CN109143713B - TPA-TPY-Fe2+Metal complex nanosheets and uses thereof - Google Patents

TPA-TPY-Fe2+Metal complex nanosheets and uses thereof Download PDF

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CN109143713B
CN109143713B CN201810680425.XA CN201810680425A CN109143713B CN 109143713 B CN109143713 B CN 109143713B CN 201810680425 A CN201810680425 A CN 201810680425A CN 109143713 B CN109143713 B CN 109143713B
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CN109143713A (en
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张�诚
蒯羽
李维军
戴玉玉
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Zhejiang University of Technology ZJUT
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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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    • 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
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
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    • 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 disclosesTPA-TPY-Fe2+Metal complex nano-flakes, said TPA-TPY-Fe2+The metal complex nanosheets are specifically prepared as follows: dissolving tris (4- (4 '-2, 2': 6 ', 2' -terpyridyl) phenyl) amine in dichloromethane to prepare a solution A with the concentration of 0.05-0.5 mmol/L dichloromethane, adding a buffer solution into the solution A, standing for layering, and then adding Fe (BF) into the solution A4)2Standing the aqueous solution until a liquid-liquid layered interface generates a target product TPA-TPY-Fe2+Metal complex nanoflakes. The metal complex nano film has excellent electrochromic performance, such as various color changes from purple to orange to turquoise along with voltage change and extremely high contrast stability, and the preparation method is simple and easy to implement and does not need harsh conditions.

