CN115850273A - Phenanthroline iron complex, preparation method and application of phenanthroline iron complex in aspect of electrochromism - Google Patents
Phenanthroline iron complex, preparation method and application of phenanthroline iron complex in aspect of electrochromism Download PDFInfo
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- FYOAILFCEUZWBX-UHFFFAOYSA-N [7-(hydroxymethyl)-1,10-phenanthrolin-4-yl]methanol Chemical compound C1=CC2=C(CO)C=CN=C2C2=C1C(CO)=CC=N2 FYOAILFCEUZWBX-UHFFFAOYSA-N 0.000 claims description 10
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Abstract
The invention relates to a phenanthroline iron complex, a preparation method and application thereof in electrochromic. The prior electrochromic material has the problems of long color-changing time, short cycle life and the like, and the electrochromic device has the problems of complex production process and the like. The invention provides a tri (4, 7-bis-hydroxymethyl) -1, 10-phenanthroline iron complex, and an electrochromic device can be constructed on the basis of the phenanthroline iron complex. The material has simple preparation process and excellent performance, and the constructed electrochromic device can realize the electrochromic function only by introducing the solution of the material into the transparent cavity, thereby avoiding using a multilayer electrochromic structure and not needing to arrange a conducting layer, an ion storage layer and positive and negative electrodes in an internal partition, completely omitting the step of depositing the electrochromic material on the surface of conductive glass or the electrode, reducing the difficulty of the production process, and simultaneously overcoming the problems of harsh production conditions, high cost and the like.
Description
Technical Field
The invention relates to an electrochromic material, and in particular relates to a phenanthroline iron complex, a preparation method and application thereof in electrochromic.
Background
Electrochromism is a phenomenon in which optical properties of a material are changed under the drive of an applied electric field, so that a reversible change occurs in color. The electrochromic device has adjustability of light absorption or light transmission under the action of an electric field, can selectively absorb or reflect external heat radiation and internal heat diffusion, reduces the consumption of a large amount of energy for keeping the office buildings, civil houses and the like cool in summer and warm in winter, finally achieves the aim of saving energy, and simultaneously achieves the aim of improving the natural illumination degree. At present, electrochromic windows are the most applied electrochromic materials, and the electrochromic windows also have certain application in the fields of anti-dazzling rearview mirrors, military camouflage and the like.
The traditional electrochromic materials are mainly divided into inorganic electrochromic materials and organic electrochromic materials, and most of the inorganic electrochromic materials are transition metal oxides and Prussian blue derivatives, such as WO 3 、TiO 2 、NiO、IrO 2 The organic electrochromic material is a solid organic film formed by polypyrrole and monomer pyrrole, viologen and the like.The inorganic color-changing material has the problems of long color-changing time, short cycle life at high temperature/low temperature and the like, and the organic film material has an ultraviolet degradation phenomenon, so that the large-scale application is unlikely to be realized.
The traditional electrochromic device has a five-layer structure, namely a transparent conducting layer (2 layers), an electrochromic layer, an electrolyte layer and an ion storage layer. At present, the processes for preparing the electrochromic device with the sandwich structure mainly comprise a magnetron sputtering method, a sol-gel method, an electrochemical deposition method, a chemical vapor deposition method and the like, but the processes all need to be operated in a high-temperature high-pressure or vacuum environment, and the prepared electrochromic device has the problems of unstable interface, nonuniform color change, long cycle life, difficult maintenance in the use process and the like. In addition, the production process of the current electrochromic device is extremely complex, and the requirements on production conditions are extremely strict, so that the production cost is always high.
Disclosure of Invention
The invention aims to provide a phenanthroline iron complex, a preparation method and application thereof in electrochromism, and aims to solve the problems of long color changing time, short cycle life at high temperature/low temperature and the like of the conventional electrochromism material, and the problems of complex production process, high production cost and the like of an electrochromism device.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
provided is a phenanthroline iron complex, wherein the phenanthroline iron complex is a tri (4, 7-bis-hydroxymethyl) -1, 10-phenanthroline iron complex, and has the structure:
wherein n is 2 or 3.
In another aspect, there is provided a method for preparing the phenanthroline complex, the method comprising:
taking 4, 7-dimethyl-1, 10 phenanthroline as a raw material, and obtaining a 4, 7-dihydroxymethyl-1, 10 phenanthroline ligand by adopting a hydrothermal synthesis method;
reacting 4, 7-dihydroxymethyl-1, 10 phenanthroline ligand with FeCl under a neutral condition 2 ·4H 2 And (3) uniformly mixing the O to obtain the tri (4, 7-hydroxymethyl) -1, 10-phenanthroline iron complex.
On the other hand, the application of the phenanthroline iron complex in the aspect of electrochromism is provided, and the application is to construct an electrochromism device based on the phenanthroline iron complex.
