述负载光催化剂多孔体层(201)紧贴于所述热敏解吸附型吸湿性材料层(301)上表面，处于所述凹槽(405)与所述上腔体(402)之间；所述排气抽样结构(1)设置于所述上腔体(402)的外壁。在本实施例中，法兰底板(406)的周围设置有环形凹槽(404)，对应上腔体(402)上设置有与环形凹槽(404)相匹配的凸起，从而使法兰底板(406)与上腔体(402)更紧密地结合；且在本实施例中，上腔体(402)为球形，以便于更好接受太阳光照射。This embodiment relates to a photolysis water hydrogen production device that combines hygroscopic materials with porous bodies, including an exhaust sampling structure (1), an atmospheric water supply structure (3), a porous catalytic structure (2), and a gas collection structure (4) ; The gas collection structure (4) includes a flange bottom plate (406) and an upper cavity (402). A groove (405) is provided in the center of the flange bottom plate (406). The atmospheric water supply structure (3) It includes a thermally sensitive desorption-type hygroscopic material layer (301), which is disposed in the groove (405); the porous catalytic structure (2) includes a light-loaded The porous body layer (201) of the catalyst, the photocatalyst-loaded porous body layer (201) is close to the upper surface of the thermosensitive desorption hygroscopic material layer (301), between the groove (405) and the Between the above-mentioned cavities (402); the exhaust sampling structure (1) is arranged on the outer wall of the upper cavities (402). In this embodiment, an annular groove (404) is provided around the flange bottom plate (406), and a protrusion matching the annular groove (404) is provided on the corresponding upper cavity (402), so that the flange The bottom plate (406) is more closely combined with the upper cavity (402); and in this embodiment, the upper cavity (402) is spherical to better receive sunlight.
在本发明的一些实施例中，所述排气抽样结构(1)包括进气阀(101)、排气阀(102)、橡胶塞(103)，所述进气阀(101)、排气阀(102)、橡胶塞(103)均设置于所述上腔体(402)的外壁并与所述上腔体(402)的内部连通。In some embodiments of the present invention, the exhaust sampling structure (1) includes an intake valve (101), an exhaust valve (102), and a rubber plug (103). The valve (102) and the rubber plug (103) are both arranged on the outer wall of the upper cavity (402) and communicate with the inside of the upper cavity (402).
在本发明的一些实施例中，在所述法兰底板(406)与所述上腔体(402)之间的连接处设置有密封垫圈(403)，所述法兰底板(406)与所述上腔体(402)之间通过多个螺栓(401)密封连接。在本实施例中，上腔体(402)与法兰底板(406)的四周均开设有多个与螺栓(401)对应的螺孔，从而保证上腔体(402)与法兰底板(406)更紧密的结合。In some embodiments of the present invention, a sealing gasket (403) is provided at the connection between the flange bottom plate (406) and the upper cavity (402), and the flange bottom plate (406) and the upper cavity (402) are The above cavities (402) are sealed and connected through a plurality of bolts (401). In this embodiment, a plurality of screw holes corresponding to the bolts (401) are provided around the upper cavity (402) and the flange bottom plate (406), thereby ensuring that the upper cavity (402) and the flange bottom plate (406) are ) closer integration.
实验例Experimental example
将5g直径为200μm的二氧化硅颗粒与浓度为2％的海藻酸钠水溶液均匀混合后，倒入尺寸为50mm×50mm×1.5mm的模具中，随后在其表面均匀喷涂0.24mol/L的CaCl2水溶液以制备多孔前驱体。静置5分钟后，将多孔前驱体放入预设温度为70℃的烘箱中烘干2h以形成二氧化硅多孔体骨架。After uniformly mixing 5g of silica particles with a diameter of 200 μm and a sodium alginate aqueous solution with a concentration of 2%, pour it into a mold with a size of 50mm×50mm×1.5mm, and then evenly spray 0.24mol/L CaCl on the surface.2 aqueous solution to prepare porous precursors. After standing for 5 minutes, the porous precursor was placed in an oven with a preset temperature of 70°C and dried for 2 hours to form a porous silica skeleton.
