Photo-thermal interface reactor, preparation method and application
By forming a highly dispersed nano-metal oxide gel layer on the surface of an attapulgite-based hydrogel, a photothermal interface reactor was developed, which solved the problems of difficult photothermal catalyst recovery and high energy consumption in traditional wastewater treatment, achieving low-carbon and high-efficiency wastewater treatment.
Patent Information
- Application Number
- CN202511050976.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-07-29
- Publication Date
- 2025-11-14
AI Technical Summary
Existing photothermal catalysts are powder materials, which are difficult to recycle and prone to secondary pollution. Furthermore, traditional wastewater treatment technologies are limited in application in remote or power-deficient areas, and have high energy consumption and operating costs.
An attapulgite-reinforced, highly dispersed nano-metal oxide gel layer is formed in situ on the surface of an attapulgite-based hydrogel, and a photothermal interface reactor is constructed. Solar energy is used to drive the catalytic degradation of organic pollutants in wastewater, and the reaction products are refluxed back into the aqueous phase through concentration gradient diffusion, achieving low-carbon and high-efficiency catalysis.
It achieves efficient degradation of organic pollutants in wastewater without consuming additional energy, reduces catalyst loss rate, maintains high dispersion of metal catalytic active species, simplifies preparation process, and reduces operating costs.
Smart Images
Figure CN120939859A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the fields of environmental functional material preparation and water treatment technology, and particularly to a photothermal interface reactor, its preparation method, and its application. Background Technology
[0002] Global freshwater resources are becoming increasingly scarce, while industrialization and urbanization have led to the generation of large amounts of wastewater containing recalcitrant organic pollutants (such as dyes, pharmaceuticals, pesticide residues, and endocrine disruptors), posing a serious threat to the environment and human health. Traditional wastewater treatment technologies (such as biological treatment, flocculation sedimentation, membrane separation, and advanced oxidation) are effective, but they generally suffer from limitations such as high energy consumption, high operating costs, complex infrastructure, and difficulty in application in remote or power-deficient areas. Solar energy is a widely distributed, clean, and pollution-free renewable energy source. Utilizing solar energy for wastewater treatment is an important way to achieve sustainable water treatment.
[0003] Photothermal catalysis using solar energy to degrade organic pollutants in wastewater is a promising green and sustainable technology. Its core lies in the efficient conversion of solar energy into chemical energy, driving the generation of highly reactive oxidizing species (such as hydroxyl radicals, superoxide radicals, and singlet oxygen), thereby non-selectively degrading organic pollutants. Currently, most photothermal catalysts are powder materials, which are difficult to recycle and prone to secondary pollution.
[0004] This invention innovatively proposes an in-situ gelation and reduction process on the surface of an attapulgite-based hydrogel with high-efficiency water transport to form an attapulgite-reinforced, highly dispersed nano-metal oxide gel layer, resulting in a photothermal interface reactor capable of degrading organic pollutants in wastewater without consuming additional energy. Leveraging its excellent electromagnetic effect, the metal oxide gel effectively absorbs and confines solar energy within the photothermal interface layer for catalytic reactions. The reaction products are then diffused back into the lower aqueous phase via concentration gradient, achieving a low-carbon, high-efficiency, multiphase catalysis objective. The resulting reactor not only has a simple preparation process but also maintains high dispersion of metal catalytic active species, reducing catalyst loss. Furthermore, this photothermal interface reactor can drive spontaneous reactions, achieving low-carbon, high-efficiency, and green catalysis. Summary of the Invention
[0005] Objective of the Invention: Addressing the problems existing in the prior art, this invention provides a photothermal interface reactor, its preparation method, and its application. This invention directly integrates a photothermal catalyst into the upper photothermal conversion interface of an evaporator, utilizing this interface as a catalytic platform for pollutant degradation. The photothermal interface reactor designed in this invention cleverly integrates highly efficient photothermal conversion and interfacial catalytic degradation functions, utilizing solar energy to achieve the separation and degradation of organic pollutants in wastewater.
