CN110057893A - A kind of preparation method and application of MOF/ macromolecule core-shell nano fibrous composite - Google Patents

A kind of preparation method and application of MOF/ macromolecule core-shell nano fibrous composite Download PDF

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CN110057893A
CN110057893A CN201910366044.9A CN201910366044A CN110057893A CN 110057893 A CN110057893 A CN 110057893A CN 201910366044 A CN201910366044 A CN 201910366044A CN 110057893 A CN110057893 A CN 110057893A
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fibrous composite
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CN110057893B (en
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王英姿
王志玲
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University of Jinan
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Abstract

The invention discloses the preparations and application of a kind of MOF/ macromolecule core-shell nano fibrous composite, belong to nanocatalytic techniques and analytical chemistry detection technique field.Cu-MOF nanofiber specifically is formed using chiral amino acid and copper metal ion, which continues to generate chirality Cu-MOF/ polyureas core-shell nano fibrous composite with di-isocyanate reaction in organic-water mixed liquid；The chiral sensor prepared using the material, can quick, high sensitivity detection chirality Tryptophan enantiomer.

Description

A kind of preparation method and application of MOF/ macromolecule core-shell nano fibrous composite
Technical field
The present invention relates to a kind of preparation method and application of MOF/ macromolecule core-shell nano fibrous composite, and in particular to A kind of preparation method of chirality Cu-MOF/ polyureas core-shell nano fibrous composite is simultaneously applied to chiral electrochemical sensor detection The application of enantiomer, belongs to nanocatalytic techniques and technical field of analytical chemistry.
Background technique
In order to develop the sensitive and selective electricity analytical method for being able to detect trace biology and environment important compound, people Always in the preparation for constantly studying new electrode material.In numerous electrode modification agent, matched by metal ion and organic ligand Position formed metal-organic framework object crystal (MOFs), due to its with high-specific surface area, it is porous, structure easy-regulating, prepare item Part is mild and superperformance in terms of improving electron transfer rate and reducing the overpotential in oxidation-reduction process, in recent years It receives more and more attention.
Polyureas is the functional group Han-NH-CO-NH- for passing through gradually polymerization generation by polyisocyanates and polyamine compounds Polymer；Polyisocyanates is reacted with water also produces polyureas, and the isocyanate group in polyisocyanates reacts raw first with water At primary amine based compound and carbon dioxide is released, it is poly- that the primary amine groups of formation further polymerize formation with isocyanate group (- NCO) Urea；Polyurea materials have many advantages, such as good water resistance, resistance to ag(e)ing, wearability, are widely used in the waterproof of concrete, metal The protection of material and lubricating grease etc..But as far as we know, up to the present, the preparation based on MOF and polyureas composite material Method has not been reported.
On the other hand, molecular formula is identical with structural formula, configuration mirror but the isomers that can not be overlapped each other, referred to as Enantiomter, abbreviation enantiomer, corresponding molecule are known as chiral molecules.It is many heavy in modern medicine, pesticide and food service industry The molecule wanted is chiral molecules.In many cases, one of enantiomer shows required physiological activity, and in enantiomer Another kind then show inactive or even toxicity.Since enantiomer shows identical physics and chemistry under achirality environment Characteristic, therefore, the identification and quantization of enantiomer usually carry out under chiral environment.Electrochemical sensing technology have it is highly selective, The advantages that instrument cost is cheap, easy to operate and real-time online detects.However, currently, electrochemistry chirality sensing research also It is in the junior stage.
Summary of the invention
Technical assignment of the invention first is that in order to make up for the deficiencies of the prior art, a kind of MOF/ macromolecule nucleocapsid is provided and is received The preparation method of rice fibrous composite, this method is raw materials used at low cost, and preparation process is simple, and energy consumption of reaction is low, has work Industry application prospect.
