A kind of flow-type photo-thermal electrochemical reaction thin-Layer Electrolytic Cell
阅读说明：本技术 一种流动式光热电化学反应薄层电解池 (A kind of flow-type photo-thermal electrochemical reaction thin-Layer Electrolytic Cell ) 是由 孙建军 冯磊 于 2019-10-12 设计创作，主要内容包括：本发明提出一种流动式光热电化学反应薄层电解池,包括用紧固件固定在一起的上部件(1)和下部件(6),且其上部件(1)和下部件(6)中间夹有膜层,其特征在于：所述上部件(1)包含有进液孔(101)、出液孔(106)、进气孔(102)、工作电极(103)、参比电极(104)、对电极(105)；所述下部件(6)包括出气孔(602)、镶嵌有透光件(601)的透光孔(611)；上部件(1)和下部件(6)中间所夹膜层自上而下依次为隔水透气上膜(2)、塑料上膜(3)、隔水透气下膜(4)、塑料下膜(5)；本发明为一体化光电热耦合催化反应电解池结构,能够使反应气体在电解过程中保持饱和状态。(The present invention proposes a kind of flow-type photo-thermal electrochemical reaction thin-Layer Electrolytic Cell, including the upper-part (1) being fixed together with fastener and lower component (6), and component (1) and lower component (6) are sandwiched between film layer thereon, it is characterised in that: the upper-part (1) include inlet opening (101), fluid hole (106), air inlet (102), working electrode (103), reference electrode (104), to electrode (105)；The lower component (6) includes venthole (602), the loophole (611) for being inlaid with transmission element (601)；Film layer folded by upper-part (1) and lower component (6) centre is followed successively by that water proof ventilative upper film (2), film (3), water proof are breathed freely lower film (4), plastics lower film (5) on plastics from top to bottom；The present invention is integrated photoelectric heat coupling catalytic reactions electrolyser construction, reaction gas can be made to keep saturation state in electrolytic process.)
1. a kind of flow-type photo-thermal electrochemical reacts thin-Layer Electrolytic Cell, the upper-part (1) including being fixed together with fastener and Lower component (6), and component (1) and lower component (6) are sandwiched between film layer thereon, it is characterised in that: the upper-part (1) includes Inlet opening (101), fluid hole (106), air inlet (102), working electrode (103), reference electrode (104), to electrode (105)； The lower component (6) includes venthole (602), the loophole (611) for being inlaid with transmission element (601)；Upper-part (1) and lower component (6) film layer folded by centre is followed successively by that water proof ventilative upper film (2), film (3), water proof are breathed freely lower film (4), plastics on plastics from top to bottom Lower film (5).
2. a kind of flow-type photo-thermal electrochemical according to claim 1 reacts thin-Layer Electrolytic Cell, it is characterised in that: described Upper-part (1) and lower component (6) are formed with rigid plastics；The upper-part (1) and lower component (6) are thin layer part；The thin layer Part can be thin layer cylindrical body or thin layer cuboid, but preferable shape is thin layer cuboid；The unilateral ruler of the thin layer cuboid Very little range is 10 mm to 100 mm, but ranges preferably from 20 mm to 60 mm；
The material range of choice of the rigid plastics includes but is not limited to polyether-ether-ketone, polytetrafluoroethylene (PTFE), polypropylene, gathers inclined difluoro Ethylene, polytrifluorochloroethylene, polyvinyl chloride, polycarbonate.
3. a kind of flow-type photo-thermal electrochemical according to claim 1 reacts thin-Layer Electrolytic Cell, it is characterised in that: described Working electrode (103), reference electrode (104) and be that diameter range of the closed set in upper-part (1) is to electrode (105) The cylinder of 0.5 mm to 20 mm；The diameter range of the cylinder is preferably 1mm to 5 mm.
4. a kind of flow-type photo-thermal electrochemical according to claim 1 reacts thin-Layer Electrolytic Cell, it is characterised in that: the work Make electrode (103), reference electrode (104) and to electrode (105) be base material be conductive material electrode；The electrode passes through Conducting wire accesses external electrochemical workstation and is electrochemically reacted excitation and control；Can be modified on the electrode setting have it is additional The material layer of function；
The material range of choice of the base material include but is not limited to graphite, platinum carbon mixing material, glass carbon, platinum, gold, palladium, silver, Copper, bismuth, antimony, tin, nickel.
