CN111926344A - Photosynthetic reaction device and method for manufacturing membrane electrode - Google Patents
Photosynthetic reaction device and method for manufacturing membrane electrode Download PDFInfo
- Publication number
- CN111926344A CN111926344A CN202010764121.9A CN202010764121A CN111926344A CN 111926344 A CN111926344 A CN 111926344A CN 202010764121 A CN202010764121 A CN 202010764121A CN 111926344 A CN111926344 A CN 111926344A
- Authority
- CN
- China
- Prior art keywords
- substrate
- electrode material
- cathode
- anode
- channel
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/16—Metallic material, boron or silicon on metallic substrates or on substrates of boron or silicon
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
- C23C14/14—Metallic material, boron or silicon
- C23C14/18—Metallic material, boron or silicon on other inorganic substrates
-
- C—CHEMISTRY; METALLURGY
- C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
- C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
- C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
- C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
- C23C14/24—Vacuum evaporation
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25D—PROCESSES FOR THE ELECTROLYTIC OR ELECTROPHORETIC PRODUCTION OF COATINGS; ELECTROFORMING; APPARATUS THEREFOR
- C25D11/00—Electrolytic coating by surface reaction, i.e. forming conversion layers
- C25D11/02—Anodisation
- C25D11/26—Anodisation of refractory metals or alloys based thereon
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Electrochemistry (AREA)
- Inorganic Chemistry (AREA)
- Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
- Physical Or Chemical Processes And Apparatus (AREA)
Abstract
The application discloses a photosynthetic reaction device and a manufacturing method of a membrane electrode, wherein the device comprises: the microchannel reaction region carrier is provided with a first channel communicated in series or in parallel; a first reaction medium inlet and a first reaction medium outlet are respectively arranged at two ends of the first channel; the membrane electrode comprises an ion exchange membrane, an anode electrode material and a cathode electrode material, wherein the anode electrode and the cathode electrode material are respectively hot-pressed on two sides of the ion exchange membrane; the first surface of the anode substrate is provided with a containing groove, and when the carrier of the microchannel reaction area is contained in the containing groove, one side of the carrier of the microchannel reaction area, which is provided with the first channel, is exposed at the first surface; the second surface of the cathode substrate is provided with a second channel matched with the first channel on the micro-channel reaction region carrier; and clamping the membrane electrode between an anode substrate and a cathode substrate, wherein an anode electrode material is attached to the first channel, and a cathode electrode material is attached to the second channel.
Description
Technical Field
The invention relates to an artificial photosynthesis technology, in particular to a portable artificial photosynthesis reaction device based on a microchannel technology, which is used for simulating the artificial photosynthesis outside the ground in an outside-ground microgravity environment.
Background
With the expansion of human exploration territory, extremely challenging space missions such as returning to the moon, manned mars and the like gradually come up with the schedule. In future manned deep space exploration activities, the living process of organisms faces basic material and energy requirements, and extraterrestrial survival is the basic requirement for realizing extraterrestrial migration and long-term living of human beings. The resources are carried on the earth to carry out manned off-site exploration, the task cost is extremely high, and the technology is difficult to realize. Therefore, the in-situ energy storage technology is vigorously developed, celestial body resources are effectively utilized, and carried substances are recycled, so that the material requirements carried by the earth can be greatly reduced, and the manned deep space exploration task is feasible. The artificial photosynthesis can convert carbon dioxide generated by human breathing or carbon dioxide and water resources in the atmosphere environment of the extraterrestrial planet into oxygen and carbon-containing fuel in a controllable manner through a photoelectrocatalysis reaction, thereby realizing the cyclic utilization of waste resources in a closed space, reducing the material supply requirements of manned space stations and manned deep space spacecrafts, and realizing the long-term survival target of human beings in other planets. The technology can effectively support future sustainable manned space missions, and is the core capability of space exploration. Therefore, the extraterrestrial artificial light synthesis technology is researched, developed and verified in stages and steps through ground experiments and space experiments, and the subsequent development of manned spaceflight is powerfully supported.
At present, the devices adopted for research of carrying out artificial photosynthesis under the ground gravity environment and realizing reduction of carbon dioxide into oxygen and hydrocarbon are generally large-scale containers. However, in the microgravity environment, the interaction mechanism of the bubble evolution in the multi-phase reaction system in the large-scale container and the three-phase region interface where the bubble, the electrolyte and the electrode surface are in contact with each other has an important influence on the material stability, the chemical reaction process control, the effective construction of the system, how to improve the conversion efficiency and the like. The over-dissolved gas is gathered near the surface of the electrode to form a supersaturated layer of dissolved gas molecules, so that the gas is separated from the surface of the electrode in the nucleation process of the supersaturated layer and moves upwards to wrap the electrolyte, and thus the single-phase free convection (micro-convection) behavior of the substance is initiated locally, the gas and the liquid cannot be effectively separated, and the reaction efficiency is reduced rapidly; on the other hand, the increase in interfacial resistance (ohmic drop) caused by the gas bubbles will affect the surface coverage of the electrodes, making the mass transfer process more difficult. Moreover, the artificial photosynthesis reaction involves three-phase reactions of gas phase, liquid phase and solid phase, and large-scale containers in the extraterrestrial space are not easy to carry, control, seal and store.
Disclosure of Invention
In view of the above, one embodiment of the present invention provides a photosynthetic reaction apparatus and a method for manufacturing a membrane electrode.
