CN106497545A - Tetrathio molybdate/1 perfluoroetane sulfonic acid root/LEuH complexs and its synthetic method - Google Patents
Tetrathio molybdate/1 perfluoroetane sulfonic acid root/LEuH complexs and its synthetic method Download PDFInfo
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- CN106497545A CN106497545A CN201610828980.3A CN201610828980A CN106497545A CN 106497545 A CN106497545 A CN 106497545A CN 201610828980 A CN201610828980 A CN 201610828980A CN 106497545 A CN106497545 A CN 106497545A
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Abstract
The embodiment of the invention discloses a kind of tetrathio molybdate/1 perfluoroetane sulfonic acid root/LEuH complexs, constitute with below formula：Eu(OH)2.41(C8H17O3S)x(MoS4)y(NO3)0.02·zH2O；The complex is dispersed in when forming colloidal nano piece suspension in the stripping solvent being made up of water and formamide, the colloidal nano piece suspension formed apparently higher than the 1 perfluoroetane sulfonic acid root/LEuH complexs for being scattered in identical stripping solvent by the suspension fluorescent emission intensity；And due to peeling off the formamide that part is instead of in solvent with water, therefore to more environment-friendly, more have application prospect.
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 used as the new stratiform of a class
Anionic materials, laminate are positively charged, and interlayer is tradable anion, therefore can pass through ion-exchange reactions and introduce in interlayer
The organic or inorganic anion of different structure and property, obtains having concurrently the multi-functional layered of laminate property and interlayer anion temper
Composite.In numerous rare earth ions, Eu3+Can be in visible region emission characteristic red spectrum, therefore, stratiform europium hydroxide
Thing (abbreviation LEuH) can be used to prepare luminescent material.But, stratiform europium hydroxide is difficult (also referred to as to peel off molten in solvent
Agent) middle stripping, therefore it is difficult to prepare thin film phosphor.Research shows, by surfactant sodium 1-octanesulfonate (OS)
Intercalation is obtained 1- perfluoroetane sulfonic acids root/LEuH complexs in LEuH interlayers, and the complex can peel off solvent, such as formamide
Middle stripping, obtains the colloidal nano piece suspension for glowing, and then can be used to prepare thin film phosphor.As formamide is that have
Machine solvent, has certain toxicity, unfriendly to environment, but if replacing (the i.e. mixing of water and formamide of part formamide with water
Thing) as stripping solvent, then the colloidal nano piece suspension fluorescent emission intensity formed by 1- perfluoroetane sulfonic acids root/LEuH complexs
Very low, using value is low.
Content of the invention
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 are scattered in the stripping solvent that water is mixed with formamide and form colloidal nano piece suspension
When, the low problem of the suspension fluorescent emission intensity.Technical scheme is as follows：
Present invention firstly provides a kind of tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs, with following chemistry
Formula is constituted：
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.
Present invention also offers colloidal nano piece suspension prepared by a kind of above-mentioned complex of application, the colloidal nano
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.
Present invention also offers the synthetic method of aforesaid tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs, bag
Include following steps：
By NO3After-LEuH, sodium 1-octanesulfonate and four thio ammonium molybdate are dispersed in water, at 70-100 DEG C, hydro-thermal is anti-
Answer 12-24 hours, reaction after terminating to post-process product, obtain tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH and be combined
Body；Wherein, the four thio ammonium molybdate is 1 with the mol ratio of sodium 1-octanesulfonate：(12-18)；Sodium 1-octanesulfonate and four sulphur
Molal quantity sum and NO for ammonium molybdate3The ratio of-LEuH molal quantitys is (5-9)：1.
In the preferred embodiment of the present invention, the four thio ammonium molybdate with the mol ratio of sodium 1-octanesulfonate is
1：(14-16)；The molal quantity sum 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, NO3- LEuH is 1-2mg/mL with the ratio of water.
In the preferred embodiment of the present invention, the post processing includes：Filter, wash, dry.