The two of technical assignment of the invention are to provide the purposes of the MOF/ macromolecule core-shell nano fibrous composite, i.e., will Identification and content analysis of the material for highly sensitive detection L-Trp and D-trp enantiomer, the detecting instrument cost It is low, analysis efficiency is high, easy to operate, operating technology require it is low.
Technical scheme is as follows:
1. a kind of preparation method of MOF/ macromolecule core-shell nano fibrous composite, steps are as follows:
(1) preparation of Cu-MOF nanofiber
48-50 mmol nitrate trihydrate copper is dissolved in 1.1-1.3 mL water, obtains the clear copper nitrate solution of blue；By 24-26 The L-Aspartic acid and 24-26 mmol sodium hydroxide of mmol is dissolved in 1.1-1.3 mL water, and clear aspartic acid alkali soluble is made Liquid；Aspartic acid aqueous slkali is added in copper nitrate solution, 2h is stored at room temperature, is filtered, chirality Cu-MOF nanofiber is made；
(2) preparation of MOF/ macromolecule core-shell nano fibrous composite
After 26-28 mmol toluene di-isocyanate(TDI) is dissolved in 30-40 mL organic solvent, 6-8 mL water is added, Cu- is added It after MOF nanofiber, is uniformly mixed, is stored at room temperature overnight, filters；Water and ethanol washing 3 times are used respectively；85 DEG C activate to perseverance Chirality Cu-MOF/ polyureas core-shell nano fibrous composite, i.e. MOF/ macromolecule core-shell nano fibrous composite is made in weight.
The Cu-MOF nanofiber, is Cu2+It is [Cu (Asp) (H with the chemical formula that aspartic acid ligand is formed2O)x]n Cu-MOF, belong to 1D crystal structure, one structural unit is by a Cu2+, aspartic acid anion Asp and a multiple water Molecular composition, Asp structural formula are as follows:¯OOCCH2CH(NH2)COO¯；
The toluene di-isocyanate(TDI), is 2,4- toluene di-isocyanate(TDI) and 2, the mixture of 6- toluene di-isocyanate(TDI) composition, Its mass ratio is 80/20；
The organic solvent, selected from one of following: acetonitrile, tetrahydrofuran, n,N-Dimethylformamide, N, N- dimethylacetamide Amine, dimethyl sulfoxide, acetone；
It is 50-60 nm nanofiber crosslinking group that the chirality Cu-MOF/ polyureas core-shell nano fibrous composite, which is by diameter, At more multi-stage porous nano-fiber composite materials with micropore, mesoporous and less than 10 μm macropore composition；
The chirality Cu-MOF/ polyureas core-shell nano fibrous composite, chirality therein are derived from chirality Cu-MOF Nanowire Dimension；Polyureas therein is active isocyanate base-NCO and Cu-MOF nanofiber surface in toluene di-isocyanate(TDI) molecule On amino and solvent in water reaction generate macromolecule, polyureas functional group be-NH-CO-NH-.
2. MOF/ macromolecule core-shell nano fibrous composite as described above is for detecting L-Trp and D-trp The application of enantiomer, steps are as follows:
(1) chiral sensor working electrode is prepared
It has polished in alumina powder, the glassy carbon electrode surface of water and ethyl alcohol cleaning, the MOF/ high score daughter nucleus of 6 μ L of drop coating Shell nano-fiber composite material solution, room temperature are dried, and the biography of MOF/ macromolecule core-shell nano fibrous composite modification has been made Sense device working electrode has obtained chiral sensor working electrode；
The MOF/ macromolecule core-shell nano fibrous composite solution is to answer the MOF/ macromolecule core-shell nano fiber of 4 mg Ultrasound 10-15 min is blended with 250 μ L ethyl alcohol, 720 μ L water, 30 μ L Nafion and is made for condensation material；
(2) chiral sensor is prepared
By working electrode, reference electrode made from step (2) and electrode is connected on electrochemical workstation, MOF/ has been made Macromolecule core-shell nano fibrous composite sensor, i.e. chiral sensor；The reference electrode is saturated calomel electrode, to electricity Extremely platinum electrode；
(3) L-Trp and D-trp enantiomer are detected
Using pH 6.0,0.1 molL-1PBS buffer solution, using chiral sensor, to the L- color ammonia of various concentration Acid and D-trp standard solution, are measured using differential pulse voltammetry, based on the current value of differential pulse voltammetry curve, Draw L-Trp and D-trp enantiomer working curve；Testing sample solution is replaced into L-Trp and D-trp standard Solution carries out the detection of L-Trp and D-trp content in sample.