According to a first aspect of the present application, there is provided a photosynthetic reaction device comprising:
the microchannel reaction region carrier is provided with a first channel communicated in series or in parallel; a first reaction medium inlet and a first reaction medium outlet are respectively arranged at two ends of the first channel;
the membrane electrode comprises an ion exchange membrane, an anode electrode material and a cathode electrode material, wherein the anode electrode material and the cathode electrode material are respectively hot-pressed on two sides of the ion exchange membrane;
the first surface of the anode substrate is provided with a containing groove, and when the microchannel reaction area carrier is contained in the containing groove, one side of the microchannel reaction area carrier, which is provided with a first channel, is exposed on the first surface;
the second surface of the cathode substrate is provided with a second channel matched with the first channel on the micro-channel reaction region carrier;
the anode substrate and the cathode substrate clamp the membrane electrode between the anode substrate and the cathode substrate in a way that the first surface and the second surface are attached, the anode electrode material is attached to the first channel, and the cathode electrode material is attached to the second channel.
As one implementation mode, the reaction area formed by the first channel is (10-50mm) × (10-50mm), and the depth and width dimensions of the first channel are respectively (100-;
the reaction area formed by the second channel is (10-50mm) × (10-50mm), and the depth and width dimensions of the second channel are respectively (100-.
In one implementation, the peripheries of the anode electrode material and the cathode electrode material are further provided with a sealing material.
As an implementation manner, a first liquid inlet and a first product outlet are arranged on the anode substrate, and both the first liquid inlet and the first product outlet are communicated with the accommodating groove;
when the microchannel reaction area carrier is accommodated in the accommodating groove, the first liquid inlet is communicated with the first reaction medium inlet, and the first product outlet is communicated with the first reaction medium outlet.
As one implementation, the cathode substrate includes a second liquid inlet, a second product outlet, and a gas inlet; a second reaction medium inlet and a second reaction medium outlet of the second channel, and a gas-liquid mixing cavity are arranged on the cathode substrate; the gas-liquid mixing cavity is communicated with the second reaction medium inlet;
the second liquid inlet and the gas inlet are communicated with the gas-liquid mixing cavity, and the second product outlet is communicated with the second reaction medium outlet.
As one implementation, the membrane electrode is made by:
preparing an anode electrode material on a quartz glass, organic glass or COC organic glass plate, a metal mesh substrate, a sheet substrate or a carbon paper substrate by adopting an anodic oxidation method, magnetron sputtering, an atomic layer deposition method or a spraying method;
preparing a cathode electrode material on a quartz glass, organic glass, COC organic glass plate or carbon paper substrate by adopting an electrochemical deposition method, a magnetron sputtering method, an atomic layer deposition method or a thermal evaporation method;
activating the ion exchange membrane in acid and alkali solution, and then soaking in deionized water for 20-40 minutes;
and hot-pressing the anode electrode material, the ion exchange membrane and the cathode electrode material into a whole in sequence by adopting a hot-pressing method to form the membrane electrode.
As one implementation, the ion exchange membrane comprises one of:
cation exchange membrane CEM, anion exchange membrane AEM, proton exchange membrane PEM, bipolar membrane BPM;
the anode material comprises one of:
titanium oxide film, ferric oxide film, zinc oxide film, bismuth vanadate film, nanotube and nanowire;
iridium oxide powder, iridium powder and carbon powder, wherein the particle size of the powder is 10-30nm, and the loading capacity is 0.2-5mg/cm2；
The cathode material comprises one of:
powders, films or nanowires of silicon, cuprous oxide, copper, gold, silver, platinum, palladium, and alloys thereof.
As one implementation, the anode substrate and the cathode substrate are stainless steel or aluminum oxide metal substrates; the first surface and the second surface are polished conductive surfaces, and the anode electrode material and the cathode electrode material are respectively electrically communicated with the polished conductive surfaces of the anode substrate and the cathode substrate.
According to a first aspect of the present application, there is provided a method of fabricating a membrane electrode, comprising:
preparing an anode electrode material on a quartz glass, organic glass or COC organic glass plate, a metal mesh substrate, a sheet substrate or a carbon paper substrate by adopting an anodic oxidation method, magnetron sputtering, an atomic layer deposition method or a spraying method;
preparing a cathode electrode material on a quartz glass, organic glass, COC organic glass plate or carbon paper substrate by adopting an electrochemical deposition method, a magnetron sputtering method, an atomic layer deposition method or a thermal evaporation method;
activating the ion exchange membrane in acid and alkali solution, and then soaking in deionized water for 20-40 minutes;
and hot-pressing the anode electrode material, the ion exchange membrane and the cathode electrode material into a whole in sequence by adopting a hot-pressing method to form the membrane electrode.
As one implementation, the ion exchange membrane comprises one of:
cation exchange membrane CEM, anion exchange membrane AEM, proton exchange membrane PEM, bipolar membrane BPM;
the anode material comprises one of:
titanium oxide film, ferric oxide film, zinc oxide film, bismuth vanadate film, nanotube and nanowire;
iridium oxide powder, iridium powder and carbon powder, wherein the particle size of the powder is 10-30nm, and the loading capacity is 0.2-5mg/cm2；
The cathode material comprises one of:
powders, films or nanowires of silicon, cuprous oxide, copper, gold, silver, platinum, palladium, and alloys thereof.
