CN109081829B - Ag (I) -organic framework material and preparation method and application thereof - Google Patents

Ag (I) -organic framework material and preparation method and application thereof Download PDF

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CN109081829B
CN109081829B CN201710443661.5A CN201710443661A CN109081829B CN 109081829 B CN109081829 B CN 109081829B CN 201710443661 A CN201710443661 A CN 201710443661A CN 109081829 B CN109081829 B CN 109081829B
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organic framework
framework material
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李程鹏
周航
杜淼
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Tianjin Normal University
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J20/00—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof
    • B01J20/22—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material
    • B01J20/223—Solid sorbent compositions or filter aid compositions; Sorbents for chromatography; Processes for preparing, regenerating or reactivating thereof comprising organic material containing metals, e.g. organo-metallic compounds, coordination complexes
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/28—Treatment of water, waste water, or sewage by sorption
    • C02F1/285—Treatment of water, waste water, or sewage by sorption using synthetic organic sorbents
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/20—Heavy metals or heavy metal compounds
    • C02F2101/22—Chromium or chromium compounds, e.g. chromates
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    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/13—Crystalline forms, e.g. polymorphs

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Abstract

The invention discloses an Ag (I) -organic framework material and a preparation method and application thereof, wherein the molecular formula of the Ag (I) -organic framework material is [ Ag (L) ]](NO3)(H2O)(CHCl3)]Each Ag1 ion is coordinated with 4 nitrogen atoms, the 4 nitrogen atoms being N1#2, N2, N5#3 and N6#1 from four L; four adjacent Ag1 ions are bridged by L to obtain a three-dimensional cation coordination network, a pore channel is formed in the middle of the three-dimensional cation coordination network, and 2 NO are dissociated in each pore channel3‑2 CHCl3Molecule and 2H2And (3) O molecules. The Ag (I) -organic framework material of the invention has simple preparation method and Cr2O7 2‑Good capture effect, and Ag (I) -organic framework material is put into the material containing Cr2O7 2‑Is left standing for 8 hours until all Cr is contained2O7 2‑Can be captured.

