CN106497545B - Tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs and its synthetic method - Google Patents
Tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs and its synthetic method Download PDFInfo
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Abstract
The embodiment of the invention discloses a kind of perfluoroetane sulfonic acid root of tetrathio molybdate/1/LEuH complexs, have following below formula composition：Eu(OH)2.41(C8H17O3S)x(MoS4)y(NO3)0.02·zH2O；The complex is dispersed in the stripping solvent being made of water and formamide when forming colloidal nano piece suspension, which, which is apparently higher than, is scattered in 1 perfluoroetane sulfonic acid root/LEuH complexs of identical stripping solvent and is formed by colloidal nano piece suspension；And due to using water more to have application prospect to more environment-friendly instead of the formamide of part in removing solvent.
Description
Technical field
The present invention relates to organic synthesis field, more particularly to tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs and
Its synthetic method.
Background technology
Stratiform rare-earth hydroxide (Layered Rare-earth Hydroxides, LRH) is as a kind of novel stratiform
Anionic materials, laminate is positively charged, and interlayer is tradable anion, therefore can be introduced in interlayer by ion-exchange reactions
The organic or inorganic anion of different structure and property obtains having both the multi-functional layered of laminate property and interlayer anion temper
Composite material.In numerous rare earth ions, Eu3+Feature red spectrum, therefore, stratiform europium hydroxide can be emitted in visible region
Object (abbreviation LEuH) can be used for preparing luminescent material.But stratiform europium hydroxide is difficult (also referred to as to be removed molten in solvent
Agent) in stripping, therefore be difficult to prepare thin film phosphor.Studies have shown that by surfactant sodium 1-octanesulfonate (OS)
1- perfluoroetane sulfonic acids root/LEuH complexs can be obtained in LEuH interlayers in intercalation, which can be in stripping solvent, such as formamide
Middle stripping, the colloidal nano piece suspension to be glowed, and then can be used for preparing thin film phosphor.Since formamide is that have
Solvent has certain toxicity, unfriendly to environment, but if replacing (the i.e. mixing of water and formamide of part formamide with water
Object) as solvent is removed, then 1- perfluoroetane sulfonic acids root/LEuH complexs are formed by colloidal nano piece suspension fluorescent emission intensity
Very low, application value is low.
Invention content
The embodiment of the invention discloses a kind of tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs, for solving 1-
Perfluoroetane sulfonic acid root/LEuH complexs, which are scattered in the stripping solvent that water is mixed with formamide, forms colloidal nano piece suspension
When, the low problem of the suspension fluorescent emission intensity.Technical solution is as follows：
Present invention firstly provides a kind of tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs, have following chemistry
Formula forms：
Eu(OH)2.41(C8H17O3S)x(MoS4)y(NO3)0.02·zH2O,
Wherein, x=0.47-0.50, y=0.04-0.06, z=1-2.
The present invention also provides a kind of colloidal nano piece suspension prepared using above-mentioned complex, the colloidal nanos
The stripping solvent of piece suspension is the mixed liquor of formamide and water.
In the preferred embodiment of the present invention, in the stripping solvent, the volume ratio of formamide and water is 1：
(1-5), preferably 1：(2-4).
In the preferred embodiment of the present invention, in the colloidal nano piece suspension, tetrathio molybdate/1-
The ratio of perfluoroetane sulfonic acid root/LEuH complexs and formamide is 1-2mg/mL.
The present invention also provides the synthetic method of tetrathio molybdate above-mentioned/1- perfluoroetane sulfonic acids root/LEuH complexs, packets
Include following steps：
By NO3After-LEuH, sodium 1-octanesulfonate and four thio ammonium molybdate are dispersed in water, hydro-thermal is anti-at 70-100 DEG C
It answers 12-24 hours, product is post-processed after reaction, it is compound to obtain tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH
Body；Wherein, the molar ratio of the four thio ammonium molybdate and sodium 1-octanesulfonate is 1：(12-18)；Sodium 1-octanesulfonate and four sulphur
The sum of molal quantity for ammonium molybdate and NO3The ratio of-LEuH molal quantitys is (5-9)：1.
In the preferred embodiment of the present invention, the molar ratio of the four thio ammonium molybdate and sodium 1-octanesulfonate is
1：(14-16)；The sum of molal quantity of sodium 1-octanesulfonate and four thio ammonium molybdate and NO3The ratio of-LEuH molal quantitys is (6.5-
7.5)：1.