Compared with the existing artificial photosynthesis device for carbon dioxide reduction reaction, the photosynthesis reaction device and the membrane electrode manufacturing method provided by the embodiment of the application have the following advantages:
traditional solid phase, liquid phase and gas phase reaction media are integrated in a micro-channel reaction region and are packaged in a metal substrate through sealing materials, and therefore the space required by the reaction is greatly reduced. The portable and modularized light source device is convenient to carry, can realize modularization and is used for the extraterrestrial artificial light synthesis reaction. The reaction based on the microchannel technology can lead the gas reaction product to be quickly separated from the surface of the electrode and be discharged out of the device along with the reaction medium through the gas-liquid shearing acting force, thereby realizing the quick gas-liquid separation even under the microgravity environment and overcoming the influence of the microgravity condition on the reaction process. The multi-physical-field regulation and control is beneficial to accurately controlling reaction conditions such as pressure, flow rate, flow ratio and the like of reaction gas and liquid, so that the optimal conditions required by a physical and chemical process are fundamentally ensured, and further, the reaction efficiency and the chemical reaction kinetics are improved. In the reaction process based on the microchannel technology, the distance from ions in gas and electrolyte to the surface of the electrode is only micron grade, so that the mass transfer rate in a reaction system is effectively improved, and the chemical reaction rate is increased.
Drawings
FIG. 1 is an exploded view of a reaction apparatus for photosynthesis according to an embodiment of the present application;
FIG. 2 is an enlarged schematic view of a channel structure according to an embodiment of the present application;
FIG. 3 is a schematic view showing the installation of a photosynthesis reaction apparatus according to an embodiment of the present application;
FIG. 4 is an enlarged schematic view of the photosynthetic reaction according to the embodiment of the present application;
FIG. 5 is a schematic diagram showing the change of current with time in the carbon dioxide reduction reaction in the example of the present application.
Detailed Description
The essence of the technical scheme of the invention is explained in detail in the following with the accompanying drawings.
In order to carry out an artificial photosynthesis reaction in an off-site environment to reduce carbon dioxide into carbon-containing organic matters and oxygen and achieve the aim of recycling in-situ resources, a portable and efficient reaction device which overcomes the influence of microgravity needs to be constructed. The application provides an extraterrestrial artificial photosynthesis reaction device based on microchannel technique can realize portable reaction, and through the accurate regulation and control parameters such as velocity of flow, pressure of micro-fluidic many physics field, improves reaction rate and reaction kinetics.
Fig. 1 is a schematic exploded view of a photosynthesis reaction apparatus according to an embodiment of the present application, and as shown in fig. 1, the photosynthesis reaction apparatus according to the embodiment of the present application includes:
the microchannel reaction region carrier is provided with a first channel communicated in series or in parallel; a first reaction medium inlet and a first reaction medium outlet are respectively arranged at two ends of the first channel; as shown in fig. 1, in the embodiment of the present application, the microchannel reaction region carrier corresponds to the carrier carrying the anode microchannel in fig. 1, and the carrier may be an acrylic organic plate, as an implementation manner, a channel with a depth and a width of 400 μm × 400 μm may be etched on an acrylic organic plate with an area of 25mm × 25mm by wet chemical etching, and holes with a diameter of 0.8 to 1.2mm may be drilled at both ends of the channel as the first reaction medium inlet and the first reaction medium outlet, respectively. Here, the diameter of the hole may be 1mm, or may be 1.1mm, 0.9mm, or the like, as shown in FIG. 2.
The membrane electrode comprises an ion exchange membrane, an anode electrode material and a cathode electrode material, wherein the anode electrode material and the cathode electrode material are respectively hot-pressed on two sides of the ion exchange membrane;
the first surface of the anode substrate is provided with a containing groove, and when the microchannel reaction area carrier is contained in the containing groove, one side of the microchannel reaction area carrier, which is provided with a first channel, is exposed on the first surface;
the second surface of the cathode substrate is provided with a second channel matched with the first channel on the micro-channel reaction region carrier;
the anode substrate and the cathode substrate clamp the membrane electrode between the anode substrate and the cathode substrate in a way that the first surface and the second surface are attached, the anode electrode material is attached to the first channel, and the cathode electrode material is attached to the second channel. The anode substrate and the cathode substrate are stainless steel or aluminum oxide metal substrates; the first surface and the second surface are polished conductive surfaces, and the anode electrode material and the cathode electrode material are respectively in contact with the polished conductive surfaces of the anode substrate and the cathode substrate.
In the embodiment of the present application, the reaction area formed by the first trench is (10-50mm) × (10-50mm), and the depth and width of the first trench are (100-; correspondingly, the reaction area formed by the second channel is (10-50mm) × (10-50mm), and the depth and width dimensions of the second channel are respectively (100-.
As shown in fig. 1, in order to ensure the sealing performance of the microchannel reaction region according to the embodiment of the present disclosure, a sealing material is further disposed on the peripheries of the anode electrode material and the cathode electrode material, so that the microchannel reaction region according to the embodiment of the present disclosure is isolated from the outside by the clamping of the anode substrate and the cathode substrate on the microchannel reaction region and the sealing ring formed by the sealing material.
In an embodiment of the present application, the anode substrate is provided with a first liquid inlet and a first product outlet, and both the first liquid inlet and the first product outlet are communicated with the accommodating groove; when the microchannel reaction area carrier is accommodated in the accommodating groove, the first liquid inlet is communicated with the first reaction medium inlet, and the first product outlet is communicated with the first reaction medium outlet. Correspondingly, the cathode substrate comprises a second liquid inlet, a second product outlet and a gas inlet; a second reaction medium inlet and a second reaction medium outlet of the second channel, and a gas-liquid mixing cavity are arranged on the cathode substrate; the gas-liquid mixing cavity is communicated with the second reaction medium inlet; the second liquid inlet and the gas inlet are communicated with the gas-liquid mixing cavity, and the second product outlet is communicated with the second reaction medium outlet.