The chiral sensor is 0.01-1.0 × 10 to the detection range of L-Trp and D-trp-8g/mL;
The beneficial technical effect of the present invention is as follows:
1) preparation of MOF/ macromolecule core-shell nano fibrous composite of the present invention, due to joined chirality in material preparation process Raw material L-Aspartic acid, induces Cu-MOF nanofiber and Cu-MOF/ polyureas core-shell nano fibrous composite is chiral material Material；
2) preparation process of MOF/ macromolecule core-shell nano fibrous composite, simple process, mild condition is easy to operate, is easy to Industrialization；
The present invention provides one kind to be based on MOF/ macromolecule core-shell nano fibrous composite electrochemistry chiral sensor, the sensing Device is to modify MOF/ macromolecule core-shell nano fibrous composite to be made in glassy carbon electrode surface, and method is simple, easy to operate.By In the chirality composite material be active isocyanate base-NCO in toluene di-isocyanate(TDI) molecule and Cu-MOF Nanowire dimension table Amino-the NH in face2Water reaction in solvent, it is multiple to generate the core-shell nano fiber that polyureas is shell, Cu-MOF nanofiber is core Condensation material, water stability significantly improve, for example, sweeping speed is 0.1 V/s, the circulation of 100 circles within the scope of -1.0 to -1.5 V Volt-ampere curve has insignificant variation；There is the material micropore, mesoporous and macropore less than 10 μm to form, large specific surface area, More active sites with tryptophan interaction are formd, synergistic effect is so that the chiral sensing based on composite material preparation Device detects L-Trp and D-trp chiral enantiomer, has wide quick response, detection range, high sensitivity, easy to operate The features such as.
Specific embodiment
The present invention will be further described below with reference to examples, but protection scope of the present invention is not only limited to implement Example, professionals in the field change to made by technical solution of the present invention, are within the scope of protection of the invention interior.
A kind of preparation method of the MOF/ macromolecule core-shell nano fibrous composite of embodiment 1
(1) preparation of Cu-MOF nanofiber
48 mmol nitrate trihydrate copper are dissolved in 1.1 mL water, obtain the clear copper nitrate solution of blue；By the L- of 24 mmol Aspartic acid and 24 mmol sodium hydroxides are dissolved in 1.1 mL water, and clear aspartic acid aqueous slkali is made；By aspartic acid alkali soluble Liquid is added in copper nitrate solution, is stored at room temperature 2h, is filtered, and chirality Cu-MOF nanofiber is made；
(2) preparation of MOF/ macromolecule core-shell nano fibrous composite
After 26 mmol toluene di-isocyanate(TDI)s are dissolved in 30 mL acetonitriles, 6 mL water are added, after Cu-MOF nanofiber is added, It is uniformly mixed, is stored at room temperature overnight, filters；Water and ethanol washing 3 times are used respectively；Chirality Cu- is made to constant weight in 85 DEG C of activation MOF/ polyureas core-shell nano fibrous composite, i.e. MOF/ macromolecule core-shell nano fibrous composite.