Furthermore, the electrochromic device comprises a photo anode, a common electrode, an anode liquid storage tank, a cathode liquid storage tank and an anode side transparent cavity, wherein the common electrode is a cathode;
the anode liquid storage tank is connected into the photo-anode and the anode side transparent cavity through a liquid conveying pipeline, and the photo-anode and the anode side transparent cavity are connected back to the anode liquid storage tank through a liquid conveying pipeline;
the cathode and the cathode liquid storage tank form a circulation through a liquid conveying pipeline;
the positive electrode liquid storage tank is filled with an anolyte containing the phenanthroline iron complex, and the negative electrode liquid storage tank is filled with a catholyte containing methyl viologen.
Or the electrochromic device comprises a common electrode, a photocathode, an anode liquid storage tank, a cathode liquid storage tank and a cathode side transparent cavity, wherein the common electrode is an anode;
the cathode liquid storage tank is connected into the photocathode and the cathode side transparent cavity through liquid conveying pipelines, and the photocathode and the cathode side transparent cavity are connected back to the cathode liquid storage tank through liquid conveying pipelines;
the anode and the anode liquid storage tank form a circulation through a liquid conveying pipeline;
the positive electrode liquid storage tank is filled with an anolyte containing the phenanthroline iron complex, and the negative electrode liquid storage tank is filled with a catholyte containing methyl viologen.
Or the electrochromic device comprises a photo anode, a photo cathode, an anode liquid storage tank, a cathode liquid storage tank, an anode side transparent cavity and a cathode side transparent cavity;
the anode liquid storage tank is connected into the photo-anode and the anode side transparent cavity through a liquid conveying pipeline, and the photo-anode and the anode side transparent cavity are connected back to the anode liquid storage tank through a liquid conveying pipeline;
the cathode liquid storage tank is connected into the photocathode and the cathode side transparent cavity through a liquid conveying pipeline, and the photocathode and the cathode side transparent cavity are connected back to the cathode liquid storage tank through a liquid conveying pipeline;
the electrolyte comprises phenanthroline iron complex, a cathode electrolyte and a positive electrode liquid storage tank, wherein the positive electrode liquid storage tank contains the positive electrode electrolyte containing the phenanthroline iron complex, and the cathode liquid storage tank contains the cathode electrolyte containing methyl viologen.
Further, the obtaining process of the anolyte is as follows:
mixing a tri (4, 7-bis-hydroxymethyl) -1, 10-phenanthroline iron complex with water to obtain a phenanthroline iron complex solution;
adding supporting electrolyte into the phenanthroline iron complex solution, and stirring and mixing;
and adding a solvent to obtain the anolyte.
Further, the process for obtaining the catholyte is as follows:
mixing methyl viologen with water to obtain a methyl viologen solution;
and adding a supporting electrolyte into the methyl viologen solution to obtain the catholyte.
Further, the supporting electrolyte is selected from NaClO 4 、KNO 3 、KCl、NaCl、Na 2 SO 4 、KClO 4 、NH 4 Cl、K 2 HPO 4 ；
The solvent is selected from acetonitrile, ethanol and methanol.
Further, the photo-anode and the photo-cathode are both semiconductor photoelectrode with PN junction, and the semiconductor structure of the photo-anode is n + -n-p + Si-Ti-Pt, the semiconductor structure of the photocathode being p + -n-n + -Si-Ti-Pt。
Compared with the prior art, the invention has the following beneficial effects:
the invention provides a tris (4, 7-hydroxymethyl) -1, 10-phenanthroline iron complex which is an electrochromic material, can rapidly generate oxidation or reduction reaction under the illumination or electrification effect so as to enable the color of a solution to generate transparent to colored forward and reverse changes, and has the advantages of simple preparation process, excellent performance, low production cost, long service life, recyclable electrolyte and the like. Based on the electrochromic material, the invention also provides an electrochromic device, the electrochromic function can be realized only by introducing the electrochromic material into a transparent container with a cavity structure, the use of the traditional multilayer electrochromic structure is avoided, a conducting layer, an ion storage layer and positive and negative electrodes are not required to be arranged in a partition manner in the electrochromic device, the step of depositing the electrochromic material on the surface of conductive glass or an electrode is completely omitted, the difficulty of the production process is reduced, and the problems of harsh production conditions, high cost and the like are also solved.