In the embodiment of the present application, the first reaction medium inlet and the first reaction medium outlet may be disposed adjacently, or disposed diagonally to the first channel; likewise, the second reaction medium inlet and the second reaction medium outlet may be disposed adjacently or may be disposed diagonally to the first channel.
In the embodiment of the application, the membrane electrode is prepared by the following steps:
preparing an anode electrode material on a quartz glass, organic glass or COC organic glass plate, a metal mesh substrate, a sheet substrate or a carbon paper substrate by adopting an anodic oxidation method, magnetron sputtering, an atomic layer deposition method or a spraying method;
preparing a cathode electrode material on a quartz glass, organic glass, COC organic glass plate or carbon paper substrate by adopting an electrochemical deposition method, a magnetron sputtering method, an atomic layer deposition method or a thermal evaporation method;
activating the ion exchange membrane in acid and alkali solution, and then soaking in deionized water for 20-40 minutes; here, the ion exchange membrane subjected to the activation treatment may be soaked in deionized water for 30 minutes.
And hot-pressing the anode electrode material, the ion exchange membrane and the cathode electrode material into a whole in sequence by adopting a hot-pressing method to form the membrane electrode.
As one implementation, the ion exchange membrane comprises one of:
cation Exchange Membrane (CEM), Anion Exchange Membrane (AEM), Proton Exchange Membrane (PEM), bipolar membrane (BPM);
the anode material comprises one of:
titanium oxide film, ferric oxide film, zinc oxide film, bismuth vanadate film, nanotube and nanowire;
iridium oxide powder, iridium powder and carbon powder, wherein the particle size of the powder is 10-30nm, and the loading capacity is 0.2-5mg/cm2；
The cathode material comprises one of:
powders, films or nanowires of silicon, cuprous oxide, copper, gold, silver, platinum, palladium, and alloys thereof.
The preparation method of the photosynthetic reaction device of the embodiment of the application comprises the following steps:
1) drawing a drawing of a metal packaging shell (an anode substrate and a cathode substrate), machining the packaging substrate by adopting a machining mode, and carrying out oxidation treatment on the surface of the substrate.
2) A channel with the depth and the width of (100-500) mu m multiplied by (100-500) mu m is etched on a quartz glass, PMMA or COC organic glass plate by adopting a wet chemical etching method. The etched channels are integrally connected in parallel or in series, as in the structure shown in fig. 2.
3) Preparing a membrane electrode by adopting an anodic oxidation method, a hydrothermal method, a magnetron sputtering or atomic layer deposition method, a spraying method and a thermal evaporation method;
the method specifically comprises the following treatment processes:
3.1) preparing TiO on titanium metal nets with different meshes by adopting an anodic oxidation method2A nanotube; adopting a hydrothermal method, magnetron sputtering or atomic layer deposition method to grow Fe on quartz glass carved with micro-channels2O3、ZnO、BiVO4A thin film or a nanowire; IrO is sprayed on carbon paper by adopting spraying method2Ir/C powder anode electrode material with the particle size of 10-30nm and the loading capacity of 0.2-5mg/cm2The thickness of the carbon paper is 100-300 mu m, and the area is (10-50) mm x (10-50) mm.
3.2) growing Cu on the metallic copper net by electrochemical deposition2An O nanowire; growing a Si film on the quartz glass carved with the micro-channel by adopting a chemical deposition method or a magnetron sputtering method; copper (Cu), silver (Ag), gold (Au), platinum (Pt), palladium (Pd) and alloy powder thereof, and a film cathode electrode material are prepared on carbon paper by a thermal evaporation method or a spraying method, wherein the thickness is 0.5-1 mu m, the thickness of the carbon paper is 100-300 mu m, and the area is (10-50) mm x (10-50) mm.
3.3) activating the ion exchange membrane in different acid and alkali solutions, and then soaking the ion exchange membrane in deionized water for about half an hour. In the present embodiment, the ion exchange membrane may be a Cation Exchange Membrane (CEM), an Anion Exchange Membrane (AEM), a Proton Exchange Membrane (PEM), a bipolar membrane (BPM), or the like.
And 3.4) hot-pressing the anode electrode material, the proton exchange membrane and the cathode electrode material in sequence by adopting a hot-pressing method to form the membrane electrode.
4) And sealing the membrane electrode prepared in the step 3) and the micro-channel chip etched in the step 2) in the substrate processed in the step 1) by using a silica gel pad and an O-shaped pad. The opposite surface of the cathode and the anode of the substrate is a polished conductive surface, and the edge of the carbon paper is in conductive contact with the conductive surface, so that the anode electrode material and the cathode electrode material are respectively in electrical conduction with the polished conductive surfaces of the anode substrate and the cathode substrate.
The micro-channel reaction device is used for carrying out photoelectrocatalysis carbon dioxide reduction reaction, and the method comprises the following steps: a cathode liquid inlet and an air inlet of the photosynthetic reaction device in the embodiment of the application are respectively connected with an electrolyte liquid storage bottle and a carbon dioxide gas bottle through pipelines (for a Flowcell reaction mode, the cathode only needs the air inlet, and the liquid inlet is used as a reserved port), and an anode liquid inlet is connected with the electrolyte liquid storage bottle; the product outlets of the cathode and the anode are respectively connected with a collecting bag. The pressure and the flow rate of gas and liquid are accurately controlled by a micro pump, so that the cathode gas and the liquid alternately flow in a columnar manner, and the flow rate is the same and is 50-300mL/h (for a Flowcell reaction mode, the gas flow rate is 300-; the flow rate of the anode liquid is 50-300 mL/h. Connecting the conductive tabs of the cathode and anode substrates of the device with an electrochemical workstation, connecting the cathode with the cathode, connecting the anode with the anode, and applying voltage to the two ends of the cathode and the anode. For the photoelectrocatalytic reaction, a light source is irradiated from a light source inlet on the substrate to the surface of the electrode material. The reaction current is stable, a large amount of bubbles are generated in the micro-channel of the chip and are discharged out of the device along with the liquid to enter the collecting bag; and extracting 0.5mL of gas from the collection bag by using a sample injection needle by an off-line method and injecting the gas into a gas chromatograph for oxygen content characterization.
