CN113387967A - Rare earth material based on diphenylamine-carbonyl benzoic acid and preparation method and application thereof - Google Patents

Rare earth material based on diphenylamine-carbonyl benzoic acid and preparation method and application thereof Download PDF

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CN113387967A
CN113387967A CN202110346059.6A CN202110346059A CN113387967A CN 113387967 A CN113387967 A CN 113387967A CN 202110346059 A CN202110346059 A CN 202110346059A CN 113387967 A CN113387967 A CN 113387967A
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rare earth
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杨颖群
李薇
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Abstract

The invention discloses a rare earth material based on diphenylamine-carbonyl benzoic acid, which has the structural formula:
Figure DDA0003000725960000011
wherein R is a water molecule. The invention also provides a preparation method and application of the rare earth material based on diphenylamine-carbonyl benzoic acid. The invention has the beneficial effects that: the rare earth material based on diphenylamine carbonyl benzoic acid can be used as a fluorescent probe for identifying dichromate ions (Cr) harmful to the environment2O7 2‑) And has high selectivity; the rare earth material based on diphenylamine carbonyl benzoic acid prepared by the method has high yield.

Description

Rare earth material based on diphenylamine-carbonyl benzoic acid and preparation method and application thereof
[ technical field ] A method for producing a semiconductor device
The invention relates to a rare earth luminescent material, in particular to a rare earth material based on diphenylamine carbonyl benzoic acid and a preparation method and application thereof.
[ background of the invention ]
The rare earth is a novel functional material with various properties such as light, magnetism, electricity, biology and the like. Rare earth ions possess unique luminescent properties due to the unique structure of their 4f electron shells, which make rare earth compounds have wide applications in medical, biological imaging, optical fiber, lighting devices, etc. The rare earth complex is obtained by ligand and rare earth ion coordination bonding, and the light-emitting principle is that the ligand absorbs energy in an ultraviolet region, and then the ligand transfers the energy of the excited state to the emission energy level of the rare earth ion in an intramolecular energy transfer mode to cause the rare earth ion to emit light.
In the related technology, the rare earth complex has the advantages of high color purity, theoretical quantum efficiency of 100 percent, long luminescence life and the like, and can be used as an ideal fluorescent material. Various applications of the existing rare earth complexes begin to appear, for example, Chinese patent CN108181285A discloses selective recognition of Cu2+The fluorescent sensor material, the application and the preparation method thereof disclose that the rare earth terbium polysaccharide hybrid luminescent material can be used as a fluorescent sensor to be applied to metal cation Cu2+Selective identification of (2); chinese patent CN108264579A discloses a hydrogel material containing macrocyclic rare earth complex, a preparation method and application thereof, wherein the hydrogel material prepared by using the macrocyclic complex of rare earth terbium shows good recognition capability to transition metal ions, especially recognition capability to Fe3+Ions. As can be seen, the application of rare earth complexes as identification materials has begun to appear, but the fluorescent materials of rare earth complexes are used for identifying dichromate ions (Cr) harmful to the environment2O7 2-) The application of the method is not researched by people.
[ summary of the invention ]
The invention discloses a rare earth material based on diphenylamine-carbonyl benzoic acid, a preparation method and application thereof, and the rare earth material can be used as a fluorescent material for identifying dichromate ions (Cr)2O7 2-)。
In order to achieve the purpose, the technical scheme of the invention is as follows:
a rare earth material based on diphenylamine carbonyl benzoic acid has the following structural formula:
Figure BDA0003000725940000021
wherein R is a water molecule.
