CN108570062B - Porous metal organic complex, preparation method thereof and application thereof in detection of ammonia gas and ammonia water - Google Patents
Porous metal organic complex, preparation method thereof and application thereof in detection of ammonia gas and ammonia water Download PDFInfo
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Abstract
The invention discloses a porous metal organic complex, a preparation method thereof and application thereof in detecting ammonia gas and ammonia water, wherein the structural unit of the complex is [ (CH)3)2NH2][Mg3(OH)(DHBDC)3(PTP)]Where DHBDC represents the divalent anion of 2, 5-dihydroxyterephthalic acid with two hydrogen atoms removed at-COOH and PTP represents 4'- (4-pyridine) -4,2':6', 4' -terpyridine. The complex can be used for selective sensing detection of ammonia gas and ammonia water, wherein the detected ammonia gas concentration can actually reach 5ppm, and the complex has a good linear relation; the method has obvious switching effect on ammonia water detection, and when the concentration of the ammonia water is more than 3ppm, the concentration of the ammonia water and the fluorescence intensity have good linear relation, so that the quantitative detection of the ammonia water can be realized.
Description
Technical Field
The invention relates to a porous metal organic complex taking 2, 5-dihydroxy terephthalic acid as a main ligand, which has good sensing performance on ammonia gas and ammonia water and can be used as a probe to detect ammonia in different states.
Background
Ammonia gas is widely used and discharged in industrial production and has strong pungent smell, corrosiveness and toxicity, the United states occupational safety and health administration recommends 25ppm ammonia concentration as a concentration limit, and 300ppm ammonia concentration can influence health to a great extent, so detection or sensing of ammonia gas has important significance in the fields of automobile industry, environmental sector, pharmaceutical industry, chemical plant and the like. It is also important that the human nose is difficult to smell low-concentration ammonia gas, and high-concentration ammonia gas can be quickly smelled, so that the detection of low-concentration ammonia gas has a practical value in many fields.
The coordination polymer is used as a crystal material with the most application prospect, and influence factors of the reaction can be regulated and controlled by reasonably selecting metal ions and organic ligands, so that the coordination polymer with some special properties and structures can be predicted and designed. In particular, some functional groups present in some open pore structures can enhance the sensing performance of such materials through static electricity, lewis acid-base action, hydrogen bonding, and the like.
Disclosure of Invention
The invention aims to provide a porous metal organic complex taking 2, 5-dihydroxyterephthalic acid as a main ligand, a preparation method of the complex and a new application of the complex.
For the above purpose, the structural unit of the porous organometallic complex used in the present invention is [ (CH)3)2NH2][Mg3(OH)(DHBDC)3(PTP)]Where DHBDC represents a divalent anion of 2, 5-dihydroxyterephthalic acid with two-COOH hydrogen atoms removed, PTP represents 4'- (4-pyridine) -4,2':6', 4' -terpyridine; the complex belongs to a hexagonal crystal system, P6(3)/mmc space group, and the unit cell parameter is
α＝90°，β＝90°，γ＝120°。
The preparation method of the porous metal organic complex comprises the following steps: adding magnesium nitrate, 2, 5-dihydroxyterephthalic acid and 4'- (4-pyridine) -4,2':6', 4' -terpyridine into a mixed solution of formic acid, N-dimethylacetamide and N, N-dimethylpropyleneurea in a volume ratio of 1: 4-8: 1-4 according to a molar ratio of 1:0.5: 0.5-1, uniformly stirring, and standing and reacting at a constant temperature of 125-135 ℃ for 4-6 days under a sealed condition to obtain the porous metal organic complex.
The porous metal organic complex has good sensing performance on ammonia gas and ammonia water, and can be used as a probe for detecting the ammonia gas and the ammonia water.
The method for detecting ammonia gas by adopting the porous metal organic complex comprises the following steps: spin coating the porous metal organic complex on an Ag-Pd electrode ceramic substrate, detecting ammonia with different concentrations by using a gas-sensitive detector, and drawing a standard curve of the ammonia concentration changing along with the relative resistance; and then detecting the relative resistance value of the ammonia gas sample to be detected, and combining a linear equation of the standard curve to obtain the concentration of the ammonia gas sample to be detected.