The electrochromic device based on the tris (4, 7-bis (hydroxymethyl) -1, 10-phenanthroline iron complex integrates photovoltaic, energy storage and color changing functions, can realize energy storage while changing color, does not consume commercial power in the whole process, and realizes self-energy supply by virtue of photovoltaic cells, thereby simplifying the structure. The flow battery energy storage system is adopted to replace the traditional solid storage battery energy storage device, and has the characteristics of high energy efficiency, long cycle life, good safety, modular design, high power density and the like. The semiconductor photovoltaic cell with the PN junction is used for replacing external power supply equipment of an electrochromic device, so that the consumption of electric energy such as thermal power and the like is reduced, and the carbon emission is reduced. The self-discharge problem in the solid electrochromic device is solved, the components of the electrolyte can be regulated or replaced at any time, and if the capacity can be increased by increasing the concentration or increasing the volume of the storage tank, the whole electrochromic device is convenient to maintain, and the service life of the electrochromic device is greatly prolonged.
The electrochromic device can be used for building glass, and can reduce a large amount of energy which is required to be consumed by cooling buildings such as office buildings, civil houses and the like in summer and warming in winter by adjusting the absorption and transmission of light and absorbing or reflecting external heat radiation, thereby achieving the purpose of energy conservation. Meanwhile, the effective indoor sunlight illumination is improved, outdoor shading facilities can be reduced, and the requirements of lighting and beauty of the existing buildings are met.
Drawings
In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the description of the embodiments or the prior art will be briefly described below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and for those skilled in the art, other drawings of the embodiments can be obtained according to the drawings without creative efforts.
FIG. 1 is a view showing the constitution of an apparatus in example 1 of the present invention.
Fig. 2 is a structure diagram of a photoelectrode of embodiment 1 of the present invention.
FIG. 3 is a diagram showing the structure of an apparatus in example 2 of the present invention.
Fig. 4 is a structure diagram of a photoelectrode of embodiment 2 of the invention.
FIG. 5 is a diagram showing the structure of an apparatus in example 3 of the present invention.
Fig. 6 is a structure diagram of a photoelectrode of embodiment 3 of the invention.
Fig. 7 is a schematic view of the present invention applied to an architectural glass.
The labels in the figure are:
001-photoanode, 002-photocathode, 003-common electrode, 004-anolyte, 005-catholyte, 006-diaphragm, 007-anode liquid storage tank, 008-cathode liquid storage tank, 009-1 pump, 010-2 pump, 011-3 pump, 012-4 pump, 013-infusion pipeline, 014-lead, 015-switch, 016-load, 017-anode side transparent cavity and 018-cathode side transparent cavity.
Detailed Description
To facilitate an understanding of the invention, the invention will now be described more fully with reference to the accompanying drawings. Preferred embodiments of the present invention are shown in the drawings. This invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein. Rather, these embodiments are provided so that this disclosure will be thorough and complete.
Throughout the description of this patent, it is to be understood that all technical and scientific terms used have the same meaning as commonly understood by one of ordinary skill in the art to which this patent belongs. In case of conflict, the present specification, including definitions, will control. Unless otherwise indicated, technical means used in the examples are conventional means well known to those skilled in the art, reagents used in the examples are commercially available, devices used in the examples are conventional devices, limitations on the means, reagents or devices cannot be understood as limitations on the patent, and the same types of means, reagents or devices for solving the same technical problems are within the protection scope of the patent.
In the description of this patent, it is understood that when an amount, concentration, or other value or parameter is expressed as a range, preferred range, or as a range defined by a list of upper preferable values and lower preferable values, this is to be understood as specifically disclosing all ranges formed from any pair of any upper range limit or preferred value and any lower range limit or preferred value, regardless of whether ranges are separately disclosed. When a range of values is described herein, unless otherwise stated, the range is intended to include the endpoints thereof and all integers and fractions within the range.
In the description of the present patent, it is to be understood that a plurality of steps are involved in describing the method, and the method should not be construed as being limited to the order of the steps of the method, and a technical solution obtained by merely changing the order of the steps when solving the same technical problem is also within the scope of the present patent.
The invention provides a phenanthroline iron complex which is a tri (4, 7-bis-hydroxymethyl) -1, 10-phenanthroline iron complex and has the structure as follows:
wherein n is 2 or 3.
Iron in the tri (4, 7-bis-hydroxymethyl) -1, 10-phenanthroline complex is hexa-coordinated metal ions, and three 4, 7-bis-hydroxymethyl-1, 10-phenanthroline are used as ligands to form a coordination compound with a central symmetry structure.
The preparation method of the phenanthroline iron complex comprises the following steps: taking 4, 7-dimethyl-1, 10 phenanthroline as a raw material, and obtaining a 4, 7-dihydroxymethyl-1, 10 phenanthroline ligand by adopting a hydrothermal synthesis method; reacting 4, 7-dihydroxymethyl-1, 10 phenanthroline ligand with FeCl under a neutral condition 2 ·4H 2 And (3) uniformly mixing the O to obtain the tri (4, 7-hydroxymethyl) -1, 10-phenanthroline iron complex. The specific synthetic route is as follows:
(1) Simultaneously adding 4, 7-dimethyl-1, 10-phenanthroline and potassium permanganate into a 30% sulfuric acid solution, heating and refluxing for 8 hours to obtain 4, 7-dicarboxy-1, 10-phenanthroline.
