CN114685802A - Silicon-based covalent organic framework photoelectrode and preparation method and application thereof - Google Patents
Silicon-based covalent organic framework photoelectrode and preparation method and application thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
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- B01J38/00—Regeneration or reactivation of catalysts, in general
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
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Abstract
The invention provides a silicon-based covalent organic framework photoelectrode and a preparation method and application thereof. According to the invention, the electron mediator is fixed on the covalent organic framework layer in a manner of forming a coordination bond, so that the electron transfer between the electron mediator and the covalent organic framework layer can be greatly promoted, and meanwhile, the photoelectrode is constructed into a stacked arrangement structure, so that the high-efficiency transfer of electrons between layers can be promoted, the electron transfer efficiency between the electron mediator and the silicon substrate is finally improved, and the in-situ recovery and utilization of the electron mediator are realized; the photoelectrode can effectively improve the catalytic activity of regeneration of photoelectrochemical coenzyme NAD (P) H, and meanwhile, the preparation method is simple and convenient, does not need complex operation, and is beneficial to large-scale application in industrial production.
Description
Technical Field
The invention belongs to the technical field of photoelectrochemistry coenzyme regeneration, relates to a photoelectrode and a preparation method thereof, and particularly relates to a silicon-based covalent organic framework photoelectrode and a preparation method and application thereof.
Background
In recent years, enzymatic reactions have been widely used in the chemical synthesis industry. Most enzymatic reactions require nicotinamide coenzymes (NAD (P) H/NAD (P))+) As a direct supplier of electrons or protons, and in industrial production, continuously supplies an auxiliaryThe enzyme is an important condition for ensuring the continuous and efficient enzymatic reaction. However, the coenzyme itself is expensive, so how to realize efficient regeneration and recycling of the coenzyme becomes an urgent problem to be solved. Currently, coenzyme regeneration can be achieved by photochemical, electrochemical, and photoelectrochemical methods, wherein photoelectrochemical coenzyme regeneration combines photochemical and electrochemical advantages: the absorption and utilization of light energy can generate additional photon-generated carriers, and the external bias can effectively separate the photon-generated carriers, and simultaneously can avoid the side reaction that coenzyme is converted into inactive substances in an electrochemical method due to overlarge external bias of a photocathode.
In a common photoelectrochemical coenzyme NAD (P) H regeneration system, electron transmission between a coenzyme molecule and a photoelectrode needs to depend on a free electron mediator as a bridge, for example, rhodium complex [ Cp-Rh (bpy) Cl ] Cl which is the most commonly used at present and has the best effect, but the problem of low electron transfer efficiency exists between the free electron mediator and the photoelectrode, and further improvement of the regeneration efficiency of the photoelectrochemical coenzyme is inhibited. Moreover, the rhodium complex is expensive, and when the rhodium complex is dissolved in a free form in a system to participate in a reaction, the rhodium complex cannot be recycled, so that a certain degree of waste is caused.
Researchers have conducted research on recycling and utilization of electron mediators in the fields of electrochemistry and photochemical coenzyme regeneration. For example, CN112708612A discloses an oxidoreductase electrode for enzyme electrocatalytic reduction and a preparation method thereof, wherein an enzyme and an electron conductor form an immobilized mixture, and an electron mediator and a coenzyme form a gel, and then are co-compounded on the surface of a substrate electrode to immobilize the enzyme and the coenzyme on the electrode. The enzyme electrode can realize in-situ regeneration of the electrocatalytic coenzyme, thereby improving the electrocatalytic reduction efficiency of the enzyme. However, the preparation process of the electrode needs to prepare the immobilized mixture and the gel in advance, the process is complex, the composite effect of the electron mediator, the electron conductor and the coenzyme on the electrode cannot be guaranteed, and the electron transfer among materials in the reaction process is influenced.
In the research of photochemical coenzyme regeneration, CN112892592A publicationA rhodium-based electron mediator [ Cp Rh (bpy) Cl is disclosed]Cl is immobilized on the photocatalyst Uio-66-NH2Surface modification of carboxylic acid bipyridyl to Uio-66-NH by amidation2Surface, and reacting with dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer to obtain [ Cp Rh (bpy) Cl]Cl immobilization and recovery and reuse to a certain extent. However, the photocatalyst itself generates relatively few photo-generated electrons and is easily recombined, so that [ Cp Rh (bpy) Cl is immobilized]The improvement of the regeneration efficiency of coenzyme NAD (P) H by the photocatalyst after Cl is limited. And the photocatalyst needs to be dried and dispersed again after being used, which also causes the loss of the photocatalyst and the electron mediator.
However, related research results are relatively lacking in the field of photoelectrochemical coenzyme regeneration, and therefore, a new photoelectrode for photoelectrochemical coenzyme nad (p) H regeneration needs to be developed to enhance the electron transfer efficiency between an electron mediator and an electrode, so that the coenzyme regeneration efficiency is effectively improved, meanwhile, the in-situ recovery and utilization of the electron mediator can be realized, the loss of the electron mediator is reduced, and the large-scale application is realized.
