Flow type photoelectrocatalysis reaction instrument
By designing a flow-type photoelectric catalytic reactor and using flow-catalytic technology to improve the reaction rate and output rate, the problems of slow reaction and low output of the static reaction tank are solved, and efficient photoelectric catalytic reaction and industrial application are achieved.
Patent Information
- Application Number
- CN202421827945.6
- Authority / Receiving Office
- CN · China
- Patent Type
- Utility models(China)
- Current Assignee / Owner
- Priority Date
- 2023-07-31
- Filing Date
- 2024-07-31
- Publication Date
- 2025-06-10
- Estimated Expiration
- 2034-07-31
AI Technical Summary
The existing static reaction tanks have slow reaction rates and low output rates in photoelectro-catalytic reactions, which are not conducive to the promotion of data collection and industrial production.
A flow-type photoelectrocatalytic reactor is designed to electrocatalyze, photocatalyze and photoelectrocatalytic treatment of the reaction fluid through the photoelectrocatalytic reaction module, and the static reaction is transformed into a dynamic continuous reaction using flow catalysis.
It improves the activity of the reaction system, improves the catalytic reaction efficiency, realizes real-time product acquisition, and conducts efficient electrosynthesis under low electrolyte or no electrolyte, which promotes the industrialization of photoelectrocatalytic reaction devices.
Smart Images
Figure CN222956380U_ABST
Abstract
Description
Technical Field
[0001] The utility model relates to the technical field of photoelectrocatalysis, and specifically relates to a flow-type photoelectrocatalytic reactor. Background Technique
[0002] The main purpose of the photoelectrocatalysis technology is to break through the bottleneck of low performance of single use of photocatalysis or electrocatalysis by the synergistic effect of photocatalysis and electrocatalysis. Pure photocatalysis uses a semiconductor photocatalyst to be excited by light to generate photoexcited electrons and holes. The electrons in the valence band of the semiconductor photocatalyst are excited to jump to the conduction band to participate in the reduction reaction, and holes are left in the valence band to participate in the oxidation reaction.
[0003] Electrocatalysis is to control the electrochemical workstation to provide an oxidation-reduction potential for the catalyst, and reduction reactions occur on the cathode electrode and oxidation reactions occur on the anode electrode respectively. At present, for the combination of photocatalysis and electrocatalysis technologies, it is beneficial to jointly regulate the activity and product selectivity of the reaction system by the conductivity of the semiconductor photocatalyst, the adjustable valence band position, and its electrocatalytic potential control.
[0004] For the technical solution of photoelectrocatalysis, a static reaction cell is usually used commercially. A typical example is photoelectrocatalytic CO 2 reduction, which has a single-chamber or double-chamber reaction cell. An electrolyte filled with saturated CO 2 gas is often used. The working electrode is suspended in the electrolyte, and the dissolved CO 2 gas participates in the reaction on the catalyst surface. However, the static reaction cell has obvious defects, such as slow reaction rate, slow production rate of reaction products, easy to reach equilibrium under specific reaction conditions, and this mode is not conducive to data collection and the promotion of industrial production development. Summary of the Invention
[0005] The technical problem to be solved by the utility model is to provide a flow-type photoelectrocatalytic reactor with a relatively fast reaction rate and high reliability in view of the obvious defects of the above-mentioned static reaction cell in the prior art, such as slow reaction rate and slow production rate of reaction products.
[0006] The utility model firstly proposes a flow-type photoelectrocatalytic reactor, including,
[0007] a photoelectrocatalytic reaction module, the photoelectrocatalytic reaction module is provided with a flow channel joint for inputting or outputting reaction fluid;
[0008] The photoelectrocatalytic reaction module is laminated by an anode plate, a flow channel thin plate, a cathode plate and an optical glass.
[0009] The flow channel thin plates are arranged on both the upper end surface and the lower end surface of the anode plate, and the anode plate and the flow channel thin plates are both provided with flow channels with the same shape;
[0010] In the first state, the reaction fluid flows in the flow channel, and light passes through the optical glass and irradiates the flow channel to catalyze the reaction of substances in the reaction fluid.
[0011] In some specific embodiments of the first aspect of the present invention, the angle between the light and the flow direction of the reaction fluid is 85-95°, preferably 90°.
[0012] In some specific embodiments of the first aspect of the present invention, the flow channels passing through the anode plate and the flow channel sheet have the same shape and size.
[0013] In some specific embodiments of the first aspect of the present invention, the flow channel passing through the anode plate and the flow channel sheet is continuously S-shaped.