As a preferred improvement of the invention, the crystallographic data of the rare earth material based on diphenylaminocarbonylbenzoic acid are as follows:
triclinic system, space group
Figure BDA0003000725940000023
Figure BDA0003000725940000024
α＝73.222(5)°,β＝88.708(5)°,γ＝82.885(4)°,
Figure BDA0003000725940000025
Dc＝1.485g/cm3,Z＝2,μ(MoKα)＝1.135mm-1F (000) ═ 1344, final deviation factor R1＝0.0855,wR2＝0.1160。
The invention also provides a preparation method of the rare earth material based on diphenylamine carbonyl benzoic acid, which comprises the following steps:
step one, adding 0.35-0.45mmol of 2-diphenylamine-carbonyl benzoic acid, 0.15-0.25mmol of 1.10-phenanthroline, 0.15-0.20mmol of terbium nitrate hexahydrate and 0.10-0.20mmol of manganese acetate tetrahydrate into a round-bottom flask, and adding 10-15ml of manganese acetate in a volume ratio (4.5-5.5): 1, a mixed solvent composed of absolute ethyl alcohol and water;
step two, controlling the temperature to be 65-75 ℃, heating in a water bath, stirring, and reacting for 7.5-8.5 hours;
step three, after the mixed solvent is cooled, filtering and keeping filtrate;
and step four, covering a layer of preservative film with small holes on the filtrate, and naturally volatilizing at room temperature to obtain a colorless crystal product, namely the rare earth material based on the diphenylamine-carbonyl benzoic acid.
As a preferable modification of the present invention, in the step one, 0.35mmol of 2-diphenylaminocarbonylbenzoic acid, 0.15mmol of 1.10-phenanthroline, 0.15mmol of terbium nitrate hexahydrate and 0.10mmol of manganese acetate tetrahydrate are added to a round-bottom flask, and 10ml of a solution of manganese acetate in a volume ratio of 4.5: 1, anhydrous ethanol and water.
As a preferable modification of the present invention, in the step one, 0.42mmol of 2-diphenylaminocarbonylbenzoic acid, 0.20mmol of 1.10-phenanthroline, 0.18mmol of terbium nitrate hexahydrate and 0.14mmol of manganese acetate tetrahydrate are added to a round-bottom flask, and 12ml of a mixture of 5: 1, anhydrous ethanol and water.
As a preferable modification of the present invention, in the step one, 0.45mmol of 2-diphenylaminocarbonylbenzoic acid, 0.25mmol of 1.10-phenanthroline, 0.20mmol of terbium nitrate hexahydrate and 0.20mmol of manganese acetate tetrahydrate are added to a round-bottom flask, and 15ml of a mixture of manganese acetate in a volume ratio of 5.5: 1, anhydrous ethanol and water.
In the second step, the temperature is controlled to be 70 ℃, and the reaction is carried out for 8 hours by heating in a water bath and stirring.
As a preferred improvement of the invention, the crystallographic data of the rare earth material based on diphenylamino carbonyl benzoic acid are as follows:
triclinic system, space group
Figure BDA0003000725940000031
Figure BDA0003000725940000032
α＝73.222(5)°,β＝88.708(5)°,γ＝82.885(4)°,
Figure BDA0003000725940000033
Dc＝1.485g/cm3,Z＝2,μ(MoKα)＝1.135mm-1F (000) ═ 1344, final deviation factor R1＝0.0855,wR2＝0.1160。
The invention also provides application of the rare earth material based on diphenylamine carbonyl benzoic acid as a fluorescent material in recognition of dichromate ions.
The invention has the beneficial effects that:
1. the rare earth material based on diphenylamine carbonyl benzoic acid can be used as a fluorescent probe for identifying dichromate ions (Cr) harmful to the environment2O7 2-) And has high selectivity;
2. the rare earth material based on diphenylamine carbonyl benzoic acid prepared by the preparation method has high yield which can reach 33-36%.
[ description of the drawings ]
In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the drawings needed to be used in the description of the embodiments are briefly introduced below, it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings can be obtained by those skilled in the art without inventive efforts, wherein:
FIG. 1 is a graph showing that rare earth materials based on diphenylamino carbonyl benzoic acid emit strong red fluorescence under a three-way ultraviolet lamp at an excitation wavelength of 254 nm;
FIG. 2 is a solid fluorescence emission spectrum of a rare earth material based on diphenylamino carbonyl benzoic acid at room temperature;
FIG. 3 is a graph of the effect of different anions on the fluorescence emission spectra of rare earth materials based on diphenylamino carbonyl benzoic acid;
FIG. 4 shows rare earth materials based on diphenylamino carbonyl benzoic acid at different concentrations (0.00-0.75 mmol.L)-1) Of Cr (C)2O7 2Emission spectra in solution;
FIG. 5 shows fluorescence intensity ratio I0I to Cr2O7 2Linear plot of concentration.