[0006] Technical solution: On the one hand, the present invention provides a method for preparing a photothermal interface reactor, comprising the following steps: Step 1: Prepare a clay slurry of a certain concentration; Step 2: Take an appropriate amount of clay slurry from Step 1, mix it with sodium alginate solution, calcium salt and gel accelerator, stir quickly and evenly, pour it into a mold and let it stand to gel. Step 3: Dissolve the inorganic metal salt in a solvent and add an appropriate amount of acid to promote dissolution and obtain a homogeneous solution; Step 4: Add dispersant to the solution in Step 3, stir well, then add coagulant and pour it onto the gel obtained in Step 2, and let the gel stand. Step 5: Immerse the hydrogel obtained in Step 4 into a reducing agent solution of a certain concentration for in-situ reduction treatment to obtain a photothermal interface reactor.
[0007] Furthermore, in step one, the clay is one or more of clay mineral materials such as attapulgite, sepiolite, bentonite, and kaolinite.
[0008] Furthermore, in step two, the mass ratio of clay to sodium alginate is 1:0.01~0.2.
[0009] Furthermore, in step two, the calcium salt is one or more of calcium carbonate, hydroxyapatite, and calcium hydrogen phosphate; the mass ratio of clay to calcium salt is 1:0~0.1. Clay contains a large amount of associated minerals, including calcium carbonate, so the calcium salt ratio here can be 0, meaning no additional calcium salt needs to be added, but the gelation speed will be slow.
[0010] Furthermore, in step two, the gelation accelerator is one or more of pyromellitic acid, gluconolactone, and borax; the mass ratio of the gelation accelerator to sodium alginate is 0~0.5:1.
[0011] Furthermore, in step two, the thickness of the gel is 0.5-10 mm.
[0012] Furthermore, in step three, the inorganic metal salt is one or more of the following inorganic metal salts: ferric chloride, aluminum chloride, bismuth chloride, bismuth nitrate, copper nitrate, and copper chloride; the concentration of the metal salt in the homogeneous solution is 0.01~1 mol / L. The solvent is one or more of ethanol, methanol, isopropanol, and water; The acid is one or a mixture of hydrochloric acid, sulfuric acid, and nitric acid; the amount of acid added is 0 to 1% of the volume of the solvent.
[0013] Furthermore, in step four, the coagulant is one or more of propylene oxide, citric acid, and thiomalic acid; In step four, the volume ratio of solvent to coagulant is 1:0.2~2.
[0014] Furthermore, in step five, the reducing agent solution is one or more of ascorbic acid, glucose, sodium borohydride, and potassium borohydride.
[0015] On the other hand, the present invention provides an application of a photothermal interface reactor prepared by any of the above methods in the photothermal catalytic degradation of organic pollutants in wastewater using solar energy.
[0016] Beneficial effects: Compared with the prior art, the specific beneficial effects of this invention are as follows: 1) This invention involves in-situ gelation and reduction on the surface of a clay-based hydrogel (water transport layer) with high efficiency water transport to form a clay-reinforced, highly dispersed nano-metal oxide gel (photothermal interface layer), resulting in a photothermal interface reactor capable of degrading organic pollutants in wastewater without consuming additional energy: the substrate reaches the photothermal interface layer from the water transport layer via concentration gradient diffusion; thanks to the good electromagnetic effect, the metal oxide gel in the photothermal interface layer effectively absorbs and confines solar energy within the photothermal interface layer for catalytic reaction, and the reaction products are then returned to the lower aqueous phase via concentration gradient diffusion, thereby achieving the goal of low-carbon and high-efficiency multiphase catalysis.
[0017] 2) The water transport layer of the photothermal interface reactor provided by the present invention is a hydrogel constructed using natural one-dimensional inorganic nano-mineral clay with strong hydrophilicity and high weather resistance. Its hierarchical porous structure can achieve efficient water transport. In addition, the photothermal interface reactor in the present invention can drive the reaction to proceed spontaneously, achieving continuous, low-carbon, and efficient green catalysis.