光催化剂分散液由光催化剂、牺牲剂、分散剂组成。光催化剂选择Pt/TiO2，牺牲剂选择乙二醇(EG)，分散剂选择乙醇(EtOH)。制作流程如下：The photocatalyst dispersion liquid consists of a photocatalyst, a sacrificial agent, and a dispersant. The photocatalyst is Pt/TiO2 , the sacrificial agent is ethylene glycol (EG), and the dispersant is ethanol (EtOH). The production process is as follows:
取20mg Pt/TiO2固体，加入0.4g乙二醇溶液与10mL乙醇溶液，用超声振动仪使溶液混合均匀，制得光催化液。Take 20 mg Pt/TiO2 solid, add 0.4 g ethylene glycol solution and 10 mL ethanol solution, and mix the solution evenly with an ultrasonic vibrator to prepare a photocatalytic liquid.
将光催化剂分散液分4次均匀地滴涂在二氧化硅多孔体骨架表面，并在每次滴涂后放入预设温度为70℃的烘箱中烘干5分钟，使光催化剂均匀地附着在多孔体骨架孔隙内，以形成负载光催化剂的多孔体。Apply the photocatalyst dispersion evenly on the surface of the silica porous body skeleton in 4 drops, and place it in an oven with a preset temperature of 70°C to dry for 5 minutes after each drop to make the photocatalyst evenly adhere. In the pores of the porous body skeleton, a porous body supporting the photocatalyst is formed.
大气补水结构选择质量分数为35％的LiCl-聚丙烯酰胺水凝胶作为热敏解吸附型吸湿性材料，具体制作流程如下：分别称取4.264g丙烯酰胺和0.027g亚甲基双丙烯酰胺，加入30ml去离子水和19.139g无水氯化锂后搅拌均匀，随后加入0.079g过硫酸铵并搅拌均匀。将配置好的溶液倒入尺寸为50mm×50mm×3mm模具，随后把模具放入透明的封闭容器中用紫外灯照射，并通入氮气作为保护气体，30min后即可成胶。For the atmospheric water replenishing structure, LiCl-polyacrylamide hydrogel with a mass fraction of 35% is selected as the thermally sensitive desorption hygroscopic material. The specific production process is as follows: weigh 4.264g acrylamide and 0.027g methylene bisacrylamide respectively. Add 30 ml of deionized water and 19.139 g of anhydrous lithium chloride and stir evenly. Then add 0.079 g of ammonium persulfate and stir evenly. Pour the prepared solution into a mold with a size of 50mm × 50mm × 3mm, and then put the mold into a transparent closed container and illuminate it with an ultraviolet lamp, and add nitrogen as a protective gas. The gel can be formed in 30 minutes.
首先将大气补水结构置于法兰底板中心的凹槽(405)内并将负载光催化剂的多孔体覆于吸湿性材料上表面，随后将上腔体通过螺栓与法兰底板进行连接、密封。将进气阀和排气阀分别与N2进气管、排气管连接，排净装置内空气后，将装置在晴天早上7：00置于户外太阳光下照射，大气补水结构中的水分在太阳光照射下，在大气补水结构在与多孔光催化剂交界面处解吸附产生水蒸气，与附着在SiO2多孔骨架上的光催化剂接触，在光照下发生催化裂解反应，产生氢气，通过取样针每间隔30min取样检测装置内的产氢量，所得结果如图4所示。First, the atmospheric water replenishing structure is placed in the groove (405) in the center of the flange bottom plate and the porous body carrying the photocatalyst is covered on the upper surface of the hygroscopic material. Then the upper cavity is connected and sealed with the flange bottom plate through bolts. Connect the air inlet valve and exhaust valve to theN2 air inlet pipe and exhaust pipe respectively. After draining the air in the device, place the device under outdoor sunlight at 7:00 in the morning on a sunny day. The moisture in the atmospheric water replenishment structure will Under the irradiation of sunlight, the atmospheric water replenishing structure desorbs at the interface with the porous photocatalyst to generate water vapor, which contacts the photocatalyst attached to the SiO2 porous skeleton and undergoes a catalytic cracking reaction under the light to produce hydrogen, which passes through the sampling needle. Samples were taken every 30 minutes to detect the hydrogen production in the device, and the results are shown in Figure 4.