The method for detecting ammonia water by adopting the porous metal organic complex comprises the following steps:
1. uniformly dispersing a porous metal organic complex in N, N-dimethylacetamide to prepare a complex suspension with the concentration of 0.1-0.25 mg/mL, then dropwise adding an ammonia water sample to be detected into the suspension, detecting by using a fluorescence spectrophotometer under the excitation of the maximum excitation wavelength 362nm, and if the maximum emission peak is 505nm, indicating that the concentration of ammonia water in the ammonia water sample to be detected is less than 3 ppm; if the maximum emission peak is at 540nm, the concentration of the ammonia water in the ammonia water sample to be detected is more than 3 ppm;
2. and for the ammonia water sample to be detected with the ammonia water concentration of more than 3ppm, detecting according to the following steps:
(1) dropwise adding ammonia water with the concentration of 3-100 ppm into complex turbid liquid with the concentration of 0.1-0.25 mg/mL, detecting the fluorescence intensity I of a system by adopting a fluorescence spectrophotometer, and drawing the concentration of the ammonia water along with the I/I3ppmStandard curve of variation wherein I3ppmCorresponding to the fluorescence intensity of the system at an ammonia concentration of 3 ppm.
(2) And (3) detecting the fluorescence intensity of the ammonia water sample to be detected, and combining the linear equation of the standard curve in the step (1) to obtain the concentration of the ammonia water in the ammonia water sample to be detected.
The invention has the following beneficial effects:
1. the invention selects 2, 5-dihydroxyterephthalic acid with redox and capable of intramolecular proton transfer as a main ligand to construct a porous metal organic complex, and simultaneously selects 4'- (4-pyridine) -4,2':6', 4' -terpyridine with large conjugation as a second ligand to be inserted, so that the obtained complex can gain and lose electrons, has certain chemical sensing, thus having certain gas-sensitive and fluorescent response capability and being capable of selectively sensing and detecting trace ammonia gas steam or liquid ammonia water.
2. The complex gas-sensitive detection of ammonia gas concentration can actually reach 5ppm, and has good linear relation; for ammonia water with the concentration of less than 3ppm, the maximum emission peak is 505nm and 3ppm through fluorescence detection, when the concentration of the ammonia water is more than 3ppm, the maximum emission peak is red-shifted to 540nm, which shows that the complex has obvious switching effect on the ammonia water, and when the concentration of the ammonia water is more than 3ppm, the concentration of the ammonia water and the fluorescence intensity have good linear relation, so that the quantitative detection of the ammonia water can be realized.
Drawings
FIG. 1 is a schematic diagram of the structure of a porous organometallic complex according to the invention.
FIG. 2 is a schematic representation of the attachment of ligand 2, 5-dihydroxy-terephthalic acid to trinuclear magnesium metal clusters in the porous organometallic complexes of the present invention.
FIG. 3 shows the connection mode of ligand 4'- (4-pyridine) -4,2':6', 4' -terpyridine and trinuclear magnesium metal cluster in the porous metal organic complex.
FIG. 4 is a three-dimensional channel structure diagram of the porous metal organic complex of the present invention.
FIG. 5 is a powder X-ray diffraction pattern of a porous organometallic complex according to the invention.
FIG. 6 is a graph showing the selectivity of gas sensitivity test on different volatile gases by using the porous metal organic complex of the present invention.
FIG. 7 is a graph showing the response of gas sensitivity tests using the porous metal organic complex of the present invention to ammonia gas of different concentrations.
FIG. 8 is a response straight line fitting graph for gas-sensitive testing of ammonia gas with different concentrations by using the porous metal organic complex.
FIG. 9 is a graph showing the response recovery time of 50ppm ammonia gas in a gas sensitive test using the porous metal organic complex of the present invention.
FIG. 10 is a graph showing the recovery of the repetitive response of a gas sensitive test using the porous metal organic complex of the present invention for 5ppm of ammonia gas.
FIG. 11 is a fluorescence intensity straight-line fitting graph of the maximum emission peak corresponding to 3-100 ppm of ammonia water in the fluorescence test of the porous metal organic complex.
Detailed Description
The invention will be further described in detail with reference to the following figures and examples, but the scope of the invention is not limited to these examples.
Example 1
Magnesium nitrate (102.6mg, 0.4mmol), 2, 5-dihydroxyterephthalic acid (39.6mg, 0.2mmol) and 4'- (4-pyridine) -4,2':6', 4' -terpyridine (31mg, 0.25mmol) were added to a 20mL glass bottle, followed by addition of a mixed solution (13mL) of formic acid and N, N-dimethylacetamide in a volume ratio of 1:8:4 to N, N-dimethylpropylurea, stirring was conducted uniformly, the glass bottle was sealed, and the reaction was allowed to stand at a constant temperature of 130 ℃ for 5 days to obtain a porous metal-organic complex with a yield of 75.2%.