[0018] 3) The photothermal interface reactor provided by this invention can be directly applied to wastewater degradation as a bulk material. Not only is the preparation process simple, but it also maintains the high dispersion of metal catalytic active species. At the same time, the rich pore structure of the gel material in the photothermal interface reactor provided by this invention can play a similar role in confinement of the catalyst, thereby reducing the loss of the catalyst and avoiding the risks of traditional pollutant degradation materials being difficult to recycle and easily causing secondary pollution to the environment when applied on a large scale. Attached Figure Description
[0019] Figure 1 A schematic diagram of the layered assembly of the photothermal interface reactor prepared in this invention and a schematic diagram of its appearance during use; Figure 2 This is an electron microscope image of the water transport layer in the photothermal interface reactor of embodiment 2; Figure 3 This is an electron microscope image of the photothermal interface layer in the photothermal interface reactor of embodiment 3. Figure 4 This is an electron microscope image of the photothermal interface layer in the photothermal interface reactor of embodiment 4. Figure 5 The ultraviolet-visible-near-infrared absorption spectrum of the photothermal interface reactor in Embodiment 4; Figure 6 This is a nitrogen adsorption-desorption curve of the photothermal interface layer in the photothermal interface reactor of embodiment 5. Figure 7 This is a pore size distribution diagram of the photothermal interface layer in the photothermal interface reactor of embodiment 5. Detailed Implementation
[0020] The present invention will now be described in detail with reference to the embodiments.
[0021] 10 mL of 10 wt% attapulgite slurry and 1 mL of 3 wt% sodium alginate solution were mixed evenly by high-speed stirring. 0.1 g of calcium carbonate powder was added and mixed evenly, followed by 0.05 g of gluconolactone powder. The mixture was stirred rapidly and poured into a mold to allow the gel to stand (5 mm thick). 3 g of aluminum chloride, 0.6 g of copper chloride, and 0.6 g of bismuth nitrate were added to 20 mL of methanol. During stirring, 0.1 mL of hydrochloric acid was added. After complete dissolution, 2 mL of polyacrylic acid and 0.2 mL of glycerol were added and stirred for 10 min. While stirring, 8 mL of propylene oxide was added dropwise to the metal salt solution. After stirring for several minutes, the mixture was poured into the mold as the upper layer of the attapulgite / sodium alginate gel and allowed to stand. After aging overnight, the assembled gel was demolded and immersed in a 1 M sodium borohydride solution for in-situ reduction to obtain a photothermal interface reactor. The upper layer of this photothermal interface reactor is a photothermal interface layer, and the lower layer is a water transport layer. Among them, the gel of the photothermal interface layer has an extremely high specific surface area, which is as high as 552 m² after drying. 2 / g, porosity exceeding 92%; this photothermal interface reactor can be used for the degradation of organic pollutants in wastewater, and it can be designed with an asymmetric structure (such as... Figure 1 As shown in the figure, the results show that its degradation efficiency for Rhodamine B in solution can reach 90%. Implementation Method 2:
[0022] 10 mL of 10 wt% attapulgite slurry and 1 mL of 3 wt% sodium alginate solution were mixed evenly by high-speed stirring. 0.08 g of calcium carbonate powder was added and mixed evenly, followed by 0.035 g of gluconolactone powder. The mixture was stirred rapidly and then poured into a mold to allow the gel to stand (3 mm thick). 2.3 g of ferric chloride, 0.6 g of cobalt nitrate, and 1.0 g of bismuth nitrate were added to 20 mL of an alcohol-water mixture (1:1). During stirring, 0.05 mL of hydrochloric acid was added. After complete dissolution, 4 mL of polyacrylic acid and 0.1 mL of glycerol were added and stirred for 10 min. While stirring, 6 mL of propylene oxide was added dropwise to the metal salt solution. After stirring for several minutes, the mixture was poured into the mold as the upper layer of the attapulgite / sodium alginate gel and allowed to stand. After aging overnight, the assembled gel was demolded and immersed in 0.5 M sodium borohydride solution for in-situ reduction to obtain a photothermal interface reactor. The upper layer of this photothermal interface reactor is a photothermal interface layer, and the lower layer is a water transport layer. The macropores in the bottom water transport layer are approximately 100 μm in diameter. Figure 2 The gel at the photothermal interface has an extremely high specific surface area, reaching as high as 432 m² after drying. 2 / g, with a porosity exceeding 90%; this photothermal interface reactor was used to degrade organic pollutants in wastewater. It can be designed with an asymmetric structure, and the results show that its degradation efficiency for tetracycline hydrochloride in solution can reach 95%. Implementation Method 3:
[0023] 10 mL of 10 wt% bentonite slurry and 1 mL of 3 wt% sodium alginate solution were mixed evenly by high-speed stirring. 0.1 g of calcium carbonate powder was added and mixed evenly, followed by 0.08 g of gluconolactone powder. The mixture was stirred rapidly and poured into a mold to allow the gel to stand (4 mm thick). 3 mL of titanium chloride, 0.6 g of copper chloride, and 0.6 g of ferric nitrate were added to 20 mL of methanol. During stirring, 0.1 mL of hydrochloric acid was added. After complete dissolution, 0.4 mL of glycerol was added and stirred for 8 min. While stirring, 12 mL of propylene oxide was added dropwise to the metal salt solution. After stirring for several minutes, the mixture was poured into the upper layer of the bentonite / sodium alginate gel in the mold and allowed to stand. After aging overnight, the assembled gel was demolded and immersed in 1M ascorbic acid solution for in-situ reduction, resulting in a photothermal interface reactor. The upper layer of this photothermal interface reactor is a photothermal interface layer, and the lower layer is a water transport layer. Among them, the gel of the photothermal interface layer has an extremely high specific surface area, which was measured to be as high as 577 m² after drying. 2 / g, with a porosity exceeding 93%, exhibiting a typical metallic aerogel structure, and a gel particle size of approximately 20 nm. Figure 3The photothermal interface reactor was used to degrade organic pollutants in wastewater. It can be designed with an asymmetric structure. The results show that its degradation efficiency for cephalothiophene in solution can reach 85%. Implementation Method 4:
[0024] 10 mL of 10 wt% sepiolite slurry and 1 mL of 3 wt% sodium alginate solution were mixed evenly by high-speed stirring. 0.1 g of calcium hydroxyphosphate powder was added and mixed evenly, followed by 0.08 g of gluconolactone powder. The mixture was stirred rapidly and poured into a mold to allow the gel to stand (4 mm thick). 4 mL of titanium chloride, 0.6 g of bismuth chloride, 0.3 g of cobalt chloride, and 0.3 g of ferric nitrate were added to 20 mL of ethanol. During stirring, 0.1 mL of hydrochloric acid was added. After complete dissolution, 0.4 mL of glycerol was added and stirred for 8 min. While stirring, 15 mL of thiomalic acid (1 M) was added dropwise to the metal salt solution. After stirring for several minutes, the mixture was poured into the upper layer of the sepiolite / sodium alginate gel in the mold and allowed to stand. After aging overnight, the assembled gel was demolded and immersed in a 1 M potassium borohydride solution for in-situ reduction to obtain a photothermal interface reactor. The upper layer of this photothermal interface reactor is a photothermal interface layer, and the lower layer is a water transport layer. Among them, the gel of the photothermal interface layer has an extremely high specific surface area, which is as high as 493 m² after drying. 2 / g, with a porosity exceeding 90%, exhibiting a typical metallic aerogel structure, and a gel particle size of approximately 25 nm. Figure 4 The light absorption rate reaches 85% (); Figure 5 The photothermal interface reactor can be used to degrade organic pollutants in wastewater. It can be designed with an asymmetric structure, and its degradation efficiency for dichlorophenol in solution can reach 95%. Implementation Method 5:
[0025] 10 mL of 10 wt% attapulgite slurry and 1 mL of 3 wt% sodium alginate solution were mixed evenly by high-speed stirring. 0.1 g of calcium hydroxyphosphate powder was added and mixed evenly, followed by 0.1 g of gluconolactone powder. The mixture was stirred rapidly and evenly, then poured into a mold and allowed to stand to gel (3 mm thick). 2 mL of titanium chloride, 1 g of bismuth chloride, 0.3 g of zinc chloride, and 1 g of ferric nitrate were added to 20 mL of isopropanol. During stirring, 0.1 mL of sulfuric acid was added. After complete dissolution, 0.5 mL of glycerol was added and stirred for 6 min. While stirring, 20 mL of thiomalic acid (1 M) was added dropwise to the metal salt solution. After stirring for several minutes, the mixture was poured into the upper layer of the attapulgite / sodium alginate gel in the mold and allowed to stand to gel. After aging overnight, the assembled gel was demolded and immersed in 1 M sodium borohydride solution for in-situ reduction to obtain a photothermal interface reactor. The upper layer of this photothermal interface reactor is a photothermal interface layer, and the lower layer is a water transport layer. Among them, the gel of the photothermal interface layer has an extremely high specific surface area, which is as high as 662 m² after drying. 2 / g ( Figure 6 The pore size is mainly concentrated below 50 nm, and the porosity exceeds 90%. Figure 7 The light absorption rate reached 90%. When this photothermal interface reactor was used to degrade organic pollutants in wastewater, it was designed with an asymmetric structure. The results showed that its degradation efficiency for trichlorophenol in solution could reach more than 90%, and the degradation efficiency increased with the irradiation time in the first 10 minutes. This indicates that the temperature of the photothermal interface reactor gradually increases after receiving light, thereby improving the degradation efficiency, and it reaches a stable state in about 10 minutes.