The essence of the technical solution of the embodiments of the present application is further illustrated by the following specific examples.
Example 1:
the extraterrestrial artificial photosynthesis reaction device based on the microchannel technology is manufactured by the following method:
1) the metal aluminum packaging substrate is processed according to a drawing drawn by SolidWorks in a machining mode, the thicknesses of the fixed bottom plate, the cathode and the anode aluminum metal substrate are all 10mm, the metal surface is subjected to anodic oxidation treatment, and aluminum oxide passivation insulating layers are formed on the side face and the outer surface.
2) And etching channels with the depth and the width of 400 mu m on an acrylic organic plate with the area of 25mm x 25mm by adopting a wet chemical etching method, and drilling holes with the diameter of 1mm at two ends of each channel as reaction medium inlets and outlets.
The resulting microchannel structure is shown in FIG. 2. It can be seen that the channel is smooth, and uniform in size.
3) And placing a 0.1mm silica gel pad at the bottom of the groove of the substrate, and placing the side of the acrylic plate with the microchannel upwards into the groove. The inlet and outlet of the micro-channel are aligned with the inlet and outlet of the substrate and communicated with an external pipeline through the internal channel of the substrate.
4) Preparing a membrane electrode by adopting a spraying and thermal evaporation method; the method specifically comprises the following processes
4.1) selecting carbon paper with the thickness of 200 mu m, cutting the carbon paper into squares with the area of 45mm x 45mm, and respectively soaking the cut carbon paper in isopropanol, ethanol and deionized water for 30 minutes. Weighing 5mg of Ir/C powder with the particle size of 20nm, dissolving the Ir/C powder in 20mL of mixed solution of absolute ethyl alcohol and deionized water, adding 0.5mL of Nafion solution into the mixed solution, stirring the solution uniformly, spraying the prepared Ir/C slurry on carbon paper to prepare an anode electrode material, wherein the loading capacity is 0.24mg/cm2。
4.2) selecting carbon paper with the thickness of 200 mu m, cutting the carbon paper into squares with the area of 45mm x 45mm, and respectively soaking the cut carbon paper in isopropanol, ethanol and deionized water for 30 minutes. An Au film with the thickness of 1 mu m is deposited on the carbon paper by a thermal evaporation method, the substrate temperature is 60 ℃, and the deposition rate is 18 nm/min.
4.3) putting the proton exchange membrane into a hydrogen peroxide solution I with the mass fraction of 5%, soaking for one hour at 80 ℃, and then soaking for half an hour in deionized water; and then placing the proton exchange membrane in a solution II of dilute sulfuric acid with the mass fraction of 5%, soaking for one hour at 80 ℃, and then soaking for half an hour in deionized water.
4.4) adopting a hot pressing method to hot press the anode electrode material, the proton exchange membrane and the cathode electrode material into an integrated membrane electrode.
5) And (3) placing the membrane electrode prepared in the step (4) between cathode and anode acrylic plates, and enabling the edge of the carbon paper to be in close contact with the conductive surface on the inner side of the metal substrate. And sealing the peripheries of the cathode carbon paper and the anode carbon paper by using a silica gel pad with the thickness of 0.4mm, and finally fastening and sealing the whole device by using screws.
The resulting packed artificial photosynthesis reactor is shown in FIG. 3. An anode substrate with a viewing window in the figure can be seen, and comprises a liquid inlet and a liquid outlet; the cathode substrate is arranged below the anode and comprises a liquid inlet, a gas inlet and a liquid outlet, the diameter of the inlet of the cathode and the diameter of the anode are phi 6 multiplied by 4, and the diameter of the outlet is phi 3 multiplied by 1. The tabs led out from the two substrates can be connected with the electrochemical workstation.
The micro-channel reaction device is used for carrying out electrocatalytic carbon dioxide reduction reaction, and the method comprises the following steps: a cathode liquid inlet and an air inlet of the device are respectively connected with an electrolyte liquid storage bottle and a carbon dioxide gas bottle through pipelines, an anode liquid inlet is connected with the electrolyte liquid storage bottle, the electrolyte is phosphate buffer saline (Pbs) solution with the concentration of 0.1mol/L, and the purity of the carbon dioxide is 99.99%. The liquid outlets of the cathode and the anode are respectively connected with the collecting bag. The pressure and the flow rate of gas and liquid are accurately controlled by a micro pump, so that cathode gas and liquid alternately flow in a columnar manner, and the flow rates are respectively 50 mL/h; the flow rate of the anode liquid was 50 mL/h. Connecting the conductive tabs of the cathode substrate and the anode substrate of the device with an electrochemical workstation, connecting the cathode with the cathode, connecting the anode with the anode, applying 2.5V voltage to the two ends of the cathode and the anode, and observing the bubble condition of the product by using a CCD camera through an observation window on the anode substrate.