In the preferred embodiment of the present invention, NO3The ratio of-LEuH and water is 1-2mg/mL.
In the preferred embodiment of the present invention, described post-process includes：It is filtered, washed, dries.
The present invention also provides the preparation methods of colloidal nano piece suspension above-mentioned, including：
After first tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs are scattered in formamide, then mix with water.
Therefore anion exchange method is used in technical scheme of the present invention, by hydro-thermal reaction by NO3- LEuH with
Tetrathio molybdate, 1- perfluoroetane sulfonic acid radical ions combine, and tetrathio molybdate and 1- perfluoroetane sulfonic acid roots is made to be inserted in LEuH jointly
Between laminate, tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs are obtained, which is dispersed in by water and formamide group
At stripping solvent in formed colloidal nano piece suspension when, which, which is apparently higher than, is scattered in identical stripping
1- perfluoroetane sulfonic acids root/LEuH complexs of exsolution agent are formed by colloidal nano piece suspension；And due in removing solvent
With water instead of the formamide of part, therefore to more environment-friendly, more there is application prospect.
Description of the drawings
In order to more clearly explain the embodiment of the invention or the technical proposal in the existing technology, to embodiment or will show below
There is attached drawing needed in technology description to be briefly described, it should be apparent that, the accompanying drawings in the following description is only this
Some embodiments of invention for those of ordinary skill in the art without creative efforts, can be with
Obtain other attached drawings according to these attached drawings.
Fig. 1 is the NO that the embodiment of the present invention 1 synthesizes31- perfluoroetane sulfonic acids root/LEuH complexs that-LEuH, embodiment 2 synthesize
And the XRD diagram of tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs of the synthesis of embodiment 3；Wherein, (a) is in Fig. 1
NO3The XRD diagram of-LEuH, (b) is the XRD diagram of 1- perfluoroetane sulfonic acids root/LEuH complexs in Fig. 1, and (c) is tetrathio molybdic acid in Fig. 1
The XRD diagram of root/1- perfluoroetane sulfonic acids root/LEuH complexs；
Fig. 2 is the NO synthesized in embodiment 13The 1- perfluoroetane sulfonic acids root/LEuH complexs and reality that-LEuH, embodiment 2 synthesize
Apply the infrared spectrogram of tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs of the synthesis of example 3；Wherein, (a) is in Fig. 2
NO3The FT-IR of-LEuH schemes, and (b) is that the FT-IR of 1- perfluoroetane sulfonic acids root/LEuH complexs schemes in Fig. 2, and (c) is tetrathio in Fig. 2
The FT-IR of molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs schemes；
The tetrathio molybdate for the 1- perfluoroetane sulfonic acids root/LEuH complexs and the synthesis of embodiment 3 that Fig. 3 synthesizes for embodiment 2/
The fluorescence spectra of 1- perfluoroetane sulfonic acids root/LEuH complexs, wherein (a) is 1- perfluoroetane sulfonic acids root/LEuH complexs in Fig. 3
Fluorescence spectra, (b) is the fluorescence spectra of tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs in Fig. 3；
The tetrathio molybdate for the 1- perfluoroetane sulfonic acids root/LEuH complexs and the synthesis of embodiment 4 that Fig. 4 synthesizes for embodiment 2/
The fluorescence spectra of 1- perfluoroetane sulfonic acids root/LEuH complexs, wherein (a) is 1- perfluoroetane sulfonic acids root/LEuH complexs in Fig. 4
Fluorescence spectra, (b) is the fluorescence spectra of tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs in Fig. 4；
The tetrathio molybdate for the 1- perfluoroetane sulfonic acids root/LEuH complexs and the synthesis of embodiment 5 that Fig. 5 synthesizes for embodiment 2/
The fluorescence spectra of 1- perfluoroetane sulfonic acids root/LEuH complexs, wherein (a) is 1- perfluoroetane sulfonic acids root/LEuH complexs in Fig. 5
Fluorescence spectra, (b) is the fluorescence spectra of tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs in Fig. 5.
Specific implementation mode
Present invention firstly provides a kind of tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs, which has
Following below formula forms：
Eu(OH)2.41(C8H17O3S)x(MoS4)y(NO3)0.02·zH2O,
Wherein, x=0.47-0.50, y=0.04-0.06, z=1-2, preferably z=1.4-1.8.
