CN113488663B - Photocatalytic fuel cells with three-dimensional permeable photoanode - Google Patents

Abstract

The invention discloses a photocatalytic fuel cell with a three-dimensional permeable photoanode, comprising an anode cover plate, a first anode flow channel plate, an anode plate, a three-dimensional permeable photoanode, a second anode flow channel plate, a proton exchange membrane, and a cathode. A flow channel plate, a cathode plate, a cathode and a cathode cover plate; it is characterized in that: the anode cover plate is provided with a liquid inlet and a liquid outlet, and the anode flow channel plate one, the anode plate and the anode flow channel plate two are respectively provided with an anode Flow channel 1, anode chamber and anode flow channel 2, the liquid inlet is communicated with anode flow channel 1, anode chamber and anode flow channel 2; the liquid outlet is communicated with anode flow channel 2; the three-dimensional permeable photoanode is placed between the anode plate and the second anode channel plate; the three-dimensional permeable photoanode uses a porous foam metal material as the base, and a photocatalyst is prepared on the surface of the porous metal foam material; the proton exchange membrane is arranged on the second anode channel plate and the cathode between the flow channel plates; the invention can be widely used in the fields of energy, chemical industry, environmental protection and the like.

Description

Photocatalytic fuel cells with three-dimensional permeable photoanode

technical field

The invention relates to a photocatalytic fuel cell, in particular to a photocatalytic fuel cell with a three-dimensional permeable photoanode.

Background technique

With the development of industry, the problem of environmental pollution is becoming more and more serious. Among the environmental pollution, the problem of water pollution is particularly serious. Every year, a large amount of sewage is discharged into rivers, lakes and seas around the world, which not only destroys the ecological environment, but also pollutes freshwater resources, seriously threatening the ecological balance of the global environment and the safety of drinking water. The wastewater directly discharged without treatment poses a serious threat to both human health and the ecological environment. The semiconductor photocatalysis technology, which has developed rapidly in recent years, is a green technology in the field of environmental purification because it directly uses clean and cheap solar energy for energy conversion, and the reaction products are pollution-free when converted into electrical energy or chemical energy. , has attracted more and more attention from scientific researchers in the world.

Although the current research on photocatalytic fuel cells is different, the main research direction is mostly to modify the photoanode catalyst material to improve its battery performance, but not from the structure of the photoanode itself. The transport of reactants in the existing photocatalytic fuel cells is dominated by diffusion, the mass transfer resistance is large, and the fuel concentration is required to be high; at the same time, the photoanode catalysts are mostly thin films with small specific surface area. This largely limits the mass transport of photocatalytic fuel cells.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention is to provide a photocatalytic fuel cell with a three-dimensional permeable photoanode.

In order to solve the above technical problems, the technical solution of the present invention is to provide a photocatalytic fuel cell with a three-dimensional permeable photoanode, comprising an anode cover plate, an anode flow channel plate, an anode plate, a three-dimensional permeable photoanode, Cathode cover plate, proton exchange membrane, cathode flow channel plate, cathode, cathode plate and cathode cover plate; it is characterized in that:

The anode cover plate is provided with a liquid inlet and a liquid outlet, the anode flow channel plate 1, the anode plate and the anode flow channel plate two are respectively provided with an anode flow channel one, an anode chamber and an anode flow channel two. The first anode flow channel, the anode chamber and the second anode flow channel are connected; the liquid outlet is connected with the second anode flow channel; the three-dimensional permeable photoanode is placed between the anode plate and the second anode flow channel plate; The photoanode adopts a porous foam metal material as the base, and a photocatalyst is prepared on the surface of the porous foam metal material; a proton exchange membrane is arranged between the second anode flow channel plate and the cathode flow channel plate, and the cathode and anode are separated by the proton exchange membrane.

The cathode flow channel plate, the cathode plate and the cathode cover plate are respectively provided with a cathode flow channel, a cathode chamber and a liquid outlet, a cathode is placed in the cathode chamber; the cathode flow channel, the cathode chamber and the liquid outlet are communicated.

The reaction solution composed of anolyte and fuel is driven by a pump and injected into the anode channel 1 from the liquid inlet. After the anode channel 1 is filled with the reaction solution, it enters the anode chamber and penetrates into the three-dimensional permeable photoanode. The light source illuminates the three-dimensional The permeable photoanode generates electricity. After the reaction solution fills all the pores of the three-dimensional permeable photoanode, the reaction solution flows out through the anode flow channel II and the liquid outlet.