The single crystal structure of the prepared complex belongs to a hexagonal crystal system, P6(3)/mmc space group, and the unit cell parameter is
α ═ 90 °, β ═ 90 °, γ ═ 120 °, and one or more μ in its basic structural units3-O as a three-dimensional structure with three Mg atoms connected in the center, each trinuclear metal cluster connecting 2, 5-dihydroxyterephthalic acid and 4'- (4-pyridine) -4,2':6', 4' -terpyridine (see figure 1), two carboxyl groups deprotonated in one 2, 5-dihydroxyterephthalic acid connecting two trinuclear metal clusters (see figure 2), and 4'- (4-pyridine) -4,2':6', 4' -terpyridine connecting three trinuclear metal clusters through three nitrogen atoms (see figure 3), resulting in a hexagonal channel formed by the trinuclear Mg metal cluster connecting with 2, 5-dihydroxyterephthalic acid, a cut of the channel by 4'- (4-pyridine) -4,2':6', 4' -terpyridine, and the three-dimensional structure has hydroxyl groups on the walls of the channels (see FIG. 4). As can be seen from FIG. 5, the powder X-ray diffraction curve of the resulting complex was matched with the single crystal data simulation curve, indicating that it had excellent crystallinity and purity.
Example 2
The invention discloses application of a porous metal organic complex in ammonia gas detection, and the specific detection method comprises the following steps:
the porous metal organic complex is coated on an Ag-Pd electrode ceramic substrate in a spinning mode, then the substrate is placed on a sample table of a CGS-1TP gas sensitive test system (Beijing Ailite Limited, China), two electrode probes are well contacted with the substrate, and volatile gas is tested. Ammonia water, methanol, ethanol, ethylene glycol, acetone, acetaldehyde, nitromethane and chloroform were taken out by a micro-sampler, and were heated on a heating table to reach a volatile gas concentration of 5ppm, and the relative resistance change of the porous metal-organic complex was measured, and the results are shown in fig. 6. As can be seen from the figure, the porous metal organic complex only responds to ammonia gas and can be used for detecting ammonia gas with different concentrations.
According to the above method, ammonia gas concentrations of 5, 10, 30, 50, 70, 90 and 100ppm are respectively detected, as shown in fig. 7, the relative resistance value increases with the increase of the ammonia gas concentration, and the following straight line equation (see fig. 8) is satisfied in the concentration range of 5-100 ppm:
S＝1.29649+0.02094[NH3]
wherein S represents a relative resistance value, [ NH ]3]Represents the concentration (ppm) of ammonia gas.
As can be seen from the response curve of 50ppm ammonia in FIG. 9, the response time is 87s, the recovery time is 127s, and both the response and recovery times are relatively fast. Meanwhile, in order to verify the stability of the complex, the relative resistance value of the complex is basically kept unchanged when the complex is continuously and repeatedly detected for 10 times by 5ppm ammonia gas (see figure 10), and the response time and the recovery time of the complex are also basically kept unchanged in the repeated process, which shows that the complex has good stability and repeatability.
Example 3
The invention relates to application of a porous metal organic complex in detecting ammonia water, which comprises the following specific detection methods:
1. adding 0.3mg of porous metal organic complex into 3mL of N, N-dimethylacetamide, performing ultrasonic treatment at room temperature for about 10 minutes to form a stable suspension, namely a complex suspension with a concentration of 0.1mg/mL, dropwise adding ammonia water with different concentrations into the suspension, and detecting with a fluorescence spectrophotometer under excitation of a maximum excitation wavelength of 362 nm. The test results showed that the maximum emission peak was at 505nm when the ammonia concentration was less than 3ppm, at 540nm when the ammonia concentration was 3ppm or more, and the fluorescence intensity gradually increased with the increase in the ammonia concentration.
2. Dropwise adding ammonia water into the complex suspension with the concentration of 0.1mg/mL to ensure that the ammonia water concentration in the system is respectively 3, 5, 10, 20, 30, 40, 50, 60, 70, 80, 90 and 100ppm, detecting the fluorescence intensity I of the system by using a fluorescence spectrophotometer, and drawing the concentration of the ammonia water along with the I/I3ppmStandard curve of variation wherein I3ppmCorresponding to the fluorescence intensity of the system at an ammonia concentration of 3 ppm. As can be seen from FIG. 11, in the concentration range of 3-100 ppm, the ammonia concentration and the fluorescence intensity have a good linear relationship, which conforms to the linear equation: I/I3ppm＝0.9682+0.01691[NH3·H2O]. Meanwhile, the complex suspension with the concentration of 0.1mg/mL and the suspension with the concentration of 100ppm of ammonia water are placed in a dark chamber and irradiated by an ultraviolet lamp, and the system is obviously changed in color after the ammonia water is added.