[ detailed description ] embodiments
The following description of the present invention is provided to enable those skilled in the art to better understand the technical solutions in the embodiments of the present invention and to make the above objects, features and advantages of the present invention more comprehensible.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual values, and between the individual values may be combined with each other to yield one or more new ranges of values, which ranges of values should be considered as specifically disclosed herein.
The invention provides a rare earth material based on diphenylamine-carbonyl benzoic acid, which has the following structural formula:
Figure BDA0003000725940000041
wherein R is a water molecule.
Specifically, the crystallography data of the rare earth material based on the diphenylamine carbonyl benzoic acid are as follows:
triclinic system, space group
Figure BDA0003000725940000042
Figure BDA0003000725940000043
α＝73.222(5)°,β＝88.708(5)°,γ＝82.885(4)°,
Figure BDA0003000725940000044
Dc＝1.485g/cm3,Z＝2,μ(MoKα)＝1.135mm-1F (000) ═ 1344, final deviation factor R1＝0.0855,wR2＝0.1160。
It can be seen that the rare earth material molecule based on diphenylamine carbonyl benzoic acid is composed of three 2-diphenylamine carbonyl benzoate radicals, one phenanthroline molecule, one coordinated water molecule, one uncoordinated water molecule and one europium (III) ion, and the whole molecule forms a mononuclear structure. The central europium (III) ion is in a coordination environment of nine atoms, wherein 7 coordinated oxygen atoms are respectively from three 2-diphenylamine carbonyl benzoate radicals and one coordinated water molecule, and the other 2 coordinated nitrogen atoms are from one phenanthroline molecule. The bond length of Eu-O is in
Figure BDA0003000725940000045
Within the normal range.
The properties of the rare earth material based on diphenylamine carbonyl benzoic acid were determined as follows:
(1) elemental analysis (C)72H54EuN5O11) As a result, theoretical value (%): c65.66, H4.13, N5.32; found (%): c65.59, H4.12, N5.31; (2) IR (KBr, cm)-1): 1712(s), 1693(s), 1645(s), 1614(s), 1589(vs), 1491(vs), 1385(vs), 847(m), 766(m), 729(m), 704(s), 619 (m); (3) under a three-way ultraviolet lamp, when excited by ultraviolet light with the wavelength of 254nm, the rare earth material emits strong red fluorescence, as shown in fig. 1.
The fluorescence spectrum is measured by using a fluorescence spectrophotometer, under the excitation of ultraviolet light at 335nm, the rare earth material based on diphenylamine-carbonyl benzoic acid has two fluorescence emission peaks at 593nm and 617nm, which respectively correspond to Eu3+Is/are as follows5D0→7F1And5D0→7F2the electron transition of (2), wherein the fluorescence intensity at 617nm is strongest, is shown in FIG. 2.
In addition, the invention also provides a preparation method of the rare earth material based on diphenylamine carbonyl benzoic acid, which comprises the following steps:
step one, adding 0.35-0.45mmol of 2-diphenylamine-carbonyl benzoic acid, 0.15-0.25mmol of 1.10-phenanthroline, 0.15-0.20mmol of terbium nitrate hexahydrate and 0.10-0.20mmol of manganese acetate tetrahydrate into a round-bottom flask, and adding 10-15ml of manganese acetate in a volume ratio (4.5-5.5): 1, a mixed solvent composed of absolute ethyl alcohol and water;
step two, controlling the temperature to be 65-75 ℃, heating in a water bath, stirring, and reacting for 7.5-8.5 hours;
preferably, the temperature is controlled at 70 ℃, the mixture is heated in a water bath and stirred, and the reaction lasts 8 hours.