Present invention also offers the preparation method of aforesaid colloidal nano piece suspension, including：
After first be scattered in tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs in formamide, then mix with water.
Therefore, anion exchange method is adopted in technical scheme, by hydro-thermal reaction by NO3- LEuH with
Tetrathio molybdate, 1- perfluoroetane sulfonic acids radical ion are combined, and make tetrathio molybdate and 1- perfluoroetane sulfonic acids root be inserted in jointly LEuH
Between laminate, tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs are obtained, the complex is dispersed in by water and formamide group
Into stripping solvent in form colloidal nano piece suspension when, the suspension fluorescent emission intensity is apparently higher than being scattered in identical stripping
The colloidal nano piece suspension formed by the 1- perfluoroetane sulfonic acids root/LEuH complexs of exsolution agent；And due to peeling off in solvent
The formamide that part be instead of with water, therefore to more environment-friendly, more has application prospect.
Description of the drawings
In order to be illustrated more clearly that the embodiment of the present invention or technical scheme of the prior art, below will be to embodiment or existing
Accompanying drawing to be used needed for having technology description is briefly described, it should be apparent that, drawings in the following description are only this
Some embodiments of invention, for those of ordinary skill in the art, on the premise of not paying creative work, can be with
Other accompanying drawings are obtained according to these accompanying drawings.
Fig. 1 is the NO of the synthesis of the embodiment of the present invention 13- LEuH, embodiment 2-in-1 into 1- perfluoroetane sulfonic acids root/LEuH complexs
And the XRD of the tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs of the synthesis of embodiment 3；Wherein, in Fig. 1, (a) is
NO3The XRD of-LEuH, the XRD of (b) for 1- perfluoroetane sulfonic acids root/LEuH complexs in Fig. 1, in Fig. 1, (c) is tetrathio molybdic acid
The XRD of root/1- perfluoroetane sulfonic acids root/LEuH complexs；
Fig. 2 is the NO synthesized in embodiment 13- LEuH, embodiment 2-in-1 into 1- perfluoroetane sulfonic acids root/LEuH complexs and reality
Apply the infrared spectrogram of the tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs of the synthesis of example 3；Wherein, in Fig. 2, (a) is
NO3The FT-IR figures of-LEuH, in Fig. 2, (b) is schemed for the FT-IR of 1- perfluoroetane sulfonic acids root/LEuH complexs, and in Fig. 2, (c) is tetrathio
The FT-IR figures of molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs；
Fig. 3 be embodiment 2-in-1 into 1- perfluoroetane sulfonic acids root/LEuH complexs and embodiment 3 synthesis tetrathio molybdate/
The fluorescence spectra of 1- perfluoroetane sulfonic acids root/LEuH complexs, wherein, in Fig. 3, (a) is 1- perfluoroetane sulfonic acids root/LEuH complexs
Fluorescence spectra, the fluorescence spectra of (b) for tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs in Fig. 3；
Fig. 4 be embodiment 2-in-1 into 1- perfluoroetane sulfonic acids root/LEuH complexs and embodiment 4 synthesis tetrathio molybdate/
The fluorescence spectra of 1- perfluoroetane sulfonic acids root/LEuH complexs, wherein, in Fig. 4, (a) is 1- perfluoroetane sulfonic acids root/LEuH complexs
Fluorescence spectra, the fluorescence spectra of (b) for tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs in Fig. 4；
Fig. 5 be embodiment 2-in-1 into 1- perfluoroetane sulfonic acids root/LEuH complexs and embodiment 5 synthesis tetrathio molybdate/
The fluorescence spectra of 1- perfluoroetane sulfonic acids root/LEuH complexs, wherein, in Fig. 5, (a) is 1- perfluoroetane sulfonic acids root/LEuH complexs
Fluorescence spectra, the fluorescence spectra of (b) for tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs in Fig. 5.
Specific embodiment
Present invention firstly provides a kind of tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs, the complex has
Below formula is constituted：
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.