5. a kind of flow-type photo-thermal electrochemical according to claim 1 reacts thin-Layer Electrolytic Cell, it is characterised in that: described Working electrode (103) is by installing heating element additional in electrode interior and temperature transducer and molding heats temperature control electrode；
The temperature transducer is temperature sensor, and the temperature sensor and the electric heating part are arranged in the working electrode The inside of shell, the temperature sensor and electric heating part are with the Automatic Temperature Control outside the working electrode by conducting wire It is connected, sealing element is fixed at one end of working electrode shell, is used for the temperature
Sensor and electric heating part are sealed in inside the electrode shell.
6. a kind of flow-type photo-thermal electrochemical according to claim 1 reacts thin-Layer Electrolytic Cell, it is characterised in that: described Transmission element (601) is cylindrical；The body diameter and altitude range are 1 mm to 20mm, and range preferably from 3 mm to 10 mm；
The material range of choice of the transmission element includes but is not limited to quartz glass, calcium fluoride crystal.
7. a kind of flow-type photo-thermal electrochemical according to claim 1 reacts thin-Layer Electrolytic Cell, it is characterised in that: described The thickness range of water proof ventilative upper film (2) and water proof ventilative lower film (4) is 0.010 mm to 0.5 mm, and thickness range is preferred For 0.010mm to 0.1 mm；
It is offered at the ventilative upper film of the water proof and the corresponding through-hole (201) of inlet, through-hole corresponding with working electrode (203) and the corresponding through-hole (204) of reference electrode and to the corresponding through-hole of electrode (205), through-hole corresponding with fluid hole (206)；The position and aperture of each through-hole respectively with inlet (101), working electrode (103), reference electrode (104), to electricity Pole (105) and fluid hole (106) are corresponded to and are matched；
Aperture and the matched loophole of transmission element (401) are provided at the ventilative lower film of the water proof；
The material of the water proof ventilative upper film (2) and water proof ventilative lower film (4) includes but is not limited to polytetrafluoroethylene (PTFE), polyethylene Film.
8. a kind of flow-type photo-thermal electrochemical according to claim 1 reacts thin-Layer Electrolytic Cell, it is characterised in that: described Film (3) on plastics, plastics lower film (5) thickness range be 0.010 mm to 5.0 mm, and thickness range be preferably 0.1 mm extremely 1.0 mm；
Film (3) offers the hole (301) for thin-Layer Electrolytic Cell pond body on the plastics, by the hole edge, the ventilative upper film of water proof (2) and water proof breathe freely lower film (4) defined by space be the electrolytic cell electrolyte main storage space；
Film (3) on the plastics, plastics lower film (5) material range of choice include being not limited to polytetrafluoroethylene (PTFE), polyethylene film.
9. a kind of flow-type photo-thermal electrochemical according to claim 1 reacts thin-Layer Electrolytic Cell, it is characterised in that: it is described go out Stomata (602) is directly or indirectly connected by seal nipple (612) and gas-guide tube (622) with a mass detector air inlet；Institute State the preferred quadrupole rod mass detector of mass detector.
10. a kind of flow-type photo-thermal electrochemical according to claim 1 reacts thin-Layer Electrolytic Cell, it is characterised in that: described Inlet opening (101), fluid hole (106), air inlet (102) and venthole (602) diameter range be 0.5 mm to 3.5mm, and Diameter range preferably 1.0 mm to 2.0 mm.
Technical field
The present invention relates to photoelectrocatalysis to react scientific instrument accessories field, especially a kind of flow-type photo-thermal electrochemical reaction Thin-Layer Electrolytic Cell.
Background technique
Green energy resource storage and the research of associated materials and environmental ecology the Study on Sustainable Development are that recent domestic is ground The hot spot studied carefully, such as electrode material research, carbon dioxide reduction and the nitrogen reduction research of secondary cell etc..It is above-mentioned in progress During research, electrochemical reaction, light-catalyzed reaction, thermal chemical reaction or combinations thereof concerted reaction are generally related to.Research It is anti-not only to need to use corresponding electrochemical reaction electrolytic cell, light-catalyzed reaction pond, heat chemistry when carrying out correlative study by personnel Ying Chi, it is also necessary to which the small organic molecule of product and the analysis with soluble gas product in respective reaction pond can be analyzed by using Test device.Such as the H generated in the experiment of analysis detection carbon dioxide reduction2、CO、HCOOH、HCOO、CH4、CH3OH etc., nitrogen The NH generated in reduction experiment research3Deng.