[0014] In some specific embodiments of the first aspect of the present invention, the side wall of the lower box body is penetrated by an elastic probe. In the first state, the elastic probe supplies power to the anode plate and the cathode plate to promote the reaction of substances in the reaction fluid.
[0015] In some specific embodiments of the first aspect of the present invention, the light is provided by a lighting module. The lighting module includes an LED light source fixed on the inner side of the box body. The LED light source is movably connected to the guide rod, and the LED light source can move freely along the guide rod to adjust the lighting position.
[0016] In some specific embodiments of the first aspect of the present invention, the light is provided by a lighting module. The lighting module includes an LED light source provided on the inner side of the box body for providing light to the photoelectrocatalytic reaction module. In some alternative embodiments, the LED light source is movably connected to the guide rod. In some alternative embodiments, the LED light source can move freely along the guide rod to adjust the lighting position.
[0017] In some specific embodiments of the first aspect of the present invention, a circuit control module is further included, and the circuit control module is used to control the light intensity, the fluid flow rate and the probe current.
[0018] In some specific embodiments of the first aspect of the present invention, a human-computer interaction module is further included, which includes a touch screen. The touch screen is installed on the front panel and is used to display the parameters in the photoelectrocatalytic reaction.
[0019] In some specific embodiments of the first aspect of the present invention, a fluid delivery module is further included. In the first state, the fluid delivery module inputs the reaction fluid into the photoelectrocatalytic reaction module.
[0020] In some specific embodiments of the first aspect of the present utility model, the fluid delivery module includes a peristaltic pump, and the peristaltic pump is fluidly connected to a flow channel joint.
[0021] Advantages of the present utility model:
[0022] In the flow-type photoelectrocatalytic reactor of the present utility model, the reaction fluid is subjected to electrocatalysis, photocatalysis, and photoelectrocatalysis by the photoelectrocatalytic reaction module. On the one hand, the activity of the test reaction system is increased by an order of magnitude compared with that in the same field. The whole system adopts flow catalysis, converting the original static photoelectrocatalysis into dynamic and continuous flow electrocatalysis, photocatalysis, and photoelectrocatalysis, greatly improving the catalytic reaction efficiency, and the products of the catalytic reaction can be obtained in real time.
[0023] On the other hand, this instrument can perform efficient electro-synthesis under low electrolyte or even no electrolyte conditions, and can easily achieve reaction amplification, which is a major breakthrough in the field of photoelectrocatalytic reaction devices; in the photoelectrocatalytic reaction module, sample injection, electrolysis, and light irradiation are integrated into one, and the electrode material and various flow channels can be freely selected. At the same time, the electrolysis output power is large and the electrolysis output accuracy is high. Description of the drawings
[0024] Figure 1 is a schematic three-dimensional structure diagram of an embodiment of the flow-type photoelectrocatalytic reactor provided by the present utility model;
[0025] Figure 2 is a schematic internal structure diagram of the box body of an embodiment of the flow-type photoelectrocatalytic reactor provided by the present utility model;
[0026] Figure 3 is an exploded view of an embodiment of the photoelectrocatalytic reaction module provided by the present utility model;
[0027] Illustration description:
[0028] 100, box body; 101, front panel; 102, bottom plate; 103, left side plate; 104, right side plate; 8, cathode plate; 200, human-computer interaction module; 300, fluid delivery module; 400, photoelectrocatalytic reaction module; 401, lower box body; 404, cathode plate; 405, flow channel sheet; 406, anode plate; 407, optical glass; 409, upper cover; 412, flow channel joint; 410, screw; 501, LED light source; 502, radiator; 503, second fan; 504, guide rod; 505, hand-tightening screw; 506, partition plate; 507, light source cover plate; 606, movable window; 601, rebound button; 602, transparent plate; 701, power switch; 702, power supply; 703, motor driver; 704, control main board; 705, electrolysis circuit board; 706, first fan; 707, circuit fixing plate; Detailed implementation manners
[0029] For a clearer understanding of the technical features, objectives, and effects of the present utility model, the specific implementation manners of the present utility model will now be described in detail with reference to the accompanying drawings.
[0030] As Figures 1-3 shown, in the first embodiment of the flow-through photoelectrocatalytic reactor of the present utility model, the flow-through photoelectrocatalytic reactor includes a box body 100, a human-machine interaction module 200, a fluid delivery module 300, a photoelectrocatalytic reaction module 400, a light illumination module 500, and a circuit control module.
[0031] Specifically, the box body 100 is formed as a hollow cuboid.
