KR101633280B1 - Organic-inorganic hybrid nanoporous silica material with high selective sensing of metal ion , manufacturing method of the materials - Google Patents
Organic-inorganic hybrid nanoporous silica material with high selective sensing of metal ion , manufacturing method of the materials Download PDFInfo
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Abstract
The present invention relates to an organic-inorganic hybrid nanoporous silica material having a high selectivity for a specific metal ion and a method for producing the same. More specifically, the present invention relates to a method for producing a nanoporous silica material having a nanometer- An organic-inorganic hybrid nano-porous silica material having high selectivity to iron ion (Fe 3+ ) as an organic-inorganic hybrid nano-porous silica material that forms a metal complex by coordination bonding of an amine or an amino group of a modified nano- And to provide a method for producing the same.
Description
The present invention relates to an organo-inorganic hybrid nanoporous silica material having a high selectivity for a specific metal ion and a method for producing the same.
As the industry develops in recent years, the amount of wastewater containing heavy metals such as copper, chromium, cobalt, mercury, lead, and iron is increasing. These heavy metal waste wastewater has a great effect on the ecosystem even in a very small amount, and removal of these heavy metal ions is essential. Therefore, it is very important to monitor these heavy metals through sensing. It is a nanoporous silica material with high surface area and nanopores as a promising candidate material.
Nanoporous silica materials are generally synthesized using a mono-molecular surfactant or polymer substance having hydrophilic and hydrophobic moieties as a template and an inorganic material based on silica as a pore wall forming material and self-assembling in an aqueous solution . The nanoporous silica material was prepared in 1992 by Beck and co-workers (Beck, JS; Vartuli, C .; Roth, WJ; Leonowicz, ME; Kresge, CT; Schmitt, KD; Chu, C. TW .; Olson, , EW McCullen, SB Higgins, JB Schlenker, JLJ Am. Chem. Soc., 1992a, 114, 10834) and Kresge et al. (Kresge, C. T., Leonowicz, M. E .; Roth, W. J., Vartuli, J. C .; Beck, J. S. Nature, 1992, 359, 710).
Also in 1998, Zhao and co-workers synthesized nanoporous silica with regular arrangement and pores of a certain size through self-assembly process in aqueous solution using block copolymer as a template and silica source as a pore wall forming material.
Nanoporous silica materials with various nanoporous structures (cubic, hexagonal, stratified, disordered), uniform pore size (2 to 30 nm) and high surface area (more than 1000 m 2 / g) Synthesized.
On the other hand, nanoporous materials having a pore wall composed of a silica material are limited in application by inert silica. Therefore, the nanoporous silica material in which the surface of nanopores is modified into organic groups has been studied by many researchers. (Wight, A. P., Davis, M. E. Chem. Rev., 2002, 102, 3589.)
Nanoporous silica materials have many silanol groups (Si-OH) on the pore surface. Therefore, an aliphatic hydrocarbon chain containing an atom such as alkoxysilane ((R'O) 3 Si (CH 2 ) n R, R '= methyl or ethyl, R = N, O, S, A cyclic aliphatic group, an aromatic group or a derivative thereof) can be modified through chemical reaction. These modified nanoporous silica materials have regular pore arrangements, uniform pore size and high surface area, and have very high applicability to macromolecule adsorption, enzyme adsorption, metal ion adsorption, catalysis, sensor, drug delivery, . And, these modified organic-inorganic hybrid nanoporous silica materials form various organometallic complexes with various organic ligands and transition metals. In particular, the combination of the lanthanide metal (atoms 57 to 71) with an organic ligand exhibits unique magnetic properties and optical properties. In previous research, Gunnlaugsson and co-workers have synthesized europium complexes with modified 1,10-phenanthroline-modified cyclic organic ligands, and found that iron (Fe (II)), copper (Cu Co (II)) ions were investigated. In this study, the largest fluorescence spectra of copper (Cu (II)) ions were observed in the case of copper (II) ions. Change. The results are presented only for the three metal ions. Further, when the europium-organic ligand complex in the form of a molecule is added to a metal ion solution to examine the change in fluorescence, it is difficult to separate the solution from the solution and it is difficult to reuse.