Under current techniques, the chemical reaction of three kinds of effect coupled in common of photoelectric heat, may have independent photoelectricity fuel factor or Its effect unique not available for coupling effect two-by-two, thus design and produce a kind of photo-thermal electrochemical reaction electrolytic cell have it is important Meaning.
To the context of detection of reaction product, discontinuous Discontinuous sampling method is generally used at present, is joined with gas-chromatography, makings With or LC-MS instrument analysis detection is carried out to reaction product.But such method can not obtain the time of correlated response product Resolution information is unfavorable for carrying out the research of correlated response mechanism in a deep going way.Flow-type thin-Layer Electrolytic Cell, the small, gas with reaction volume Body product can quickly diffuse through water proof ventilated membrane and enter mass spectrum sample introduction pipeline, realize and carry out in real time to electrochemical reaction product Analysis detection (CN201910254193.6).In the patent to electrode and reference electrode respectively with the molten sample intake passage of electrolytic cell It is connected with sample output passage by threeway, reaction gas (such as CO2Or N2) the contactless channel inside electrolytic cell.Both make reaction gas Concentration before sample introduction in the electrolytic solution has had reached saturation, but with the progress for being catalyzed reaction in electrolytic cell, in electrolytic cell The concentration of reaction gas can gradually decrease in portion's electrolyte, be extremely difficult to the saturation state of reaction gas in electrolyte.How to change Make reaction gas (such as CO in the electrolyte of photoelectrocatalysis electrolytic cell into electrolyser construction2Or N2) under normal pressure or appropriate pressure Reach saturation, is problem in the urgent need to address.
Summary of the invention
The present invention proposes a kind of flow-type photo-thermal electrochemical reaction thin-Layer Electrolytic Cell, anti-for integrated photoelectric heat coupling and catalyzing Electrolyser construction is answered, reaction gas can be made to keep saturation state in electrolytic process.
The present invention uses following technical scheme.A kind of flow-type photo-thermal electrochemical reacts thin-Layer Electrolytic Cell, including with fastening The upper-part (1) and lower component (6) that part is fixed together, and component (1) and lower component (6) are sandwiched between film layer thereon, it is described Upper-part (1) includes inlet opening (101), fluid hole (106), air inlet (102), working electrode (103), reference electrode (104), to electrode (105)；The lower component (6) includes venthole (602), the loophole for being inlaid with transmission element (601) (611)；Film layer folded by upper-part (1) and lower component (6) centre is followed successively by water proof ventilative upper film (2) from top to bottom, film on plastics (3), water proof ventilative lower film (4), plastics lower film (5).
The upper-part (1) and lower component (6) are formed with rigid plastics；The upper-part (1) and lower component (6) are thin layer Part；The thin layer part can be thin layer cylindrical body or thin layer cuboid, but preferable shape is thin layer cuboid；The thin layer is rectangular The single side size range of body is 10 mm to 100 mm, but ranges preferably from 20 mm to 60 mm；
The material range of choice of the rigid plastics includes but is not limited to polyether-ether-ketone, polytetrafluoroethylene (PTFE), polypropylene, gathers inclined difluoro Ethylene, polytrifluorochloroethylene, polyvinyl chloride, polycarbonate.
The working electrode (103), reference electrode (104) and be closed set in upper-part (1) to electrode (105) Diameter range is the cylinder of 0.5 mm to 20 mm；The diameter range of the cylinder is preferably 1mm to 5 mm.
The working electrode (103), reference electrode (104) and to electrode (105) be base material be conductive material electricity Pole；The electrode passes through conducting wire (working electrode lead (113), reference electrode lead (114), to contact conductor (115)) access External electrochemical workstation is electrochemically reacted excitation and control；The material that setting has additional function can be modified on the electrode The bed of material；
Working electrode lead includes temperature heating temperature control line；
The material range of choice of the base material include but is not limited to graphite, platinum carbon mixing material, glass carbon, platinum, gold, palladium, silver, Copper, bismuth, antimony, tin, nickel.
The working electrode (103) is molding and installing heating element and temperature transducer additional in electrode interior adds Hot temperature control electrode；
The temperature transducer is temperature sensor, and the temperature sensor and the electric heating part are arranged in the working electrode The inside of shell, the temperature sensor and electric heating part are with the Automatic Temperature Control outside the working electrode by conducting wire It is connected, sealing element is fixed at one end of working electrode shell, is used for the temperature
Sensor and electric heating part are sealed in inside the electrode shell.