A photograph of a CCD of an electrocatalytic carbon dioxide reduction reaction using a microchannel reactor is shown in FIG. 4. It can be seen that a large number of bubbles are generated in the channel and are discharged into the collection bag with the liquid after a voltage is applied across the electrodes.
Example 2:
the preparation method of the extraterrestrial artificial photosynthesis reaction device based on the microchannel technology comprises the following steps:
1) and processing the metal aluminum packaging substrate according to a drawing drawn by SolidWorks in a machining mode, wherein the thicknesses of the cathode and anode aluminum metal substrates are both 10mm, carrying out anodic oxidation treatment on the metal surface, and forming an aluminum oxide passivation insulating layer on the side surface and the outer surface.
2) A wet chemical etching method is adopted to etch a channel with the depth and the width of 400 Mum multiplied by 400 Mum on a PMMA organic plate with the area of 25mm multiplied by 25mm, and holes with the diameter of 1mm are drilled at the two ends of the channel to be used as a reaction medium inlet and outlet.
3) And placing a 0.1mm silica gel pad at the bottom of the groove of the substrate, and placing the side of the acrylic plate with the microchannel upwards into the groove. The inlet and outlet of the micro-channel are aligned with the inlet and outlet of the substrate and communicated with an external pipeline through the internal channel of the substrate.
4) Preparing a membrane electrode by adopting an anodic oxidation method and a thermal evaporation method; the method specifically comprises the following processes:
4.1) putting the proton exchange membrane into a hydrogen peroxide solution I with the mass fraction of 5%, soaking for one hour at 80 ℃, and then soaking for half an hour in deionized water; and then placing the proton exchange membrane in a solution II of dilute sulfuric acid with the mass fraction of 5%, soaking for one hour at 80 ℃, and then soaking for half an hour in deionized water.
4.2) a 150-mesh metal titanium mesh was cut into a rectangle having a size of 3cm × 3.5cm, sonicated with ethanol water, and passed through a hydrochloric acid solution (concentrated hydrochloric acid: ultrapure water at a ratio of 1:20) was removed of oxides on the surface, and then the film was dried. Electrolyte is filled in a beaker made of polytetrafluoroethylene materials, and the electrolyte comprises the following components: 0.5g NH4F+0.5mL H2O +122.5mL ethylene glycol. The electrochemical oxidation was carried out at a voltage of 60V for about 2 hours using a titanium mesh as an anode and a platinum electrode as a cathode.
4.3) a 150-mesh metal titanium mesh was cut into a rectangle having a size of 3cm × 3.5cm, sonicated with ethanol water, and passed through a hydrochloric acid solution (concentrated hydrochloric acid: ultrapure water at a ratio of 1:20) was removed of oxides on the surface, and then the film was dried. And (3) evaporating and plating a 500nm Au film on the titanium mesh by adopting a thermal evaporation method.
4.4) selecting carbon paper with the thickness of 200 mu m, cutting the carbon paper into squares with the area of 45mm x 45mm, and respectively soaking the cut carbon paper in isopropanol, ethanol and deionized water for 30 minutes.
4.5) growing TiO by hot pressing2The titanium mesh, the carbon paper, the proton exchange membrane and the titanium mesh for growing the Au film are hot-pressed into an integrated membrane electrode in sequence.
5) And (3) placing the membrane electrode prepared in the step (4) between cathode and anode acrylic plates, and enabling the edges of the carbon paper and the titanium mesh to be in close contact with the conductive surface on the inner side of the metal substrate. And sealing the peripheries of the cathode electrode material and the anode electrode material by using a silica gel pad with the thickness of 0.4mm, and finally fastening and sealing the whole device by using screws.
The micro-channel reaction device is used for carrying out electrocatalytic carbon dioxide reduction reaction, and the method comprises the following steps: the cathode liquid inlet and the air inlet of the device are respectively connected with an electrolyte liquid storage bottle and a carbon dioxide gas bottle through pipelines, the anode liquid inlet is connected with the electrolyte liquid storage bottle, the electrolyte is a Pbs solution with the concentration of 0.1mol/L, and the purity of the carbon dioxide is 99.99%. The liquid outlets of the cathode and the anode are respectively connected with the collecting bag. The pressure and the flow rate of gas and liquid are accurately controlled by a micro pump, so that cathode gas and liquid alternately flow in a columnar manner, and the flow rates are respectively 50 mL/h; the flow rate of the anode liquid was 50 mL/h. Connecting the conductive tabs of the cathode and anode substrates of the device with an electrochemical workstation, connecting the cathode with the cathode, connecting the anode with the anode, applying 2.0V voltage to the two ends of the cathode and the anode, and measuring the magnitude and the change condition of the reaction current.
Fig. 5 shows the change of the current with time in the electrocatalytic carbon dioxide reduction reaction performed by the photosynthesis reaction apparatus according to the embodiment of the present application. It can be seen that when 2.0V voltage is applied across the cathode and anode, the current can reach 40mA after the reaction is stabilized.
Furthermore, the features and benefits of the present invention are described with reference to exemplary embodiments. Accordingly, the invention is expressly not limited to these exemplary embodiments illustrating some possible non-limiting combination of features which may be present alone or in other combinations of features.
Other embodiments of the disclosure will be apparent to those skilled in the art from consideration of the specification and practice of the disclosure disclosed herein. This application is intended to cover any variations, uses, or adaptations of the invention following, in general, the principles of the invention and including such departures from the present disclosure as come within known or customary practice within the art to which the invention pertains. It is intended that the specification and examples be considered as exemplary only, with a true scope and spirit of the invention being indicated by the following claims.