Description

TPA-TPY-Fe2+Metal complex nanosheets and uses thereof
Technical Field
The invention relates to TPA-TPY-Fe2+A metal complex nano-flake, a preparation method and application thereof.
Background
Electrochromic is a new research field, and has the following advantages: the suitable working temperature range is large; the energy consumption is low, and the matching with an integrated circuit is easy; the color adjustable range is wide and continuous color change can be realized; has memory function, and the color change can be maintained in open circuit state. Electrochromic materials are classified into organic electrochromic materials and inorganic electrochromic materials, and organic electrochromic materials are also classified into organic micromolecular electrochromic materials and conductive polymer electrochromic materials. The conductive polymer electrochromic material is widely researched due to abundant color display and extremely fast response speed, but the stability of the conductive polymer electrochromic material is greatly insufficient compared with that of an inorganic electrochromic material.
The complex formed by the ligand through coordination bond with a metal atom or ion is called a metal complex. Metal complexes have received extensive attention and research in the field of photovoltaic applications because of their simple preparation and their particular structure, which leads to unusual and rather attractive electrochemical and photophysical properties.
Nanoflakes are a new type of material with a two-dimensional structure, superior to graphene, having a variety of excellent properties, such as high and balanced carrier mobility. The successful preparation of graphene and its excellent properties have made it increasingly more attractive to find other nanoflakes, such as metal oxides, metal sulfides and metal hydroxides. Recently, nanoflakes formed from molecular, atomic and ionic components have gained much attention.
Disclosure of Invention
An object of the present invention is to provide a metal complex nanosheet prepared from tris (4- (4 ' -2,2 ': 6 ', 2 "-terpyridyl) phenyl) amine (TPA-TPY) and ferrous ions and having excellent photoelectric properties, and also to provide a simple preparation method thereof.
The invention adopts the following technical scheme for solving the technical problems:
TPA-TPY-Fe prepared from tri (4- (4 '-2, 2': 6 ', 2' -terpyridyl) phenyl) amine and ferrous ion2+Metal complex nanoplatelets, said TPA-TPY-Fe2+The metal complex nanosheets are specifically prepared as follows:
dissolving tris (4- (4 '-2, 2': 6 ', 2' -terpyridyl) phenyl) amine in dichloromethane to prepare a solution A with the concentration of 0.05-0.5 mmol/L dichloromethane, adding a buffer solution into the solution A, standing for layering, and then adding Fe (BF) into the solution A4)2Standing the aqueous solution until a target product TPA-TPY-Fe is generated at a liquid-liquid layered interface2+Metal complex nanoplatelets; the adding amount of the deionized water is 0.3-3 mL/mL (preferably 1mL/mL) based on the volume of the solution A; said Fe (BF)4)2The concentration of the aqueous solution is 25-100 mmol/L; said Fe (BF)4)2The adding amount of the aqueous solution is 0.3-3 mL/mL (preferably 1mL/mL) based on the volume of the solution A.
Further, the concentration of the solution A is preferably 0.1 mmol/L.
Further, said Fe (BF)4)2The concentration of the aqueous solution of (4) is preferably 50 mmol/L.
Further, the standing time is preferably 4-10 days, and more preferably 8 days.
Furthermore, the invention provides the metal complex nano-flake which can be used for preparing electrochromic materials.
The EDS shows that the element content proves that the nano-film is formed in a coordination complexing mode, the photophysical property of the nano-film is represented by an ultraviolet-visible light absorption spectrum, and the electrochromism and stability performance of the nano-film are represented by an electrochemical workstation.
Compared with the prior art, the invention has the following beneficial effects:
(1) the preparation method is simple and easy to implement, and does not need harsh conditions.
(2) The metal complex nano-film has excellent electrochromic performance, such as various color changes from purple to orange to turquoise along with voltage change and extremely high contrast stability.
(3) The metal complex provided by the invention has electrochromic property and can be used in the fields of intelligent windows and the like.
Drawings
FIG. 1 is a diagram showing a metal complex nanosheet prepared in example 1 attached to ITO.
FIG. 2 shows the chemical structure of tris (4- (4 '-2, 2': 6 ', 2' -terpyridine) phenyl) amine, one of the starting materials for the metal complex nanosheets prepared in example 1.
FIG. 3 is a schematic view of a method for preparing metal complex nanosheets as obtained in example 1.
FIG. 4 is a color chart of the metal complex nanosheets produced in example 1 at 0V, 1.3V and 1.6V, respectively.
FIG. 5 is a UV absorption diagram of the metal complex nanosheets produced in example 1.
FIG. 6 is a contrast chart of the metal complex nanosheets produced in example 1.
Fig. 7 is a graph showing contrast stability of the metal complex nanosheets prepared in example 1.
FIG. 8 is a graph showing response time of the metal complex nanosheets produced in example 1.
Fig. 9 is a graph showing contrast stability of the metal complex nanosheets prepared in example 2.
Detailed Description
The invention will be further described with reference to specific examples, but the scope of the invention is not limited thereto.
Example 1
2ml of 0.1mmol/L dichloromethane solution of tris (4- (4 '-2, 2': 6 ', 2' -terpyridyl) phenyl) amine is poured into a 10ml beaker, 2ml deionized water is added to form a liquid-liquid interface, and 50mmol/L dissolved Fe (BF) is added4)22ml of the deionized water solution, standing for 8 days, generating metal complex nano sheets on a liquid-liquid interface, and attaching the metal complex nano sheets to the ITO glass by adopting a fishing method.
The metal complex nanosheets prepared in example 1 were subjected to EDS testing and the results are shown in table 1, wherein N: fe ═ 5.2 approaches its theoretical ratio N: fe ═ 6, indicating that tris (4- (4 ' -2,2 ': 6 ', 2 "-terpyridine) phenyl) amine does form metal complex nanoplatelets with ferrous ions through complexation.
Table 1 is an EDS chart of the metal complex nanosheets produced in example 1
Figure GDA0002893458010000041
Figure GDA0002893458010000051
The metal complex nano-flake prepared in example 1 is loaded on ITO glass, and an ultraviolet absorption test is performed in a three-electrode system, as shown in FIG. 5, the absorption values at about 450nm, 580nm and 780nm under different voltages are obviously changed, which indicates that the composite film really has electrochromic phenomenon.
The contrast test of the three-electrode system was performed on the metal complex nanosheets prepared in example 1, as shown in fig. 6, and the maximum difference in transmittance was about 80%, i.e., the maximum contrast was about 80%, indicating that the color change contrast of the composite film was relatively high.
The metal complex nanosheets prepared in example 1 were supported on ITO glass and subjected to a contrast stability test in a three-electrode system, as shown in fig. 7, the contrast did not have any tendency to decrease in contrast after 2000s of the cycle test, indicating that the composite film had considerably superior contrast stability.
The three-electrode system is characterized in that a working electrode is ITO glass loaded with metal complex nano sheets, a counter electrode is a platinum electrode, a reference electrode is an Ag/AgCl electrode, and the electrolyte is 0.1mol/L acetonitrile solution of tetrabutyl ammonium perchlorate. The test voltage range is 0-1.6V, and the sweep rate is 0.1V/s.
The ultraviolet absorption test, the contrast test and the contrast stability test are realized by an ultraviolet absorption instrument and an electrochemical workstation, the test wavelength range is 300nm-1100nm, the model of the ultraviolet absorption instrument is UV-1800, and the model of the electrochemical workstation is chi660 e.
Example 2
0.05mmol/L of tris (4- (4 '-2, 2': 6 ', 2' -terpyridyl) phenyl) amine in dichloromethane (1 ml) is poured into a 10ml beaker, then 3ml of deionized water is added to form a liquid-liquid interface, and 25mmol/L of dissolved Fe (BF) is added4)23ml of the deionized water solution, standing for 8 days, generating metal complex nano sheets on a liquid-liquid interface, and attaching the metal complex nano sheets to the ITO glass by adopting a fishing method.
When the metal complex nano-flake prepared in example 2 is loaded on ITO glass and subjected to a contrast test in a three-electrode system, the result is shown in fig. 9, where the maximum transmittance difference is about 18%, i.e. the maximum contrast is about 18%, which indicates that the discoloration contrast of the composite film is less desirable.
Example 3
3ml of a 0.5mmol/L dichloromethane solution of tris (4- (4 '-2, 2': 6 ', 2' -terpyridyl) phenyl) amine was poured into a 10ml beaker, 1ml deionized water was added to form a liquid-liquid interface, and 100mmol/L solution of Fe (BF) dissolved therein was added4)21ml of the deionized water solution, standing for 8 days, generating a metal complex nano sheet on a liquid-liquid interface, and attaching the metal complex nano sheet to the ITO glass by adopting a fishing method.