A kind of preparation method of the MOF/ macromolecule core-shell nano fibrous composite of embodiment 2
(1) preparation of Cu-MOF nanofiber
50 mmol nitrate trihydrate copper are dissolved in 1.3 mL water, obtain the clear copper nitrate solution of blue；By the L- of 26 mmol Aspartic acid and 26 mmol sodium hydroxides are dissolved in 1.3 mL water, and clear aspartic acid aqueous slkali is made；By aspartic acid alkali soluble Liquid is added in copper nitrate solution, is stored at room temperature 2h, is filtered, and chirality Cu-MOF nanofiber is made；
(2) preparation of MOF/ macromolecule core-shell nano fibrous composite
After 28 mmol toluene di-isocyanate(TDI)s are dissolved in 40 mL n,N-Dimethylformamide, 8 mL water are added, Cu- is added It after MOF nanofiber, is uniformly mixed, is stored at room temperature overnight, filters；Water and ethanol washing 3 times are used respectively；85 DEG C activate to perseverance Chirality Cu-MOF/ polyureas core-shell nano fibrous composite, i.e. MOF/ macromolecule core-shell nano fibrous composite is made in weight.
A kind of preparation method of the MOF/ macromolecule core-shell nano fibrous composite of embodiment 3
(1) preparation of Cu-MOF nanofiber
49 mmol nitrate trihydrate copper are dissolved in 1.2 mL water, obtain the clear copper nitrate solution of blue；By the L- of 25 mmol Aspartic acid and 25 mmol sodium hydroxides are dissolved in 1.2 mL water, and clear aspartic acid aqueous slkali is made；By aspartic acid alkali soluble Liquid is added in copper nitrate solution, is stored at room temperature 2h, is filtered, and chirality Cu-MOF nanofiber is made；
(2) preparation of MOF/ macromolecule core-shell nano fibrous composite
After 27 mmol toluene di-isocyanate(TDI)s are dissolved in 35 mL acetone, 7 mL water are added, after Cu-MOF nanofiber is added, It is uniformly mixed, is stored at room temperature overnight, filters；Water and ethanol washing 3 times are used respectively；Chirality Cu- is made to constant weight in 85 DEG C of activation MOF/ polyureas core-shell nano fibrous composite, i.e. MOF/ macromolecule core-shell nano fibrous composite.
The characterization of 4 material of embodiment
Cu-MOF nanofiber prepared by embodiment 1, embodiment 2 or embodiment 3 carries out XRD analysis, and confirmation is Cu2+The day and The chemical formula that aspartic acid ligand is formed is [Cu (Asp) (H2O)x] n Cu-MOF, belong to 1D crystal structure, one structural unit is By a Cu2+, an aspartic acid anion Asp and multiple hydrones composition, Asp structural formula are as follows:¯OOCCH2CH(NH2) COO¯；
The toluene di-isocyanate(TDI) is bought by local Chemical market, is 2,4- toluene di-isocyanate(TDI) and 2, and 6- toluene two is different The mixture of cyanate composition, mass ratio 80/20；
It is 50-60 nm that the chirality Cu-MOF/ polyureas core-shell nano fibrous composite, which is by diameter through scanning electron microscope analysis, The multi-stage porous nanofiber composite wood with micropore, mesoporous and macropore composition less than 10 μm of nanofiber crosslinking composition Material；
The chirality Cu-MOF/ polyureas core-shell nano fibrous composite, chirality therein are derived from chirality Cu-MOF Nanowire Dimension；Polyureas therein is active isocyanate base-NCO and Cu-MOF nanofiber surface in toluene di-isocyanate(TDI) molecule On amino and solvent in water reaction generate macromolecule, polyureas functional group be-NH-CO-NH-.
