CN109143713A - A kind of TPA-TPY-Fe2+Metal complex nano flake and the preparation method and application thereof - Google Patents
A kind of TPA-TPY-Fe2+Metal complex nano flake and the preparation method and application thereof Download PDFInfo
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- CN109143713A CN109143713A CN201810680425.XA CN201810680425A CN109143713A CN 109143713 A CN109143713 A CN 109143713A CN 201810680425 A CN201810680425 A CN 201810680425A CN 109143713 A CN109143713 A CN 109143713A
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- G—PHYSICS
- G02—OPTICS
- G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
- G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
- G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour
- G02F1/15—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour based on an electrochromic effect
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K9/00—Tenebrescent materials, i.e. materials for which the range of wavelengths for energy absorption is changed as a result of excitation by some form of energy
- C09K9/02—Organic tenebrescent materials
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
- C09K2211/00—Chemical nature of organic luminescent or tenebrescent compounds
- C09K2211/18—Metal complexes
- C09K2211/187—Metal complexes of the iron group metals, i.e. Fe, Co or Ni
Abstract
The invention discloses a kind of TPA-TPY-Fe2+Metal complex nano flake, the TPA-TPY-Fe2+Metal complex nano flake is specifically prepared as follows: by three (4- (4 ' -2,2 ': 6 ', 2 "-terpyridyl) phenyl) amine be dissolved in be configured in methylene chloride concentration be 0.05~0.5mmol/L methylene chloride solution A, into the solution A be added buffer deionized water stratification after add Fe (BF4)2Aqueous solution, stand to liquid liquid layering interfaces generate target product TPA-TPY-Fe2+Metal complex nano flake.Metal complex nano thin-film of the present invention has excellent electrochromic property, such as change and possess high contrast stability to the multiple color of grass green again from purple to Chinese red as voltage changes to exist, preparation method is simple, does not need exacting terms.
Description
Technical field
The present invention relates to a kind of TPA-TPY-Fe2+Metal complex nano flake and the preparation method and application thereof.
Background technique
Electrochromism has the advantage that as a kind of novel research field: suitable operating temperature range is big；Energy consumption
It is small, it is easy to match with integrated circuit；Color tunable range is very wide and can realize continuous discoloration；With memory function, discoloration is being opened
It can still be kept in the state of road.Electrochromic material is divided into organic electrochromic material and inorganic electrochromic material, and organic
Electrochromic material is divided into small organic molecule electrochromic material and conducting polymer electrochromic material again.Conducting polymer electricity
Cause off-color material because the response speed that its color abundant shows and is exceedingly fast widely is studied, but its stability is relatively inorganic
Electrochromic material but has biggish deficiency.
Ligand is called metal complex by the complex that coordinate bond is formed with metallic atom or ion.Metal complex by
In its preparation, simple and its special construction causes it with extraordinary and quite attracting electrochemistry and Photophysics, because
This, receives significant attention and studies in photovoltaic applications field.
Nano flake is a kind of new material with two-dimensional structure, and outstanding person therein is graphene, is had more
The outstanding property of kind, such as high and balanced carrier mobility.The successful preparation of graphene and its excellent property make people
Increase the dynamics for finding other nano flakes, such as metal oxide, metal sulfide and metal hydroxides.In the recent period,
It is that the nano flake that component is formed even more has obtained extensive concern by molecule, atom and ion.
Summary of the invention
One of the objects of the present invention is to provide one kind by three (4- (4 ' -2,2 ': 6 ', 2 "-terpyridyl) phenyl) amine
(TPA-TPY) and metal complex nano flake ferrous ion preparation and with excellent photoelectric properties it, while lying also in and mentioning
For its a kind of simple preparation method.
The present invention adopts the following technical scheme that in order to solve the technical problem
The TPA-TPY-Fe of one kind (4- (4 ' -2,2 ': 6 ', 2 "-terpyridyl) phenyl) amine and ferrous ion preparation by three2+
Metal complex nano flake, the TPA-TPY-Fe2+Metal complex nano flake is specifically prepared as follows:
(4- (4 ' -2,2 ': 6 ', 2 "-terpyridyl) phenyl) amine is dissolved in methylene chloride that be configured to concentration be 0.05 by three
The solution A of~0.5mmol/L methylene chloride adds after buffer deionized water stratification is added into the solution A
Fe(BF4)2Aqueous solution, stand to liquid liquid layering interfaces generate target product TPA-TPY-Fe2+Metal complex nanometer thin
Piece；The additional amount of the deionized water is calculated as 0.3~3mL/mL (preferably 1mL/mL) with the volume of the solution A；It is described
Fe (BF4)2The concentration of aqueous solution is 25~100mmol/L；Fe (the BF4)2The additional amount of aqueous solution is with described molten
The volume of liquid A is calculated as 0.3~3mL/mL (preferably 1mL/mL).
Further, the concentration of the solution A is preferably 0.1mmol/L.
Further, the Fe (BF4)2The concentration of aqueous solution be preferably 50mmol/L.
Further, the time of repose is preferably 4~10 days, and more preferably 8 days.
Further, the present invention provides the metal complex nano flake and can be used for preparing electrochromic material.