Description

Ag (I) -organic framework material and preparation method and application thereof
Technical Field
The invention belongs to the technical field of organic preparation, and particularly relates to an Ag (I) -organic framework material, and a preparation method and application thereof.
Background
Conventional cr (vi) adsorption has various methods including ion exchange, membrane separation, chemical reduction and electrolysis. The use of ion exchange to remove cr (vi) from water is a particularly attractive option because of its many outstanding advantages such as high sensitivity and selectivity and simplicity of operation. Conventional materials typically use two types of materials, inorganic zeolites or Layered Double Hydroxides (LDHs) and organosol-gel adsorbents or polymeric resins. These inorganic ion exchangers have the disadvantages of slow kinetics, poor selectivity and low adsorption capacity, while their organic counterparts exhibit limitations in thermal and chemical stability. Therefore, the method has profound significance for researching a new material which can capture or exchange the oxygen-containing acid radical metal anion pollutants and has higher removal efficiency.
Disclosure of Invention
In view of the shortcomings of the prior art, the invention aims to provide a method for adsorbing Cr on Ag (I) -organic framework material2O7 2-The use of (1).
The purpose of the invention is realized by the following technical scheme.
A preparation method of Ag (I) -organic framework material, wherein the molecular formula of the Ag (I) -organic framework material is [ Ag (L) ]](NO3)(H2O)(CHCl3)]Wherein L is 3- (2-pyridyl) -4- (4-pyridyl) -5- (3-pyridyl) -1,2, 4-triazole, and the molecular formula of L is as follows:
Figure GDA0002667185340000011
the preparation method comprises the following steps:
1) put L into CHCl3In solution to give L-CHCl3A solution; mixing AgNO3Placing the mixture in deionized water and uniformly mixing to obtain AgNO3An aqueous solution;
2) at the L-CHCl3Placing ethyl acetate as buffer solution on the solution, and placing the AgNO on the ethyl acetate3Standing the water solution at room temperature of 20-25 ℃ in the dark for at least 120 hours to obtain colorless crystals, namely the Ag (I) -organic framework material,
wherein, the L and AgNO3The amount ratio of the substances of (a) is 1: 1.
In the above technical scheme, the AgNO3AgNO in aqueous solution3The concentration of (b) is 0.02-0.03 mol/L.
In the above technical solution, L is-CHCl3The concentration of L in the solution is 0.02-0.03 mol/L.
In the above technical scheme, the ethyl acetate and the AgNO3The volume ratio of the aqueous solution is (0.9-1.1): 1.
the Ag (I) -organic framework material has a molecular formula of [ Ag (L)](NO3)(H2O)(CHCl3)]And L has the molecular formula:
Figure GDA0002667185340000021
each Ag1 ion is coordinated with 4 nitrogen atoms, the 4 nitrogen atoms being N1#2, N2, N5#3 and N6#1 from four L; four adjacent Ag1 ions are bridged by L to obtain a three-dimensional cation coordination network, a pore channel is formed in the middle of the three-dimensional cation coordination network, and 2 NO are dissociated in each pore channel 3-2 CHCl3Molecule and 2H2And (3) O molecules.
In the above technical scheme, the bond length and bond angle of the Ag (I) -organic framework material are
Length of the bond
Figure GDA0002667185340000022
Figure GDA0002667185340000031
Key angle
Figure GDA0002667185340000032
The crystallographic data of the Ag (I) -organic framework material are as follows:
Figure GDA0002667185340000041
the Ag (I) -organic framework material adsorbs Cr2O7 2-The Ag (I) -organic framework material is put into the material containing Cr2O7 2-Is allowed to stand in the aqueous solution of (1).
In the technical scheme, 0.2mmol of Ag (I) -organic framework material is put into the furnace body containing 0.1mmol of Cr2O7 2-After standing the aqueous solution of (1) for 8 hours, all of the Cr is contained2O7 2-All can be captured, and the adsorption capacity is 276 mg/g.
In the above technical solution, the ag (i) -organic framework material detects the Cr2O7 2-Has a lower limit of 50ppb and 98.1% of the Cr2O7 2-Can be captured.
Compared with the prior art, the Ag (I) -organic framework material has simple preparation method and Cr2O7 2-Good capture effect, and Ag (I) -organic framework material is put into the material containing Cr2O7 2-Is left standing for 8 hours until all Cr is contained2O7 2-Can be captured.
Drawings
FIG. 1 shows an Ag (1) center and an L ligand of an Ag (I) -organic framework material of the present invention;
FIG. 2 shows the main skeleton of the Ag (I) -organic skeleton material of the present invention.
Detailed Description