A kind of MOF/ macromolecule core-shell nano fibrous composite of embodiment 5. is for detecting L-Trp and D-trp The application of enantiomer
(1) chiral sensor working electrode is prepared
It has polished in alumina powder, the glassy carbon electrode surface of water and ethyl alcohol cleaning, the MOF/ high score daughter nucleus of 6 μ L of drop coating Shell nano-fiber composite material solution, room temperature are dried, and the biography of MOF/ macromolecule core-shell nano fibrous composite modification has been made Sense device working electrode has obtained chiral sensor working electrode；
The MOF/ macromolecule core-shell nano fibrous composite solution is the MOF/ high score daughter nucleus for preparing 4 mg embodiments 1 13 min of ultrasound are blended with 250 μ L ethyl alcohol, 720 μ L water, 30 μ L Nafion and are made for shell nano-fiber composite material；
(2) chiral sensor is prepared
By working electrode, reference electrode made from step (2) and electrode is connected on electrochemical workstation, MOF/ has been made Macromolecule core-shell nano fibrous composite sensor, i.e. chiral sensor；The reference electrode is saturated calomel electrode, to electricity Extremely platinum electrode；
(3) L-Trp and D-trp enantiomer are detected
Using pH 6.0,0.1 molL-1PBS buffer solution, using chiral sensor, to the L- color ammonia of various concentration Acid and D-trp standard solution, are measured using differential pulse voltammetry, based on the current value of differential pulse voltammetry curve, Draw L-Trp and D-trp enantiomer working curve；Testing sample solution is replaced into L-Trp and D-trp standard Solution carries out the detection of L-Trp and D-trp content in sample；
Detection range to L-Trp and D-trp solution is 0.01-1.0 × 10-7g/mL。
A kind of MOF/ macromolecule core-shell nano fibrous composite of embodiment 6. is for detecting L-Trp and D-trp The application of enantiomer
Method is with embodiment 5, the MOF/ macromolecule core-shell nano fibrous composite alternate embodiment 1 that only prepares embodiment 2 Composite material.
Detection range to L-Trp and D-trp solution is 0.01-1.0 × 10-7g/mL。
A kind of MOF/ macromolecule core-shell nano fibrous composite of embodiment 7. is for detecting L-Trp and D-trp The application of enantiomer
Method is with embodiment 5, the MOF/ macromolecule core-shell nano fibrous composite alternate embodiment 1 that only prepares embodiment 3 Composite material.
Detection range to L-Trp and D-trp solution is 0.01-1.0 × 10-7g/mL。

Claims (8)

1. a kind of preparation method of MOF/ macromolecule core-shell nano fibrous composite, which is characterized in that steps are as follows:
The preparation of Cu-MOF nanofiber
48-50 mmol nitrate trihydrate copper is dissolved in 1.1-1.3 mL water, obtains the clear copper nitrate solution of blue；By 24-26 The L-Aspartic acid and 24-26 mmol sodium hydroxide of mmol is dissolved in 1.1-1.3 mL water, and clear aspartic acid alkali soluble is made Liquid；Aspartic acid aqueous slkali is added in copper nitrate solution, 2h is stored at room temperature, is filtered, chirality Cu-MOF nanofiber is made；
The preparation of MOF/ macromolecule core-shell nano fibrous composite
After 26-28 mmol toluene di-isocyanate(TDI) is dissolved in 30-40 mL organic solvent, 6-8 mL water is added, Cu- is added It after MOF nanofiber, is uniformly mixed, is stored at room temperature overnight, filters；Water and ethanol washing 3 times are used respectively；85 DEG C activate to perseverance Chirality Cu-MOF/ polyureas core-shell nano fibrous composite, i.e. MOF/ macromolecule core-shell nano fibrous composite is made in weight.
2. the preparation method of MOF/ macromolecule core-shell nano fibrous composite as described in claim 1, which is characterized in that institute Cu-MOF nanofiber is stated, is Cu2+It is [Cu (Asp) (H with the chemical formula that aspartic acid ligand is formed2O)x] n Cu-MOF, belong to 1D crystal structure, one structural unit are by a Cu2+, an aspartic acid anion Asp and multiple hydrones composition, Asp structural formula are as follows:¯OOCCH2CH(NH2)COO¯。
3. the preparation method of MOF/ macromolecule core-shell nano fibrous composite as described in claim 1, which is characterized in that institute Toluene di-isocyanate(TDI) is stated, is 2,4- toluene di-isocyanate(TDI) and 2, the mixture of 6- toluene di-isocyanate(TDI) composition, quality Than being 80/20.