The present invention EDS show wherein constituent content prove its be by ligand complex by way of form nano thin-film,
Its photophysical property is characterized by uv-visible absorption spectroscopy, its electrochromism and stabilization are characterized by electrochemical workstation
Performance.
Compared with prior art, the beneficial effects are mainly reflected as follows:
(1) of the present invention preparation method is simple, does not need exacting terms.
(2) metal complex nano thin-film of the present invention has excellent electrochromic property, such as with voltage
Change to exist and changes and possess high contrast stability to the multiple color of grass green again from purple to Chinese red.
(3) its electrochromic property having of metal complex of the present invention can be used for the fields such as smart window.
Detailed description of the invention
Fig. 1 is the pictorial diagram that metal complex nano flake made from embodiment 1 is attached to ITO.
Fig. 2 be metal complex nano flake made from embodiment 1 one of raw material three (4- (4 ' -2,2 ': 6 ', 2 "-three
Bipyridyl) phenyl) amine chemical structural formula.
Fig. 3 is the preparation method schematic diagram of metal complex nano flake made from embodiment 1.
Fig. 4 is the color diagram in 0V, 1.3V and 1.6V respectively of metal complex nano flake made from embodiment 1.
Fig. 5 is the UV absorption figure of metal complex nano flake made from embodiment 1.
Fig. 6 is the contrast figure of metal complex nano flake made from embodiment 1.
Fig. 7 is the contrast stability diagram of metal complex nano flake made from embodiment 1.
Fig. 8 is the response time figure of metal complex nano flake made from embodiment 1.
Fig. 9 is the contrast stability diagram of metal complex nano flake made from embodiment 2.
Specific embodiment
The present invention is described further combined with specific embodiments below, but protection scope of the present invention is not limited in
This.
Embodiment 1
The dichloromethane solution 2ml of 0.1mmol/L tri- (4- (4 ' -2,2 ': 6 ', 2 "-terpyridyl) phenyl) amine is poured into
In 10ml beaker, the rear 2ml deionized water that is added forms liquid-liquid interface, adds 50mmol/L dissolved with Fe (BF4)2Deionized water
Solution 2ml then stands 8 days, generates metal complex nano flake in liquid-liquid interface, is affixed to ITO using the method for fishing for
On glass.
EDS test is carried out to metal complex nano flake prepared by embodiment 1, testing result is as shown in table 1, wherein N:
Fe=5.2 is close to its theoretical proportions N:Fe=6, (4- (4 ' -2,2 ': 6 ', the 2 "-terpyridyl) phenyl that illustrates three) amine and ferrous
Ion passes through cooperation complexing really and forms metal complex nano flake.
Table 1 is the EDS table of metal complex nano flake made from embodiment 1
The metal complex nano flake prepared to embodiment 1 is supported on ito glass, is carried out in three-electrode system purple
Outer absorption test, as shown in figure 5, the absorption value under different voltages at about 450nm, 580nm and 780nm all occurs obviously
Change, illustrates that laminated film is implicitly present in electrochromism phenomenon.
The contrast for carrying out three-electrode system to metal complex nano flake prepared by embodiment 1 is tested, such as Fig. 6, thoroughly
The rate maximum difference of mistake is about 80%, i.e., contrast maximum value is about 80%, illustrates that the discoloration contrast of laminated film is quite high.
The metal complex nano flake prepared to embodiment 1 is supported on ito glass, is carried out in three-electrode system pair
Than degree stability test, as shown in fig. 7, after loop test 2000s contrast do not have it is any will reduce downward trend,
Illustrate that laminated film has quite outstanding contrast stability.
The three-electrode system is negative for working electrode and is loaded with the ito glass of metal complex nano flake, to electrode
For platinum electrode, reference electrode is Ag/AgCl electrode, and the electrolyte used is that the acetonitrile of the tetrabutylammonium perchlorate amine of 0.1mol/L is molten
Liquid.Test voltage range is 0-1.6V, and sweeping speed is 0.1V/s.
The UV absorption test, contrast test and contrast stability test are all by UV absorption instrument and electricity
For chem workstation come what is realized, test wavelength range is 300nm-1100nm, UV absorption instrument model UV-1800, electrochemistry
Work station model chi660e.
Embodiment 2
The dichloromethane solution 1ml of 0.05mmol/L tri- (4- (4 ' -2,2 ': 6 ', 2 "-terpyridyl) phenyl) amine is poured into
In 10ml beaker, the rear 3ml deionized water that is added forms liquid-liquid interface, adds 25mmol/L dissolved with Fe (BF4)2Deionized water
Solution 3ml then stands 8 days, generates metal complex nano flake in liquid-liquid interface, is affixed to ITO using the method for fishing for
On glass.
The metal complex nano flake prepared to embodiment 2 is supported on ito glass, is carried out in three-electrode system pair
It is tested than degree, as a result as shown in figure 9, transmissivity maximum difference is about 18%, i.e., contrast maximum value is about 18%, is illustrated multiple
The discoloration contrast for closing film is more undesirable.