Accordingly, the present inventors have found that by modifying the pore surface of a nano-pore silica material with an aliphatic organosilica functional group containing an amino group and adding a transition metal thereto, an organo-inorganic hybrid nano-porous silica material capable of sensing various metal ions and an easy- The present invention has been completed to provide a manufacturing method.
It is an object of the present invention to provide an organic-inorganic hybrid nanoporous silica material having a high selectivity for a specific metal ion and a method for producing the same, and more particularly, to a method for preparing a silica precursor To provide a nanoporous silica material having a very regular and uniform pore size by self-assembly and a method of manufacturing the same.
The present invention relates to (S3) a process for producing a nanoporous silica material from which a template has been removed by heat treating a template-silica composite; (S4) surface modification of the pore wall surface of the nanoporous silica material with a silane compound functionalized with an amine or an amino group; And (S5) coordinating the amine or amino group of the silane compound with a metal compound to form a metal complex; Wherein the organic nanoporous silica nanoporous silica nanoporous material is a nanoporous silica nanoporous material.
According to an embodiment of the present invention, the template-silica composite comprises: (S1) preparing a solution of a polymer that is a structure-forming template; And (S2) mixing the solution with a silica precursor, which is a nano-pore wall constituent, and hydrothermally reacting to prepare a template-nanoporous silica composite; ≪ / RTI >
According to one embodiment of the present invention, the solution of the polymer of step (S1) may be prepared by mixing the polymer with distilled water under an acid catalyst.
According to one embodiment of the present invention, the structure-forming mold is a binary block copolymer of polyethylene oxide-polyethylethylene (PEO-PEE) or a triple copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO) Block copolymers.
According to an embodiment of the present invention, the silica precursor as the nano-pore wall constituent may be tetraethoxysilane, tetramethoxysilane, tetrachlorosilane, tetrabromosilane, or a mixture thereof.
According to an embodiment of the present invention, the silica precursor may be mixed in an amount of 150 to 300 parts by weight based on 100 parts by weight of the template.
According to an embodiment of the present invention, the preset temperature of step (S3) may be in the range of 400 to 700 ° C.
According to one embodiment of the present invention, the amine or amino group-functionalized silane compound is selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-methyl- Aminopropyltriethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- (2-aminoethyl) - aminocyclotrimethoxysilane, 4-aminocyclotriethoxysilane, p-aminophenyltrimethoxysilane, and p-aminophenyltriethoxysilane.
According to an embodiment of the present invention, the metal compound of the step (S5) may include at least one metal selected from the group consisting of europium (Eu), terbium (Tb), thorium (Tm) May include.
According to an embodiment of the present invention, the organic-inorganic hybrid nano-porous silica material may have a surface area of 500 to 1000 m 2 / g and an average pore diameter of 2 to 30 nm.
The present invention provides an organic-inorganic hybrid nanoporous silica material prepared by the above-described method.
According to one embodiment of the present invention, the organic-inorganic hybrid nanoporous silica material may have a pore arrangement of hexagonal, cubic, layered or disordered structure.
According to an embodiment of the present invention, the organic-inorganic hybrid nanoporous silica material may have a surface area of 500 to 1000 m 2 / g and an average pore diameter of 2 to 30 nm.
The present invention can exhibit selective adsorption capability for specific metal ions including the organic-inorganic hybrid nanoporous silica material.
According to an embodiment of the present invention, the specific metal ion may include an iron ion (Fe 3+ ).
According to an embodiment of the present invention, the adsorption selectivity for the iron ion (Fe 3+ ) may be 95 to 99.99%.
According to the above-described structure, a method of manufacturing an organic-inorganic hybrid nano-porous silica material having a large surface area by a simple and easy process can be provided by having pores having an average diameter of nanometer size and regular pore arrangement .
In addition, the organic-inorganic hybrid nano-porous silica material can be modified with a metal complex in which a silane compound and a metal compound are coordinated to the silica material surface to provide an adsorbent having high selectivity for iron ions, And it has an advantage that the adsorbent used can be easily separated from the solution.
FIG. 1 is a schematic view of a synthesis process of a nanoporous silica material having nanometer-sized uniform pores and regular pore arrangement.
2 is a schematic view showing a mechanism of pore wall formation when trimethoxy silane is used as a pore wall forming material.
Figure 3 shows a representative nanostructure of a nanoporous silica material.
4 is a schematic view of a process for synthesizing the organic-inorganic hybrid nano-porous silica material (Eu / APTMS / SBA-15) of Example 1. Fig.