Present invention also offers the preparation method of above-mentioned complex, comprises the following steps：
By NO3After-LEuH, sodium 1-octanesulfonate and four thio ammonium molybdate are dispersed in water, at 70-100 DEG C, hydro-thermal is anti-
Answer 12-24 hours, reaction after terminating to post-process product, that is, obtain tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH multiple
Fit；Wherein, the four thio ammonium molybdate is 1 with the mol ratio of sodium 1-octanesulfonate：(12-18)；Sodium 1-octanesulfonate and four
The molal quantity sum of ammonium thiomolybdate and NO3The ratio of-LEuH molal quantitys is (5-9)：1.
In specific implementation process, it is preferable that the four thio ammonium molybdate is 1 with the mol ratio of sodium 1-octanesulfonate：
(14-16)；The molal quantity sum of sodium 1-octanesulfonate and four thio ammonium molybdate and NO3The ratio of-LEuH molal quantitys is (6.5-
7.5)：1.
In building-up process, the methods such as ultrasound can be passed through and accelerate NO3- LEuH, sodium 1-octanesulfonate and tetrathio molybdic acid
Rate of dispersion of the ammonium in water, allows them to be uniformly dispersed in water as early as possible.As for the consumption of water, can be according to actual conditions
And the reaction kit for being used determines, it is preferable that can be by NO3- LEuH determines water with the ratio of water for 1-2mg/mL
Consumption.
It should be noted that in this application, described NO3- LEuH refers to interlayer anion for NO3 -Stratiform europium hydrogen
Oxide, its synthetic method is not in the prior art it has been reported that here of the present invention is repeated.
After hydro-thermal reaction terminates, need to post-process product, can include：It is filtered, washed and dried process.Specifically
, after hydro-thermal reaction terminates, first product at reduced pressure can be filtered, then carry out carrying out washing treatment to filtered solid with water, one
As repeat 3-4 time after, at 30-50 DEG C vacuum drying treatment 6-12 hour be obtained the higher tetrathio molybdate of purity/
1- perfluoroetane sulfonic acids root/LEuH complexs.
It should be noted that above-mentioned hydro-thermal reaction, be filtered, washed and dried process be experiment side commonly used in the art
Method, in above-mentioned processing procedure, laboratory apparatus and equipment, concrete operation method used can be by those skilled in the art according to reality
Border situation is selected, and here is not described in detail and specifically limits.In tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs
Building-up process in medicine used and reagent, in the case of without specified otherwise, can be synthesized by prior art or
Commercially buy.
Explanation is needed further exist for, water used in this application is preferably deionized water.
When fluorescence property test is carried out to above-mentioned complex, inventor is found surprisingly that above-mentioned complex is scattered in
By formamide and the stripping solvent for mixing of water, so as to be formed during colloidal nano piece suspension, obtained colloidal nano
Piece suspension has stronger red light emitting intensity.This is based on, the invention provides a kind of application tetrathio molybdate/1- octanes
Colloidal nano piece suspension prepared by sulfonate radical/LEuH complexs, the stripping solvent of the colloidal nano piece suspension is formamide
Mixed liquor with water.Described stripping solvent is commonly referred to as stratiform rare-earth hydroxide being peeled off into 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 combined
The ratio of body and formamide is 1-2mg/mL.
Above-mentioned colloidal nano piece suspension can be obtained by the following method：First by tetrathio molybdate/1- perfluoroetane sulfonic acids
After root/LEuH complexs are scattered in formamide, then mix with water.
Accompanying drawing in below in conjunction with the embodiment of the present invention, to the embodiment of the present invention in technical scheme carry out clear, complete
Site preparation is described, it is clear that described embodiment is only a part of embodiment of the invention, rather than whole embodiment.It is based on
Embodiment in the present invention, it is every other that those of ordinary skill in the art are obtained under the premise of creative work is not made
Embodiment, belongs to the scope of protection of the invention.