Disclosure of Invention
In view of the problems in the prior art, the invention aims to provide a silicon-based covalent organic framework photoelectrode and a preparation method and application thereof, wherein the silicon-based covalent organic framework photoelectrode comprises a silicon substrate, and an electron conduction layer, a covalent organic framework layer and an electron medium layer which are sequentially arranged on one side of the silicon substrate from bottom to top; according to the invention, the electron mediator is fixed on the covalent organic framework layer in a covalent bond forming manner, so that the electron transfer between the electron mediator and the covalent organic framework layer can be greatly promoted, meanwhile, the photoelectrode is constructed into a stacked structure, so that the high-efficiency transfer of electrons between layers can be promoted, the electron transfer efficiency between the electron mediator and the silicon substrate is finally improved, the in-situ recovery and utilization of the electron mediator are realized, and the excessive waste of the expensive electron mediator can be effectively avoided; the photoelectrode can effectively improve the catalytic activity of regeneration of photoelectrochemical coenzyme NAD (P) H, and meanwhile, the preparation method is simple and convenient, does not need complex operation, and is beneficial to large-scale application in industrial production.
In order to achieve the purpose, the invention adopts the following technical scheme:
in a first aspect, the invention provides a silicon-based covalent organic framework photoelectrode, which comprises a silicon substrate, and an electron conduction layer, a covalent organic framework layer and an electron medium layer which are sequentially arranged on one side of the silicon substrate from bottom to top.
The covalent organic framework layer is arranged on the photoelectric electrode, so that the connection between an electron mediator and the photoelectric electrode can be realized, and the electron mediator is connected to the covalent organic framework layer, so that the electron transfer between the electron mediator and the photoelectric electrode can be promoted; by constructing an electron conduction layer, the covalent organic framework layer can be fixed, and the electron transfer between layers can be promoted; by constructing the laminated arrangement structure, the electron transfer efficiency between the electron mediator and the photoelectrode can be promoted finally, the fixation, in-situ recovery and utilization of the electron mediator are realized, and the catalytic activity of the regeneration of the photoelectrochemical coenzyme NAD (P) H is further improved.
The following technical solutions are preferred technical solutions of the present invention, but not limited to the technical solutions provided by the present invention, and technical objects and advantageous effects of the present invention can be better achieved and achieved by the following technical solutions.
As a preferred embodiment of the present invention, the material of the silicon substrate includes any one of single crystal silicon, polycrystalline silicon, or amorphous silicon, or a combination of at least two of them, and typical but non-limiting examples of the combination include a combination of single crystal silicon and polycrystalline silicon, a combination of polycrystalline silicon and amorphous silicon, or a combination of single crystal silicon and amorphous silicon.
The silicon substrate is selected because the monocrystalline silicon, the polycrystalline silicon or the amorphous silicon material is a narrow-bandgap semiconductor material, can effectively absorb and utilize the energy of visible light, generates more photo-generated electrons, has good conductivity and stability, and can provide continuous and stable output in the reaction environment of coenzyme regeneration.
As a preferable embodiment of the present invention, the material of the electron conducting layer includes graphene.
Preferably, the graphene has a single-layer structure.
According to the invention, graphene is selected as an electron conduction layer, on one hand, the silicon substrate can be prevented from being corroded in a coenzyme regeneration reaction environment, on the other hand, the pi electron structure of graphene is beneficial to forming a two-dimensional structure on the surface of a covalent organic framework layer with the same pi electron structure, so that the covalent organic framework layer is fixed, meanwhile, the graphene has excellent conductivity, and the pi electron structures of the graphene and the covalent organic framework layer are overlapped by directly contacting the graphene and the covalent organic framework layer, so that electrons can be transferred between the two layers; it should be noted that the graphene used in the present invention is a high-quality thin film prepared by a CVD method, and has the advantage of high regularity of graphene structure, and a nanocarbon material similar to graphene, such as graphene oxide, redox graphene, carbon nanotubes, etc., is not suitable for being used as a material for the electron conducting layer of the present invention because of relatively poor degree of order and low quality of graphene structure, otherwise, the problems of reduced adhesion of the electron conducting layer to a silicon wafer and reduced protection capability will be caused, and finally, the stability of the photoelectrode is deteriorated and the use requirement cannot be met.
As a preferred embodiment of the present invention, the material of the covalent organic framework layer comprises COF containing bipyridyl structure.
A covalent-organic framework (COF) is a crystalline organic copolymer formed by covalently connecting small organic molecular units, has the advantages of low density, high specific surface area, good electrical conductivity, easy modification and functionalization and the like, and is widely applied to the fields of gas storage and separation, heterogeneous catalysis, energy storage materials, photoelectricity, sensing, drug delivery and the like; the design and adjustment of the structure and the property of the material can be realized by changing the organic unit of the material or selecting different monomers, so that a target ligand can be easily embedded or connected in the structure of the COF material through the design of the structure of the COF material so as to realize immobilization and further utilization; the invention relates to a method for preparing a crystal form of a crystal form.