All chemicals are commercially available and the water used in the embodiments is deionized water. The samples of C, H,and N, IR spectroscopy by Bruker sensor 27 OPUS FT-IR, tabletting with KBr, at 4000-–1The test was carried out within the range of (1). PXRD (X-ray powder diffraction) spectra were recorded using a Rigaku D/tetra X ultra-high-speed position sensitive detector with a test voltage of 40kV, a current of 100mA, a light source of Cu-K a, scanned over a range of 5-80 deg.. Ultraviolet-absorption spectra (UV-Vis) were collected on a PerkinElmer Lambda 35 spectrometer and inductively coupled plasma Mass Spectrometry (ICP-MS) was performed on the sample at HNO3After degradation, was dissolved in deionized water and measured in a Perkin-Elmer ELAN 9000.
The technical scheme of the invention is further explained by combining specific examples.
1) 30.1mg L (0.1mmol) was placed in 4mL CHCl3In solution to give L-CHCl3A solution; adding 0.1mmol of AgNO3(17.0mg) was placed in 4mL deionized water and mixed well to give 4mL AgNO3An aqueous solution; ag (I) -organic framework material is [ Ag (L)](NO3)(H2O)(CHCl3)]And L has the molecular formula:
Figure GDA0002667185340000051
(Synthesis: A.V.Desai, B.Manna, Angew.chem.int.Ed.,2016,55, 7811-one 7815.),
2) mixing L with-CHCl3The solution was placed at the bottom of the tube at 4mL L-CHCl34mL of ethyl acetate was placed on the solution as a buffer, and 4mL of AgNO was added3The aqueous solution is carefully placed on the buffer solution, and after standing for about 120 hours at room temperature of 20-25 ℃ in the dark, colorless crystals, namely Ag (I) -organic framework material ([ Ag (L) ]), are obtained on the tube wall](NO3)(H2O)(CHCl3)]) Yield 85% (51.5 mg).
Elemental analysis C18H14AgN7O4Cl3Calculated values: c, 35.64; h, 2.33; n, 16.16%. Experimental results C, 35.78; h, 2.46; n, 16.28%. FT-IR (KBr, cm)–1):3400b,2251m,1588m,1567w,1501w,1452s,1383vs,1164w,988w,837w,789w,745w,719m,686w,631w,607w。
X-ray single crystal diffraction analysis showed that the asymmetric ligand unit consisted of one Ag1 center and one L ligand (as shown in figure 1). Each Ag1 ion is coordinated by four types of nitrogen atoms (N1#2, N2, N5#3, and N6#1) from different L ligands, adjacent Ag (1) ions are bridged by the ligands L to give a three-dimensional cationic coordination network, and nitrate anions and solvents are contained as guests in the channels. Pore size for anion exchange observed along the a axis of the crystal of
Figure GDA0002667185340000061
Is uniform and one-dimensional. Calculation of the porosity of the host framework of Ag (I) -organic framework materials by the PLATON program shows
Figure GDA0002667185340000062
(33.6% of unit cell volume) (as shown in FIG. 2). In this structure, both the Ag1 ion and the L ligand can be considered as 4-connected network nodes, and the resulting cationic framework can be simplified to a single-node network topology.
The bond length and the bonding angle of the obtained Ag (I) -organic framework material are
Figure GDA0002667185340000063
Figure GDA0002667185340000071
The crystallographic data of the Ag (I) -organic framework material are obtained as follows:
Figure GDA0002667185340000072
0.2mmol of the crystalline sample Ag (I) -organic framework material was simply immersed in 0.1mmol of K under ambient conditions (298K)2Cr2O7To carry out anion exchange in an aqueous solution. Absorbing the supernatant liquid for ultraviolet at proper time intervalsThe test characterizes the adsorption capacity. Ag (I) -organic framework materials show almost 100% Cr2O7 2-Can be captured in 8 hours, and the adsorption capacity is 276 mg/g.
Selective exchange:
of equal importance to the adsorption capacity are the exchange rate and selectivity of anion capture, which are determinants of the adsorption efficiency of practical wastewater treatment. To test the selectivity of the system for dichromate capture, 0.1mmol of synthesized Ag (I) -organic framework material was immersed in 0.1mmol of K2Cr2O7And metal salt (n times) (the metal salt contains CH)3CO2 –、SO4 2–、NO3 –、BF4 –、CF3CO2 –And CH3SO3 –) The reaction was carried out at room temperature for two days. FT-IR test results of anion exchanged crystals indicate that dichromate preferentially exchanges with Ag (I) -organic framework materials.
Table 1 shows the selection ratio of Ag (I) -organic framework material to the following metal salt.
Figure GDA0002667185340000081
Exchange of ultra low Cr (VI) ion detection limit
The maximum pollution level of cr (vi) as defined by the united states Environmental Protection Agency (EPA) is 0.1ppm for surface water and 0.05ppm for drinking water. It must therefore be able to capture dichromate in contaminated water at ppm or even ppb levels as a good material. As an initial test of very dilute concentrations, we carried out anion exchange at different concentrations monitored by ICP-MS in the detection ranges of 10ppm, 5ppm, 1ppm, 500ppb, 100ppb and 50 ppb.
Table 2 shows that different concentrations of Ag (I) -organic framework material adsorb different concentrations of K2Cr2O7The adsorption rate of (3).
Figure GDA0002667185340000082
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.