The catholyte is driven by a pump and enters the cathode flow channel opened by the cathode flow channel plate. After the cathode flow channel is filled with catholyte, it flows into the cathode chamber, reaches the cathode, and then flows out from the liquid outlet; the purpose of using dual chambers The purpose is to reduce the mixed potential generated by the fuel at the cathode; the reaction liquid flows in an osmotic manner to enhance the transfer of substances inside the cell, so that the purpose of oxidizing reactants and generating electricity at the same time can be achieved even under the condition of low concentration fuel.

In the photocatalytic fuel cell with three-dimensional permeable photoanode of the present invention, sunlight irradiates the reactor vertically from the photoanode side, and a peristaltic pump is used to inject fuel and anolyte into the anode chamber through the liquid inlet. When the photoanode is irradiated by sunlight, the electrons in the valence band will transition to the conduction band, thereby exciting and generating electron-hole pairs. The holes have strong oxidizing properties, and the fuel is oxidized into CO ₂ , and the electrons are transferred to the cathode to reduce oxygen. The purpose of oxidizing reactants at the same time to generate electricity. Under the condition of low concentration, the permeable photoanode is used to promote the material transfer inside the photoanode, which can make the photoanode catalyst react with the reactant fuel more fully. sufficient to cause a decrease in battery performance.

According to the preferred solution of the photocatalytic fuel cell with a three-dimensional permeable photoanode of the present invention, the three-dimensional permeable photoanode is prepared by anodizing on the surface of the base material to prepare a titanium dioxide nanotube array; or the three-dimensional permeable photoanode The photoanode is prepared by sol-gel method or vapor deposition method on the surface of the base material to prepare titanium dioxide nanoparticles; or the three-dimensional permeable photoanode is prepared by hydrothermal method on the surface of the base material. Titanium dioxide nanorods.

According to the preferred solution of the photocatalytic fuel cell with three-dimensional permeable photoanode according to the present invention, the base material adopts porous metal foam, and the porous metal foam is prepared by using 3D printing technology; or the porous metal foam It is prepared by sintering metal powder or by adding pore-forming agent to metal powder.

According to the preferred solution of the photocatalytic fuel cell with a three-dimensional permeable photoanode of the present invention, the cathode is a self-breathing cathode, and the surface of the cathode is loaded with a catalyst.

According to the preferred solution of the photocatalytic fuel cell with a three-dimensional permeable photoanode according to the present invention, the reaction solution composed of the anolyte and the fuel is a mixed solution of methanol and alkali.

The beneficial effects of the photocatalytic fuel cell with the three-dimensional permeable photoanode described in the present invention are: the present invention changes the material transport mode of the reactants from diffusion to convection, strengthens the material transport inside the cell, and has more advantages under low-concentration fuel conditions , more suitable for removing low-concentration industrial wastewater or for detecting low-concentration solutions; the invention can be widely used in the fields of energy, chemical industry, environmental protection and the like.

Description of drawings

FIG. 1 is a schematic structural diagram of a photocatalyst fuel cell with a permeable photoanode according to the present invention.

FIG. 2 is a performance diagram of a photocatalyst fuel cell with a permeable photoanode according to the present invention.

Detailed ways

The present invention will be further described in detail below with reference to the examples, but the embodiments of the present invention are not limited thereto.

Referring to FIG. 1, a photocatalytic fuel cell with a three-dimensional permeable photoanode includes an anode cover plate 1, an anode flow channel plate 2, an anode plate 4, a three-dimensional permeable photoanode 6, and an anode flow channel plate two arranged in sequence. 7. Proton exchange membrane 11 , cathode flow channel plate 9 , cathode plate 12 and cathode cover plate 15 .

The anode cover plate 1 is provided with a liquid inlet 16 and a liquid outlet 17, and the anode flow channel plate one 2, the anode plate 4 and the anode flow channel plate two 7 are respectively provided with an anode flow channel one 3, an anode chamber 5 and an anode. The second flow channel 8, the liquid inlet 16 is communicated with the anode flow channel one 3, the anode chamber 5 and the anode flow channel two 8; The via hole 17a provided on the upper is communicated with the anode flow channel 28; the three-dimensional permeable photoanode 6 is placed between the anode plate 4 and the anode flow channel plate 27; the three-dimensional permeable photoanode 6 is made of porous foam metal material. The proton exchange membrane 11 is arranged between the anode flow channel plate 2 7 and the cathode flow channel plate 9, and the cathode and anode are separated by the proton exchange membrane 11.

The cathode flow channel plate 9, the cathode plate 12 and the cathode cover plate 15 are respectively provided with a cathode flow channel 10, a cathode chamber 13 and a liquid outlet, and the cathode chamber 13 is placed with a cathode 14; connected to the outlet.

The reaction solution composed of anolyte and fuel is driven by a pump and injected into the anode channel 1 from the liquid inlet 16. After the anode channel 1 is filled with the reaction solution, it enters the anode chamber 5 and penetrates into the three-dimensional permeable photoanode 6. The light source illuminates the three-dimensional permeable photoanode 6 to generate electricity. After the reaction solution fills all the pores of the three-dimensional permeable photoanode 6 , the reaction solution flows out through the anode flow channel 2 8 and the liquid outlet 17 .

The catholyte is driven by the pump and enters the cathode flow channel 10 opened by the cathode flow channel plate 9. After the cathode flow channel 10 is filled with the catholyte solution, it flows into the cathode chamber 13 and reaches the cathode 14, and then flows out from the liquid outlet 17; The purpose of using the dual chamber is to reduce the mixed potential generated by the fuel at the cathode; the reaction liquid flows in an osmotic manner to enhance the transfer of substances inside the cell, so that the oxidation reactant and the simultaneous generation of electricity can be achieved even under low-concentration fuel conditions.

The three-dimensional permeable photoanode 6 is connected to the cathode 14 by an external circuit.

In a specific embodiment, the three-dimensional permeable photoanode 6 is prepared by anodizing method on the surface of the base material to prepare a titanium dioxide nanotube array; or the three-dimensional permeable photoanode 6 is made by using a sol-gel method on the surface of the base material. Or a vapor deposition method is used to prepare titania nanoparticles; or the three-dimensional permeable photoanode 6 is to prepare titania nanorods on the surface of the base material by a hydrothermal method. In short, the porous photoanode catalysts are re-constructed on the surface of the three-dimensional structured photoanode base material. TiO2 nanotube arrays, TiO2 nanoparticles, and TiO2 nanorods all serve as photoanode catalysts.

In a specific embodiment, the base material is a porous metal foam, and the porous metal foam is prepared by using 3D printing technology; or the porous metal foam is prepared by sintering metal powder or adding pores to the metal powder agent obtained.

The cathode is a self-breathing cathode, and the catalyst supported on the surface of the cathode is a platinum catalyst, so as to avoid the limitation of the cathode reaction.

The reaction solution composed of the electrolyte solution and the fuel adopts a mixed solution of methanol and alkali, such as potassium hydroxide and methanol. Bottom and top plates are made of corrosion-resistant polymer or glass.

In a specific embodiment, 3D printing technology is used to prepare foamed titanium as a photoanode catalyst carrier, and then an anodization method is used to prepare a photoanode catalyst. Specifically, the foamed titanium is placed in an anodizing reaction solution for constant-voltage anodization, and then oxidized After calcination in a tube furnace, the obtained three-dimensional permeable photoanode with titanium dioxide nanotube arrays. This solution can reduce the contact resistance. The anodic oxidation reaction solution is an aqueous ethylene glycol solution containing an appropriate amount of NH ₄ F.

The specific preparation steps of the photoanode include: first, place the titanium foam in a mixed solution with a mass ratio of ethanol and acetone of 1:1, and ultrasonically vibrate for 30 minutes to remove impurities and grease on the surface of the titanium foam, and then place the titanium foam in deionized water. Ultrasonic vibration for 10min, then blow dry the titanium foam in a nitrogen atmosphere, place it in a mixed solution with a volume ratio of HF:HNO ₃ : ethylene glycol of 1:4:10 for chemical polishing, remove the surface oxide layer, and complete the foam. The pretreatment process of titanium; followed by anodic oxidation, use a graduated cylinder to measure 5mL of deionized water and 95mL of ethylene glycol to prepare a solution, then add an appropriate amount of ammonium fluoride to prepare a 0.5w% ammonium fluoride mixed solution, stir magnetically until The ammonium fluoride powder is completely dissolved to obtain the required electrolyte, and constant-voltage anodic oxidation is performed at a suitable voltage to finally obtain a three-dimensional permeable photoanode.