1 NO of embodiment3The synthesis and structure of-LEuH is characterized
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 the aqueous solution, the aqueous solution is transferred in reactor and is passed through in the aqueous solution
N23 minutes, then 70 DEG C of hydro-thermal reactions 18 hours.After reaction terminates, the product that suction filtration is obtained is washed with deionized product
Carry out suction filtration afterwards again, 2 times repeatedly, be then vacuum dried 24 hours at 40 DEG C, obtain 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 synthesis3The C of-LEuH, H, N content；The plasma inductive produced using Spectro Analypical Instruments GmbH
Atomic Emission Spectrometer AES (ICP) (model：SPECTROARCOSEOP) NO synthesized in the embodiment of the present invention 1 is measured3- LEuH's
Eu contents, so that 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 elementary analysis of-LEuH and icp analysis data
Adopt3- LEuH three times, synthesized go out NO3- LEuH is applied to each reality below
Apply example.
The synthesis and structure of 2 1- perfluoroetane sulfonic acids root of embodiment/LEuH complexs is characterized
By 0.10g (0.42mmol) NO3- LEuH and 0.6488g (3.0mmol) sodium 1-octanesulfonate are added to 80mL deionizations
In water, ultrasound makes which be uniformly dispersed, then is placed in 100mL reactors hydro-thermal reaction 24 hours at 70 DEG C, after reaction terminates, cold
But to room temperature, the solid product that suction filtration is obtained carries out suction filtration again after being washed with deionized product, 3 times repeatedly；Finally at 40 DEG C
Lower vacuum drying 12 hours, obtains the compound composite 0.136g of white powder 1- perfluoroetane sulfonic acid root/LEuH.
Determined using instrument same as Example 1 and test condition the 1- perfluoroetane sulfonic acid roots that go out synthesized by the present embodiment/
The content of C, H, N and Eu of LEuH complexs, the 1- perfluoroetane sulfonic acids root/LEuH so as to calculate synthesis in the embodiment of the present invention are multiple
Fit chemical composition is
Eu(OH)2.41(C8H17O3S)0.64(NO3)0.01·0.8H2O, related data are as shown in table 2.
2 embodiment of table 2-in-1 into complex elementary analysis and icp analysis data
The synthesis of 3 tetrathio molybdate of embodiment/1- perfluoroetane sulfonic acids root/LEuH complexs and sign
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 which be uniformly dispersed, then is placed in 100mL reactors
Hydro-thermal reaction 24 hours at 70 DEG C, after reaction terminates, are cooled to room temperature, and the solid product that suction filtration is obtained is washed with deionized water
Suction filtration carried out after washing product again, 3 times repeatedly；Last vacuum drying 12 hours at 40 DEG C, obtain yellowish-brown powder tetrathio
Molybdate/1- perfluoroetane sulfonic acids root/LEuH complex 0.132g.
Elementary analysis：
Elemental analyser (the model produced using German Elementar companies：Vario EL) measure synthesis in embodiment 3
Tetrathio molybdate/1- perfluoroetane sulfonic acids root/C of LEuH complexs, H, N content；Using Spectro Analypical Instruments GmbH
Plasma inductive Atomic Emission Spectrometer AES (the ICP) (model of production：SPECTROARCOSEOP) measure in embodiment 3
The content of the Eu and Mo of the complex of synthesis, the chemical composition so as 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 elementary analysis of the complex of the synthesis of 3 embodiment of table 3 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, and it is 4.5-70 ° to scan big angular region, and little angular region is 0.8-
Under conditions of 6 °, the NO synthesized in embodiment 1 is measured3- LEuH, embodiment 2-in-1 into 1- perfluoroetane sulfonic acids root/LEuH complexs and
Tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complex the XRDs of the synthesis of embodiment 3, as shown in Figure 1.