(2) Adding 4, 7-dicarboxyl-1, 10 phenanthroline into a solution containing 10% of methanol and 30% of sulfuric acid, heating and refluxing for 30 hours to obtain 4, 7-dimethoxyamide-1, 10 phenanthroline.
(3) Adding 4, 7-dimethoxyamide-1, 10 phenanthroline and sodium borohydride into a 60% ethanol solution, and heating and refluxing for 15 hours to obtain 4, 7-dihydroxymethyl-1, 10 phenanthroline.
(4) Adding 4, 7-dihydroxymethyl-1, 10-phenanthroline and ferrous chloride tetrahydrate into an acetonitrile water solution with a volume ratio of 1.
In addition, the tri (4, 7-dihydroxymethyl) -1, 10-phenanthroline iron complex can be oxidized by applying positive potential through an electrochemical method to obtain a higher valence tri (4, 7-dihydroxymethyl) -1, 10-phenanthroline iron complex.
The tris (4, 7-bis (hydroxymethyl) -1, 10-phenanthroline iron complex obtained by the method is an ideal electrochromic material, can be applied to the electrochromic field, and can be used for constructing an electrochromic device. The tris (4, 7-bis (hydroxymethyl) -1, 10-phenanthroline iron complex serving as an electrochromic active substance in an electrochromic device can rapidly generate oxidation or reduction reaction under the action of illumination or electrification so as to enable the color of a solution to generate positive and negative changes from transparency to coloring, so that in the process, color change, self-power supply and energy storage can be realized, and the electrochromic device can be applied to related fields.
The electrochromic device comprises an anode and a cathode, wherein the anode can be a common electrode 003 or a photoanode 001, the cathode can be a common electrode 003 or a photocathode 002, and the anode and the cathode are not simultaneously arranged to be the common electrode 003. The electrochromic device also comprises an anode liquid storage tank 007, a cathode liquid storage tank 008 and a transparent cavity. The transparent cavity is arranged in cooperation with the photo-anode 001 and the photo-cathode 002: when the device is provided with the photo anode 001, an anode side transparent cavity 017 is configured for the photo anode 001 and the anode liquid storage tank 007; when the device has a photocathode 002, a cathode side transparent cavity 018 is provided for the photocathode 002 and the cathode reservoir 008.
The photo anode 001 and the photo cathode 002 are both semiconductor photoelectrode with PN junction, the semiconductor structure of the photo anode 001 is n + -n-p + Si-Ti-Pt, the semiconductor structure of photocathode 002 being p + -n-n + -Si-Ti-Pt。
The anode liquid storage tank 007 is internally provided with an anolyte 004 which can be prepared by adopting a tris (4, 7-bis-hydroxymethyl) -1, 10-phenanthroline iron complex, and the process is as follows:
s1: mixing a tri (4, 7-bis-hydroxymethyl) -1, 10-phenanthroline iron complex with water to obtain a phenanthroline iron complex solution;
s2: adding supporting electrolyte into the phenanthroline iron complex solution, and stirring and mixing;
s3: solvent is added to obtain anolyte 004.
The cathode electrolyte 005 is arranged in the cathode liquid storage tank 008, contains cathode pairing active substances, can be prepared by adopting methyl viologen, and comprises the following steps:
s1: mixing methyl viologen with water to obtain a methyl viologen solution;
s2: a supporting electrolyte is added to the methyl viologen solution to obtain a catholyte 005.
The supporting electrolyte is selected from NaClO 4 、KNO 3 、KCl、NaCl、Na 2 SO 4 、KClO 4 、NH 4 Cl、K 2 HPO 4 And the solvent is selected from acetonitrile, ethanol, methanol, and the like.
The electrochromic device can adopt the following three structural forms:
example 1: anode-anode side electrolyte color change for PV light
As shown in fig. 1 and 2, the electrochromic device includes a photo-anode 001, a common electrode 003, an anode reservoir 007, a cathode reservoir 008, and an anode-side transparent cavity 017, where the common electrode 003 is a cathode. A diaphragm 006 is provided between the photo anode 001 and the common electrode 003, and a lead 014, a switch 015, and a load 016 are connected thereto.
The anode liquid storage tank 007 is connected to the bottom of the photoanode 001 through a liquid conveying pipeline 013 and a No. 1 pump 009, and is connected back to the anode liquid storage tank 007 through the liquid conveying pipeline 013 after the electrochemical reaction is finished, so that the cycle is repeated. Meanwhile, the anode liquid storage tank 007 is connected to the anode side transparent cavity 017 through a liquid conveying pipeline 013 and a No. 3 pump 011, and after the anode side transparent cavity 017 is filled with electrolyte, the electrolyte flows into the anode liquid storage tank 007 through the liquid conveying pipeline 013 to circulate in a reciprocating mode. The cathode and cathode liquid storage tank 008 is circulated through a liquid delivery pipe 013 and a No. 2 pump 010.