Preferably, the covalent organic framework layer has a thickness of 5 to 30nm, such as 5nm, 10nm, 15nm, 20nm, 25nm or 30nm, but not limited to the recited values, and other values not recited within the above range of values are equally applicable.
In the invention, the thickness of the covalent organic framework layer can be controlled to ensure good electron transmission effect among the covalent organic framework layer, the electron conduction layer and the electron mediator layer, and the excessive thickness of the covalent organic framework layer can cause the reduction of the catalytic activity of coenzyme regeneration.
In a preferred embodiment of the present invention, the electron mediator layer includes a metal complex.
Preferably, the metal complex comprises [ Cp × rh (bpy) Cl ] Cl.
Because the rhodium complex is the most widely used electronic mediator with the best effect in the field of coenzyme NAD (P) H regeneration, the rhodium complex is preferably used as the electronic mediator layer, and metal ions in the complex can realize effective connection with a covalent organic framework layer with a bipyridyl structure, so that the rhodium complex is most conveniently selected as the electronic mediator layer in the invention, and the catalytic effect is best; it is worth mentioning that [ Cp Rh (bpy) Cl]When Cl is dissolved in a solvent to form a solution, [ Cp + Rh (bpy) Cl]Cl is hydrolyzed to generate [ Cp Rh (bpy) H2O]2+But the two functions are the same.
In a second aspect, the present invention provides a method for preparing a silicon-based covalent organic framework photoelectrode according to the first aspect, the method comprising the steps of:
(1) preparing and cleaning a silicon substrate;
(2) preparing an electron conduction layer on one side of the silicon substrate obtained in the step (1) to obtain a first complex;
(3) immersing the first complex in the step (2) in a precursor solution of a covalent organic framework layer, and growing the covalent organic framework layer on one side of an electron conduction layer of the first complex by adopting a solvothermal method to obtain a second complex;
(4) and (4) immersing the second complex in the step (3) in an electron mediator solution, and stirring to form an electron mediator layer on one side of the covalent organic framework layer of the second complex, thereby obtaining the silicon-based covalent organic framework photoelectrode.
It is worth to be noted that, when the first complex in the step (3) of the present invention is immersed in a precursor solution of a covalent organic framework layer, the electron conducting layer needs to be kept to be placed upward, so that the covalent organic framework layer grows more completely and uniformly, which is beneficial to the stability of the performance of the photoelectrode product; similarly, when the second complex in the step (4) is immersed in the solution of the electron mediator, the covalent organic framework layer needs to be kept upward, so that the electron mediator is more fully loaded.
As a preferred technical solution of the present invention, before the cleaning in step (1), the silicon substrate is cut to a target size.
Preferably, the cleaning of step (1) comprises ultrasonic cleaning.
Preferably, the cleaning of step (1) comprises ultrasonic cleaning using acetone, isopropanol and ethanol in sequence.
Preferably, the electronic conducting layer in the step (2) is transferred to the surface of the silicon substrate in the step (1) by a chemical etching method, a metal foil with graphene growing is prepared at first, a polymer supporting layer is spin-coated on the graphene, then the metal foil is removed by using an etching solution to obtain a graphene/polymer film, the graphene/polymer film is transferred to the silicon substrate after being washed by water for multiple times, the graphene/polymer film is dried and then soaked in a remover to remove the polymer, and finally the graphene/polymer film is washed by using a cleaning agent to obtain a first complex.
Preferably, the polymer comprises polymethyl methacrylate.
Preferably, the etching solution comprises a mixed aqueous solution of copper sulfate and hydrochloric acid.
Preferably, the remover comprises acetone.
Preferably, the cleaning agent comprises isopropyl alcohol and/or water.
As a preferred embodiment of the present invention, the solute of the precursor solution of the covalent organic framework layer in step (3) includes a monomeric solute a and a bipyridyl solute B.
The monomer A is selected to connect the monomer B containing the bipyridyl group to form a covalent organic framework, the bipyridyl solute B is selected to introduce the bipyridyl functional group into the covalent organic framework material, and then the connection of an electronic mediator is realized by utilizing the bipyridyl functional group, so that the material of the covalent organic framework layer can be not only COF containing the bipyridyl structure, but also some metal organic framework Materials (MOF) with the bipyridyl structure can be suitable for the invention.
Preferably, the monomeric solute A comprises 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin.
Preferably, the bipyridyl solute B comprises 2,2 '-bipyridyl-5, 5' -dicarbaldehyde.
Preferably, the mass ratio of the monomeric solute A to the bipyridyl solute B in the precursor solution of the covalent organic framework layer in the step (3) is (1 to 3):1, for example, 1:1, 1.2:1, 1.4:1, 1.6:1, 1.8:1, 2:1, 2.2:1, 2.4:1, 2.6:1, 2.8:1 or 3:1, but not limited to the recited values, and other values not recited in the above numerical range are also applicable.