In Fig. 1, (a) is NO3, there are the series of features such as 0.85nm, 0.42nm, 0.32nm and spreads out in the XRD of-LEuH in the figure
Peak is penetrated, NO is described3- LEuH is layer structure.Interlamellar spacing is 0.85nm；Diffraction peak shape is sharp, illustrates that degree of crystallinity is very high.
In Fig. 1 (b) for 1- perfluoroetane sulfonic acids root/LEuH complexs XRD, and in Fig. 1 (c) be tetrathio molybdate/
1- perfluoroetane sulfonic acids root/LEuH complex XRDs；
In Fig. 1 (b), in Fig. 1 (c) as can be seen that the complex that embodiment 2 and embodiment 3 synthesizes still keeps stratiform knot
Structure.(b) occurs in that 2.04,1.02,0.68,0.51,0.41nm a set of diffraction maximum in FIG, and interlamellar spacing is 2.04nm, interlayer
Away from increase, 1- perfluoroetane sulfonic acids root insertion LEuH interlayers are described.In Fig. 1, (c) increased 0.90,0.45nm compared with (b) in Fig. 1
Deng some new diffraction maximums, illustrate that now interlayer has two-phase.Additionally, the color of two species complexs is clearly distinguished from, embodiment 2
The complex of synthesis is white, and the complex of the synthesis of embodiment 3 is yellowish-brown, illustrates tetrathio molybdate with 1- perfluoroetane sulfonic acids
Root is successfully introduced interlayer.
Infrared spectrum (FT-IR) is analyzed
FTIS (the FT-IR) (model produced using Nicolet companies of the U.S.：Nicolet360)
To the NO synthesized in embodiment 13- LEuH, embodiment 2-in-1 into 1- perfluoroetane sulfonic acids root/LEuH complexs and embodiment 3 synthesis
Tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs carry out IR Characterization and (using KBr pressed disc methods, scan under room temperature, survey
Examination scope is 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 flexural vibrations for H-O-H, 1383cm-1Locate as free NO3 -Characteristic absorption, lower wave number 581cm-1There are Eu-O vibrations in place
Absorb.FT-IR collection of illustrative plates of (b) in Fig. 2 for 1- perfluoroetane sulfonic acids root/LEuH complexs, 3448cm-1Flexible for laminate O-H shakes
Dynamic absorption, 1641cm-1The flexural vibrations for being absorbed as H-O-H at place.2924cm-1、2855cm-1For-CH in aliphatic carbon chain2Special
Some stretching vibrations absorb, 1171cm-1、1049cm-1There is SO in place3 -The characteristic absorption of group, illustrates that tetrathio molybdate is inserted
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-1C h bond stretching vibration specific to place's aliphatic carbon chain absorbs, and 1173cm-1、
1051cm-1Place SO3 -The characteristic absorption of group.Below illustrate in tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs
Middle 1- perfluoroetane sulfonic acids root is successively inserted into LEuH interlayers.As the infrared vibration of inorganic ions tetrathio molybdate is not obvious, do not see
Observe its corresponding infrared absorption band.But the presence that can clearly judge tetrathio molybdate from its color and elementary analysis.
Spectrofluorimetry
Sepectrophotofluorometer (the model produced using Australian VARIAN companies：Cary Eclipse) to embodiment
2-in-1 into 1- perfluoroetane sulfonic acids root/LEuH complexs and embodiment 3 synthesis tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH multiple
Zoarium carries out fluorometric investigation, and fluorescence spectrum is as shown in Figure 3；Wherein,
In Fig. 3, (a) is the emission spectrum that 1- perfluoroetane sulfonic acids root/LEuH complexs are scattered in colloidal nano piece suspension
(in test, exciting slit is 5nm, and transmite slit is 5nm, excitation wavelength 394nm)；In Fig. 3, (b) is that tetrathio molybdate/1- is pungent
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, is added
10mL formamides, continuous oscillation obtain gluey stripper after 8 hours.1mL strippers are then taken out, after adding 3mL water, is mixed
Arrive colloidal nano piece suspension.It should be noted that the fluorometric investigation condition all same of the two.