Claims (10)
1. A photosynthetic reaction device, the device comprising:
the microchannel reaction region carrier is provided with a first channel communicated in series or in parallel; a first reaction medium inlet and a first reaction medium outlet are respectively arranged at two ends of the first channel;
the membrane electrode comprises an ion exchange membrane, an anode electrode material and a cathode electrode material, wherein the anode electrode material and the cathode electrode material are respectively hot-pressed on two sides of the ion exchange membrane;
the first surface of the anode substrate is provided with a containing groove, and when the microchannel reaction area carrier is contained in the containing groove, one side of the microchannel reaction area carrier, which is provided with a first channel, is exposed on the first surface;
the second surface of the cathode substrate is provided with a second channel matched with the first channel on the micro-channel reaction region carrier;
the anode substrate and the cathode substrate clamp the membrane electrode between the anode substrate and the cathode substrate in a way that the first surface and the second surface are attached, the anode electrode material is attached to the first channel, and the cathode electrode material is attached to the second channel.
2. The apparatus of claim 1, wherein the first trench forms a reaction area of (10-50mm) × (10-50mm), and the depth and width of the first trench are (100-;
the reaction area formed by the second channel is (10-50mm) × (10-50mm), and the depth and width dimensions of the second channel are respectively (100-.
3. The photosynthesis reaction apparatus according to claim 1, wherein a sealing material is further provided around the anode electrode material and the cathode electrode material.
4. The photosynthesis reaction apparatus according to claim 1, wherein the anode substrate is provided with a first liquid inlet and a first product outlet, and both the first liquid inlet and the first product outlet are communicated with the accommodating tank;
when the microchannel reaction area carrier is accommodated in the accommodating groove, the first liquid inlet is communicated with the first reaction medium inlet, and the first product outlet is communicated with the first reaction medium outlet.
5. The photosynthesis reaction apparatus according to claim 4, wherein the cathode substrate includes a second liquid inlet, a second product outlet, and a gas inlet; a second reaction medium inlet and a second reaction medium outlet of the second channel, and a gas-liquid mixing cavity are arranged on the cathode substrate; the gas-liquid mixing cavity is communicated with the second reaction medium inlet;
the second liquid inlet and the gas inlet are communicated with the gas-liquid mixing cavity, and the second product outlet is communicated with the second reaction medium outlet.
6. The photosynthesis reaction apparatus according to any one of claims 1 to 5, wherein the membrane electrode is formed by:
preparing an anode electrode material on a quartz glass, organic glass or COC organic glass plate, a metal mesh substrate, a sheet substrate or a carbon paper substrate by adopting an anodic oxidation method, magnetron sputtering, an atomic layer deposition method or a spraying method;
preparing a cathode electrode material on a quartz glass, organic glass, COC organic glass plate or carbon paper substrate by adopting an electrochemical deposition method, a magnetron sputtering method, an atomic layer deposition method or a thermal evaporation method;
activating the ion exchange membrane in acid and alkali solution, and then soaking in deionized water for 20-40 minutes;
and hot-pressing the anode electrode material, the ion exchange membrane and the cathode electrode material into a whole in sequence by adopting a hot-pressing method to form the membrane electrode.
7. The photosynthesis reaction apparatus of claim 6, wherein the ion exchange membrane comprises one of:
cation exchange membrane CEM, anion exchange membrane AEM, proton exchange membrane PEM, bipolar membrane BPM;
the anode material comprises one of:
titanium oxide film, ferric oxide film, zinc oxide film, bismuth vanadate film, nanotube and nanowire;
iridium oxide powder, iridium powder and carbon powder, wherein the particle size of the powder is 10-30nm, and the loading capacity is 0.2-5mg/cm2；
The cathode material comprises one of:
powders, films or nanowires of silicon, cuprous oxide, copper, gold, silver, platinum, palladium, and alloys thereof.
8. The photosynthetic reaction device of claim 6 wherein the anode substrate and the cathode substrate are stainless steel or aluminum oxide metal substrates; the first surface and the second surface are polished conductive surfaces, and the anode electrode material and the cathode electrode material are respectively electrically communicated with the polished conductive surfaces of the anode substrate and the cathode substrate.
9. A method of making a membrane electrode, the method comprising:
preparing an anode electrode material on a quartz glass, organic glass or COC organic glass plate, a metal mesh substrate, a sheet substrate or a carbon paper substrate by adopting an anodic oxidation method, magnetron sputtering, an atomic layer deposition method or a spraying method;
preparing a cathode electrode material on a quartz glass, organic glass, COC organic glass plate or carbon paper substrate by adopting an electrochemical deposition method, a magnetron sputtering method, an atomic layer deposition method or a thermal evaporation method;
activating the ion exchange membrane in acid and alkali solution, and then soaking in deionized water for 20-40 minutes;
and hot-pressing the anode electrode material, the ion exchange membrane and the cathode electrode material into a whole in sequence by adopting a hot-pressing method to form the membrane electrode.