根据图4结果显示晴朗天气下，实验例装置单日产氢量达到194mmol/m2(4345.6mL/m2)，具有较高的产氢效果，且吸湿性材料能够在夜晚吸湿过程中将白天光照下的释水量全部吸湿回来，完成恢复，可以实现大气补水。According to the results in Figure 4, under clear weather, the hydrogen production of the experimental device in a single day reaches 194mmol/m2 (4345.6mL/m2 ), which has a high hydrogen production effect, and the hygroscopic material can absorb light during the day during the night. All the released water will be absorbed back to complete the recovery, which can achieve atmospheric replenishment.
综上，本发明提供了一种利用吸湿性材料与多孔体结合的光解水产氢方法及装置，巧妙地将光催化剂与多孔体进行复合，形成体催化反应，并利用吸湿性材料的大气补水技术提供水源，保证充足的反应原材料。在提高光催化效率的同时，还降低了光催化产氢的成本；装置结构简单，操作容易，适用于有充足光照的内陆和沿海地区，具有潜在的实用价值与应用前景。In summary, the present invention provides a method and device for photolyzing water and producing hydrogen by combining a hygroscopic material with a porous body. It cleverly combines the photocatalyst with the porous body to form a body catalytic reaction, and utilizes the atmospheric water replenishment of the hygroscopic material. Technology provides water sources to ensure sufficient reaction raw materials. While improving the photocatalytic efficiency, it also reduces the cost of photocatalytic hydrogen production; the device has a simple structure and is easy to operate. It is suitable for inland and coastal areas with sufficient sunlight, and has potential practical value and application prospects.
在本说明书的描述中，参考术语“一个实施例”、“一些实施例”、“示例”、“具体示例”、或“一些示例”等的描述意指结合该实施例或示例描述的具体特征、结构、材料或者特点包含于本发明的至少一个实施例或示例中。在本说明书中，对上述术语的示意性表述不必须针对的是相同的实施例或示例。而且，描述的具体特征、结构、材料或者特点可以在任一个或多个实施例或示例中以合适的方式结合。此外，在不相互矛盾的情况下，本领域的技术人员可以将本说明书中描述的不同实施例或示例以及不同实施例或示例的特征进行结合和组合。In the description of this specification, reference to the terms "one embodiment," "some embodiments," "an example," "specific examples," or "some examples" or the like means that specific features are described in connection with the embodiment or example. , structures, materials or features are included in at least one embodiment or example of the invention. In this specification, the schematic expressions of the above terms are not necessarily directed to the same embodiment or example. Furthermore, the specific features, structures, materials or characteristics described may be combined in any suitable manner in any one or more embodiments or examples. Furthermore, those skilled in the art may combine and combine different embodiments or examples and features of different embodiments or examples described in this specification unless they are inconsistent with each other.
尽管上面已经示出和描述了本发明的实施例，可以理解的是，上述实施例是示例性的，不能理解为对本发明的限制，本领域的普通技术人员在本发明的范围内可以对上述实施例进行变化、修改、替换和变型。Although the embodiments of the present invention have been shown and described above, it can be understood that the above-mentioned embodiments are illustrative and should not be construed as limitations of the present invention. Those of ordinary skill in the art can make modifications to the above-mentioned embodiments within the scope of the present invention. The embodiments are subject to changes, modifications, substitutions and variations.
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| CN202311427261.7ACN117566686A (en) | 2023-10-31 | 2023-10-31 | A method and device for photolyzing water to produce hydrogen by using hygroscopic materials and porous bodies to replenish atmospheric water |
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| CN202311427261.7ACN117566686A (en) | 2023-10-31 | 2023-10-31 | A method and device for photolyzing water to produce hydrogen by using hygroscopic materials and porous bodies to replenish atmospheric water |
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