Preferably, the concentration of the monomeric solute A in the solution of the covalent organic framework layer precursor in step (3) is 30-75 mg/L, such as 30mg/L, 35mg/L, 40mg/L, 45mg/L, 50mg/L, 55mg/L, 60mg/L, 65mg/L, 70mg/L or 75mg/L, but not limited to the recited values, and other values not recited in the above range of values are also applicable.
Preferably, the concentration of the bipyridyl solute B in the solution of the covalent organic framework layer precursor in step (3) is 20 to 50mg/L, for example, 20mg/L, 25mg/L, 30mg/L, 35mg/L, 40mg/L, 45mg/L, or 50mg/L, but not limited to the recited values, and other values not recited in the above-mentioned range of values are also applicable.
Preferably, the solvent of the covalent organic framework material precursor solution of step (3) comprises tetrahydrofuran, ethanol and acetic acid.
Preferably, in the solution of the covalent organic framework layer precursor in step (3), the volume ratio of tetrahydrofuran, ethanol and acetic acid is (1-3): 2-7): 1, for example, 2:6:1, 1:7:1, 3:5:1, 2:5:1, 1:6:1, 2:7:1, 3:6:1, 3:7:1 or 1:5:1, but not limited to the recited values, and other values not recited in the above range of values are also applicable.
Preferably, the reaction temperature of the solvothermal method in step (3) is 100 to 160 ℃, for example, 100 ℃, 105 ℃, 120 ℃, 125 ℃, 130 ℃, 135 ℃, 140 ℃, 145 ℃, 150 ℃, 155 ℃ or 160 ℃, but not limited to the recited values, and other values not recited within the above-mentioned range of values are also applicable.
Preferably, the reaction time of the solvothermal method in step (3) is 1 to 10 days, for example, 1 day, 2 days, 3 days, 4 days, 5 days, 6 days, 7 days, 8 days, 9 days or 10 days, but is not limited to the recited values, and other values not recited within the above-mentioned range of values are also applicable.
Preferably, the solvothermal method in step (3) is performed under the protection of an inert gas.
Preferably, the inert gas comprises any one of argon, nitrogen, helium or xenon or a combination of at least two thereof.
Preferably, the stirring time in step (4) is 2-8 h, such as 2h, 3h, 4h, 5h, 6h, 7h or 8h, but not limited to the recited values, and other values not recited in the above range of values are also applicable.
Preferably, the solvent raw material of the electron mediator solution in the step (4) comprises methanol.
Preferably, the solute raw material of the electron mediator solution in the step (4) comprises dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer.
As a preferred technical scheme of the invention, the preparation method comprises the following steps:
(1) preparing a silicon substrate used by an electrode, cutting the silicon substrate to a target size, and carrying out ultrasonic cleaning by sequentially using acetone, isopropanol and ethanol;
(2) preparing a metal foil with graphene growing, spin-coating a polymethyl methacrylate supporting layer on the graphene, removing the metal foil by using a mixed aqueous solution of copper sulfate and hydrochloric acid as an etching solution to obtain a graphene/polymethyl methacrylate film, washing the graphene/polymethyl methacrylate film for multiple times, transferring the washed graphene/polymethyl methacrylate film to a silicon substrate, drying, soaking the film in acetone serving as a remover to remove polymethyl methacrylate, washing the film by using isopropanol and/or water, and drying the film by using inert gas to form an electron conducting layer to obtain a first complex;
(3) ultrasonically dissolving a monomer solute A and a bipyridyl solute B which are mixed by tetrahydrofuran, ethanol and acetic acid in a mass ratio of (1-3): 1 by using a mixed solvent composed of tetrahydrofuran, ethanol and acetic acid in a volume ratio of (1-3): 1 to form a precursor solution of a covalent organic framework layer, wherein the concentration of the monomer solute A is 30-75 mg/L, and the concentration of the bipyridyl solute B is 20-50 mg/L, transferring the precursor solution of the covalent organic framework layer to the bottom of a polytetrafluoroethylene lining of a reaction kettle, immersing the first complex in the step (2) in the precursor solution of the covalent organic framework layer, keeping an electron conduction layer upward, introducing an inert gas to remove oxygen in the solution, carrying out a solvothermal reaction at 100-160 ℃ for 1-10 days, and growing the covalent organic framework layer on one side of the electron conduction layer of the first complex, taking out after the reaction is finished, cleaning the reaction product by using ethanol, and drying the reaction product by using inert gas to obtain a second complex;
(4) immersing the second complex in the step (3) in a methanol solution of an electronic medium, keeping the covalent organic framework layer upwards, stirring for 2-8 h to enable one side of the covalent organic framework layer of the second complex to form the electronic medium layer, taking out and cleaning the electronic medium layer with methanol after the reaction is finished, and drying the electronic medium layer with inert gas to obtain the silicon-based covalent organic framework photoelectrode;
wherein, the inert gas in the steps (2), (3) and (4) comprises any one of argon, nitrogen, helium or xenon or the combination of at least two of the argon, the nitrogen, the helium and the xenon.