[0026] The above embodiments are only for illustrating the technical concept and features of the present invention, and are intended to enable those skilled in the art to understand the content of the present invention and implement it accordingly. They should not be construed as limiting the scope of protection of the present invention. All equivalent transformations or modifications made in accordance with the spirit and essence of the present invention should be covered within the scope of protection of the present invention.
Claims
1. A method for preparing a photothermal interface reactor, characterized in that, Includes the following steps: Step 1: Prepare a clay slurry of a certain concentration; Step 2: Take an appropriate amount of clay slurry from Step 1, mix it with sodium alginate solution, calcium salt and gel accelerator, stir quickly and evenly, pour it into a mold and let it stand to gel. Step 3: Dissolve the inorganic metal salt in a solvent and add an appropriate amount of acid to promote dissolution and obtain a homogeneous solution; Step 4: Add dispersant to the solution in Step 3, stir well, then add coagulant and pour it onto the gel obtained in Step 2, and let the gel stand. Step 5: Immerse the hydrogel obtained in Step 4 into a reducing agent solution of a certain concentration for in-situ reduction treatment to obtain a photothermal interface reactor.
2. The method for preparing the photothermal interface reactor according to claim 1, characterized in that: In step one, the clay is one or more of clay mineral materials such as attapulgite, sepiolite, bentonite, and kaolinite.
3. The method for preparing the photothermal interface reactor according to claim 1, characterized in that: In step two, the mass ratio of clay to sodium alginate is 1:0.01~0.
2.
4. The method for preparing the photothermal interface reactor according to claim 1, characterized in that: In step two, the calcium salt is one or more of calcium carbonate, hydroxyapatite, and dicalcium phosphate; the mass ratio of clay to calcium salt is 1:0~0.
1.
5. The method for preparing the photothermal interface reactor according to claim 1, characterized in that: In step two, the gelation accelerator is one or more of pyromellitic acid, gluconolactone, and borax; the mass ratio of the gelation accelerator to sodium alginate is 0~0.5:
1.
6. The method for preparing the photothermal interface reactor according to claim 1, characterized in that: In step two, the thickness of the gel is 0.5-10 mm.
7. The method for preparing the photothermal interface reactor according to claim 1, characterized in that: In step three, the inorganic metal salt is one or more of the following inorganic metal salts: ferric chloride, aluminum chloride, bismuth chloride, bismuth nitrate, copper nitrate, copper chloride, cobalt chloride, titanium chloride, zinc chloride, and ferric nitrate; the concentration of the metal salt in the homogeneous solution is 0.01~1 mol / L. The solvent is one or more of ethanol, methanol, isopropanol, and water; The acid is one or a mixture of hydrochloric acid, sulfuric acid, and nitric acid; the amount of acid added is 0 to 1% of the volume of the solvent.
8. The method for preparing the photothermal interface reactor according to claim 1, characterized in that: In step four, the coagulant is one or more of propylene oxide, citric acid, and thiomalic acid; In step four, the volume ratio of solvent to coagulant is 1:0.2~2.
9. The method for preparing the photothermal interface reactor according to claim 1, characterized in that: In step five, the reducing agent solution is one or more of ascorbic acid, glucose, sodium borohydride, and potassium borohydride.
10. The application of a photothermal interface reactor prepared by any one of claims 1-9 in the photothermal catalytic degradation of organic pollutants in wastewater using solar energy.