An anolyte 004 containing a phenanthroline iron complex is arranged in the anode liquid storage tank 007. Preparing 0.001mol/L solution by adopting a tris (4, 7-dihydroxymethyl) -1, 10-phenanthroline iron complex and deionized water, adding a supporting electrolyte NaCl, wherein the concentration of the supporting electrolyte in the aqueous solution of the tris (4, 7-dihydroxymethyl) -1, 10-phenanthroline iron complex is 0.1mol/L, fully stirring and mixing uniformly, adding acetonitrile accounting for 1% of the volume fraction of the electrochromic active substance solution, and mixing uniformly to obtain an anolyte 004.
The cathode reservoir 008 contains a cathode electrolyte 005 containing a cathode pairing active material. The negative electrode pairing active substance adopts methyl viologen solution with the concentration of 0.001mol/L and adopts 1mol/L KClO 4 As the supporting electrolyte, the solvent is water.
Processing polyethylene into a transparent device with a planar surface shape by adopting an injection molding integrated preparation process to serve as an anode side transparent cavity 017, wherein the volume of the cavity is 0.01m 2 The radius of the channels on the top and bottom substrates was 0.0001m.
The energy storage implementation manner of the embodiment is as follows:
the semiconductor structure of the photo-anode is n + -n-p + Si-Ti-Pt, when the sunlight irradiates the photo anode, the photo-generated carriers are generated on the PN junction of the semiconductor structure, and the holes are formed by n + Region flow direction p + Region, electron is composed of + Zone flow direction n + And at the moment, the photoproduction holes are captured by the electroactive substances on the interface of the anolyte, so that tri (4, 7-bis-hydroxymethyl) -1, 10-phenanthroline iron is subjected to oxidation reaction, photoproduction electrons are led into one side of the catholyte through an external circuit so that methylviologen is subjected to reduction reaction, the conversion from light energy to chemical energy is realized in the process, and the energy conversion efficiency reaches 94%.
The color-changing energy-saving implementation manner of the embodiment is as follows:
when light is emitted, the No. 3 pump 011 is turned on, the flow rate of the pump is set to be 40mL/min, at the moment, a part of anolyte is directly led into the anode side transparent cavity 017, at the moment, the tris (4, 7-hydroxymethyl) -1, 10-phenanthroline iron complex is continuously oxidized along with a photoproduction hole, the color of the solution is gradually changed from reduced colorless to oxidized red, at the moment, the average transmittance of the transparent cavity at 508-520nm is 8.3%, at the moment, the red transparent cavity can block sunlight outside, so that the temperature of the interior of a room is prevented from rising, and the use of refrigeration equipment such as an indoor air conditioner is reduced. When no light is emitted, the embodiment can be used as a photovoltaic flow battery, the working principle is the same as that of a common flow battery, the flow battery outputs electric energy by external load, the tris (4, 7-bis-hydroxymethyl) -1, 10-phenanthroline iron complex in the anolyte undergoes reduction reaction, the color of the solution is gradually changed from red in an oxidation state to colorless in a reduction state, and the average transmittance of the transparent cavity at the position of 508-520nm is 93%.
Example 2: PV photocathode-cathode side electrolyte discoloration
As shown in fig. 3 and 4, the electrochromic device includes a common electrode 003, a photocathode 002, an anode reservoir 007, a cathode reservoir 008, and a cathode-side transparent cavity 018, the common electrode 003 being an anode. A diaphragm 006 is provided between the common electrode 003 and the photocathode 002, and a lead 014, a switch 015, and a load 016 are connected thereto.
The cathode liquid storage tank 008 is connected to the bottom of the photocathode 002 through a liquid conveying pipeline 013 and a No. 2 pump 010, and is connected to the cathode liquid storage tank 008 through the liquid conveying pipeline 013 after the electrochemical reaction is finished, so that the operation is repeated. Meanwhile, the cathode liquid storage tank 008 is connected to the cathode transparent cavity 018 through a liquid conveying pipeline 013 and a No. 4 pump 012, and after the electrolyte in the cathode transparent cavity 018 is filled, the electrolyte flows into the cathode liquid storage tank 008 through the liquid conveying pipeline 013, so that the electrolyte is circulated in a reciprocating mode. The anode and anode liquid storage tank 007 forms a circulation through a transfusion pipeline 013 and a No. 1 pump 009.