The present invention also provides the preparation methods of above-mentioned complex, include the following steps：
By NO3After-LEuH, sodium 1-octanesulfonate and four thio ammonium molybdate are dispersed in water, hydro-thermal is anti-at 70-100 DEG C
It answers 12-24 hours, product is post-processed to get multiple to tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH after reaction
It is fit；Wherein, the molar ratio of the four thio ammonium molybdate and sodium 1-octanesulfonate is 1：(12-18)；Sodium 1-octanesulfonate and four
The sum of molal quantity of ammonium thiomolybdate and NO3The ratio of-LEuH molal quantitys is (5-9)：1.
In specific implementation process, it is preferable that the molar ratio of the four thio ammonium molybdate and sodium 1-octanesulfonate is 1：
(14-16)；The sum of molal quantity of sodium 1-octanesulfonate and four thio ammonium molybdate and NO3The ratio of-LEuH molal quantitys is (6.5-
7.5)：1.
In the synthesis process, NO can be accelerated by the methods of ultrasound3- LEuH, sodium 1-octanesulfonate and tetrathio molybdic acid
The rate of dispersion of ammonium in water allows them to be uniformly dispersed in water as early as possible.It, can be according to actual conditions as the dosage of water
And used reaction kit determines, it is preferable that can be by NO3The ratio of-LEuH and water determines water for 1-2mg/mL
Dosage.
It should be noted that in this application, described NO3- LEuH refers to that interlayer anion is NO3 -Stratiform europium hydrogen
Oxide, synthetic method is in the prior art it has been reported that the present invention is herein without repeating.
After hydro-thermal reaction, needs to post-process product, may include：It is filtered, washed and dried processing.Specifically
, after hydro-thermal reaction, first product at reduced pressure can be filtered, carrying out washing treatment then carried out with water to the solid filtered, one
As repeat 3-4 times after, can be obtained within vacuum drying treatment 6-12 hours at 30-50 DEG C the higher tetrathio molybdate of purity/
1- perfluoroetane sulfonic acids root/LEuH complexs.
It should be noted that above-mentioned hydro-thermal reaction, to be filtered, washed and dried processing be experiment side commonly used in the art
Method, laboratory apparatus and equipment, concrete operation method used in above-mentioned processing procedure can be by those skilled in the art according to reality
Border situation selection, is not described in detail and specifically limits herein.In tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs
Building-up process used in drug and reagent, unless otherwise specified, can by the prior art synthesize or
It buys on the market.
Explanation is needed further exist for, water used is preferably deionized water in this application.
Inventor is found surprisingly that above-mentioned complex is scattered in when carrying out fluorescence property test to above-mentioned complex
By the stripping solvent of formamide and water mixed, when to form colloidal nano piece suspension, obtained colloidal nano
Piece suspension has stronger red light emitting intensity.Based on this, the present invention provides a kind of application tetrathio molybdate/1- octanes
The stripping solvent of colloidal nano piece suspension prepared by sulfonate radical/LEuH complexs, the colloidal nano piece suspension is formamide
With the mixed liquor of water.Described stripping solvent is commonly referred to as to remove stratiform rare-earth hydroxide at list in the art
The solvent of layer LRH nanometer sheets.In specific implementation process, in the stripping solvent, the volume ratio of formamide and water is 1：(1-
5), preferably 1：(2-4).In the colloidal nano piece suspension, tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH is compound
The ratio of body and formamide is 1-2mg/mL.
Above-mentioned colloidal nano piece suspension can be made by the following method：First by tetrathio molybdate/1- perfluoroetane sulfonic acids
After root/LEuH complexs are scattered in formamide, then mix with water.
Following will be combined with the drawings in the embodiments of the present invention, and technical solution in the embodiment of the present invention carries out clear, complete
Site preparation describes, it is clear that described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.It is based on
Embodiment in the present invention, those of ordinary skill in the art are obtained every other without creative efforts
Embodiment shall fall within the protection scope of the present invention.