In a third aspect, the invention provides an application of the silicon-based covalent organic framework photoelectrode in the first aspect in coenzyme NAD (P) H regeneration.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) according to the invention, the covalent organic framework layer is arranged on the photoelectric electrode, so that the electronic mediator can be fixed on the covalent organic framework layer in a covalent bond forming manner, the electron transfer between the covalent organic framework layer and the electronic mediator is greatly promoted, the in-situ recovery and utilization of the electronic mediator are realized, and the excessive waste of the expensive electronic mediator can be effectively avoided;
(2) the electron conduction layer is arranged on the photoelectric electrode, so that the covalent organic framework layer can be fixed, the overlapping of the pi electron structure between the electron conduction layer and the covalent organic framework layer is favorable for the efficient transfer of electrons, and the electron conduction layer can prevent the silicon substrate from being corroded in a coenzyme regeneration reaction environment;
(3) according to the invention, the photoelectrode is constructed into a stacked structure, so that electrons can be promoted to be efficiently transferred between layers, the electron transfer efficiency between an electron mediator and a silicon substrate is finally improved, and the photoelectrode can effectively improve the catalytic activity of photoelectrochemistry coenzyme regeneration;
(4) the preparation method is simple and convenient, the raw materials are easy to obtain, complex operation is not needed, and the large-scale application in industrial production is facilitated.
Drawings
FIG. 1 is an atomic force microscope image of a silicon-based covalent organic framework photoelectrode obtained in example 1 of the present invention;
FIG. 2 is a scanning electron microscope image of a silicon-based covalent organic framework photoelectrode obtained in example 1 of the present invention;
FIG. 3 is a schematic diagram of a silicon-based covalent organic framework photoelectrode obtained in the present invention in a coenzyme NAD (P) H regeneration reaction;
FIG. 4 is a scanning electron microscope image of silicon-based covalent organic framework photoelectrode obtained in example 5, example 6 and example 7 of the present invention;
FIG. 5 is a test chart of the electrochemical active surface area of the silicon-based covalent organic framework photoelectrode obtained in example 5, example 6 and example 7 of the invention;
FIG. 6 is a test chart of the electrochemical active surface area of the silicon-based covalent organic framework photoelectrode obtained in example 1, example 5, example 8 and example 9 of the invention;
FIG. 7 is a graph showing the conversion efficiency of the Si-based covalent organic framework photoelectrode obtained in example 1 and example 5 of the present invention in the regeneration reaction of coenzyme NAD (P) H.
Detailed Description
The technical scheme of the invention is further explained by the specific implementation mode in combination with the attached drawings. It should be understood by those skilled in the art that the examples are only for the understanding of the present invention and should not be construed as the specific limitations of the present invention.
Example 1
The embodiment provides a preparation method of a silicon-based covalent organic framework photoelectrode, which comprises the following steps:
(1) preparing a silicon substrate used by an electrode, cutting P-type silicon into the size of 1cm multiplied by 1cm, and carrying out ultrasonic cleaning by sequentially using acetone, isopropanol and ethanol;
(2) preparing a metal foil with graphene growing, spin-coating a polymethyl methacrylate supporting layer on the graphene, removing the metal foil by using a mixed aqueous solution of copper sulfate and hydrochloric acid as an etching solution to obtain a graphene/polymethyl methacrylate film, washing the graphene/polymethyl methacrylate film for multiple times, transferring the washed graphene/polymethyl methacrylate film onto a silicon substrate, drying, soaking the film in a remover acetone to remove polymethyl methacrylate, washing the film by using isopropanol and/or water, and blow-drying the film by using nitrogen to form an electron conduction layer to obtain a first complex;
(3) ultrasonically dissolving 0.3mg of 5,10,15, 20-tetra (4-aminophenyl) porphyrin and 0.2mg of 2,2 '-bipyridine-5, 5' -dicarboxaldehyde by using a mixed solvent consisting of 2mL of tetrahydrofuran, 6mL of ethanol and 1mL of acetic acid to form a precursor solution of a covalent organic framework layer, transferring the precursor solution of the covalent organic framework layer to the bottom of a polytetrafluoroethylene lining of a reaction kettle, immersing the first complex in the precursor solution of the covalent organic framework layer in the step (2), keeping an electron conduction layer upwards, introducing an inert gas to remove oxygen in the solution, carrying out solvothermal reaction at 120 ℃ for 3 days to grow the covalent organic framework layer on one side of the electron conduction layer of the first complex, taking out the covalent organic framework layer after the reaction is finished, and cleaning the covalent organic framework layer by using ethanol, then blowing the mixture by using nitrogen to obtain a second complex;
(4) and (3) immersing the second complex in the step (3) in a methanol solution of an electron mediator, keeping the covalent organic framework layer upwards, stirring for 6 hours to enable one side of the covalent organic framework layer of the second complex to form an electron mediator layer, taking out the second complex after the reaction is finished, cleaning the second complex with methanol, and drying the second complex with nitrogen to obtain the silicon-based covalent organic framework photoelectrode.