Claims (8)

1. Adsorption of Ag (I) -organic framework material on Cr2O7 2-The use of (A) said Ag (I) -organic framework material having the formula [ Ag (L) ]](NO3)(H2O)(CHCl3)]Wherein L is 3- (2-pyridyl) -4- (4-pyridyl) -5- (3-pyridyl) -1,2, 4-triazole, and the molecular formula of L is as follows:
Figure FDA0002667185330000011
the preparation method of the Ag (I) -organic framework material comprises the following steps:
1) put L into CHCl3In solution to give L-CHCl3A solution; mixing AgNO3Placing the mixture in deionized water and uniformly mixing to obtain AgNO3An aqueous solution;
2) at the L-CHCl3Placing ethyl acetate as buffer solution on the solution, and placing the AgNO on the ethyl acetate3Standing the water solution at room temperature of 20-25 ℃ in the dark for at least 120 hours to obtain colorless crystals, namely the Ag (I) -organic framework material,
wherein, the L and AgNO3The amount ratio of the substances of (a) to (b) is 1: 1;
placing the Ag (I) -organic framework material into a container containing Cr2O7 2-Is left standing in the aqueous solution of (1), Cr2O7 2-The average adsorption rate of (A) is 96.4-100%.
2. Use according to claim 1, wherein said AgNO3In aqueous solution AgNO3The concentration of (b) is 0.02-0.03 mol/L.
3. Use according to claim 2, wherein said L is-CHCl3The concentration of L in the solution is 0.02-0.03 mol/L.
4. Use according to claim 3, wherein said ethyl acetate and said AgNO are3The volume ratio of the aqueous solution is (0.9-1.1): 1.
5. the use according to any one of claims 1 to 4, wherein each Ag1 ion is coordinated to 4 nitrogen atoms, the 4 nitrogen atoms being N1#2, N2, N5#3 and N6#1 from four L's; four adjacent Ag1 ions are bridged by L to obtain a three-dimensional cation coordination network, a pore channel is formed in the middle of the three-dimensional cation coordination network, and 2 NO are dissociated in each pore channel3 -2 CHCl3Molecule and 2H2An O molecule;
the crystallographic data of the Ag (I) -organic framework material are as follows:
Figure FDA0002667185330000021
6. use according to claim 5, wherein the Ag (I) -organic framework material has a bond length and a bond angle of
Figure FDA0002667185330000022
Figure FDA0002667185330000031
7. Use according to claim 6Characterized in that 0.2mmol of the Ag (I) -organic framework material is put into the container containing 0.1mmol of Cr2O7 2-After standing the aqueous solution of (1) for 8 hours, all of the Cr is contained2O7 2-All can be captured, and the adsorption capacity is 276 mg/g.
8. Use according to claim 6, wherein Ag (I) -organic framework material detects the Cr2O7 2-The lower limit of (B) is 50 ppb.
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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516270A (en) * 2011-11-17 2012-06-27 天津师范大学 Metallic silver coordination polymer with two-dimensional lamellar structure, and preparation and application thereof
CN102516271A (en) * 2011-12-06 2012-06-27 天津师范大学 Metallic silver coordination polymer with three-dimensional network structure, and preparation method and application thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102516270A (en) * 2011-11-17 2012-06-27 天津师范大学 Metallic silver coordination polymer with two-dimensional lamellar structure, and preparation and application thereof
CN102516271A (en) * 2011-12-06 2012-06-27 天津师范大学 Metallic silver coordination polymer with three-dimensional network structure, and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
"A New Energetic Complex [Co(2,4,3-tpt)2(H2O)2]•2NO3: Synthesis,Structure, and Catalytic Thermal Decomposition for Ammonium Perchlorate";Li Bing等;《Zeitschrift fuer Anorganische und Allgemeine Chemie》;20150916;第641卷;2371-2375页 *
"Distinct 1D Cd(II) coordination polymers constructed by three isomeric tripyridyltriazole building blocks and thiocyanate anions";Guo Jian-Hua等;《Inorganic Chemistry Communications》;20120524;第22卷;77-81页 *
"Tracking the Superefficient Anion Exchange of a Dynamic Porous Material Constructed by Ag(I) Nitrate and Tripyridyltriazole via Multi-Step Single-Crystal-To-Single-Crystal Transformations";Li Cheng-Peng等;《ACS Applied Materials & Interfaces》;20170216;第9卷;7202-7208页 *

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