1 NO of embodiment3The synthesis and structure of-LEuH characterizes
By 0.446g (1mmol) Eu (NO3)3·6H2O、0.846g(10mmol)NaNO3, six first of 0.07g (0.5mmol)
Urotropine is dissolved in 65mL de aerated waters, obtains aqueous solution, which is transferred in reaction kettle and is passed through into the aqueous solution
N23 minutes, then 70 DEG C of hydro-thermal reactions 18 hours.After reaction, the product filtered, is washed with deionized product
It is filtered again afterwards, 2 times repeatedly, is then dried in vacuo 24 hours at 40 DEG C, obtains white powder NO3-LEuH
0.196g。
Elemental analyser (the model produced using German Elementar companies：Vario EL) measure the embodiment of the present invention 1
The NO of middle synthesis3C, H of-LEuH, N content；The plasma inductive coupling produced using Spectro Analypical Instruments GmbH
Atomic Emission Spectrometer AES (ICP) (model：SPECTROARCOSEOP the NO synthesized in the embodiment of the present invention 1) is measured3- LEuH's
Eu contents, to calculate the NO synthesized in the embodiment of the present invention 13The chemical composition of-LEuH is Eu (OH)2.41(NO3)0.59·
0.77H2O, related data are as shown in table 1.
1 NO of table3The elemental analysis of-LEuH and icp analysis data
It adopts and repeats synthesis NO with the aforedescribed process3- LEuH three times, it is synthesized go out NO3- LEuH is applied to subsequent each reality
Apply example.
The synthesis and structure of 2 1- perfluoroetane sulfonic acids root of embodiment/LEuH complexs characterizes
By 0.10g (0.42mmol) NO3- LEuH and 0.6488g (3.0mmol) sodium 1-octanesulfonate are added to 80mL deionizations
In water, ultrasound makes it be uniformly dispersed, then is placed in 100mL reaction kettles hydro-thermal reaction 24 hours at 70 DEG C, after reaction, cold
But to room temperature, the solid product filtered is filtered again after product is washed with deionized, 3 times repeatedly；Finally at 40 DEG C
Lower vacuum drying 12 hours, obtains white powder 1- perfluoroetane sulfonic acids root/compound composite 0.136g of LEuH.
Measured using instrument and test condition same as Example 1 the 1- perfluoroetane sulfonic acids root that goes out synthesized by the present embodiment/
The content of C, H, N and Eu of LEuH complexs, it is multiple to calculate the 1- perfluoroetane sulfonic acids root/LEuH synthesized in the embodiment of the present invention
Fit chemical composition is
Eu(OH)2.41(C8H17O3S)0.64(NO3)0.01·0.8H2O, related data are as shown in table 2.
The elemental analysis of the complex of 2 embodiment 2 of table synthesis and icp analysis data
The synthesis of 3 tetrathio molybdate of embodiment/1- perfluoroetane sulfonic acids root/LEuH complexs and characterization
By 0.10g (0.42mmol) NO3- LEuH, 0.6099g (2.82mmol) sodium 1-octanesulfonates and 0.0469g
(0.18mmol) four thio ammonium molybdate is added in 80mL deionized waters, and ultrasound makes it be uniformly dispersed, then is placed in 100mL reaction kettles
Hydro-thermal reaction 24 hours are cooled to room temperature after reaction at 70 DEG C, and the solid product filtered is washed with deionized water
It is filtered again after washing product, 3 times repeatedly；It is finally dried in vacuo 12 hours at 40 DEG C, obtains the powdered tetrathio of yellowish-brown
Molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs 0.132g.
Elemental analysis：
Elemental analyser (the model produced using German Elementar companies：Vario EL) it measures and is synthesized in embodiment 3
Tetrathio molybdate/1- perfluoroetane sulfonic acids root/C, H of LEuH complexs, N content；Using Spectro Analypical Instruments GmbH
Plasma inductive coupling Atomic Emission Spectrometer AES (ICP) (model of production：SPECTROARCOSEOP it) measures in embodiment 3
The content of the Eu and Mo of the complex of synthesis, the chemical composition to calculate the complex synthesized in embodiment 3 are Eu
(OH)2.41(C8H17O3S)0.48(MoS4)0.05(NO3)0.02·1.8H2O, related data are as shown in table 3.
The elemental analysis of the complex of 3 embodiment 3 of table synthesis and icp analysis data
X-ray diffraction (X-ray diffraction, XRD) is analyzed
Using Philips X'Pert diffractometers, in CuK α targets, wavelength X=0.15418nm, flying-spot tube pressure, pipe stream difference
For 40mA, 40kV, step-length is 0.2 °, and sweep time is 10 steps/second, scans ranging from 4.5-70 ° of big angle, and small angular region is 0.8-
Under conditions of 6 °, the NO synthesized in embodiment 1 is measured3- LEuH, embodiment 2 synthesize 1- perfluoroetane sulfonic acids root/LEuH complexs and
Tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complex XRD diagram that embodiment 3 synthesizes, as shown in Figure 1.