Example 2
This example provides a method for preparing a silicon-based covalent organic framework photoelectrode, which is identical to example 1 except that 0.6mg of 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin and 0.3mg of 2,2 '-bipyridine-5, 5' -dicarbaldehyde were ultrasonically dissolved in step (3), a solvothermal reaction was carried out at 140 ℃ for 2 days, and stirring was carried out for 4 hours in step (4).
Example 3
This example provides a method for preparing a silicon-based covalent organic framework photoelectrode, which is identical to example 1 except that 0.45mg of 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin and 0.3mg of 2,2 '-bipyridine-5, 5' -dicarboxaldehyde were ultrasonically dissolved using a mixed solvent of 1mL of tetrahydrofuran, 7mL of ethanol, and 1mL of acetic acid, a solvothermal reaction was performed at 160 ℃ for 1 day, and stirring was performed for 8 hours in step (4).
Example 4
This example provides a method for preparing a silicon-based covalent organic framework photoelectrode, which is identical to example 1 except that a mixed solvent of 3mL of tetrahydrofuran, 5mL of ethanol and 1mL of acetic acid was used to ultrasonically dissolve 0.6mg of 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin and 0.2mg of 2,2 '-bipyridine-5, 5' -dicarboxaldehyde, a solvothermal reaction was carried out at 100 ℃ for 8 days, and stirring was carried out for 2 hours in step (4).
Example 5
This example provides a method for preparing a silicon-based covalent organic framework photoelectrode, which is identical to that of example 1 except that the stirring is carried out for 2 hours in step (4).
Example 6
This example provides a method for preparing a silicon-based covalent organic framework photoelectrode, which is identical to example 1 except that 0.45mg of 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin and 0.3mg of 2,2 '-bipyridine-5, 5' -dicarboxaldehyde were dissolved by sonication in step (3) and stirred for 2 hours in step (4).
Example 7
This example provides a method for preparing a silicon-based covalent organic framework photoelectrode, which is identical to example 1 except that 0.6mg of 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin and 0.4mg of 2,2 '-bipyridine-5, 5' -dicarboxaldehyde were dissolved by sonication in step (3) and stirred for 2 hours in step (4).
Example 8
This example provides a method for preparing a silicon-based covalent organic framework photoelectrode, which is identical to that of example 1 except that the stirring is carried out for 4 hours in step (4).
Example 9
This example provides a method for preparing a silicon-based covalent organic framework photoelectrode, which is identical to that of example 1 except that stirring is carried out for 8 hours in step (4).
Fig. 1 is an atomic force microscope image of the silicon-based covalent organic framework photoelectrode obtained in example 1, wherein thickness data of the covalent organic framework layer is obtained by measuring thicknesses of three scribe areas in the image, and the result shows that the thickness of the covalent organic framework layer grown in the embodiment is between 10nm and 30 nm.
Fig. 2 is a scanning electron microscope image of the silicon-based covalent organic framework photoelectrode obtained in example 1, from which it can be seen that a good covalent organic framework layer can be grown on an area of the silicon substrate having the electron conduction layer, while the covalent organic framework layer on an area without the electron conduction layer has a poor growth, which indicates that the arrangement of the electron conduction layer helps the covalent organic framework layer to form a two-dimensional planar structure depending on the action of the pi electron structure, and the electron conduction layer plays a very good role as a growth template.
Fig. 3 is a schematic diagram of the silicon-based covalent organic framework photoelectrode obtained in examples 1 to 9 in a coenzyme nad (p) H regeneration reaction, and it can be seen that a path of electron transfer is from a silicon substrate to a covalent organic framework layer, then to an electron mediator through a channel formed by a covalent bond, and finally to a reaction system of coenzyme regeneration from the electron mediator.
Fig. 4(a) - (c) respectively correspond to the scanning electron microscope images of the silicon-based covalent organic framework photoelectrode obtained in examples 5, 6 and 7, and compare examples 5, 6 and 7, in the precursor solution of the covalent organic framework layer, the dosage of the monomer solute a and the bipyridine solute B is gradually increased, which is beneficial to forming a thicker and more complete covalent organic framework layer and can lead to the increase of the surface roughness of the photoelectrode; fig. 5 is a test chart of the electrochemical active surface areas of examples 5, 6 and 7, and it can be seen that the electrochemical active surface area of the photoelectrode is gradually increased, that is, the increase of the surface roughness of the photoelectrode finally results in the optimization of the electrochemical active surface area of the obtained photoelectrode; however, it does not mean that the more the monomer solute a and the bipyridyl solute B are, the better the usage amount is, otherwise the covalent organic framework layer of the obtained photoelectrode is too thick, and the electron transfer between the electron conduction layer and the electron mediator is affected, and similarly, if the usage amount of the monomer solute a and the bipyridyl solute B is insufficient, the covalent organic framework layer of the obtained photoelectrode is incompletely grown, a complete planar two-dimensional structure cannot be formed, the number of adsorbable sites supplied to the electron mediator is correspondingly reduced, and the coenzyme regeneration efficiency is finally affected.