[0032] Among them, the box body 100 is formed by the cooperation and connection of a front panel 101, a bottom plate 102, a left side plate 103, and a right side plate 104. The bottom plate 102 and the back panel form an L-shaped structure, and the left side plate 103 and the upper cover 409 form an L-shaped structure.
[0033] Furthermore, the photoelectrocatalytic reaction module 400 is disposed on one side of the box body 100, and is used for electrocatalysis, photocatalysis, and photoelectrocatalysis of the introduced fluid to obtain the products of the catalytic reaction.
[0034] Specifically, the photoelectrocatalytic reaction module 400 is formed by laminating a lower box body 401, an anode plate 406, a flow channel thin sheet 405, a cathode plate 404, an optical glass 407, and an upper cover 409;
[0035] On one side of the lower box body 401, a flow channel joint 412 is provided, which is used for inputting and outputting reaction fluid;
[0036] On both the upper end face and the lower end face of the anode plate 406, flow channel thin sheets 405 are provided. A flow channel consistent with the flow channel thin sheet 405 is opened inside the anode plate 406. Specifically, the flow channel penetrates through the anode plate 406, and the flow channel thin sheet 405 penetrates through a flow channel consistent with the anode plate 406. As Figure 3 shown, after the anode plate 406 and the flow channel thin sheet 405 are laminated, a plurality of flow channels together form a flow path for the reaction fluid. In some alternative embodiments, the flow channel is a continuous S shape. In some alternative embodiments, the shape of the flow channel is waveform.
[0037] The upper cover 409 has a hollow structure in the middle, and receives light through the optical glass 407 to form a light illumination path.
[0038] The side wall of the lower box body is penetrated by an elastic probe. In the first state, that is, in the working state, the elastic probe supplies power to the anode plate and the cathode plate to promote the reaction of substances in the reaction fluid.
[0039] The upper cover has a hollow structure in the middle, or it can be described that there is a through-hole in the middle of the upper cover. In the first state, that is, in the working state, light passes through the through-hole and the optical glass in sequence and irradiates on the reaction fluid.
[0040] In the first state, that is, in the working state, there is a reaction fluid flowing in the flow channel. Light passes through the optical glass and irradiates on the flow channel, catalyzing the reaction of substances in the reaction fluid. The light forms a 90° angle with the flow direction of the reaction fluid.
[0041] Application Example 1:
[0042] Put 0.3 mmol of 4-methylquinoline, 0.45 mmol of potassium isopropylfluoroborate, 5 mol% of the photocatalyst MesAcrClO 4 , 0.3 mmol of the electrolyte Et 4 NBF 4 in a glass bottle, add 0.3 mmol of trifluoroacetic acid, 4 mL of CH 3 CN and 2 mL of H 2 O. Bubble the reaction mixture with argon for 10 minutes. After bubbling, insert the inlet tube of the peristaltic pump into the bottom of the solution, turn on the peristaltic pump of the instrument and set the flow rate to 0.2 mL min -1 , set the current of the instrument to 40 mA (the anode material is graphite and the cathode is platinum), and turn on the 450 nm light source to adjust the power to 20 W. After the instrument runs stably for 10 min, start to receive the electrolytic effluent, and the yield of compound 3 is 98%.
[0043]
[0044] Application Example 2:
[0045] Put 0.3 mmol of 4-methylquinoline, 0.9 mmol of cyclohexanecarboxylic acid, 5 mol% of CeCl 3 ·7H 2 O and 0.15 mmol of nBu 4 NCl in a glass bottle, and then add 2 mL of hexafluoroisopropanol and 3 mL of trifluoroethanol. Bubble the reaction mixture with argon for 10 minutes, and then add 0.3 mmol of concentrated hydrochloric acid. Insert the inlet tube of the peristaltic pump into the bottom of the solution, turn on the peristaltic pump of the instrument and set the flow rate to 0.2 mL min-1, set the current of the instrument to 45 mA (the anode material is graphite and the cathode is platinum), and turn on the 392 nm light source to adjust the power to 20 W. After the instrument runs stably for 10 min, start to receive the electrolytic effluent, and the yield of compound 5 is 97%.