Step three, after the mixed solvent is cooled, filtering and keeping filtrate;
and step four, covering a layer of preservative film with small holes on the filtrate, and naturally volatilizing at room temperature to obtain a colorless crystal product, namely the rare earth material based on the diphenylamine-carbonyl benzoic acid.
The rare earth material based on diphenylamine-carbonyl benzoic acid prepared by the preparation method has high yield which can reach 33-36%.
The method for preparing the rare earth material based on diphenylamino carbonyl benzoic acid provided by the invention is explained in detail by specific examples 1-3.
Example 1
The invention provides a preparation method of a rare earth material based on diphenylamine-carbonyl benzoic acid, which comprises the following steps:
step one, adding 0.35mmol of 2-diphenylamine carbonyl benzoic acid, 0.15mmol of 1.10-phenanthroline, 0.15mmol of terbium nitrate hexahydrate and 0.10mmol of manganese acetate tetrahydrate into a round-bottom flask, and adding a mixture of 10ml of manganese acetate tetrahydrate, wherein the volume ratio is 4.5: 1, a mixed solvent composed of absolute ethyl alcohol and water;
step two, controlling the temperature to be 70 ℃, heating in a water bath, stirring, and reacting for 8 hours;
step three, after the mixed solvent is cooled, filtering and keeping filtrate;
and step four, covering a layer of preservative film with small holes on the filtrate, and naturally volatilizing at room temperature to obtain a colorless crystal product, namely the rare earth material based on the diphenylamine-carbonyl benzoic acid.
Example 2
The invention provides a preparation method of a rare earth material based on diphenylamine-carbonyl benzoic acid, which comprises the following steps:
step one, adding 0.42mmol of 2-diphenylamine carbonyl benzoic acid, 0.20mmol of 1.10-phenanthroline, 0.18mmol of terbium nitrate hexahydrate and 0.14mmol of manganese acetate tetrahydrate into a round-bottom flask, and adding 12ml of manganese acetate in a volume ratio of 5: 1, anhydrous ethanol and water.
Step two, controlling the temperature to be 70 ℃, heating in a water bath, stirring, and reacting for 8 hours;
step three, after the mixed solvent is cooled, filtering and keeping filtrate;
and step four, covering a layer of preservative film with small holes on the filtrate, and naturally volatilizing at room temperature to obtain a colorless crystal product, namely the rare earth material based on the diphenylamine-carbonyl benzoic acid.
Example 3
The invention provides a preparation method of a rare earth material based on diphenylamine-carbonyl benzoic acid, which comprises the following steps:
step one, adding 0.45mmol of 2-diphenylamine carbonyl benzoic acid, 0.25mmol of 1.10-phenanthroline, 0.20mmol of terbium nitrate hexahydrate and 0.20mmol of manganese acetate tetrahydrate into a round-bottom flask, and adding 15ml of manganese acetate with the volume ratio of 5.5: 1, a mixed solvent composed of absolute ethyl alcohol and water;
step two, controlling the temperature to be 70 ℃, heating in a water bath, stirring, and reacting for 8 hours;
step three, after the mixed solvent is cooled, filtering and keeping filtrate;
and step four, covering a layer of preservative film with small holes on the filtrate, and naturally volatilizing at room temperature to obtain a colorless crystal product, namely the rare earth material based on the diphenylamine-carbonyl benzoic acid.