The transmission element (601) is cylindrical；The body diameter and altitude range are 1 mm to 20mm, and range is excellent 3 mm are selected as to 10 mm；
The material range of choice of the transmission element includes but is not limited to quartz glass, calcium fluoride crystal.
The thickness range of the water proof ventilative upper film (2) and water proof ventilative lower film (4) is 0.010 mm to 0.5 mm, and Thickness range is preferably 0.010mm to 0.1 mm；
The material of the water proof ventilative upper film (2) and water proof ventilative lower film (4) includes but is not limited to polytetrafluoroethylene (PTFE), polyethylene Film.
Film (3) on the plastics, plastics lower film (5) thickness range be 0.010 mm to 5.0 mm, and thickness range is excellent 0.1 mm is selected as to 1.0 mm；
Film (3) offers the hole (301) for thin-Layer Electrolytic Cell pond body on the plastics, by the hole edge, the ventilative upper film of water proof (2) and water proof breathe freely lower film (4) defined by space be the electrolytic cell electrolyte main storage space；
Film (3) on the plastics, plastics lower film (5) material range of choice include being not limited to polytetrafluoroethylene (PTFE), polyethylene film.
It is offered at the ventilative upper film of the water proof and the corresponding through-hole (201) of inlet, through-hole corresponding with working electrode (203) and the corresponding through-hole (204) of reference electrode and to the corresponding through-hole of electrode (205), through-hole corresponding with fluid hole (206)；The position and aperture of each through-hole respectively with inlet (101), working electrode (103), reference electrode (104), to electricity Pole (105) and fluid hole (106) are corresponded to and are matched；
Aperture and the matched loophole of transmission element (401) are provided at the ventilative lower film of the water proof；
The venthole (602) by seal nipple (612) and gas-guide tube (622) and a mass detector air inlet it is direct or It connects connected；The preferred quadrupole rod mass detector of mass detector.
The inlet opening (101), fluid hole (106), air inlet (102) and venthole (602) diameter range be 0.5 Mm to 3.5mm, and diameter range preferably 1.0 mm to 2.0 mm.
The venthole (602) directly or indirectly connect with the injection port of mass detector, realizes anti-to photoelectricity thermocatalytic It answers product to carry out difference mass spectrum to analyze real-time, quickly.
The present invention has the advantages that the research of the coupling integrated catalysis reaction of photoelectric heat not only may be implemented in the present invention, also Reaction gas can be made to remain that saturation state, the gas molecules generated in reaction can pass through water proof in electrolytic process Air ventilation membrane imported into the sample introduction pipeline of mass spectrometer in real time, realize to respective reaction product can time resolution test and analyze, have Conducive to the research to reaction mechanism.
Detailed description of the invention
The present invention is described in more detail with reference to the accompanying drawings and detailed description:
Attached drawing 1 is decomposition diagram of the invention；
Attached drawing 2 is that upper-part is looked up to schematic diagram；
Attached drawing 3 is the vertical view of lower component to schematic diagram；
In figure: 1- upper-part；The ventilative upper film of 2- water proof；Film on 3- plastics；4- water proof is breathed freely lower film；5- plastics lower film；The lower part 6- Part；
101- inlet opening；102- air inlet；103- working electrode；104- reference electrode；105- is to electrode；106- fluid hole； 108- fixation hole and fixing piece；111- inlet connector；112- air inlet connections；113- working electrode lead；114- reference electricity Pole lead；115- is to contact conductor；116- liquid outlet connector；121- inlet connecting tube；122- air inlet connecting tube；126- goes out Liquid mouth connecting tube；
201- through-hole corresponding with inlet；203- through-hole corresponding with working electrode；204- through-hole corresponding with reference electrode； 205- with to the corresponding through-hole of electrode；206- through-hole corresponding with fluid hole；
301- is used for the hole of thin-Layer Electrolytic Cell pond body；
401- loophole；
601- transmission element；602- venthole；612- seal nipple；622- gas-guide tube.
Specific embodiment
As shown in Figure 1-3, a kind of flow-type photo-thermal electrochemical reacts thin-Layer Electrolytic Cell, including it is fixed together with fastener Upper-part 1 and lower component 6, and component 1 and lower component 6 are sandwiched between film layer thereon, and the upper-part 1 includes inlet opening 101, fluid hole 106, air inlet 102, working electrode 103, reference electrode 104, to electrode 105；The lower component 6 includes outlet Hole 602, the loophole 611 for being inlaid with transmission element 601；Film layer folded by among upper-part 1 and lower component 6 be followed successively by from top to bottom every Film 3, water proof ventilative lower film 4, plastics lower film 5 on the ventilative upper film 2 of water, plastics.