5 is a schematic view showing a process of adsorbing metal ions in an aqueous solution using the organic-inorganic hybrid nano-porous silica material (Eu / APTMS / SBA-15) of Example 2. FIG.
6 is a flow chart showing the process of synthesizing the A. nano-porous silica material (SBA-15) of Example 1. FIG.
7 is a flow chart showing the process of synthesizing a nanoporous silica material (APTMS / SBA-15) surface-modified with the B. silane compound (3- (aminopropyl) trimethoxysilane, APTMS)
8 is a flow chart showing a process of synthesizing the organic-inorganic hybrid nano-porous silica material (Eu / APTMS / SBA-15) of Example 1. Fig.
FIG. 9 is a flowchart showing a process for selective sensing of metal ions in an aqueous solution using the organic-inorganic hybrid nano-porous silica material (Eu / APTMS / SBA-15) of Example 2. FIG.
10 shows an X-ray scattering diffraction pattern of A. SBA-15, B. APTMS / SBA-15 and C. Eu / APTMS / SBA-15 of Example 1. FIG.
11 is a transmission electron micrograph of SBA-15 (a and b) and Eu / APTMS / SBA-15 (c and d) according to the present invention.
12 is (a) nitrogen isotherm adsorption / desorption curve and (b) nano pore distribution diagram of SBA-15 and Eu / APTMS / SBA-15 according to the present invention.
13 is an infrared spectroscopy of SBA-15, APTMS / SBA-15 and Eu / APTMS / SBA-15 according to the present invention.
FIG. 14 is a graph showing the results of experiments of SBA-15, APTMS / SBA-15, Eu / APTMS / SBA-15 and various metal ion solutions (Fe 3+ , Cu 2+ , Cr 3+ , Co 2+ , Hg 2+ , Pb < 2 + > and Zn < 2 + >) of Eu / APTMS / SBA-15.
15 is a graph showing the results of a comparison of Eu / APTMS / SBA-15 according to the present invention with various metal ion solutions (Fe 3+ , Cu 2+ , Cr 3+ , Co 2+ , Hg 2+ , Pb 2+ and Zn 2+ ) Lt; 2 > of the fluorescence spectra peaks of the solution after the treatment.
The organic-inorganic hybrid nano-porous silica material for metal ion selective sensing according to the present invention and the method for producing the same are described below. However, unless otherwise defined in the technical terms and scientific terms used herein, And a description of known functions and configurations that may unnecessarily obscure the gist of the present invention will be omitted in the following description.
First, terms used in this specification are defined as follows.
In the present invention, " structure forming template " means a template used for forming the structure, " nano pore " means that the average diameter of the pores is 2 to 30 nm, and " organic-inorganic hybrid nano- Material " means a silica material having adsorptivity to metal ions.
The present invention provides a method for easily fabricating an organic-inorganic hybrid nanoporous silica material for highly selective sensing of metal ions by a simple process.
The present invention relates to (S1) preparing a mixed solution by mixing a polymer which is a structural forming template with distilled water under an acidic condition; (S2) mixing a silica precursor, which is a nano-pore wall constituting material, into the mixed solution and hydrothermal reaction to prepare a template-nanoporous silica composite; (S3) heat treating and removing the template of the template-silica composite; (S4) surface modification of the pore wall surface of the nanoporous silica material with a silane compound functionalized with an amine or an amino group; And (S5) coordinating the amine or amino group of the silane compound with a metal compound to form a metal complex; Wherein the organic nanoporous silica nanoporous silica nanoporous material is a nanoporous silica nanoporous material.
In step (S2), as shown in FIG. 1, the silica precursor is used as a pore wall forming material, the block copolymer is used as a structure forming template, and the mixture is self-assembled with a sol- ), A hydrothermal reaction may be performed to prepare a template-nanoporous silica composite, and the step may further include drying (Fig. 1-step 2). At this time, the drying may be performed at 60 to 100 ° C for 1 to 24 hours, and the drying temperature and time may be appropriately adjusted depending on the type or characteristics of the template-nanoporous silica composite.
The hydrothermal reaction is preferably carried out at 80 to 100 ° C. The acid catalyst used may be, for example, hydrochloric acid, sulfuric acid, nitric acid, acetic acid or a mixture thereof. Is preferably carried out under a hydrochloric acid catalyst.