An anolyte 004 containing a phenanthroline iron complex is arranged in the anode liquid storage tank 007. Preparing 0.1mol/L solution by adopting a tris (4, 7-bis-hydroxymethyl) -1, 10-phenanthroline iron complex and deionized water, adding a supporting electrolyte KCl, wherein the concentration of the supporting electrolyte in the tris (4, 7-bis-hydroxymethyl) -1, 10-phenanthroline iron complex aqueous solution is 1mol/L, fully stirring and uniformly mixing, adding ethanol accounting for 10% of the volume fraction of the paired active substance solution, and uniformly mixing the solution to obtain an anode electrolyte 004.
The cathode electrolyte solution 00 containing cathode pairing active substances in the cathode liquid storage tank 0085. The cathode electrochromic active substance adopts methyl viologen solution with the concentration of 0.1mol/L and adopts 1mol/LNaClO 4 As the supporting electrolyte, the solvent is water.
Processing polypropylene into a transparent device with a curved surface by adopting a blow molding integrated preparation process to serve as a cathode side transparent cavity 018, wherein the volume of the cavity is 0.1m 2 The radius of the channels on the top and bottom substrates was 0.001m.
The energy storage implementation manner of the embodiment is as follows:
the semiconductor structure of the photocathode is p + -n-n + Si-Ti-Pt, when the sunlight irradiates the photocathode, the photo-generated carriers are generated on the PN junction of the semiconductor structure, and the holes are formed by n + Region flow direction p + Region, electron is composed of + Zone flow direction n + And at the moment, photo-generated electrons are captured by electroactive substances on a cathode electrolyte interface, so that methyl viologen is subjected to reduction reaction, and the common electrode on the anode side loses electrons so that tris (4, 7-bis (hydroxymethyl) -1, 10-phenanthroline iron is subjected to oxidation reaction, so that the conversion from light energy to chemical energy is realized in the process, and the energy efficiency of the photovoltaic flow battery reaches 90%.
The color-changing energy-saving implementation manner of the embodiment is as follows:
when light is emitted, the No. 4 pump 012 is turned on, the flow rate of the pump is set to be 100mL/min, at the moment, a part of catholyte is directly led into the transparent cavity, methyl viologen is continuously reduced by photoproduction electrons, the color of the solution is gradually changed from colorless in an oxidation state to blue in a reduction state, the average transmittance of the transparent cavity at 450-452nm is 4.1%, and the blue transparent cavity blocks the sun outside, so that the temperature of the indoor part is prevented from rising, and the use of refrigeration equipment such as an indoor air conditioner is reduced. When no light is emitted, the liquid flow battery can be used as a photovoltaic liquid flow battery, the working principle is the same as that of a common liquid flow battery, when the liquid flow battery outputs electric energy by external load, methyl viologen in the cathode electrolyte is subjected to oxidation reaction, the color of the solution is gradually changed from reduction state blue to oxidation state colorless, and the average transmittance of the transparent cavity at 450-452nm is 95%.
Example 3: electrolyte on two sides of PV (photovoltaic) anode and photocathode simultaneously changes color
As shown in fig. 5 and 6, the electrochromic device includes a photo anode 001, a photo cathode 002, an anode reservoir 007, a cathode reservoir 008, an anode side transparent cavity 017, and a cathode side transparent cavity 018. A diaphragm 006 is provided between the photo anode 001 and the photo cathode 002, and a lead 014, a switch 015, and a load 016 are connected thereto.
The anode liquid storage tank 007 is connected to the bottom of the light anode 001 through a liquid conveying pipeline 013 and a No. 1 pump 009, and is connected to the anode liquid storage tank 007 through the liquid conveying pipeline 013 after the electrochemical reaction is finished, so that the operation is performed in a reciprocating manner. Meanwhile, the anode liquid storage tank 007 is connected to the anode side transparent cavity 017 through a liquid conveying pipeline 013 and a No. 3 pump 011, and after the anode side transparent cavity 017 is filled with electrolyte, the electrolyte flows into the anode liquid storage tank 007 through the liquid conveying pipeline 013 to circulate in a reciprocating mode.
The cathode liquid storage tank 008 is connected to the bottom of the photocathode 002 through a liquid conveying pipeline 013 and a No. 2 pump 010, and is connected to the cathode liquid storage tank 008 through the liquid conveying pipeline 013 after the electrochemical reaction is finished, so that the operation is repeated. Meanwhile, the cathode liquid storage tank 008 is connected to the cathode transparent cavity 018 through a liquid conveying pipeline 013 and a No. 4 pump 012, and after the electrolyte in the cathode transparent cavity 018 is filled, the electrolyte flows into the cathode liquid storage tank 008 through the liquid conveying pipeline 013, so that the electrolyte is circulated in a reciprocating mode.