[0046]
[0047] Comparative Example 1:
[0048] Add 1 mmol of diphenyl ether (Compound 1), 2 mmol of pyrazole (Compound 2), 0.05 mmol of 10-methyl-9-mesityl acridine perchlorate, 0.2 mmol of 2,2,6,6-tetramethylpiperidine oxide, and 0.1 mmol of tetraethylammonium tetrafluoroborate to a round-bottom flask. Under nitrogen, add 12 mL of 1,2-dichloroethane. Insert the inlet tube of the peristaltic pump into the perforated rubber stopper and quickly replace it with the non-perforated rubber stopper of the round-bottom flask. Then, bubble the solution with a nitrogen balloon for 15 minutes. After bubbling, insert the inlet tube of the peristaltic pump to the bottom of the solution, turn on the peristaltic pump of the instrument and set the flow rate to 0.2 mL min -1 , set the instrument current to 65 mA, turn on the 395 nm light source and adjust the power to 20 W. After the instrument runs stably for 10 min, start to collect the electrolytic effluent, and the yield of Compound 3 is 27%.
[0049]
[0050] Using this technical solution, the fluid to be reacted is electrocatalytically, photocatalytically, and photoelectrocatalytically treated by the photoelectrocatalytic reaction module 400. On the one hand, the activity of the reaction system is tested to be improved by several orders of magnitude compared with the same field. The whole system adopts flow catalysis, converting the original static photoelectrocatalysis into dynamic and continuous flow electrocatalysis, photocatalysis, and photoelectrocatalysis, greatly improving the catalytic reaction efficiency, and the product of the catalytic reaction can be obtained in real time;
[0051] On the other hand, this instrument can perform high-efficiency electro-synthesis under low electrolyte or even no electrolyte conditions and easily realize reaction amplification, which is a major breakthrough in the field of photoelectrocatalytic reaction devices; in the photoelectrocatalytic reaction module 400, sampling, electrolysis, and light irradiation are integrated into one, and the electrode material and various flow channels can be freely selected. At the same time, the electrolysis output power is large and the electrolysis output accuracy is high.
[0052] In some embodiments, as Figure 3 shown, the side wall of the lower box body 401 is provided with double through holes for passing through elastic probes (not shown), and one side wall of the lower box body 401 is provided with double threaded holes for installing the flow channel joint 412. Screws 410 are used to fixedly lock the photoelectrocatalytic reaction module 400 to prevent liquid leakage.
[0053] Furthermore, the elastic probe (not shown) has positive and negative poles, which are used to quickly energize the photoelectrocatalytic reaction module 400.
[0054] In some embodiments, in order to ensure the continuity of the fluid to be reacted introduced, a fluid delivery module 300 can be set in the reactor, which is set on one side of the photoelectrocatalytic reaction module 400,
[0055] The output end of the fluid delivery module 300 is connected to the liquid inlet end of the photoelectrocatalytic reaction module 400 through an infusion hose, providing the fluid to be reacted for the photoelectrocatalytic reaction module 400.
[0056] Among them, the fluid delivery module 300 includes a peristaltic pump and an infusion hose installed on the front panel 101. The peristaltic pump realizes the function of adjustable flow rate through the touch screen, and is used to provide a liquid flow with stable flow rate for the photoelectrocatalytic reaction module 400.
[0057] The wall thickness of the peristaltic pump infusion hose is 0.86 mm, the maximum number of channels is 1, and the number of roller shafts is 10.
[0058] In some embodiments, as Figure 2 shown, the reactor further includes a lighting module 500. The lighting module 500 serves as a light source and is used to provide a light source for the photoelectrocatalytic reaction module 400. It includes an LED light source 501 fixed inside the box body 100, a light source cover plate 507, and a partition plate 506 outside the box body 100. The LED light source 501 is movably fixed to the guide rod 504 through a hand-tightening screw 505. The LED light source 501 is fixed with a radiator 502 and a second fan 503.
[0059] The LED light source 501 can adjust different lighting powers. The LED light source 501 can move freely along the guide rod 504 to adjust the lighting position. The hand-tightening screw 505 is used to fix the position of the LED light source 501 on the guide rod 504. The partition plate 506 and the light source cover plate 507 are used to isolate an independent space for the LED light source 501.
[0060] In some embodiments, a movable window 600 is provided on one side of the box body 100. One end of the movable window 600 is equipped with a rebound button 601 for realizing rotary opening and closing. The movable window 600 is inlaid with a transparent plate 602 for viewing the lighting module 500 inside.
[0061] In some embodiments, as Figure 2 shown, it further includes a circuit control module, which includes a control main board 704, a power switch 701 fixed to the bottom plate 102, and a first fan 706.
[0062] The power switch 701 is connected to the power supply 702. The power supply 702 is fixed to the motor driver 703 on the right side. The right side of the motor driver 703 is fixedly connected to the electrolysis circuit board 705.
[0063] The control main board 704 is installed at the rear of the human-computer interaction module 200. The electrolysis circuit board 705 is transferred to the bottom plate 102 through a circuit fixing plate 707.