Fig. 6 is a test chart of electrochemical active surface areas of examples 1, 5, 8 and 9, and it can be found by comparing examples 1, 5, 8 and 9 that, in step (4) of the preparation method, the stirring time of the second complex in the electron mediator solution is properly prolonged, which is beneficial to increasing the electrochemical active surface area, wherein when the stirring time is 6h, i.e. the photoelectrode obtained in example 1 has the largest electrochemical active surface area, but when the stirring time is 8h in example 9, the electrochemical active area of the photoelectrode obtained starts to be reduced, and at this time, too much electron mediator is anchored on the surface of the photoelectrode, and the photo-generated electron holes are more easily recombined, thereby affecting the coenzyme regeneration efficiency.
FIG. 7 is a graph of the conversion efficiency of the Si-based covalent organic framework photoelectrode obtained in example 1 and example 5 in the regeneration reaction of coenzyme NAD (P) H, and it can be seen from the graph that in the test of 100min, the Si-based covalent organic framework photoelectrode obtained in example 1 always has higher conversion efficiency than that of example 5, and at 100min, the conversion efficiency is about 4 times that of example 5, because the stirring time in step (4) of the preparation method described in example 1 is 6H, the amount of the electron mediator anchored on the surface of the covalent organic framework layer can be increased, the electrochemical active surface area of the photoelectrode obtained is sufficiently increased, and thus higher conversion efficiency can be obtained; in contrast, in the step (4) of the preparation method described in example 5, the stirring time is the minimum value of 2 hours in the preferred range, so the number of the electron mediators connected to the obtained photoelectrode is relatively small, the electrochemical active surface area is small, and the coenzyme regeneration efficiency of the obtained photoelectrode is reduced.
The applicant declares that the present invention illustrates the detailed structural features of the present invention through the above embodiments, but the present invention is not limited to the above detailed structural features, that is, it does not mean that the present invention must be implemented depending on the above detailed structural features. It should be understood by those skilled in the art that any modifications of the present invention, equivalent substitutions of selected components of the present invention, additions of auxiliary components, selection of specific modes, etc., are within the scope and disclosure of the present invention.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention.
It should be noted that the various technical features described in the above embodiments can be combined in any suitable manner without contradiction, and the invention is not described in any way for the possible combinations in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (10)
1. The silicon-based covalent organic framework photoelectrode is characterized by comprising a silicon substrate, and an electron conduction layer, a covalent organic framework layer and an electron medium layer which are sequentially arranged on one side of the silicon substrate from bottom to top.
2. The silicon-based covalent organic framework photoelectrode of claim 1, wherein the material of the silicon substrate comprises any one of single crystal silicon, polycrystalline silicon, or amorphous silicon, or a combination of at least two of the same.
3. The silicon-based covalent organic framework photoelectrode of claim 1 or 2 wherein the material of the electron conducting layer comprises graphene;
preferably, the graphene has a single-layer structure.
4. The silicon-based covalent organic framework photoelectrode of any one of claims 1 to 3 wherein the material of the covalent organic framework layer comprises a COF comprising a bipyridine structure;
preferably, the thickness of the covalent organic framework layer is 5-30 nm.
5. The silicon-based covalent organic framework photoelectrode of any one of claims 1 to 4 wherein the electron mediator layer comprises a metal complex;
preferably, the metal complex comprises [ Cp × rh (bpy) Cl ] Cl.
6. A method of making a silicon-based covalent organic framework photoelectrode as claimed in any one of claims 1 to 5 comprising the steps of:
(1) preparing and cleaning a silicon substrate;
(2) preparing an electron conduction layer on one side of the silicon substrate obtained in the step (1) to obtain a first complex;
(3) immersing the first complex in the step (2) in a precursor solution of a covalent organic framework layer, and growing the covalent organic framework layer on one side of an electron conduction layer of the first complex by adopting a solvothermal method to obtain a second complex;
(4) and (4) immersing the second complex in the step (3) in an electron mediator solution, and stirring to form an electron mediator layer on one side of the covalent organic framework layer of the second complex, thereby obtaining the silicon-based covalent organic framework photoelectrode.
7. The method of claim 6, wherein the silicon substrate is cut to a target size prior to the cleaning of step (1);
preferably, the cleaning of step (1) comprises ultrasonic cleaning;
preferably, the cleaning in step (1) comprises ultrasonic cleaning by sequentially using acetone, isopropanol and ethanol;
preferably, the electronic conducting layer in the step (2) is transferred to the surface of the silicon substrate in the step (1) by a chemical etching method, a metal foil with graphene growing is prepared at first, a polymer supporting layer is spin-coated on the graphene, then the metal foil is removed by using an etching solution to obtain a graphene/polymer film, the graphene/polymer film is transferred to the silicon substrate after being washed by water for multiple times, the graphene/polymer film is dried and then soaked in a remover to remove the polymer, and finally the graphene/polymer film is washed by using a cleaning agent to obtain a first complex;
preferably, the polymer comprises polymethyl methacrylate;
preferably, the etching solution comprises a mixed aqueous solution of copper sulfate and hydrochloric acid;
preferably, the removal agent comprises acetone;
preferably, the cleaning agent comprises isopropyl alcohol and/or water.