An anolyte 004 containing a phenanthroline iron complex is arranged in the anode liquid storage tank 007. Preparing 0.01mol/L solution by adopting a tris (4, 7-hydroxymethyl) -1, 10-phenanthroline iron complex and deionized water, and adding a supporting electrolyte NH 4 And Cl, wherein the concentration of the supporting electrolyte in the aqueous solution of tris (4, 7-bis-hydroxymethyl) -1, 10-phenanthroline iron complex is 0.1mol/L, the supporting electrolyte is fully stirred and uniformly mixed, then methanol accounting for 5% of the volume fraction of the solution is added, and the solution is uniformly mixed to obtain the anolyte.
Inside the cathode reservoir 008 is a cathode electrolyte 005 containing a cathode partner active material. The cathode electrochromic active substance adopts methyl viologen solution with the concentration of 0.01mol/L and adopts 0.1mol/LNa 2 SO 4 As the supporting electrolyte, the solvent is water.
Processing transparent resin into transparent devices with planar surface by adopting an extrusion molding integrated preparation process, wherein the transparent devices are used as an anode side transparent cavity 017 and a cathode side transparent cavity 018, and the cavities have a volume of 0.001m 2 The radius of the channels on the top and bottom substrates was 0.0001m.
The energy storage implementation manner of the embodiment is as follows:
the semiconductor structure of the photo-anode is n + -n-p + Si-Ti-Pt, the semiconductor structure of the photocathode being p + -n-n + Si-Ti-Pt, when the sunlight irradiates the photo anode and the photo cathode simultaneously, the photo-generated carriers are generated on the PN junction of the semiconductor structure, and the holes are formed by n + Region flow direction p + Region, electron is composed of + Zone flow direction n + At the moment, a photoproduction hole generated at one side of the photoanode is captured by an electroactive substance on an anolyte interface, so that the tris (4, 7-hydroxymethyl) -1, 10-phenanthroline iron complex is subjected to an oxidation reaction, a photoproduction electron generated at one side of the photocathode is captured by the electroactive substance on a catholyte interface, so that methyl viologen is subjected to a reduction reaction, and the photoproduction electron generated at one side of the photoanode and a photoproduction hole generated at one side of the photocathode are subjected to 22553extinction through an external circuit, so that the conversion from light energy to chemical energy is realized in the process, and the energy efficiency of the battery reaches 92 percent.
The color-changing energy-saving implementation manner of the embodiment is as follows:
when light is emitted, the No. 3 pump 011 and the No. 4 pump 012 are turned on, the flow rate of the pumps is set to be 50mL/min, at the moment, a part of the anode electrolyte and a part of the cathode electrolyte are respectively and directly introduced into the two transparent cavities, the photo-generated holes on one side of the photo-anode continuously oxidize the tris (4, 7-hydroxymethyl) -1, 10-phenanthroline iron complex, the color of the solution is gradually changed from the colorless in the reduction state to the red in the oxidation state, the average transmittance of the transparent cavities at 508-520nm is 8.3%, at the moment, the red color change device can block the sunlight outside, so that the temperature of the indoor part is prevented from rising, and the use of refrigeration equipment such as an indoor air conditioner is reduced. The photoproduction electrons on one side of the photocathode continuously reduce methyl viologen, the color of the solution is gradually changed from colorless in an oxidation state to blue in a reduction state, the average transmittance of the transparent cavity at 450-452nm is 4.1%, and the blue color-changing device can block the sun outside, so that the temperature of the indoor part is prevented from rising, and the use of refrigeration equipment such as an indoor air conditioner is reduced. When no light is emitted, the embodiment can be used as a photovoltaic flow battery, the working principle is the same as that of a common flow battery, the flow battery outputs electric energy by external load, the tris (4, 7-bis-hydroxymethyl) -1, 10-phenanthroline iron complex in the anolyte undergoes reduction reaction, the color of the solution is gradually changed from red in an oxidation state to colorless in a reduction state, and the average transmittance of the electrochromic device at the position of 508-520nm is 93%. And (3) carrying out oxidation reaction on methyl viologen in the catholyte, gradually changing the color of the solution from reduced blue to oxidized colorless, and ensuring that the average transmittance of the transparent cavity at 450-452nm is 95%.
As shown in fig. 7, in the above embodiment, the transparent cavity in the electrochromic device can be used as architectural glass, and of course, the electrochromic device can also be applied to other occasions requiring color change, and has the effects of energy storage, color change, energy saving, and the like.
The present invention has been described in terms of specific examples, which are provided to aid understanding of the invention and are not intended to be limiting. For a person skilled in the art to which the invention pertains, several simple deductions, modifications or substitutions may be made according to the idea of the invention.
Claims (10)
1. The phenanthroline iron complex is characterized in that:
the phenanthroline iron complex is a tri (4, 7-bis-hydroxymethyl) -1, 10-phenanthroline iron complex, and has the structure:
wherein n is 2 or 3.