(a) is NO in Fig. 13There are the series of features such as 0.85nm, 0.42nm, 0.32nm in the figure and spreads out in the XRD diagram of-LEuH
Peak is penetrated, illustrates NO3- LEuH is layer structure.Interlamellar spacing is 0.85nm；Diffraction peak shape is sharp, illustrates that crystallinity is very high.
In Fig. 1 (b) be 1- perfluoroetane sulfonic acids root/LEuH complexs XRD diagram and Fig. 1 in (c) be tetrathio molybdate/
1- perfluoroetane sulfonic acids root/LEuH complex XRD diagram；
The complex that embodiment 2 and embodiment 3 synthesize it can be seen from (c) in (b), Fig. 1 in Fig. 1 still keeps stratiform knot
Structure.There is 2.04,1.02,0.68,0.51,0.41nm a set of diffraction maximum, interlamellar spacing 2.04nm, interlayer in (b) in Fig. 1
Away from increase, illustrate that 1- perfluoroetane sulfonic acid roots are inserted into LEuH interlayers.(c) increases 0.90,0.45nm compared with (b) in Fig. 1 in Fig. 1
Deng some new diffraction maximums, illustrate that there are two-phases for interlayer at this time.In addition, the color of two species complexs has significant difference, embodiment 2
The complex of synthesis is white, and the complex that embodiment 3 synthesizes is yellowish-brown, illustrates tetrathio molybdate with 1- perfluoroetane sulfonic acids
Root is successfully introduced interlayer.
Infrared spectrum (FT-IR) is analyzed
Fourier Transform Infrared Spectrometer (the FT-IR) (model produced using Nicolet companies of the U.S.：Nicolet360)
To the NO synthesized in embodiment 13What the 1- perfluoroetane sulfonic acids root/LEuH complexs and embodiment 3 that-LEuH, embodiment 2 synthesize synthesized
Tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs carry out IR Characterization and (use KBr pressed disc methods, scan at room temperature, survey
Try ranging from 4000-400cm-1), FT-IR figures are as shown in Figure 2.
(a) in Fig. 2 is NO3The FT-IR collection of illustrative plates of-LEuH；3500cm-1For the absorption of laminate O-H, 1641cm-1The suction at place
Receive the bending vibration for being H-O-H, 1383cm-1Place is free NO3 -Characteristic absorption, lower wave number 581cm-1There are Eu-O vibrations in place
It absorbs.(b) in Fig. 2 is the FT-IR collection of illustrative plates of 1- perfluoroetane sulfonic acids root/LEuH complexs, 3448cm-1Flexible for laminate O-H shakes
It is dynamic to absorb, 1641cm-1The bending vibration for being absorbed as H-O-H at place.2924cm-1、2855cm-1For-CH in aliphatic carbon chain2It is special
Some stretching vibrations absorb, 1171cm-1、1049cm-1There is SO in place3 -The characteristic absorption of group illustrates that tetrathio molybdate is inserted into
Interlayer.(c) in Fig. 2 is the FT-IR collection of illustrative plates of tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs, still can from figure
Observe 2923cm-1、2854cm-1Locate c h bond stretching vibration absorption and 1173cm specific to aliphatic carbon chain-1、
1051cm-1Locate SO3 -The characteristic absorption of group.The above description shows that in tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs
Middle 1- perfluoroetane sulfonic acids root is successively inserted into LEuH interlayers.Due to the infrared vibration unobvious of inorganic ions tetrathio molybdate, do not see
Observe its corresponding infrared absorption band.But the presence for judging tetrathio molybdate can be understood from its color and elemental analysis.