4. the preparation method of MOF/ macromolecule core-shell nano fibrous composite as described in claim 1, which is characterized in that institute Organic solvent is stated, selected from one of following: acetonitrile, tetrahydrofuran, n,N-Dimethylformamide, n,N-dimethylacetamide, diformazan Base sulfoxide, acetone.
5. the preparation method of MOF/ macromolecule core-shell nano fibrous composite as described in claim 1, which is characterized in that institute Chiral Cu-MOF/ polyureas core-shell nano fibrous composite is stated, is that 50-60 nm nanofiber is crosslinked the tool formed by diameter The more multi-stage porous nano-fiber composite materials being made of micropore, mesoporous and less than 10 μm macropore.
6. the preparation method of MOF/ macromolecule core-shell nano fibrous composite as described in claim 1, which is characterized in that institute Chiral Cu-MOF/ polyureas core-shell nano fibrous composite is stated, chirality therein is derived from chirality Cu-MOF nanofiber；Wherein Polyureas, be active isocyanate base-NCO in toluene di-isocyanate(TDI) molecule and the amino on Cu-MOF nanofiber surface And the macromolecule that the water reaction in solvent generates, polyureas functional group are-NH-CO-NH-.
7. the MOF/ macromolecule core-shell nano fibrous composite of preparation method preparation as described in claim 1 is for detecting L- The application of tryptophan and D-trp enantiomer.
8. the application of detection L-Trp and D-trp enantiomer as claimed in claim 7, which is characterized in that step is such as Under:
(1) chiral sensor working electrode is prepared
It has polished in alumina powder, the glassy carbon electrode surface of water and ethyl alcohol cleaning, the MOF/ high score daughter nucleus of 6 μ L of drop coating Shell nano-fiber composite material solution, room temperature are dried, and the biography of MOF/ macromolecule core-shell nano fibrous composite modification has been made Sense device working electrode has obtained chiral sensor working electrode；
The MOF/ macromolecule core-shell nano fibrous composite solution is to answer the MOF/ macromolecule core-shell nano fiber of 4 mg Ultrasound 10-15 min is blended with 250 μ L ethyl alcohol, 720 μ L water, 30 μ L Nafion and is made for condensation material；
(3) chiral sensor is prepared
By working electrode, reference electrode made from step (2) and electrode is connected on electrochemical workstation, MOF/ has been made Macromolecule core-shell nano fibrous composite sensor, i.e. chiral sensor；The reference electrode is saturated calomel electrode, to electricity Extremely platinum electrode；
Detect L-Trp and D-trp enantiomer
Using pH 6.0,0.1 molL-1PBS buffer solution, using chiral sensor, to the L-Trp of various concentration It with D-trp standard solution, is measured using differential pulse voltammetry, based on the current value of differential pulse voltammetry curve, is drawn L-Trp and D-trp enantiomer working curve processed；Replace L-Trp and D-trp standard molten testing sample solution Liquid carries out the detection of L-Trp and D-trp content in sample.
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CN111440286A (en) * 2020-03-12 2020-07-24 济南大学 Preparation method and application of chiral Co-MOF/CoSR/PU core-shell composite material
CN111443117A (en) * 2020-03-12 2020-07-24 济南大学 Preparation method and application of bimanual β -CD @ Cu-MOF nano composite sensor
CN113224383A (en) * 2021-03-29 2021-08-06 中南大学 Composite solid electrolyte membrane based on metal-organic framework material and preparation method and application thereof
CN113224383B (en) * 2021-03-29 2022-12-13 中南大学 Composite solid electrolyte membrane based on metal-organic framework material and preparation method and application thereof
CN115591583A (en) * 2022-09-28 2023-01-13 北京理工大学(Cn) Preparation method and application of cellulose-MOF core-shell structure

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