The invention also provides a method for identifying dichromate ions (Cr) by using the rare earth material based on the diphenylamine carbonyl benzoic acid as a fluorescent material2O7 2-) Application of the aspect. Experiments prove that the application of the rare earth material based on diphenylamine carbonyl benzoic acid as a fluorescent material is as follows:
under the same test conditions, the fully ground rare earth materials based on diphenylamino carbonyl benzoic acid were added to a concentration of 0.01mol.L each-1Different anions of (I)-、C2O4 2-、Ac-、IO3 -、F-、SiO3 2-、S2O8 2-、H2Sb2O7 2-、PO4 3-、S2O3 2-、SO4 2-、Cl-、ClO3 -、B4O7 2-、CO3 2-、WO4 2-、NO3 -、SO3 2-、NO2 -、Br-And Cr2O7 2-) Fluorescence emission spectra of rare earth materials based on diphenylamino-benzoic acid were measured in solution and in blank liquid (water) (see fig. 3). From FIG. 3, it can be seen thatIn I-、C2O4 2-、Ac-、IO3 -、F-、SiO3 2-、S2O8 2-、H2Sb2O7 2-、PO4 3-、S2O3 2-、SO4 2-、Cl-、ClO3 -、B4O7 2-、CO3 2-、WO4 2-、NO3 -、SO3 2-、NO2 -、Br-When the rare earth material based on diphenylamine carbonyl benzoic acid is in the solution and the blank solution, the rare earth material based on diphenylamine carbonyl benzoic acid has two fluorescence emission peaks at 593nm and 617nm, and the fluorescence peak intensity is almost not changed; and in Cr2O7 2-When in solution, the fluorescence intensity of rare earth materials based on diphenylamine carbonyl benzoic acid is quenched significantly. From this, it is known that p-Cr is a rare earth material based on diphenylamino carbonyl benzoic acid2O7 2-In response, Cr is expected to be2O7 2-The fluorescent probe of (1).
To further study Cr2O7 2-Influence on fluorescence emission intensity of rare earth material based on diphenylamine carbonyl benzoic acid, and adding the rare earth material into Cr with different concentrations under the same detection condition2O7 2-In solution, its fluorescence emission spectrum was measured (see FIG. 4). As shown in FIG. 4, p-Cr is rare earth material based on diphenylamine-carbonyl benzoic acid2O7 2-The rare earth material has high fluorescence sensitivity, and the comparison of the intensity change of the fluorescence peak of the rare earth material at 617nm shows that: (1) with Cr2O7 2-The fluorescence intensity gradually weakens when the concentration is increased; (2) the fluorescence intensity of rare earth materials based on diphenylamine-carbonyl-benzoic acid in a blank solution is set as I0In Cr2O7 2-The fluorescence intensity in the solution is I, the ratio thereof (I)0I) and Cr2O7 2-The solution concentration is 0.00-0.75mmol.L-1Exhibits a linear relationship in rangeSystem (see fig. 5) with a linear equation of I0/I＝0.9517+2794.9[Cr2O7 2-]，R2＝0.9964。
The experimental results show that: are respectively at I-、C2O4 2-、Ac-、IO3 -、F-、SiO3 2-、S2O8 2-、H2Sb2O7 2-、PO4 3-、S2O3 2-、SO4 2-、Cl-、ClO3 -、B4O7 2-、CO3 2-、WO4 2-、NO3 -、SO3 2-、NO2 -And Br-The fluorescence emission spectrum intensity of the rare earth material based on the diphenylamine carbonyl benzoic acid is almost not changed when the rare earth material is in the solution; and in Cr2O7 2-When in solution, the fluorescence of rare earth materials based on diphenylamino carbonyl benzoic acid is quenched significantly. The rare earth material p-Cr based on diphenylamine-carbonyl benzoic acid2O7 2-Has response and high selectivity, and the rare earth material based on diphenylamine carbonyl benzoic acid can be expected to be Cr2O7 2--The fluorescent probe of (1).
The invention has the beneficial effects that:
1. the rare earth material based on diphenylamine carbonyl benzoic acid can be used as a fluorescent probe for identifying dichromate ions (Cr) harmful to the environment2O7 2-) And has high selectivity;
2. the rare earth material based on diphenylamine-carbonyl benzoic acid prepared by the preparation method has high yield which can reach 33-36%.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the described embodiments. Various changes, modifications, substitutions and alterations to these embodiments will occur to those skilled in the art without departing from the spirit and scope of the present invention.

Claims (9)

1. A rare earth material based on diphenylamine carbonyl benzoic acid is characterized by having a structural formula shown as follows:
Figure FDA0003000725930000011
wherein R is a water molecule.
