CN111957299A - Functionalized copper-based MOFs material and preparation method and application thereof - Google Patents
Functionalized copper-based MOFs material and preparation method and application thereof Download PDFInfo
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- CN111957299A CN111957299A CN202010837139.7A CN202010837139A CN111957299A CN 111957299 A CN111957299 A CN 111957299A CN 202010837139 A CN202010837139 A CN 202010837139A CN 111957299 A CN111957299 A CN 111957299A
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- 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
- B01J20/226—Coordination polymers, e.g. metal-organic frameworks [MOF], zeolitic imidazolate frameworks [ZIF]
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- 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
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- 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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/10—Biological treatment of water, waste water, or sewage
Abstract
The invention discloses a functionalized copper-based MOFs material, and a preparation method and application thereof. The functional copper-based MOFs material is prepared by adopting copper salt, organic ligand and defect-causing agent. The functional copper-based MOFs material prepared by the invention has a micron structure, large specific surface area and more active sites, so that heavy metal ions in sewage can be quickly removed, the saturated adsorption capacity is higher, the adsorption capacity of the material to lead ions is about 700mg/g, and the adsorption effect of the material is obviously higher than that of an adsorbent in the prior art. In addition, the preparation method of the functionalized copper-based MOFs material is simple, and the prepared functionalized copper-based MOFs material has good repeatability and has wide application prospect in the aspect of heavy metal pollution control by being used as an adsorption material.
Description
Technical Field
The invention belongs to the technical field of functional materials, and particularly relates to a functional copper-based MOFs material, a preparation method and application thereof, in particular to application of the functional copper-based MOFs material as an adsorbent in removal of heavy metal ions in sewage.
Background
With the increase of population and the rapid development of social economy, the water environment pollution problem in China is more and more serious. The per capita water resource in China only reaches 1/4 of the per capita water resource in the world, about half of cities in China lack water, however, the water quality deterioration causes the problem of water resource shortage and frosts. The industrial sewage is discharged into the river channel without being treated, and brings endless harm to rivers, people, livestock and other organisms nearby. The sewage contains harmful substances such as mercury, chromium, nickel, copper, lead, cadmium, iron, nitrogen, phenol and the like, which can not only deform or stop aquatic organisms in rivers, but also the crops irrigated by the sewage are withered or contain toxin in grains, and people and livestock eat the grains or vegetables, so that some poisoning and some diseases are caused, and the industrial and agricultural production and the physical health of people are influenced.
The existing sewage treatment method comprises a chemical precipitation method, an adsorption method, an electrolysis method, a membrane separation method, an ion exchange method and a biological method, wherein the adsorption method is based on a physical or chemical adsorption principle, and has the advantages of obvious removal effect on pollutants difficult to degrade, strong selectivity, good adsorption effect, low energy consumption, simple operation, cheap and easily-obtained raw materials and the like, and is favored by researchers.
In the past research, natural materials such as activated carbon, fly ash, bentonite, lignin, chitosan, kaolin, zeolite and the like, and acquired synthetic materials such as carbon-based materials, silicon oxide and the like are common adsorbing materials, but the problems of small pore diameter, small specific surface area and incomplete pore channel arrangement exist generally, so that the industrial application of the adsorbing materials is limited.
The present application has been made for the above reasons.
Disclosure of Invention
Aiming at the problems or defects in the prior art, the invention aims to provide a functionalized copper-based MOFs material, and a preparation method and application thereof. The metal organic framework Materials (MOFs) are organic-inorganic hybrid porous materials which are formed by self-assembly of metal ions or metal clusters and organic ligands and have a three-dimensional periodic grid structure, and have the advantages of high porosity and specific surface area, regular spatial network structure, strong controllability of pore size and the like.
In order to achieve one of the above objects of the present invention, the present invention adopts the following technical solutions:
a preparation method of a functional copper-based MOFs material is prepared by adopting copper salt, organic ligand and defect-causing agent.
Specifically, the functionalized copper-based MOFs material is prepared by the following method, and comprises the following steps:
(1) dissolving an organic ligand in absolute ethyl alcohol to obtain an organic ligand solution; then adding a defect-causing agent into the organic ligand solution according to the proportion, and uniformly mixing to obtain a solution 1;
(2) dissolving soluble copper salt in water to obtain soluble salt water solution containing copper ions;
(3) and (3) uniformly mixing the soluble salt water solution containing copper ions in the step (2) with the solution 1 obtained in the step (1) to obtain a solution 2, transferring the solution 2 into a reaction kettle, sealing, heating the reaction kettle to 50-200 ℃, reacting for 1-24 h at a constant temperature, and after the reaction is finished, centrifuging or filtering, washing and drying the product to obtain the functionalized copper-based MOFs material.