Claims (4)
1. The application of the porous metal organic complex in detecting ammonia gas, wherein the structural unit of the porous metal organic complex is [ (CH)3)2NH2][Mg3(OH)(DHBDC)3(PTP)]Where DHBDC represents a divalent anion of 2, 5-dihydroxyterephthalic acid with two-COOH hydrogen atoms removed, PTP represents 4'- (4-pyridine) -4,2':6', 4' -terpyridine; the complex belongs to a hexagonal crystal system,P6(3)/mmcspace group, unit cell parameters Å =16.9671 Å, b =16.9671 Å, c =15.3079 Å, α =90 °, β= 90°，γ=120°。
2. Use of the porous metal organic complex according to claim 1 for detecting ammonia gas, characterized in that: spin coating the porous metal organic complex on an Ag-Pd electrode ceramic substrate, detecting ammonia with different concentrations by using a gas-sensitive detector, and drawing a standard curve of the ammonia concentration changing along with the relative resistance; and then detecting the relative resistance value of the ammonia gas sample to be detected, and combining a linear equation of the standard curve to obtain the concentration of the ammonia gas sample to be detected.
3. The application of porous metal organic complex in detecting ammonia water, wherein the structural unit of the porous metal organic complex is [ (CH)3)2NH2][Mg3(OH)(DHBDC)3(PTP)]Where DHBDC represents a divalent anion of 2, 5-dihydroxyterephthalic acid with two-COOH hydrogen atoms removed, PTP represents 4'- (4-pyridine) -4,2':6', 4' -terpyridine; the complex belongs to a hexagonal crystal system,P6(3)/mmcspace group, unit cell parameters Å =16.9671 Å, b =16.9671 Å, c =15.3079 Å, α =90 °, β= 90°，γ=120°。
4. Use of a porous metal organic complex according to claim 3 for detecting ammonia, characterized in that:
(1) uniformly dispersing a porous metal organic complex in N, N-dimethylacetamide to prepare a complex suspension with the concentration of 0.1-0.25 mg/mL, then dropwise adding an ammonia water sample to be detected into the suspension, detecting by using a fluorescence spectrophotometer under the excitation of the maximum excitation wavelength 362nm, and if the maximum emission peak is 505nm, indicating that the concentration of ammonia water in the ammonia water sample to be detected is less than 3 ppm; if the maximum emission peak is at 540nm, the concentration of the ammonia water in the ammonia water sample to be detected is more than 3 ppm;
(2) and for the ammonia water sample to be detected with the ammonia water concentration of more than 3ppm, detecting according to the following steps:
firstly, ammonia water with the concentration of 3-100 ppm is dripped into complex turbid liquid with the concentration of 0.1-0.25 mg/mL, the fluorescence intensity I of a system is detected by a fluorescence spectrophotometer, and the concentration of the ammonia water is drawn along with the I/I3ppmStandard curve of variation wherein I3ppmThe fluorescence intensity of the system corresponding to the ammonia concentration of 3 ppm;
and secondly, detecting the fluorescence intensity of the ammonia water sample to be detected, and combining a linear equation of the standard curve in the step ① to obtain the concentration of the ammonia water in the ammonia water sample to be detected.
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| CN109400634B (en) * | 2018-11-30 | 2020-10-16 | 陕西师范大学 | 2, 5-dihydroxy indium terephthalate complex, preparation method thereof and application of complex in fluorescence detection of hydrazine hydrate |
| CN109485870B (en) * | 2018-11-30 | 2021-03-05 | 陕西师范大学 | Stable porous cobalt complex, preparation method thereof and application thereof in adsorption and separation of gas micromolecules |
| CN115368639B (en) * | 2022-08-11 | 2023-05-30 | 桂林理工大学 | Carboxymethyl starch/polyvinyl alcohol-based nanocomposite with ultraviolet blocking and ammonia response functions and preparation method thereof |
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| CN105080490A (en) * | 2015-08-04 | 2015-11-25 | 华南理工大学 | Magnesite-chrome bimetallic MOFs adsorbent MIL-101 (Cr, Mg) and preparation method thereof |
| CN106832317A (en) * | 2017-01-19 | 2017-06-13 | 陕西师范大学 | One class tetrazole porous coordination and preparation method thereof |
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| CN106832317A (en) * | 2017-01-19 | 2017-06-13 | 陕西师范大学 | One class tetrazole porous coordination and preparation method thereof |
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