2. The rare earth material based on diphenylamine-carbonylbenzoic acid as claimed in claim 1, wherein the crystallographic data of the rare earth material based on diphenylamine-carbonylbenzoic acid is as follows:
triclinic system, space group
Figure FDA0003000725930000012
Figure FDA0003000725930000013
α＝73.222(5)°,β＝88.708(5)°,γ＝82.885(4)°,
Figure FDA0003000725930000014
Dc＝1.485g/cm3,Z＝2,μ(MoKα)＝1.135mm-1F (000) ═ 1344, final deviation factor R1＝0.0855,wR2＝0.1160。
3. A method for preparing a rare earth material based on diphenylamino carbonyl benzoic acid as claimed in claim 1, characterized in that it comprises the following steps:
step one, adding 0.35-0.45mmol of 2-diphenylamine-carbonyl benzoic acid, 0.15-0.25mmol of 1.10-phenanthroline, 0.15-0.20mmol of terbium nitrate hexahydrate and 0.10-0.20mmol of manganese acetate tetrahydrate into a round-bottom flask, and adding 10-15ml of manganese acetate in a volume ratio (4.5-5.5): 1, a mixed solvent composed of absolute ethyl alcohol and water;
step two, controlling the temperature to be 65-75 ℃, heating in a water bath, stirring, and reacting for 7.5-8.5 hours;
step three, after the mixed solvent is cooled, filtering and keeping filtrate;
and step four, covering a layer of preservative film with small holes on the filtrate, and naturally volatilizing at room temperature to obtain a colorless crystal product, namely the rare earth material based on the diphenylamine-carbonyl benzoic acid.
4. The method for preparing a rare earth material based on diphenylamine carbonyl benzoic acid as claimed in claim 3, wherein, in the step one, 0.35mmol of 2-diphenylamine carbonyl benzoic acid, 0.15mmol of 1.10-phenanthroline, 0.15mmol of terbium nitrate hexahydrate and 0.10mmol of manganese acetate tetrahydrate are added into a round bottom flask, and 10ml of manganese acetate in a volume ratio of 4.5: 1, anhydrous ethanol and water.
5. The method for preparing a rare earth material based on diphenylamine carbonyl benzoic acid as claimed in claim 3, wherein, in the step one, 0.42mmol of 2-diphenylamine carbonyl benzoic acid, 0.20mmol of 1.10-phenanthroline, 0.18mmol of terbium nitrate hexahydrate and 0.14mmol of manganese acetate tetrahydrate are added into a round bottom flask, and 12ml of manganese acetate in a volume ratio of 5: 1, anhydrous ethanol and water.
6. The method for preparing a rare earth material based on diphenylamine carbonyl benzoic acid as claimed in claim 3, wherein, in the step one, 0.45mmol of 2-diphenylamine carbonyl benzoic acid, 0.25mmol of 1.10-phenanthroline, 0.20mmol of terbium nitrate hexahydrate and 0.20mmol of manganese acetate tetrahydrate are added into a round bottom flask, and 15ml of manganese acetate in a volume ratio of 5.5: 1, anhydrous ethanol and water.
7. The method for preparing a rare earth material based on diphenylamine-carbonylbenzoic acid as claimed in claim 3, wherein, in the second step, the temperature is controlled to be 70 ℃, the heating in water bath and the stirring are carried out, and the reaction is carried out for 8 hours.
8. The method for preparing the rare earth material based on the diphenylamine carbonyl benzoic acid as claimed in claim 3, wherein the crystallographic data of the rare earth material based on the diphenylamine carbonyl benzoic acid are as follows:
triclinic system, space group
Figure FDA0003000725930000021
Figure FDA0003000725930000022
α＝73.222(5)°,β＝88.708(5)°,γ＝82.885(4)°,
Figure FDA0003000725930000023
Dc＝1.485g/cm3,Z＝2,μ(MoKα)＝1.135mm-1F (000) ═ 1344, final deviation factor R1＝0.0855,wR2＝0.1160。
9. Use of a rare earth material based on diphenylamino carbonyl benzoic acid as defined in claim 1 as a fluorescent material for identification of dichromate ions.
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CN101302228A (en) * 2008-06-27 2008-11-12 北京化工大学 Rare earth aromatic carboxylic acid organic complex and preparation thereof

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