10. The method of claim 9, wherein the ion exchange membrane comprises one of:
cation exchange membrane CEM, anion exchange membrane AEM, proton exchange membrane PEM, bipolar membrane BPM;
the anode material comprises one of:
titanium oxide film, ferric oxide film, zinc oxide film, bismuth vanadate film, nanotube and nanowire;
iridium oxide powder, iridium powder and carbon powder, wherein the particle size of the powder is 10-30nm, and the loading capacity is 0.2-5mg/cm2；
The cathode material comprises one of:
powders, films or nanowires of silicon, cuprous oxide, copper, gold, silver, platinum, palladium, and alloys thereof.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010764121.9A CN111926344A (en) | 2020-08-01 | 2020-08-01 | Photosynthetic reaction device and method for manufacturing membrane electrode |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202010764121.9A CN111926344A (en) | 2020-08-01 | 2020-08-01 | Photosynthetic reaction device and method for manufacturing membrane electrode |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN111926344A true CN111926344A (en) | 2020-11-13 |
Family
ID=73315748
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202010764121.9A Pending CN111926344A (en) | 2020-08-01 | 2020-08-01 | Photosynthetic reaction device and method for manufacturing membrane electrode |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111926344A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113481525A (en) * | 2021-06-08 | 2021-10-08 | 中国空间技术研究院 | Electrochemical reactor and electrochemical reaction system |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733020A (en) * | 2009-12-10 | 2010-06-16 | 山东东岳神舟新材料有限公司 | Fiber reinforced fluorine-containing crosslinked ion membrane and preparation method thereof |
| CN106040013A (en) * | 2016-06-24 | 2016-10-26 | 盐城师范学院 | Bipolar membrane and preparation method thereof |
| CN106133198A (en) * | 2014-04-14 | 2016-11-16 | 富士通株式会社 | Light compositing device |
| CN109599580A (en) * | 2018-12-24 | 2019-04-09 | 天津理工大学 | A kind of ultra-thin membrane electrode and its preparation method and application for neat liquid fuel cell |
| CN111193043A (en) * | 2020-01-07 | 2020-05-22 | 北京化工大学 | Anode catalyst for proton exchange membrane fuel cell and synthetic method thereof |
-
2020
- 2020-08-01 CN CN202010764121.9A patent/CN111926344A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101733020A (en) * | 2009-12-10 | 2010-06-16 | 山东东岳神舟新材料有限公司 | Fiber reinforced fluorine-containing crosslinked ion membrane and preparation method thereof |
| CN106133198A (en) * | 2014-04-14 | 2016-11-16 | 富士通株式会社 | Light compositing device |
| CN106040013A (en) * | 2016-06-24 | 2016-10-26 | 盐城师范学院 | Bipolar membrane and preparation method thereof |
| CN109599580A (en) * | 2018-12-24 | 2019-04-09 | 天津理工大学 | A kind of ultra-thin membrane electrode and its preparation method and application for neat liquid fuel cell |
| CN111193043A (en) * | 2020-01-07 | 2020-05-22 | 北京化工大学 | Anode catalyst for proton exchange membrane fuel cell and synthetic method thereof |
Non-Patent Citations (1)
| Title |
|---|
| 冯德强等: ""地外人工光合成装置研制与试验"", 《中国空间科学技术》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113481525A (en) * | 2021-06-08 | 2021-10-08 | 中国空间技术研究院 | Electrochemical reactor and electrochemical reaction system |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Cao et al. | Dominating role of aligned MoS2/Ni3S2 nanoarrays supported on three-dimensional Ni foam with hydrophilic interface for highly enhanced hydrogen evolution reaction | |
| Wu et al. | Efficient nitric oxide reduction to ammonia on a metal-free electrocatalyst | |
| Feng et al. | Sub-3 nm Co3O4 nanofilms with enhanced supercapacitor properties | |
| US8764953B2 (en) | System and method for chemical potential energy production | |
| JP6082728B2 (en) | Electrode for water splitting reaction and method for producing the same | |
| Zhang et al. | Regulation strategy of transition metal oxide-based electrocatalysts for enhanced oxygen evolution reaction | |
| EP1913965A1 (en) | Photolytic apparatus for oxygenating and removing carbon dioxide | |
| CN1426494A (en) | Electric cells, components and methods | |
| EP2593402A1 (en) | Photocatalytic water splitting | |
| Min et al. | Heterostructures in two-dimensional colloidal metal chalcogenides: Synthetic fundamentals and applications | |
| CN106006929B (en) | A kind of method of the round-the-clock processing sewage of photoelectrocatalysis film coupling microbiological fuel cell | |
| EP1454036B1 (en) | Photolytic oxygenator with carbon dioxide fixation and separation | |
| KR100626619B1 (en) | The manufacturing method of microchannel reactor with coated catalyst inside the metallic microchannel and reactor thereof | |
| CN108074752A (en) | A kind of method that photoreduction met hod prepares graphene-based planarization micro super capacitor | |
| CN105749914A (en) | Symmetric difunctional photocatalyst, double-chamber photoreactor and method for photocatalytic reduction of carbon dioxide | |
| CN111926344A (en) | Photosynthetic reaction device and method for manufacturing membrane electrode | |
| CN107749316A (en) | Diamond schottky isotope battery and preparation method thereof | |
| Mai et al. | Effective fabrication and electrochemical oxygen evolution reaction activity of gold multipod nanoparticle core–cobalt sulfide shell nanohybrids | |
| Liu et al. | Mechanism exploration and catalyst design for hydrogen evolution reaction accelerated by density functional theory simulations | |
| Liu et al. | Atomic-scale engineering of cation vacancies in two-dimensional unilamellar metal oxide nanosheets for electricity generation from water evaporation | |
| CN107945901A (en) | A kind of quantum dot beta voltaic element | |
| Sun et al. | Interfacial design to enhance photocatalytic hydrogen evolution via optimizing energy and mass flows | |
| Rarotra et al. | Graphite/RGO coated paper μ-electrolyzers for production and separation of hydrogen and oxygen | |
| US7410557B2 (en) | Hydrogen activating apparatus | |
| KR20110065971A (en) | Method of fabricating graphene oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |