CN110511248B - Metal crown ether complex, single-layer film formed by self-assembly of metal crown ether complex and application of single-layer film - Google Patents
Metal crown ether complex, single-layer film formed by self-assembly of metal crown ether complex and application of single-layer film Download PDFInfo
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- 150000003983 crown ethers Chemical class 0.000 title claims abstract description 38
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 37
- 239000002184 metal Substances 0.000 title claims abstract description 37
- 238000001338 self-assembly Methods 0.000 title claims description 9
- 239000002356 single layer Substances 0.000 title abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 45
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 14
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 24
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims description 19
- 238000000034 method Methods 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 13
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 12
- 230000004048 modification Effects 0.000 claims description 11
- 238000012986 modification Methods 0.000 claims description 11
- 238000002791 soaking Methods 0.000 claims description 11
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 11
- 239000012498 ultrapure water Substances 0.000 claims description 11
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 9
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 9
- 125000003396 thiol group Chemical group [H]S* 0.000 claims description 9
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 8
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007864 aqueous solution Substances 0.000 claims description 5
- 239000003054 catalyst Substances 0.000 claims description 5
- 238000004140 cleaning Methods 0.000 claims description 5
- 239000002904 solvent Substances 0.000 claims description 5
- UUEWCQRISZBELL-UHFFFAOYSA-N 3-trimethoxysilylpropane-1-thiol Chemical compound CO[Si](OC)(OC)CCCS UUEWCQRISZBELL-UHFFFAOYSA-N 0.000 claims description 4
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 4
- 238000011068 loading method Methods 0.000 claims description 4
- 238000002156 mixing Methods 0.000 claims description 4
- 229910052700 potassium Inorganic materials 0.000 claims description 4
- 239000011591 potassium Substances 0.000 claims description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 3
- 230000000844 anti-bacterial effect Effects 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 3
- 238000007306 functionalization reaction Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 claims description 3
- 239000002808 molecular sieve Substances 0.000 claims description 3
- 239000002094 self assembled monolayer Substances 0.000 claims description 3
- 239000013545 self-assembled monolayer Substances 0.000 claims description 3
- URGAHOPLAPQHLN-UHFFFAOYSA-N sodium aluminosilicate Chemical compound [Na+].[Al+3].[O-][Si]([O-])=O.[O-][Si]([O-])=O URGAHOPLAPQHLN-UHFFFAOYSA-N 0.000 claims description 3
- WAEMQWOKJMHJLA-UHFFFAOYSA-N Manganese(2+) Chemical compound [Mn+2] WAEMQWOKJMHJLA-UHFFFAOYSA-N 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000003213 activating effect Effects 0.000 claims description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 229910001437 manganese ion Inorganic materials 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 239000010408 film Substances 0.000 claims 9
- 238000004519 manufacturing process Methods 0.000 claims 2
- 238000003745 diagnosis Methods 0.000 claims 1
- 201000010099 disease Diseases 0.000 claims 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 claims 1
- 239000010409 thin film Substances 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 5
- 150000002500 ions Chemical group 0.000 abstract description 4
- 238000002360 preparation method Methods 0.000 abstract description 4
- 230000002776 aggregation Effects 0.000 abstract description 3
- 238000004220 aggregation Methods 0.000 abstract description 2
- 238000007210 heterogeneous catalysis Methods 0.000 abstract description 2
- 230000002779 inactivation Effects 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- 239000010410 layer Substances 0.000 abstract 1
- 229910021645 metal ion Inorganic materials 0.000 abstract 1
- 229910001414 potassium ion Inorganic materials 0.000 description 10
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000013078 crystal Substances 0.000 description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 3
- 238000012512 characterization method Methods 0.000 description 3
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 3
- 238000001035 drying Methods 0.000 description 3
- -1 iron ion Chemical class 0.000 description 3
- 239000013081 microcrystal Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000006277 sulfonation reaction Methods 0.000 description 3
- BEZVGIHGZPLGBL-UHFFFAOYSA-N 2,6-diacetylpyridine Chemical compound CC(=O)C1=CC=CC(C(C)=O)=N1 BEZVGIHGZPLGBL-UHFFFAOYSA-N 0.000 description 2
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000003595 spectral effect Effects 0.000 description 2
- 238000005406 washing Methods 0.000 description 2
- MPCRDALPQLDDFX-UHFFFAOYSA-L Magnesium perchlorate Chemical compound [Mg+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O MPCRDALPQLDDFX-UHFFFAOYSA-L 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 229910001429 cobalt ion Inorganic materials 0.000 description 1
- XLJKHNWPARRRJB-UHFFFAOYSA-N cobalt(2+) Chemical compound [Co+2] XLJKHNWPARRRJB-UHFFFAOYSA-N 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- AXZAYXJCENRGIM-UHFFFAOYSA-J dipotassium;tetrabromoplatinum(2-) Chemical compound [K+].[K+].[Br-].[Br-].[Br-].[Br-].[Pt+2] AXZAYXJCENRGIM-UHFFFAOYSA-J 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000002815 homogeneous catalyst Substances 0.000 description 1
- TUJKJAMUKRIRHC-UHFFFAOYSA-N hydroxyl Chemical compound [OH] TUJKJAMUKRIRHC-UHFFFAOYSA-N 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- LHOWRPZTCLUDOI-UHFFFAOYSA-K iron(3+);triperchlorate Chemical compound [Fe+3].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O LHOWRPZTCLUDOI-UHFFFAOYSA-K 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 150000002678 macrocyclic compounds Chemical class 0.000 description 1
- 239000011572 manganese Substances 0.000 description 1
- AIFGVOMWPFMOCN-UHFFFAOYSA-L manganese(2+);diperchlorate;hexahydrate Chemical compound O.O.O.O.O.O.[Mn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O AIFGVOMWPFMOCN-UHFFFAOYSA-L 0.000 description 1
- 238000001819 mass spectrum Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- 239000013335 mesoporous material Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000002715 modification method Methods 0.000 description 1
- 238000005232 molecular self-assembly Methods 0.000 description 1
- 238000005580 one pot reaction Methods 0.000 description 1
- 229920000172 poly(styrenesulfonic acid) Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229940005642 polystyrene sulfonic acid Drugs 0.000 description 1
- 229910001487 potassium perchlorate Inorganic materials 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000010992 reflux Methods 0.000 description 1
- 238000002390 rotary evaporation Methods 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000000547 structure data Methods 0.000 description 1
- 238000006557 surface reaction Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- PADPILQDYPIHQQ-UHFFFAOYSA-L zinc;diperchlorate;hexahydrate Chemical compound O.O.O.O.O.O.[Zn+2].[O-]Cl(=O)(=O)=O.[O-]Cl(=O)(=O)=O PADPILQDYPIHQQ-UHFFFAOYSA-L 0.000 description 1
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2217—At least one oxygen and one nitrogen atom present as complexing atoms in an at least bidentate or bridging ligand
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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- C07F15/02—Iron compounds
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- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
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- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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Abstract
The invention discloses a metal crown ether complex, which is bonded with metal ions on the surface of a substrate in a coordination mode to form a monomolecular layer film, and the metal crown ether complex is modified on the surface of the substrate, so that the problem of metal catalytic center inactivation caused by mu-O bridging aggregation under an alkaline condition is solved. The metal crown ether complex can specifically recognize K+The ions form a monolayer film on the surface of the substrate, so that the metal complex can obtain better stability, and new properties can be given to the surface of the substrate, so that the metal crown ether complex has better application prospect and can be better applied to heterogeneous catalysis, the raw materials are easy to obtain, and the experimental equipment and the preparation method are simple.
Description
Technical Field
The invention belongs to the field of molecular self-assembly chemistry and the technical field of surface treatment and functionalization of materials, and particularly relates to a surface modification technology for forming a self-assembly film by utilizing a metal crown ether complex and a self-assembly method thereof.
Background
Based on acylhydrazone pentadentate ligands formed by dehydrating condensation of 2, 6-Diacetylpyridine (DAP) and hydrazide, a series of heptadentate metal complexes are obtained by bonding with different metals, but when the catalytic properties of the complexes are studied, the metal centers are easily inactivated by mu-O bridging to form polymers under alkaline conditions. We partially solved the ubiquitous problems of such homogeneous catalysts by complex design: for example, a dinuclear heptacomplex compound with crown ether functional groups is designed and synthesized, and the spectral characterization proves that the central crown ether can be used for K+Ion-specific recognition and the structure of the stable compound was demonstrated by crystal characterization.
In view of the crown ethers of the pair K+Ion specificity recognition, and considering the K-rich content in a plurality of mesoporous molecular sieves and ion exchange resins+The characteristic of ions is that the crown ether hepta-coordination metal complex can be dispersed in the mesopores only by simple soaking, and the mesopore property of 4-10nm can be ensuredThe binuclear complex is fully accommodated and enough mass transfer space is reserved, so that the problem of catalyst failure caused by mu-O bridging aggregation is fundamentally solved.
Through the hydroxyl free treatment and a series of modification on the surface of the substrate, the surface covered by potassium ions can be obtained, and thus the self-organized metal complex single-layer film can be obtained through the specific recognition of the crown ether functional group to the potassium ions. The molecular membrane self-assembly method by the complex is an effective method which is beneficial to controlling the assembly structure and the form. The self-assembly metal complex monomolecular film has practical application in various fields such as electrode modification, catalyst loading, antibacterial glass functionalization and the like. By loading the metal with other catalytic centers on the surface of the substrate, not only can the metal complex catalyst obtain better stability and redox activity, but also new properties can be endowed to the surface of the substrate.
Disclosure of Invention
In view of the above problems, the present invention provides a novel surface modification method, and a self-assembled monolayer film is formed on the surface of a substrate by using a metal crown ether complex. After the surface of a substrate is modified, potassium ions are fixed on the surface of the substrate, and the specificity recognition of the metal crown ether complex on the potassium ions is utilized, so that the self-assembled molecular monolayer is constructed on the surface of the substrate. Has the characteristics of simple and convenient operation and high stability.
The invention provides a metal crown ether complex, which has the following structural formula:
wherein M represents a transition metal ion; sol stands for solvent molecule.
Preferably, M represents an iron ion, a cobalt ion or a manganese ion. Sol represents a molecule of N, N-dimethylformamide or a molecule of methanol.
Further, the molecular structure of the metal crown ether complex can be the following structure (the middle circle represents the allowable space in the inner cavity):
the invention also provides a self-assembly metal complex monomolecular film which is obtained by self-assembly of the metal crown ether complex.
The invention also protects the application of the metal crown ether complex monomolecular film in the fields of electrode modification, catalyst loading and antibacterial glass functionalization.
Further, the invention provides a preparation method of the self-assembled metal complex monomolecular film, which comprises the following steps:
s1, activating a monomolecular film substrate to obtain an activated substrate with hydroxyl;
s2, combining the activated substrate with hydroxyl with a silane coupling agent with a mercapto functional group to expose the mercapto;
s3, further sulfonating the exposed sulfydryl, and treating with a potassium hydroxide solution to obtain a potassium ionized interface;
and S4, mixing the substrate ionized by potassium with a metal crown ether complex, and self-assembling to form a two-dimensional ordered self-assembled monolayer film.
Preferably, in the step S1, the substrate is quartz glass, ITO glass, an alumina film, glass, SBA-15, MCM-41 or ZSM-5 mesoporous molecular sieve; or polystyrene sulfonic acid and polystyrene with the surface directly subjected to sulfonation treatment.
Preferably, the substrate with hydroxyl groups after being activated in the step S1 is obtained by mixing concentrated sulfuric acid and hydrogen peroxide for soaking, soaking in organic acid, heating for micro-boiling for 30min, and then ultrasonically cleaning with an alcohol solvent.
Preferably, the silane coupling agent in step S2 is 3-mercaptopropyltrimethoxysilane.
Preferably, in step S2, the substrate material is soaked in a toluene solution of a silane coupling agent and reacted at 120 ℃ for 6 hours, so that the substrate is combined with the silane coupling agent.
Preferably, the method for sulfonating the mercapto group in step S3 is as follows: at room temperature, soaking the substrate connected with the silane coupling agent in an aqueous solution of hydrogen peroxide and methanol, wherein the weight ratio of hydrogen peroxide: methanol: the mass ratio of the ultrapure water is 1: 3: 10, then soaked with 200ml of 0.5M sulfuric acid, and finally washed with ultrapure water to remove the acid remaining on the surface.
Preferably, in step S3, the substrate is soaked in 0.1M KOH aqueous solution.
Compared with the prior art, the invention has the beneficial effects that:
a) the metal crown ether complex is self-assembled with potassium ions on the surface of the modified substrate in a coordination mode, so that crown ether complex molecules are fixed on the surface of the substrate, and the problem of metal catalytic center inactivation caused by mu-O bridging agglomeration under an alkaline condition is solved.
b) The metal crown ether complex can specifically recognize K+Therefore, a monolayer film is formed on the surface of the substrate, the metal complex can obtain better stability, and new properties can be endowed to the surface of the substrate and the mesoporous material. Widens the application range of the metal crown ether complex and is better applied to heterogeneous catalysis.
c) The raw materials are easy to obtain, the experimental equipment and the preparation method are simple to operate, and the obtained molecular monolayer film is uniform and sufficient in modification and good in stability.
Drawings
FIGS. 1-5 are schematic flow charts of the present invention for a surface modification technique by using a crown complex with other catalytic centers to form a self-assembled film and a self-assembling method thereof, wherein:
FIG. 1 is a hydroxyl radical on the surface of a liberalized substrate;
FIG. 2 is a schematic representation showing the use of silane coupling agents attached to hydroxyl groups on the surface of a substrate, covering the surface with a mercapto group;
FIG. 3 is a sulfonation treatment of a thiol group on a substrate surface;
FIG. 4 is a graph of energy vs. K according to crown ethers+Ion specificity recognition, namely fixing the metal crown ether complex on the surface of a substrate;
FIG. 5 is a schematic view of FIGS. 1 to 4.
FIG. 6 is mass spectral data of a metal crown ether complex.
FIG. 7 is an ultraviolet-visible absorption spectrum of a crown ether metal complex.
FIG. 8 shows the process of specific recognition of a crown ether metal complex.
Detailed Description
The following description of the embodiments of the present invention will be made with reference to the accompanying drawings. It should be noted that the description of the embodiments is provided to help understanding of the present invention, but the present invention is not limited thereto. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
The invention is described in detail below with reference to the figures and the specific examples.
Example 1
The metal crown ether complex is prepared by adopting a one-pot method.
2, 6-diacetylpyridine (163 mg,1 mmol) and manganese perchlorate hexahydrate (362 mg,1 mmol) were dissolved in methanol solution, heated to 60 ℃ with constant stirring, and diethylene glycol dihydrazide (162 mg,1 mmol) was added slowly. After the addition was complete, reflux was carried out at 85 ℃ for 12 h. After the reaction was completed, the solvent was removed by rotary evaporation under reduced pressure, and dried in vacuo to obtain a yellow solid. The yellow solid was dissolved in DMF and diffused with ether to give after a few days a pale yellow crystallite, designated crown-1, which was tested and resolved by XRD to give the crystal structure as follows. Crown-1 belongs to a binuclear heptadentate complex and is bridged by an oxygen-ether bond to form a metal organic covalent macrocycle.
The crystal structure data is as follows:
empirical formula: c42H70Mn2N14O10
Molecular weight: 1040.99
Crystal system, space group: monoclinic system, C2/C (15)
Unit cell parameters:
a =12.8869(7) α= 90°.
b =22.7641(19) β =93.290(1) °.
c =26.1382(15)γ= 90°.
unit cell volume 7655.23 Å-3
Mass spectra and uv characterization are shown in fig. 6 and fig. 7, respectively:
example 2
Preparation of Metal crown Ether Complex molecular Single layer film
The substrate is ITO glass, and 3-mercaptopropyl trimethoxysilane is adopted as a silane coupling agent.
1) Placing the ITO glass in ultrapure water, acetone and ethanol in sequence, ultrasonically cleaning for 30min respectively, and then drying by using nitrogen;
2) soaking ITO glass in mixed solution of hydrogen peroxide and concentrated sulfuric acid (H)2SO4：H2O2= 7: 3 (v/v)) boiling for 30min, and washing with ultrapure water to obtain exposed hydroxyl, as shown in FIG. 2;
3) putting the ITO glass in the step 2) into a reaction kettle, adding 1ml of 3-mercaptopropyltrimethoxysilane solution, taking 10ml of toluene as a solvent, reacting for 6 hours at 120 ℃, taking out, and cleaning the surface of the glass with alcohol and ultrapure water to obtain a surface with a mercapto group modification, wherein the surface is shown in figure 3;
4) the ITO glass in step 3) is first immersed in a mixed aqueous solution of hydrogen peroxide and methanol at room temperature (hydrogen peroxide: methanol: the mass ratio of the ultrapure water is 1: 3: 10) then soaking the substrate by 200ml of 0.5M sulfuric acid, finally cleaning the substrate by ultrapure water, and drying the substrate by nitrogen to obtain a sulfonate-covered surface, as shown in FIG. 4;
5) and putting the ITO glass after sulfonation reaction into 0.1M KOH aqueous solution for soaking for 1h, so that potassium ions are attached to the surface of the substrate. Then, the residual potassium ions on the surface of the substrate are washed away by using ultrapure water. It was then soaked in a 0.05M solution of the metal crown ether complex molecule for 6 h. Taking out, washing with ultrapure water, and drying with nitrogen to obtain the substrate modified by the self-assembled molecular monolayer film of the metal crown ether complex, as shown in FIGS. 1-5.