From Fig. 3 (a) as can be seen that 1- perfluoroetane sulfonic acids root/LEuH complexs most strong emission peak peak position at 615nm,
Corresponding Eu3+Feature red emission.From Fig. 3, (b) is as can be seen that tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs
Most strong emission peak peak position at 614nm, also present Eu3+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 phases ratio, the ruddiness of tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs
Emissive porwer is greatly enhanced, and about strengthens 10 times.
The synthesis of 4 tetrathio molybdate of embodiment/1- perfluoroetane sulfonic acids root/LEuH complexs and sign
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 which be uniformly dispersed, then is placed in 100mL reactors
Hydro-thermal reaction 16 hours at 85 DEG C, after reaction terminates, are cooled to room temperature, and the solid product that suction filtration is obtained is washed with deionized water
Suction filtration carried out after washing product again, 3 times repeatedly；Last vacuum drying 12 hours at 40 DEG C, obtain yellowish-brown powder tetrathio
The compound composite 0.130g of molybdate/1- perfluoroetane sulfonic acids root/LEuH.
With instrument same as Example 3 and test condition measure in embodiment 4 synthesize complex C, H, N, Eu and
The content of Mo, the chemical composition so as 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 elementary analysis of the complex of the synthesis of 4 embodiment of table 4 and icp analysis data
Spectrofluorimetry
Using equipment same as Example 3 and test condition 2-in-1 to embodiment into 1- perfluoroetane sulfonic acids root/LEuH be combined
Tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH the complexs of body and the synthesis of embodiment 4 carry out fluorometric investigation, and fluorescence spectrum is such as
Shown in Fig. 4；
In Fig. 4, (a) is launching light when 1- perfluoroetane sulfonic acids root/LEuH complexs are scattered in colloidal nano piece suspension
Spectrum；In Fig. 4, (b) is sending out when tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs are scattered in colloidal nano piece suspension
Penetrate spectrum；
Analysis Fig. 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, also present Eu3+Feature red emission.Tetrathio molybdate/1- perfluoroetane sulfonic acid roots/
The red light emitting intensity of LEuH complexs is greatly enhanced, and with 1- perfluoroetane sulfonic acids root/LEuH composite bulk phases ratio, about strengthens 12 times.
The synthesis of 5 tetrathio molybdate of embodiment/1- perfluoroetane sulfonic acids root/LEuH complexs and sign
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 which be uniformly dispersed, then is placed in 100mL reactors
Hydro-thermal reaction 12 hours at 95 DEG C, after reaction terminates, are cooled to room temperature, and the solid product that suction filtration is obtained is washed with deionized water
Suction filtration carried out after washing product again, 3 times repeatedly；Last vacuum drying 12 hours at 40 DEG C, obtain yellowish-brown powder tetrathio
The compound composite 0.130g of molybdate/1- perfluoroetane sulfonic acids root/LEuH.
With instrument same as Example 3 and test condition measure in embodiment 5 synthesize complex C, H, N, Eu and
The content of Mo, the chemical composition so as 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 elementary analysis of the complex of the synthesis of 5 embodiment of table 5 and icp analysis data
Spectrofluorimetry
Using equipment same as Example 3 and test condition 2-in-1 to embodiment into 1- perfluoroetane sulfonic acids root/LEuH be combined
Tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH the complexs of body and the synthesis of embodiment 5 carry out fluorometric investigation, and fluorescence spectrum is such as
Shown in Fig. 5；
In Fig. 5, (a) is launching light when 1- perfluoroetane sulfonic acids root/LEuH complexs are scattered in colloidal nano piece suspension
Spectrum；In Fig. 5, (b) is sending out when tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs are scattered in colloidal nano piece suspension
Penetrate spectrum；
Analysis Fig. 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, also present Eu3+Feature red emission.Tetrathio molybdate/1- perfluoroetane sulfonic acid roots/
The red light emitting intensity of LEuH complexs is greatly increased, and with 1- perfluoroetane sulfonic acids root/LEuH composite bulk phases ratio, about strengthens 10 times.