The upper-part 1 and lower component 6 are formed with rigid plastics；The upper-part 1 and lower component 6 are thin layer part；It is described Thin layer part can be thin layer cylindrical body or thin layer cuboid, but preferable shape is thin layer cuboid；The list of the thin layer cuboid Side size range is 10 mm to 100 mm, but ranges preferably from 20 mm to 60 mm；
The material range of choice of the rigid plastics includes but is not limited to polyether-ether-ketone, polytetrafluoroethylene (PTFE), polypropylene, gathers inclined difluoro Ethylene, polytrifluorochloroethylene, polyvinyl chloride, polycarbonate.
The working electrode 103, reference electrode 104 and be diameter range of the closed set in upper-part 1 to electrode 105 For 0.5 mm to the cylinder of 20 mm；The diameter range of the cylinder is preferably 1mm to 5 mm.
The working electrode 103, reference electrode 104 and to electrode 105 be base material be conductive material electrode；It is described Electrode accesses external electrochemical operation by conducting wire (working electrode lead 113, reference electrode lead 114, to contact conductor 115) Station is electrochemically reacted excitation and control；The material layer that setting has additional function can be modified on the electrode；
Working electrode lead includes temperature heating temperature control line；
The material range of choice of the base material include but is not limited to graphite, platinum carbon mixing material, glass carbon, platinum, gold, palladium, silver, Copper, bismuth, antimony, tin, nickel.
The working electrode 103 is molding and installing heating element and temperature transducer additional in electrode interior heats Temperature control electrode；
The temperature transducer is temperature sensor, and the temperature sensor and the electric heating part are arranged in the working electrode The inside of shell, the temperature sensor and electric heating part are with the Automatic Temperature Control outside the working electrode by conducting wire It is connected, sealing element is fixed at one end of working electrode shell, is used for the temperature
Sensor and electric heating part are sealed in inside the electrode shell.
The transmission element 601 is cylindrical；The body diameter and altitude range are 1 mm to 20mm, and range is preferred For 3 mm to 10 mm；
The material range of choice of the transmission element includes but is not limited to quartz glass, calcium fluoride crystal.
The breathe freely thickness range of lower film 4 of the ventilative upper film 2 of the water proof and water proof is 0.010 mm to 0.5 mm, and thickness 0.010mm is ranged preferably to 0.1 mm；
The material of the ventilative upper film 2 of the water proof and the ventilative lower film 4 of water proof includes but is not limited to polytetrafluoroethylene (PTFE), polyethylene film.
Film 3 on the plastics, plastics lower film 5 thickness range be 0.010 mm to 5.0 mm, and thickness range is preferably 0.1 mm to 1.0 mm；
Film 3 offers the hole 301 for thin-Layer Electrolytic Cell pond body on the plastics, by the hole edge, the ventilative upper film 2 of water proof and every Space defined by the ventilative lower film 4 of water is the main storage space of the electrolytic cell electrolyte；
Film 3 on the plastics, plastics lower film 5 material range of choice include being not limited to polytetrafluoroethylene (PTFE), polyethylene film.
It is offered at the ventilative upper film of the water proof and the corresponding through-hole 201 of inlet, through-hole corresponding with working electrode And the corresponding through-hole 204 of reference electrode and to the corresponding through-hole of electrode 205, through-hole 206 corresponding with fluid hole 203,；It is each The position and aperture of through-hole respectively with inlet 101, working electrode 103, reference electrode 104, to electrode 105 and fluid hole 106 It corresponds to and matches；
Aperture and the matched loophole 401 of transmission element are provided at the ventilative lower film of the water proof；
The venthole 602 passes through seal nipple 612 and gas-guide tube 622 and a direct or indirect phase of mass detector air inlet Even；The preferred quadrupole rod mass detector of mass detector.
The inlet opening 101, fluid hole 106, air inlet 102 and venthole 602 diameter range be 0.5 mm extremely 3.5mm, and diameter range preferably 1.0 mm to 2.0 mm.
The venthole 602 is directly or indirectly connect with the injection port of mass detector, is realized to photoelectricity heat catalysis Product carries out difference mass spectrum and analyzes real-time, quickly.