[0064] In some embodiments, it further includes a human-computer interaction module 200, which includes a touch screen. The touch screen is installed on the front panel 101 and is used to display the parameters in the photoelectrocatalytic reaction.
[0065] In this embodiment, in the photoelectrocatalytic reaction module 400, specifically, the anode plate 406 is made of a graphite plate, the cathode plate 8 is made of a stainless steel plate, the screw 410 is an M4 hexagon socket head screw, and the sealing flow channel material is selected as FEP.
[0066] The working principle of this embodiment is as follows:
[0067] The fluid delivery module 300 includes a peristaltic pump. The peristaltic pump is used to receive the fluid for the photoelectrocatalytic reaction and deliver it to the first flow channel joint 412 of the photoreaction module through an infusion hose. The reaction fluid passes through the flow channel sheet 405 and is simultaneously electrocatalyzed by the electrode composed of the anode plate 406 and the cathode plate 404. Moreover, the light path formed by the hollow structure of the upper cover 409 passes through the optical glass 407 to perform photocatalysis on the reaction fluid. Therefore, the reaction fluid is simultaneously in the dynamic reactions of electrocatalysis and photocatalysis. After the reaction is complete, the reaction product flows out from the second flow channel joint 412 along the flow channel sheet 405, thereby realizing the fluidization of the dynamic continuous catalysis of the photoelectrocatalytic reaction.
[0068] The embodiments of the present invention have been described above in conjunction with the accompanying drawings. However, the present invention is not limited to the above specific embodiments. The above specific embodiments are merely illustrative and not restrictive. Under the inspiration of the present invention, those of ordinary skill in the art can also make many forms without departing from the spirit and scope protected by the claims of the present invention. All of these are within the protection scope of the present invention.
Claims
1. A flow-type photoelectrocatalytic reactor, characterized in that: include, A photoelectrocatalytic reaction module, wherein the photoelectrocatalytic reaction module is provided with a flow channel joint, and the flow channel joint is used to input or output a reaction fluid; The photoelectrocatalytic reaction module is composed of a lower box body, an anode plate, a flow channel sheet, a cathode plate, and optical glass stacked together; The flow channel sheet is disposed on the upper end surface and the lower end surface of the anode plate, and the anode plate and the flow channel sheet are both provided with flow channels; In the first state, the reaction fluid flows in the flow channel, and light passes through the optical glass and irradiates the reaction fluid, catalyzing the reaction of substances in the reaction fluid.
2. The flow-type photoelectrocatalytic reactor according to claim 1, characterized in that: The side wall of the lower box body is penetrated by an elastic probe. In a first state, the elastic probe energizes the anode plate and the cathode plate to promote the reaction of substances in the reaction fluid.
3. The flow-type photoelectrocatalytic reactor according to claim 1, characterized in that: The light and the flow direction of the reaction fluid form an angle of 85-95 degrees.
4. The flow-type photoelectrocatalytic reactor according to claim 1, characterized in that: The light beam forms an angle of 90° with the flow direction of the reaction fluid.
5. The flow-type photoelectrocatalytic reactor according to claim 1, characterized in that: The flow channels arranged on the anode plate and the flow channel sheet have the same shape and size.
6. The flow-type photoelectrocatalytic reactor according to claim 1, characterized in that: The flow channel arranged on the anode plate and the flow channel sheet is in a continuous S shape.
7. The flow-type photoelectrocatalytic reactor according to claim 1, characterized in that: The light is provided by an illumination module, which includes an LED light source arranged on the inner side of the box body to provide light to the photoelectrocatalytic reaction module, and / or the LED light source is movably connected to the guide rod, and / or the LED light source can move freely along the guide rod to adjust the illumination position.
8. The flow-type photoelectrocatalytic reactor according to claim 1, characterized in that: It also includes a circuit control module, which is used to control the light intensity, fluid flow rate and probe current.
9. The flow-type photoelectrocatalytic reactor according to claim 1, characterized in that: It also includes a human-computer interaction module, which includes a touch screen installed on the front panel and is used to display parameters in the photoelectrocatalytic reaction.
10. The flow-type photoelectrocatalytic reactor according to claim 1, characterized in that: It also includes a fluid delivery module, and in a first state, the fluid delivery module inputs reaction fluid to the photoelectrocatalytic reaction module.
11. The flow-type photoelectrocatalytic reactor according to claim 10, characterized in that: The fluid delivery module comprises a peristaltic pump, and the peristaltic pump is fluidically connected to the flow channel joint.