The silica precursor may be tetraethoxysilane, tetramethoxysilane, tetrachlorosilane, tetrabromosilane, or a mixture thereof. However, it is not limited thereto. The silica precursor may be used to form -Si-O-Si- The template used to form the nano-pores can be a binary block copolymer of polyethylene oxide-polyethyl ethylene (PEO-PEE) or a polyethylene oxide-polypropylene oxide-polyethylene Oxide (PEO-PPO-PEO).
The polyethylene oxide-polyethylethylene (PEO-PEE) or polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO) used as the template has a number average The number average molecular weight (Mn) is preferably in the range of 4000 to 8000, and the number average molecular weight can be measured by gel permeation chromatography (GPC). The silica precursor may be mixed in an amount of 150-300 parts by weight with respect to 100 parts by weight of the template and may be mixed with 180-250 parts by weight in order to make the pore
In step (S3), the template of the template-nanoporous silica composite is heat treated to remove the nanoporous silica material (FIG. 1 - step 3), and the heat treatment temperature is 400 to 700 ° C. And the heat treatment temperature can be appropriately adjusted within the range according to the type of the mold.
As shown in FIG. 2, a mechanism for producing a silica material having nano pores using the silica precursor is, for a non-limiting example, the step of forming silanol by hydrolysis of tetramethoxysilane as the silica precursor (Step 1), and the dehydration reaction between the silanols takes place, -Si-O-Si-bonds are formed and crosslinked (step 2) to form a silica material having nanopores.
The nanoporous silica material prepared as described above may have a pore arrangement of a hexagonal, cubic, layered or disordered structure as shown in FIG.
In step (S4), the surface of the pore wall of the nanoporous silica material is surface-modified with a silane compound functionalized with an amine or an amino group. In step (S5), an amine or an amino group of the silane compound and a metal compound coordinate- Complexes can be formed to produce organo-inorganic hybrid nanoporous silica materials, a non-limiting example of which is schematically illustrated in FIG.
As shown in Fig. 4, the silanol group (Si-OH) and the silane compound (Si-OH) functionalized with an amine or an amino group on the pore wall surface of the nanoporous silica material (SBA-15) (APTMS / SBA-15, Step 1), and a metal compound (Eu (NO 3 ) 3 H 2 O) containing a transition metal was prepared by reacting the surface (3- (aminopropyl) trimethoxysilane, APTMS) Can be used to form a metal complex on the pore wall surface (EuAPTMS / SBA-15) (step 2).
The amine or amino functionalized silane compound used for surface modification of the nanoporous silica material can be, for example, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-methyl- Aminopropyltrimethoxysilane, N- (2-aminoethyl) -3-aminopropyltrimethoxysilane, N- -Aminopropyltriethoxysilane, 4-aminocyclotrimethoxysilane, 4-aminocyclotriethoxysilane, p-aminophenyltrimethoxysilane, aniline and p-aminophenyltriethoxysilane. , And the silane compound functionalized with an amine or an amino group is not limited thereto.
The metal compound capable of forming a metal complex by coordinating with an amine or an amino group of the silane compound is selected from the group consisting of europium (Eu), terbium (Tb), thorium (Tm) and erbium (Er) Eu (NO 3 ) 3 , EuCl 3 , EuBr 3 , EuF 3 , Eu (CH 3 CO 2 ) 3 , Eu 2 (C 2 O 4 ) 3, Eu 2 (SO 4 ) 3 or Eu (ClO 4 ) 3 .
The nanoporous silica material prepared by the above method provides the nanoporous silica material. The nanoporous silica material may exhibit selective adsorption ability for a specific metal ion and may have a pore arrangement of a hexagonal, cubic, layered or disordered structure. Here, the average pore diameter may be 2 to 30 nm, and the surface area of the silica material may be 500 to 1000 m 2 / g. Preferably, the nanoporous silica material may be a silica material having a hexagonal or cubic structure of pore arrangements having an average pore diameter of 5 to 20 nm and a surface area of 600 to 800 m 2 / g.