Can be seen that using the mixed liquor of water and formamide as stripping solvent by the fluorescence spectrum of the various embodiments described above
When preparing colloidal nano piece suspension, the 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 on the premise of stronger red light emitting intensity is kept, 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 peel off solvent, by
In the ratio of the ratio in solvent shared by water of peeling off significantly larger than formamide, the consumption of formamide therefore can be greatly reduced, right
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.Specific embodiment used herein is set forth to the principle of the present invention and embodiment, above
The explanation of embodiment is only intended to help and understands the method for the present invention and its central idea.It should be pointed out that general for this area
For logical technical staff, under the premise without departing from the principles of the invention, some improvement and modification can also be carried out to the present invention, this
A little improvement and modification also fall into the protection of the claims in the present invention.
Claims (9)
1. a kind of tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs, it is characterised in that constitute with below formula：
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.
2. the colloidal nano piece suspension that prepared by the complex described in a kind of application claim 1, it is characterised in that the colloid
The stripping solvent of nanometer sheet suspension is the mixed liquor of formamide and water.
3. colloidal nano piece suspension as claimed in claim 2, it is characterised in that in the stripping solvent, formamide and
The volume ratio of water is 1：(1-5), preferably 1：(2-4).
4. colloidal nano piece suspension as claimed in claim 2, it is characterised 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 synthetic method of the tetrathio molybdate described in claim 1/1- perfluoroetane sulfonic acids root/LEuH complexs, its feature exist
In comprising the following steps：
By NO3After-LEuH, sodium 1-octanesulfonate and four thio ammonium molybdate are dispersed in water, hydro-thermal reaction 12- at 70-100 DEG C
24 hours, reaction was post-processed to product after terminating, and obtains tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs；Its
In, the four thio ammonium molybdate is 1 with the mol ratio of sodium 1-octanesulfonate：(12-18)；Sodium 1-octanesulfonate and tetrathio molybdic acid
The molal quantity sum of ammonium and NO3The ratio of-LEuH molal quantitys is (5-9)：1.
6. method as claimed in claim 5, it is characterised in that the mol ratio of the four thio ammonium molybdate and sodium 1-octanesulfonate
For 1：(14-16)；The molal quantity sum of sodium 1-octanesulfonate and four thio ammonium molybdate and NO3The ratio of-LEuH molal quantitys is (6.5-
7.5)：1.
7. synthetic method as claimed in claim 5, it is characterised in that NO3- LEuH is 1-2mg/mL with the ratio of water.
8. synthetic method as claimed in claim 5, it is characterised in that the post processing includes：Filter, wash, dry.
9. the preparation method of the colloidal nano piece suspension as described in any one in claim 2-4, it is characterised in that bag
Include：
After first be scattered in tetrathio molybdate/1- perfluoroetane sulfonic acids root/LEuH complexs in formamide, then mix with water.
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| US20150336050A1 (en) * | 2014-05-20 | 2015-11-26 | Northwestern University | Polysulfide intercalated layered double hydroxides for metal capture applications |
| CN105733558A (en) * | 2016-03-14 | 2016-07-06 | 北京师范大学 | Coumarin-3-carboxylic acid/1-octanesulfonic acid/LEuH complex and synthesis method thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US20150336050A1 (en) * | 2014-05-20 | 2015-11-26 | Northwestern University | Polysulfide intercalated layered double hydroxides for metal capture applications |
| CN105733558A (en) * | 2016-03-14 | 2016-07-06 | 北京师范大学 | Coumarin-3-carboxylic acid/1-octanesulfonic acid/LEuH complex and synthesis method thereof |
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| CN110346339A (en) * | 2019-07-18 | 2019-10-18 | 京师北中横琴科技研究院有限公司 | Application of the nitrate anion type stratiform europium hydroxide in detection molybdate |
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