Claims (8)

1. TPA-TPY-Fe2+Metal complex nanoplatelets characterized by: the TPA-TPY-Fe2+The metal complex nanosheets are specifically prepared as follows:
dissolving tris (4- (4 '-2, 2': 6 ', 2' -terpyridyl) phenyl) amine in dichloromethane to prepare a solution A with the concentration of 0.05-0.5 mmol/L dichloromethane, adding deionized water into the solution A, standing for layering, and then adding Fe (BF) into the solution A4)2Standing the aqueous solution until a target product TPA-TPY-Fe is generated at a liquid-liquid layered interface2+Metal complex nanoplatelets; the addition amount of the deionized water is 0.3-3 mL/mL calculated by the volume of the solution A; said Fe (BF)4)2The concentration of the aqueous solution is 25-100 mmol/L; said Fe (BF)4)2The adding amount of the aqueous solution is 0.3-3 mL/mL based on the volume of the solution A.
2. The TPA-TPY-Fe as in claim 12+Metal complex nanoplatelets characterized by: the concentration of the solution A is 0.1 mmol/L.
3. The TPA-TPY-Fe as in claim 12+Metal complex nanoplatelets characterized by: said Fe (BF)4)2The concentration of the aqueous solution of (4) was 50 mmol/L.
4. The TPA-TPY-Fe as in claim 12+Metal complex nanoplatelets characterized by: the standing time is 4-10 days.
5. TPA-TPY-Fe as in claim 42+Metal complex nanoplatelets characterized by: the standing time is 8 days.
6. The TPA-TPY-Fe as in claim 12+Metal complex nanoplatelets characterized by: the deionized water is added in an amount of 1mL/mL based on the volume of the solution A.
7. TPA-TPY-Fe as in claim 1 or 32+Metal complex nanoplatelets characterized by: said Fe (BF)4)2The amount of the aqueous solution added was 1mL/mL based on the volume of the solution A.
8. The TPA-TPY-Fe as in claim 12+The metal complex nano-flake can be used for preparing electrochromic materials.
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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
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
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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