Spectrofluorimetry
Sepectrophotofluorometer (the model produced using Australian VARIAN companies：Cary Eclipse) to embodiment
Tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH that the 1- perfluoroetane sulfonic acids root/LEuH complexs and embodiment 3 of 2 synthesis synthesize is multiple
Zoarium carries out fluorometric investigation, and fluorescence spectrum is as shown in Figure 3；Wherein,
(a) is the emission spectrum that 1- perfluoroetane sulfonic acids root/LEuH complexs are scattered in colloidal nano piece suspension in Fig. 3
(exciting slit is 5nm, transmite slit 5nm, excitation wavelength 394nm in test)；(b) is that tetrathio molybdate/1- is pungent in Fig. 3
Alkyl sulfonic acid root/LEuH complexs be scattered in colloidal nano piece suspension emission spectrum (in test exciting slit be 5nm, transmitting
Slit is 5nm, excitation wavelength 279nm)；
The colloidal nano piece suspension of above-mentioned two complex is prepared as follows respectively：0.02g complexs are weighed, are added
10mL formamides, continuous oscillation obtain gluey stripper after 8 hours.1mL strippers are then taken out, after 3mL water is added, are mixed
To colloidal nano piece suspension.It should be noted that the fluorometric investigation condition all same of the two.
From (a) in Fig. 3 as can be seen that the most strong emission peak peak position of 1- perfluoroetane sulfonic acids root/LEuH complexs is at 615nm,
Corresponding Eu3+Feature red emission.(b) is as can be seen that tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs from Fig. 3
Most strong emission peak peak position at 614nm, Eu is also presented3+Feature red emission.As seen from Figure 3, with non-intercalation tetrathio molybdenum
The 1- perfluoroetane sulfonic acids root of acid group/LEuH composite bulk phase ratios, the feux rouges of tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs
Emissive porwer greatly enhances, and about enhances 10 times.
The synthesis of 4 tetrathio molybdate of embodiment/1- perfluoroetane sulfonic acids root/LEuH complexs and characterization
By 0.10g (0.42mmol) NO3- LEuH, 0.7743g (3.58mmol) sodium 1-octanesulfonates and 0.0522g
(0.20mmol) four thio ammonium molybdate is added in 80mL deionized waters, and ultrasound makes it be uniformly dispersed, then is placed in 100mL reaction kettles
Hydro-thermal reaction 16 hours are cooled to room temperature after reaction at 85 DEG C, and the solid product filtered is washed with deionized water
It is filtered again after washing product, 3 times repeatedly；It is finally dried in vacuo 12 hours at 40 DEG C, obtains the powdered tetrathio of yellowish-brown
Molybdate/1- perfluoroetane sulfonic acids root/compound composite the 0.130g of LEuH.
With instrument and test condition same as Example 3 measure the complex synthesized in embodiment 4 C, H, N, Eu and
The content of Mo, the chemical composition to calculate the complex synthesized in embodiment 4 are Eu (OH)2.41(C8H17O3S)0.50
(MoS4)0.04(NO3)0.02·1.4H2O, related data are as shown in table 4.
The elemental analysis of the complex of 4 embodiment 4 of table synthesis and icp analysis data
Spectrofluorimetry
The 1- perfluoroetane sulfonic acids root/LEuH synthesized to embodiment 2 using equipment and test condition same as Example 3 is compound
Tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs that body and embodiment 4 synthesize carry out fluorometric investigation, and fluorescence spectrum is such as
Shown in Fig. 4；
(a) is transmitting light when 1- perfluoroetane sulfonic acids root/LEuH complexs are scattered in colloidal nano piece suspension in Fig. 4
Spectrum；(b) is hair when tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs are scattered in colloidal nano piece suspension in Fig. 4
Penetrate spectrum；
Analysis chart 4 can obtain the conclusion similar with Fig. 3, tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs
Most strong emission peak peak position at 614nm, Eu is also presented3+Feature red emission.Tetrathio molybdate/1- perfluoroetane sulfonic acids root/
The red light emitting intensity of LEuH complexs greatly enhances, and with 1- perfluoroetane sulfonic acids root/LEuH composite bulk phase ratios, about enhances 12 times.
The synthesis of 5 tetrathio molybdate of embodiment/1- perfluoroetane sulfonic acids root/LEuH complexs and characterization
By 0.10g (0.42mmol) NO3- LEuH, 0.4196g (1.94mmol) sodium 1-octanesulfonates and 0.0417g
(0.16mmol) four thio ammonium molybdate is added in 80mL deionized waters, and ultrasound makes it be uniformly dispersed, then is placed in 100mL reaction kettles
Hydro-thermal reaction 12 hours are cooled to room temperature after reaction at 95 DEG C, and the solid product filtered is washed with deionized water
It is filtered again after washing product, 3 times repeatedly；It is finally dried in vacuo 12 hours at 40 DEG C, obtains the powdered tetrathio of yellowish-brown
Molybdate/1- perfluoroetane sulfonic acids root/compound composite the 0.130g of LEuH.