The invention adopts the porous metal foam as the photoanode carrier, and the solution can completely flow through the photoanode under the driving of the pump, so as to enhance the material transport inside the photoanode, and it is more advantageous under the condition of low concentration fuel. The specific performance is shown in Figure 2.

Although embodiments of the present invention have been shown and described, it will be understood by those of ordinary skill in the art that various changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, The scope of the invention is defined by the claims and their equivalents.

Claims (5)

1. A photocatalytic fuel cell with a three-dimensional permeable photoanode, comprising an anode cover plate (1), an anode flow channel plate (2), an anode plate (4), a three-dimensional permeable photoanode (6) arranged in sequence , anode flow channel plate two (7), proton exchange membrane (11), cathode flow channel plate (9), cathode plate (12), cathode (14), and cathode cover plate (15); it is characterized in that: The anode cover plate (1) is provided with a liquid inlet (16) and a liquid outlet (17), and the anode flow channel plate one (2), the anode flow channel plate (4) and the anode flow channel plate two (7) are respectively provided with a liquid inlet (16) and a liquid outlet (17). Anode flow channel one (3), anode chamber (5) and anode flow channel two (8), liquid inlet (16) and anode flow channel one (3), anode chamber (5) and anode flow channel two ( 8) communicate with each other; the liquid outlet (17) is communicated with the anode flow channel two (8); the three-dimensional permeable photoanode (6) is placed between the anode plate (4) and the anode flow channel plate two (7); The three-dimensional permeable photoanode (6) uses a porous foam metal material as a base, and a photocatalyst is prepared on the surface of the porous foam metal material; the proton exchange membrane (11) is arranged on the anode flow channel plate two (7) and the cathode flow channel Between the plates (9), the cathode and anode are separated by a proton exchange membrane (11); The cathode flow channel plate (9), the cathode plate (12) and the cathode cover plate (15) are respectively provided with a cathode flow channel (10), a cathode chamber (13) and a liquid outlet, and the cathode chamber (13) is placed in the cathode chamber (13). the cathode (14); the cathode flow channel (10), the cathode chamber (13) and the liquid outlet are communicated; The reaction solution composed of the anolyte and the fuel is driven by a pump, and is injected into the anode flow channel 1 from the liquid inlet (16). (6) infiltration, the light source illuminates the three-dimensional permeable photoanode (6) to generate electricity, and after the reaction solution fills all the pores of the three-dimensional permeable photoanode (6), the reaction solution passes through the anode flow channel two (8), the liquid outlet (17) Outflow; The catholyte is driven by the pump and enters the cathode flow channel (10) opened by the cathode flow channel plate (9). After the cathode flow channel (10) is filled with the catholyte, it flows into the cathode chamber (13) and reaches the cathode (14). ), and then flow out from the liquid outlet (17); the purpose of using a double chamber is to reduce the mixed potential generated by the fuel at the cathode; the reaction liquid flows in a permeable manner to strengthen the transfer of materials inside the battery, so that the low-concentration fuel conditions can also be It can achieve the purpose of oxidizing reactants and generating electricity at the same time. 2. A photocatalytic fuel cell with a three-dimensional permeable photoanode according to claim 1, characterized in that: the three-dimensional permeable photoanode (6) is prepared by using anodizing method on the surface of the base material to prepare nanometer titanium dioxide. tube array; or the three-dimensional permeable photoanode (6) is prepared by using a sol-gel method or a vapor deposition method on the surface of the substrate material to prepare titanium dioxide nanoparticles; or the three-dimensional permeable photoanode (6) is a substrate material The surface of titanium dioxide nanorods was prepared by hydrothermal method. 3. The photocatalytic fuel cell with a three-dimensional permeable photoanode according to claim 2, wherein the base material is a porous metal foam, and the porous metal foam is prepared by using a 3D printing technology; Or the porous metal foam is prepared by sintering metal powder or by adding a pore-forming agent to the metal powder. 4 . The photocatalytic fuel cell with a three-dimensional permeable photoanode according to claim 1 , wherein the cathode is a self-breathing cathode, and the surface of the cathode is loaded with a catalyst. 5 . 5 . The photocatalytic fuel cell with a three-dimensional permeable photoanode according to claim 1 , wherein the reaction solution composed of the electrolyte solution and the fuel is a mixed solution of methanol and alkali. 6 .

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