The present invention also provides an organic-inorganic hybrid nanoporous adsorbent comprising the nanoporous silica material. The organic-inorganic hybrid nanoporous adsorbent can have a selective adsorption capacity for a specific metal ion, and the specific metal ion includes, but is not limited to, iron ions (Fe 3+ ), copper (Cu 2+ ), chromium Cr 3+ ), cobalt (Co 2+ ), mercury (Hg 2+ ), lead (Pb 2+ ) or zinc (Zn 2+ ), preferably iron ions (Fe 3+ ).
At this time, when the iron ion (Fe 3+ ) is adsorbed by using the organic-inorganic hybrid nanoporous adsorbent comprising the nanoporous silica material, adsorption selectivity to the iron ion (Fe 3+ ) is 95 to 99.99% Fe 3+ ), and a non-limiting example for selective sensing of metal ions using the organic-inorganic hybrid nano-pore adsorbent is schematically shown in FIG.
Hereinafter, a method of manufacturing a dissimilar metal composite of the present invention and an electrode using the same will be described with reference to specific examples, but the scope of the claims of the present invention is not limited thereto.
[Example 1] Synthesis of organic-inorganic hybrid nano-porous silica material (Eu / APTMS / SBA-15)
A. Synthesis of Nanoporous Silica Material (SBA-15)
16 g of a block copolymer (PEO 20 -PPO 70 -PEO 20 , number average molecular weight = 5800, P123) was dissolved in 500 ml of water (Step S61 in FIG. 6) and 80 ml of 35% hydrochloric acid aqueous solution was added - step S62), and the mixture was stirred at 35 DEG C for 1 hour (Fig. 6, step S63). Then, 36.9 ml of tetramethoxysilane was added to the reaction solution (FIG. 6, step S64), stirred at 35 ° C for 30 minutes, and then aged for 24 hours at rest (FIG. Thereafter, hydrothermal reaction was carried out in a stationary state at 100 DEG C for 24 hours (Fig. 6, step S66). The reaction product was filtered with filter paper, washed with water, and dried at 80 DEG C for 12 hours to prepare a template-nanoporous silica composite (FIG. 6, step S67). The template-nanoporous silica composite was heat-treated at 550 ° C. for 4 hours in air to remove the template (FIG. 6, step S68) to obtain a sample of nanoporous silica material (SBA-15) S69).
B. Synthesis of nanoporous silica material (APTMS / SBA-15) surface-modified with silane compound (3- (aminopropyl) trimethoxysilane, APTMS)
120 ml toluene solution in which 0.1 M concentration of 3- (aminopropyl) trimethoxysilane was dissolved was added to 1.2 g of the nanoporous silica material (SBA-15) (Fig. 7, step S71). This was reacted at 60 DEG C for 24 hours to synthesize a nanoporous silica material surface-modified with 3- (aminopropyl) trimethoxysilane (Fig. 7, step S71). 7-step S73) and dried at 80 DEG C for 12 hours (Fig. 7, step S74) to obtain a silane compound (3- (aminopropyl) trimethoxysilane, APTMS (APTMS / SBA-15) (Fig. 7, step S75). The surface modified nanoporous silica material (APTMS / SBA-15)
C. Synthesis of Organic-Inorganic Hybrid Nanoporous Silica Material (Eu / APTMS / SBA-15)
0.8 g compound (3- (aminopropyl) trimethoxysilane, APTMS) a surface-modified nanoporous silica materials to 1.0 x 10 (APTMS / SBA- 15) -2 M nitrite europium (Eu (NO 3) 3 ) (Fig. 8-step S81). Then, the mixture was stirred at room temperature (25 ° C) for 5 hours to synthesize an organic-inorganic hybrid nano-pore silica material (Eu / APTMS / SBA-15) (FIG. Inorganic hybrid nano-pore silica material (Eu / APTMS / SBA-SBA) was prepared by washing with distilled water and washing with distilled water (Fig. 8- 15) sample was obtained (Fig. 8-step S85).
Identification and evaluation of the product material
FIG. 10 shows a nanoporous silica material (APTMS / SBA-15) surface-modified with a nanoporous silica material (SBA-15), a silane compound (3- (aminopropyl) trimethoxysilane, APTMS) and an organo-inorganic hybrid nano The x-ray scattering diffraction pattern of the pore silica material (Eu / APTMS / SBA-15) was analyzed and shown.