With instrument and test condition same as Example 3 measure the complex synthesized in embodiment 5 C, H, N, Eu and
The content of Mo, the chemical composition to calculate the complex synthesized in embodiment 5 are Eu (OH)2.41(C8H17O3S)0.47
(MoS4)0.06(NO3)0.02·1.5H2O, related data are as shown in table 5.
The elemental analysis of the complex of 5 embodiment 5 of table synthesis and icp analysis data
Spectrofluorimetry
The 1- perfluoroetane sulfonic acids root/LEuH synthesized to embodiment 2 using equipment and test condition same as Example 3 is compound
Tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs that body and embodiment 5 synthesize carry out fluorometric investigation, and fluorescence spectrum is such as
Shown in Fig. 5；
(a) is transmitting light when 1- perfluoroetane sulfonic acids root/LEuH complexs are scattered in colloidal nano piece suspension in Fig. 5
Spectrum；(b) is hair when tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs are scattered in colloidal nano piece suspension in Fig. 5
Penetrate spectrum；
Analysis chart 5 can obtain the conclusion similar with Fig. 3, tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs
Most strong emission peak peak position at 614nm, Eu is also presented3+Feature red emission.Tetrathio molybdate/1- perfluoroetane sulfonic acids root/
The red light emitting intensity of LEuH complexs greatly increases, and with 1- perfluoroetane sulfonic acids root/LEuH composite bulk phase ratios, about enhances 10 times.
Using the mixed liquor of water and formamide as stripping solvent it can be seen from the fluorescence spectrum of the various embodiments described above
When preparing colloidal nano piece suspension, tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs of embodiment 3-5 synthesis
Red light emitting intensity will be significantly better than the red light emitting intensity of 1- perfluoroetane sulfonic acids root/LEuH complexs prepared by embodiment 2.Also
It is to say under the premise of keeping stronger red light emitting intensity, using the tetrathio molybdate synthesized by the present invention/1- octane sulphurs
When acid group/LEuH complexs prepare colloidal nano piece suspension, can using the mixed liquor of water and formamide as stripping solvent, by
It is significantly larger than the ratio of formamide in removing the ratio in solvent shared by water, therefore the dosage of formamide can be greatly reduced, it is right
It is more environment-friendly, more there is application prospect.
Above to tetrathio molybdate provided by the present invention/1- perfluoroetane sulfonic acids root/LEuH complexs and its synthetic method
It is described in detail.Principle and implementation of the present invention are described for specific embodiment used herein, above
The explanation of embodiment is merely used to help understand the method and its central idea of the present invention.It should be pointed out that for the general of this field
, without departing from the principle of the present invention, can be with several improvements and modifications are made to the present invention for logical technical staff, this
A little improvement and modification also fall into the protection of the claims in the present invention.
Claims (5)
1. a kind of colloidal nano piece suspension prepared by application tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs, special
Sign is that the stripping solvent of the colloidal nano piece suspension is the mixed liquor of formamide and water；
The tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs are formed with following below formula：
Eu(OH)2.41(C8H17O3S)0.47(MoS4)0.06(NO3)0.02·1.5H2O。
2. colloidal nano piece suspension as described in claim 1, which is characterized in that in the stripping solvent, formamide and
The volume ratio of water is 1：(1-5).
3. colloidal nano piece suspension as claimed in claim 2, which is characterized in that in the stripping solvent, formamide and
The volume ratio of water is 1：(2-4).
4. colloidal nano piece suspension as described in claim 1, which is characterized in that in the colloidal nano piece suspension,
The ratio of tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs and formamide is 1-2mg/mL.
5. the preparation method of the colloidal nano piece suspension as described in any one of claim 1-4, which is characterized in that packet
It includes：
After first tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs are scattered in formamide, then mix with water.
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| Controllable luminescence of layered rare-earth hydroxide composites with a fluorescent molecule: blue emission by delamination in formamide;Qingyang Gu et al;《Chem. C ommun.》;20141202;2514-2517 * |
| Highly Selective and E fficient Removal of Heavy Metals by LayeredDouble Hydroxide Intercalated with the MoS42- ion;Lijiao Ma et al.;《J. Am. Chem. Soc.》;20160131;2858-2866 * |
| MoS4/OS-LEuH复合体的合成与发光性;谢林霞等;《中国化学会第30届学术年会》;20160701;摘要 * |
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