Embodiment 3
The dichloromethane solution 3ml of 0.5mmol/L tri- (4- (4 ' -2,2 ': 6 ', 2 "-terpyridyl) phenyl) amine is poured into
In 10ml beaker, the rear 1ml deionized water that is added forms liquid-liquid interface, adds 100mmol/L dissolved with Fe (BF4)2Deionized water
Solution 1ml after then standing 8 days, is generated metal complex nano flake in liquid-liquid interface, is affixed to using the method for fishing for
On ito glass.
Claims (8)
1. a kind of TPA-TPY-Fe2+Metal complex nano flake, it is characterised in that: the TPA-TPY-Fe2+Metal complex
Object nano flake is specifically prepared as follows:
By three (4- (4 ' -2,2 ': 6 ', 2 "-terpyridyl) phenyl) amine be dissolved in methylene chloride be configured to concentration be 0.05~
The solution A of 0.5mmol/L methylene chloride adds Fe (BF after deionized water stratification is added into the solution A4)2's
Aqueous solution stands in liquid liquid layering interfaces and generates target product TPA-TPY-Fe2+Metal complex nano flake；It is described go from
The additional amount of sub- water is calculated as 0.3~3mL/mL with the volume of the solution A；Fe (the BF4)2The concentration of aqueous solution is 25
~100mmol/L；Fe (the BF4)2The additional amount of aqueous solution is calculated as 0.3~3mL/mL with the volume of the solution A.
2. TPA-TPY-Fe as described in claim 12+Metal complex nano flake, it is characterised in that: the solution A
Concentration is 0.1mmol/L.
3. TPA-TPY-Fe as described in claim 12+Metal complex nano flake, it is characterised in that: the Fe (BF4)2
Aqueous solution concentration be 50mmol/L.
4. TPA-TPY-Fe as described in claim 12+Metal complex nano flake, it is characterised in that: when the described standing
Between be 4~10 days.
5. TPA-TPY-Fe as claimed in claim 42+Metal complex nano flake, it is characterised in that: when the described standing
Between be 8 days.
6. TPA-TPY-Fe as described in claim 12+Metal complex nano flake, it is characterised in that: the deionized water
Additional amount 1mL/mL is calculated as with the volume of the solution A.
7. TPA-TPY-Fe as claimed in claim 1 or 32+Metal complex nano flake, it is characterised in that: the Fe
(BF4)2The additional amount of aqueous solution is calculated as 1mL/mL with the volume of the solution A.
8. TPA-TPY-Fe as described in claim 12+Metal complex nano flake can be used for preparing electrochromic material.
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| CN201810680425.XA CN109143713B (en) | 2018-06-27 | 2018-06-27 | TPA-TPY-Fe2+Metal complex nanosheets and uses thereof |
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| CN201810680425.XA CN109143713B (en) | 2018-06-27 | 2018-06-27 | TPA-TPY-Fe2+Metal complex nanosheets and uses thereof |
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| CN109143713B CN109143713B (en) | 2021-05-11 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112250881A (en) * | 2020-10-23 | 2021-01-22 | 南京林业大学 | Alkyl chain bridged terpyridyl iron coordination polymer electrochromic material |
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| US7230107B1 (en) * | 2004-12-29 | 2007-06-12 | E. I. Du Pont De Nemours And Company | Metal quinoline complexes |
| CN101002506A (en) * | 2004-03-31 | 2007-07-18 | E.I.内穆尔杜邦公司 | Triarylamine compounds for use as charge transport materials |
| US20070181874A1 (en) * | 2004-12-30 | 2007-08-09 | Shiva Prakash | Charge transport layers and organic electron devices comprising same |
| CN101484386A (en) * | 2006-07-13 | 2009-07-15 | 东海旅客铁道株式会社 | Coating liquid, titanium oxide thin-film formed using coating liquid, and method of forming the same |
| CN103492402B (en) * | 2011-02-25 | 2017-04-12 | 洛桑联邦理工学院 | Improved redox couple for electrochemical and optoelectronic devices |
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| CN101002506A (en) * | 2004-03-31 | 2007-07-18 | E.I.内穆尔杜邦公司 | Triarylamine compounds for use as charge transport materials |
| US7230107B1 (en) * | 2004-12-29 | 2007-06-12 | E. I. Du Pont De Nemours And Company | Metal quinoline complexes |
| US20070181874A1 (en) * | 2004-12-30 | 2007-08-09 | Shiva Prakash | Charge transport layers and organic electron devices comprising same |
| CN101484386A (en) * | 2006-07-13 | 2009-07-15 | 东海旅客铁道株式会社 | Coating liquid, titanium oxide thin-film formed using coating liquid, and method of forming the same |
| CN103492402B (en) * | 2011-02-25 | 2017-04-12 | 洛桑联邦理工学院 | Improved redox couple for electrochemical and optoelectronic devices |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112250881A (en) * | 2020-10-23 | 2021-01-22 | 南京林业大学 | Alkyl chain bridged terpyridyl iron coordination polymer electrochromic material |
| CN112250881B (en) * | 2020-10-23 | 2022-06-14 | 南京林业大学 | Alkyl chain bridged terpyridyl iron coordination polymer electrochromic material |
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