As a result, SBA-15 shows four peaks (100, 110, 200, 210) out of the five peaks well separated. It was confirmed that nanopores were well arranged in a hexagonal structure, and 5 peaks were also well separated in the surface modified APTMS / SBA-15. Thus, after the surface modification, the nanoporous structure maintains a well-arranged hexagonal structure Respectively. In addition, Eu-APTMS / SBA-15 showed an x-ray scattering diffraction pattern showing a typical hexagonal structure, indicating that the organic-inorganic hybrid nanoporous silica material (Eu / APTMS / SBA-15) I could confirm.
FIGS. 11 (a) and 11 (b) show transmission electron micrographs of SBA-15, and FIGS. 11 (c) and (d) show the results of an organic / inorganic hybrid nanoporous silica material (Eu / APTMS / SBA- Was observed by a transmission electron microscope. 11 (a) and 11 (c) are transmission electron micrographs when viewed parallel to the direction of the nanopore channels, and FIGS. 11 (b) and 11 (d) Transmission electron microscopy showed that both samples (SBA-15 and Eu / APTMS / SBA-15) had well-ordered nanoporous structures, consistent with the results of the X-ray scattering diffraction pattern in FIG. .
Figure 12 shows (a) the nitrogen isotherm adsorption / desorption curves of SBA-15 and Eu / APTMS / SBA-15 and (b) the nano pore distribution diagrams showing (a) nitrogen isotherm adsorption / desorption curves, (B) the nano pore distribution shows that the surface area of SBA-15 is 870 m 2 / g and the average pore diameter is 6.6 nm. The Eu / APTMS /
The surface area and average pore diameter of the organic-inorganic hybrid nano-pore silica material (Eu / APTMS / SBA-15) were slightly reduced compared to SBA-15. This indicates that the amine of the silane compound Or a metal complex in which an amino group and a metal compound are coordinated to each other, as a result of which the surface of the pore wall is well modified with the metal complex.
13 shows infrared spectroscopy of SBA-15, APTMS / SBA-15 and Eu / APTMS / SBA-15 of the present invention. In the APTMS / SBA-15 surface-modified with SBA-15 with 3- (aminopropyl) trimethoxysilane, the peak intensity at 970 cm -1 indicating the silanol (Si-OH) group present in SBA-15 , And it was confirmed that two peaks at 2935 cm -1 and 2851 cm -1 representing aliphatic CH groups by the 3- (aminopropyl) trimethoxysilane group and one at 1556 cm -1 by the NH group Was successfully modified using 3- (aminopropyl) trimethoxysilane on the pore surface of the nanoporous silica material (SBA-15). In addition, the organic-inorganic hybrid nano-porous silica material (Eu / APTMS / SBA-15) was also able to confirm an infrared spectral spectrum similar to APTMS / SBA-15, It was confirmed that metal complexes were successfully synthesized on the surface of nanopores without disappearance of trimethoxysilane group.
[Example 2] Adsorption of metal ions in an aqueous solution using an organic-inorganic hybrid nano-porous silica material (Eu / APTMS / SBA-15)
To each 4 ml of aqueous solution of Fe 3+ , Cu 2+ , Cr 3+ , Co 2+ , Hg 2+ , Pb 2+ and Zn 2+ ions dissolved in a concentration of 1.0 × 10 -2 M, 0.08 g of organic- Hybrid nano-pore silica material (Eu / APTMS / SBA-15) was added (FIG. 9-step S91). Then, the mixture was stirred at room temperature (25 DEG C) for 1 hour (FIG. 9-step S92).
Identification and evaluation of metal ion adsorption
As shown in FIG. 5, in an aqueous solution in which Fe 3+ , Cu 2+ , Cr 3+ , Co 2+ , Hg 2+ , Pb 2+ and Zn 2+ ions were dissolved at a concentration of 1.0 × 10 -2 M, Inorganic hybrid nano-pore adsorbent containing a nanoporous silica material (Eu / APTMS / SBA-15) was added to selectively detect the metal ions. The results were analyzed by X-ray diffraction diffraction pattern, nitrogen isotherm adsorption / desorption, transmission electron microscope, Infrared spectroscopy and fluorescence spectroscopy.