2. The method for preparing a phenanthroline complex according to claim 1, wherein the phenanthroline complex is prepared by using the following steps:
the method comprises the following steps:
4, 7-dimethylol-1, 10 phenanthroline ligand is obtained by taking 4, 7-dimethyl-1, 10 phenanthroline as a raw material and adopting a hydrothermal synthesis method;
reacting 4, 7-dihydroxymethyl-1, 10 phenanthroline ligand with FeCl under a neutral condition 2 ·4H 2 And (3) uniformly mixing the O to obtain the tri (4, 7-hydroxymethyl) -1, 10-phenanthroline iron complex.
3. The use of a phenanthroline complex according to claim 1 in electrochromism, wherein the phenanthroline complex is characterized in that:
the application is to construct an electrochromic device based on the phenanthroline iron complex.
4. Use according to claim 3, characterized in that:
the electrochromic device comprises a photo-anode (001), a common electrode (003), an anode liquid storage tank (007), a cathode liquid storage tank (008) and an anode side transparent cavity (017), wherein the common electrode (003) is a cathode;
the anode liquid storage tank (007) is connected to the light anode (001) and the anode side transparent cavity (017) through a liquid conveying pipeline (013), and the light anode (001) and the anode side transparent cavity (017) are connected back to the anode liquid storage tank (007) through the liquid conveying pipeline (013);
the cathode and the cathode liquid storage tank (008) form a circulation through a liquid conveying pipeline (013);
the electrolyte comprises an anolyte (004) containing the phenanthroline iron complex in an anode liquid storage tank (007), and a catholyte (005) containing methyl viologen in a cathode liquid storage tank (008).
5. Use according to claim 3, characterized in that:
the electrochromic device comprises a common electrode (003), a photocathode (002), an anode liquid storage tank (007), a cathode liquid storage tank (008) and a cathode side transparent cavity (018), wherein the common electrode (003) is an anode;
the cathode liquid storage tank (008) is connected into the photocathode (002) and the cathode side transparent cavity (018) through a liquid conveying pipeline (013), and the photocathode (002) and the cathode side transparent cavity (018) are connected back to the cathode liquid storage tank (008) through the liquid conveying pipeline (013);
the anode and the anode liquid storage tank (007) form a circulation through a liquid conveying pipeline (013);
the electrolyte comprises an anolyte (004) containing the phenanthroline iron complex in an anode liquid storage tank (007), and a catholyte (005) containing methyl viologen in a cathode liquid storage tank (008).
6. Use according to claim 3, characterized in that:
the electrochromic device comprises a photo-anode (001), a photo-cathode (002), an anode liquid storage tank (007), a cathode liquid storage tank (008), an anode side transparent cavity (017) and a cathode side transparent cavity (018);
the anode liquid storage tank (007) is connected into the light anode (001) and the anode side transparent cavity (017) through a liquid conveying pipeline (013), and the light anode (001) and the anode side transparent cavity (017) are connected back into the anode liquid storage tank (007) through the liquid conveying pipeline (013);
the cathode liquid storage tank (008) is connected into the photocathode (002) and the cathode side transparent cavity (018) through a liquid conveying pipeline (013), and the photocathode (002) and the cathode side transparent cavity (018) are connected back to the cathode liquid storage tank (008) through the liquid conveying pipeline (013);
the electrolyte solution storage tank (007) is filled with an anolyte (004) containing the phenanthroline iron complex, and the cathode liquid storage tank (008) is filled with a catholyte (005) containing methyl viologen.
7. Use according to claim 4, 5 or 6, characterized in that:
the process for obtaining the anolyte (003) is as follows:
mixing a tri (4, 7-bis-hydroxymethyl) -1, 10-phenanthroline iron complex with water to obtain a phenanthroline iron complex solution;
adding supporting electrolyte into the phenanthroline iron complex solution, and stirring and mixing;
adding a solvent to obtain the anolyte (003).
8. Use according to claim 7, characterized in that:
the catholyte (004) is obtained by the following steps:
mixing methyl viologen with water to obtain a methyl viologen solution;
adding a supporting electrolyte into the methyl viologen solution to obtain the catholyte (004).
9. Use according to claim 8, characterized in that:
the supporting electrolyte is selected from NaClO 4 、KNO 3 、KCl、NaCl、Na 2 SO 4 、KClO 4 、NH 4 Cl、K 2 HPO 4 ；
The solvent is selected from acetonitrile, ethanol and methanol.
10. Use according to claim 6, characterized in that:
the photo anode (001) and the photo cathode (002) are both semiconductor photo electrodes with PN junctions, and the semiconductor structure of the photo anode (001) is n + -n-p + -Si-Ti-Pt, the semiconductor structure of the photocathode (002) being p + -n-n + -Si-Ti-Pt。
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