Experimental example 1
Testing its specific recognition of ions:
firstly, dispersing the microcrystal crown-1 (688 mg,1 mmol) in an ethanol solution, adding potassium perchlorate (138 mg,1 mmol), magnesium perchlorate (223 mg,1 mmol), anhydrous ferric perchlorate (372, 1 mmol) and zinc perchlorate hexahydrate (372 mg,1 mmol) into the solution, and standing for 2 hours after all the microcrystal crown-1 (688 mg,1 mmol) is dissolved. The microcrystals of crown-1 are collected, the change of the structure is characterized by XRD, and as shown in figure 8, the specific recognition of potassium ions by the metal crown ether complex is shown by analyzing the crystal structures before and after soaking.
The embodiments of the present invention are not intended to limit the present invention. Those skilled in the art can make numerous possible variations and modifications to the present teachings, or modify equivalent embodiments to equivalent variations, without departing from the scope of the present teachings, using the methods and techniques disclosed above. Therefore, any simple modification, equivalent change and modification made to the above embodiments according to the technical essence of the present invention are still within the scope of the protection of the technical solution of the present invention, unless the contents of the technical solution of the present invention are departed.
Claims (9)
1. A metal crown ether complex, wherein the metal crown ether complex has the following structural formula:
wherein M represents a divalent manganese ion; sol stands for N, N-dimethylformamide molecule.
2. A self-assembled monomolecular film of a metal complex comprising the crown ether complex of claim 1 obtained by self-assembly.
3. The use of the metal crown ether complex monomolecular film according to claim 2 in the fields of electrode modification, catalyst loading and antibacterial glass functionalization for non-disease treatment or diagnosis purposes.
4. A method for producing the self-assembled metal complex monomolecular film according to claim 2, comprising the steps of:
s1, activating a monomolecular film substrate to obtain an activated substrate with hydroxyl;
s2, combining the activated substrate with hydroxyl with a silane coupling agent with a mercapto functional group to expose the mercapto;
s3, further sulfonating the exposed sulfydryl, and treating with a potassium hydroxide solution to obtain a potassium ionized interface;
and S4, mixing the substrate ionized by potassium with a metal crown ether complex, and self-assembling to form a two-dimensional ordered self-assembled monolayer film.
5. The method of claim 4, wherein the substrate in step S1 is selected from the group consisting of alumina thin film, glass, SBA-15, MCM-41, and ZSM-5 mesoporous molecular sieves.
6. The method for preparing the self-assembled metal complex monomolecular film according to claim 4, wherein the substrate with the hydroxyl group after being activated in the step S1 is obtained by mixing concentrated sulfuric acid and hydrogen peroxide for soaking, soaking in organic acid, heating for slight boiling for 30min, and then ultrasonically cleaning by using alcohol solvent.
7. The method for preparing a self-assembled metal complex monomolecular film according to claim 4, wherein the silane coupling agent in the step S2 is 3-mercaptopropyltrimethoxysilane.
8. The method for preparing a self-assembled metal complex monomolecular film according to claim 4, wherein the substrate material is soaked in a toluene solution of a silane coupling agent and reacted at 120 ℃ for 6 hours in step S2, so that the substrate is bonded to the silane coupling agent.
9. The method for producing a self-assembled metal complex monomolecular film according to claim 4, wherein the method for sulfonating the mercapto group in step S3 comprises: at room temperature, soaking the substrate connected with the silane coupling agent in an aqueous solution of hydrogen peroxide and methanol, wherein the weight ratio of hydrogen peroxide: methanol: the mass ratio of the ultrapure water is 1: 3: 10, then soaked with 200ml of 0.5M sulfuric acid, and finally washed with ultrapure water to remove the acid remaining on the surface.
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