8. The method of claim 6 or 7, wherein the solutes of the precursor solution of the covalent organic framework layer of step (3) comprise a monomeric solute A and a bipyridyl solute B;
preferably, the monomeric solute A comprises 5,10,15, 20-tetrakis (4-aminophenyl) porphyrin;
preferably, the bipyridyl solute B comprises 2,2 '-bipyridyl-5, 5' -dicarbaldehyde;
preferably, the mass ratio of the monomer solute A to the bipyridyl solute B in the precursor solution of the covalent organic framework layer in the step (3) is (1-3): 1;
preferably, in the precursor solution of the covalent organic framework layer in the step (3), the concentration of the monomer solute A is 30-75 mg/L;
preferably, in the precursor solution of the covalent organic framework layer in the step (3), the concentration of the bipyridyl solute B is 20-50 mg/L;
preferably, the solvent of the precursor solution of the covalent organic framework layer in the step (3) comprises tetrahydrofuran, ethanol and acetic acid;
preferably, in the precursor solution of the covalent organic framework layer in the step (3), the volume ratio of tetrahydrofuran, ethanol and acetic acid is (1-3): (2-7): 1;
preferably, the reaction temperature of the solvothermal method in the step (3) is 100-160 ℃;
preferably, the reaction time of the solvothermal method in the step (3) is 1-10 days;
preferably, the solvothermal method in the step (3) is carried out under the protection of inert gas;
preferably, the inert gas comprises any one of argon, nitrogen, helium or xenon or a combination of at least two of the same;
preferably, the stirring time in the step (4) is 2-8 h;
preferably, the solvent raw material of the electron mediator solution in the step (4) comprises methanol;
preferably, the solute raw material of the electron mediator solution in the step (4) comprises dichloro (pentamethylcyclopentadienyl) rhodium (III) dimer.
9. The method of any one of claims 6-8, wherein the method comprises the steps of:
(1) preparing a silicon substrate used by an electrode, cutting the silicon substrate to a target size, and sequentially carrying out ultrasonic cleaning by using acetone, isopropanol and ethanol;
(2) preparing a metal foil with graphene growing, spin-coating a polymethyl methacrylate supporting layer on the graphene, removing the metal foil by using a mixed aqueous solution of copper sulfate and hydrochloric acid as an etching solution to obtain a graphene/polymethyl methacrylate film, washing the graphene/polymethyl methacrylate film for multiple times, transferring the washed graphene/polymethyl methacrylate film onto a silicon substrate, drying, soaking the film in a remover acetone to remove polymethyl methacrylate, washing the film by using isopropanol and/or water, and blow-drying the film by using inert gas to form an electron conduction layer to obtain a first complex;
(3) ultrasonically dissolving a monomer solute A and a bipyridyl solute B which are mixed by tetrahydrofuran, ethanol and acetic acid in a mass ratio of (1-3): 1 by using a mixed solvent composed of tetrahydrofuran, ethanol and acetic acid in a volume ratio of (1-3): 1 to form a precursor solution of a covalent organic framework layer, wherein the concentration of the monomer solute A is 30-75 mg/L, and the concentration of the bipyridyl solute B is 20-50 mg/L, transferring the precursor solution of the covalent organic framework layer to the bottom of a polytetrafluoroethylene lining of a reaction kettle, immersing the first complex in the step (2) in the precursor solution of the covalent organic framework layer, keeping an electron conduction layer upward, introducing an inert gas to remove oxygen in the solution, carrying out a solvothermal reaction at 100-160 ℃ for 1-10 days, and growing the covalent organic framework layer on one side of the electron conduction layer of the first complex, taking out after the reaction is finished, cleaning the reaction product by using ethanol, and drying the reaction product by using inert gas to obtain a second complex;
(4) immersing the second complex in the step (3) in a methanol solution of an electronic medium, keeping the covalent organic framework layer upwards, stirring for 2-8 h to enable one side of the covalent organic framework layer of the second complex to form the electronic medium layer, taking out and cleaning the electronic medium layer with methanol after the reaction is finished, and drying the electronic medium layer with inert gas to obtain the silicon-based covalent organic framework photoelectrode;
wherein, the inert gas in the steps (2), (3) and (4) comprises any one of argon, nitrogen, helium or xenon or the combination of at least two of the argon, the nitrogen, the helium and the xenon.
10. Use of a silicon-based covalent organic framework photoelectrode according to any one of claims 1 to 5 in the regeneration of coenzyme NAD (P) H.
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| CN115725083B (en) * | 2022-11-18 | 2023-09-29 | 中国科学院福建物质结构研究所 | Covalent organic framework material, electrode material and use thereof in aqueous photo-charged proton batteries |
| CN116063692A (en) * | 2023-02-19 | 2023-05-05 | 广东工业大学 | Metal-based covalent organic framework nano-enzyme and preparation method and application thereof |
| CN116063692B (en) * | 2023-02-19 | 2023-08-08 | 广东工业大学 | Metal-based covalent organic framework nano-enzyme and preparation method and application thereof |
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