Fig. 14 is a graph showing the effect of various metal ion solutions (Fe3 + , Cu2 + , Cr3 + , Co2 + , Hg2 + , Pb2 + and Fe3 +) on SBA-15, APTMS / SBA-15 and Eu / APTMS / SBA- Lt; / RTI > and Zn2 + ). The spectra of Eu / APTMS / SBA-15 were characterized by the fluorescence spectra of 5 D o → 7 F 1 , 5 D o → 7 F 2 and 5 F at 587.6 nm, 612.2 nm and 642.1 nm, respectively, D o → it was confirmed that the peak corresponding to the 7 F 3 transition.
When the Eu / APTMS / SBA-15 samples were treated with various metal ion solutions, the reduction in the intensity of these three peaks was due to the interaction between the europium-complexes modified with nanopores and the metal ions .
In particular, the peak observed at 612.2 nm was observed to show a tendency to decrease in peak intensity. It was confirmed that the treatment with a solution containing iron (Fe 3+ ) ion shows a remarkable decrease in peak intensity. The decrease in peak intensity in the fluorescence spectra can be analyzed to confirm adsorption selectivity for metal ions have.
For a more clear comparison, the change in peak intensity at 612.2 nm was plotted when various metal ion solutions were treated for Eu / APTMS / SBA-15 samples, as shown in Fig. It can be seen that peak intensity decreases for all metal ions, especially for iron (Fe 3+ ) ions, the peak intensity is close to zero at 612.2 nm.
From these results, it can be confirmed that Eu / APTMS / SBA-15 has a strong sensing ability for iron (Fe 3+ ) ions among various heavy metal ions.
While the present invention has been particularly shown and described with reference to exemplary embodiments thereof, it is to be understood that the invention is not limited to the disclosed embodiments, but, on the contrary, is intended to cover various modifications and similarities. Accordingly, the scope of the present invention should not be limited to the above-described embodiments, but should be determined by the following claims.
Claims (16)
(S4) surface modification of the pore wall surface of the nanoporous silica material with a silane compound functionalized with an amine or an amino group; And
(S5) a metal compound containing at least one metal selected from the group consisting of europium (Eu), terbium (Tb), thorium (Tm) and erbium (Er) ; Lt; RTI ID = 0.0 > 1, < / RTI >
The above-mentioned mold-silica composite,
(S1) preparing a solution of a polymer that is a template-forming template; And
(S2) mixing a silica precursor, which is a nano-pore wall constituent, into the solution and hydrothermal reaction to prepare a template-nanoporous silica composite; Lt; RTI ID = 0.0 > 1, < / RTI >
Wherein the solution of the polymer in step (S1) is prepared by mixing the polymer with distilled water under an acid catalyst.
The structure-forming template may be a binary block copolymer of polyethylene oxide-polyethylethylene (PEO-PEE) or an organic-inorganic hybrid nanocomposite that is a ternary block copolymer of polyethylene oxide-polypropylene oxide-polyethylene oxide (PEO-PPO-PEO) Lt; / RTI >
Wherein the silica precursor as the nano-pore wall constituent material is tetraethoxysilane, tetramethoxysilane, tetrachlorosilane, tetrabromosilane or a mixture thereof.
Wherein the silica precursor is mixed in an amount of 150 to 300 parts by weight based on 100 parts by weight of the template.
And the heat treatment temperature in the step (S3) is in the range of 400 to 700 占 폚.
The silane compound functionalized with the amine or amino group may be at least one selected from the group consisting of 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-methyl-3-aminopropyltrimethoxysilane, Aminopropyltrimethoxysilane, 4-aminocyclotrimethoxysilane, 4-aminocyclotrimethoxysilane, 4-aminopropyltrimethoxysilane, N- (2-aminoethyl) Inorganic hybrid nano-porous silica material, which is at least one selected from the group consisting of aminocyclotriethoxysilane, p-aminophenyltrimethoxysilane, aniline and p-aminophenyltriethoxysilane.
Wherein the organic-inorganic hybrid nanoporous silica material has a surface area of 500 to 1000 m 2 / g and an average pore diameter of 2 to 30 nm.
Wherein the organic-inorganic hybrid nanoporous silica material has a pore arrangement of hexagonal, cubic, layered or disordered structure.
Wherein the organic-inorganic hybrid nanoporous silica material has a surface area of 500 to 1000 m < 2 > / g and an average pore diameter of 2 to 30 nm.
Wherein the specific metal ion comprises iron ions (Fe < 3 + >).
Wherein the adsorption selectivity to the iron ion (Fe 3+ ) is 95 to 99.99%.
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