Further, in the above technical scheme, the organic ligand in step (1) is trimesic acid.
Further, in the above technical scheme, the defect agent in the step (1) is N- (4-carboxyphenyl) thiourea.
Further, in the above technical solution, the soluble copper salt in the step (2) is any one of copper acetate, copper nitrate and copper sulfate, and preferably copper nitrate trihydrate.
Further, in the above technical scheme, the molar ratio of the soluble copper salt, the organic ligand and the defect-causing agent is 1: 0.45-0.5: 0.007 to 0.025.
Preferably, in the above technical scheme, the molar ratio of the soluble copper salt, the organic ligand and the defect-causing agent is 1: 0.46: 0.007 to 0.025.
Further, in the technical scheme, the concentration of the organic ligand in the organic ligand solution in the step (1) is 0.1-0.2 mol/L.
Further, according to the technical scheme, the concentration of the defect-causing agent in the solution 1 in the step (1) is 0.003 mol/L-0.008 mol/L.
Specifically, in the above technical solution, in the step (2), in order to reduce the influence of trace ions contained in the common water on the functionalized copper-based MOFs material prepared by the present invention, the water used in the step is preferably ultrapure water.
Further, according to the technical scheme, the concentration of the copper ions in the soluble salt water solution containing the copper ions in the step (2) is 0.27-0.3 mol/L.
Further, in the above technical solution, the washing conditions in step (3) are preferably as follows: the solvent for washing was absolute ethanol, and washing was performed 3 times.
Further, in the above technical solution, the drying conditions in the step (3) are preferably: drying at 50 deg.C for 12 h.
The function and reaction principle of the raw materials of the invention (as shown in figure 6) are as follows:
the functional copper-based MOFs material is formed by connecting dimeric copper, organic ligands trimesic acid and N- (4-carboxyphenyl) thiourea, wherein Cu2+Are connected together through bonding force, and the axial direction is very weak water molecule force, thereby forming a primary unit body of the MOFs material. N- (4-carboxyphenyl) thiourea is used for replacing part of trimesic acid to participate in the reaction, so that not only the MOFs structure generates defects, but also new functional groups are introduced, thereby achieving the purpose of improving the adsorption performance of the MOFs material.
The second purpose of the invention is to provide the functionalized copper-based MOFs material prepared by the method.
The third purpose of the invention is to provide the application of the functional copper-based MOFs material prepared by the method as an adsorbent in removing heavy metal ions in sewage.
Further, according to the technical scheme, the heavy metal ions are Hg2+、Co2+、Ni2+、Cd2+、Pb2+Any one or more of.
The adsorbent for removing heavy metal ions in sewage comprises the functional copper-based MOFs material prepared by the method.
The fourth purpose of the invention is to provide a method for removing heavy metal ions in sewage by using the functionalized copper-based MOFs material, which comprises the following steps:
adjusting the pH value of the sewage containing the heavy metal ions to be treated to 3-6, then adding the functional copper-based MOFs material into the sewage, carrying out constant-temperature oscillation adsorption for 5 min-12 h at the temperature of 15-45 ℃, filtering and separating after the adsorption is finished, and taking clear liquor to obtain the treated water body.
Further, in the technical scheme, the concentration of the heavy metal ions to be treated in the sewage is preferably 50 mg/L-230 mg/L.
Further, according to the technical scheme, the adding amount of the functional copper-based MOFs material is 0.1-2 g per liter of sewage.
Preferably, in the technical scheme, the adding amount of the functional copper-based MOFs material is 0.1-0.5 g per liter of sewage.
Specifically, when the pH value of the sewage to be treated is lower than 3, the functionalized copper-based MOFs material can be corroded by acid and dissociated; when the pH value of the sewage to be treated is higher than 6, the heavy metal ions related to the adsorption of the invention can generate hydroxide precipitates by themselves, and the removal efficiency of the functionalized copper-based MOFs materials under the conditions can be influenced.
Compared with the prior art, the invention has the following beneficial effects:
(1) the functional copper-based MOFs material has a micron structure, large pore size, large specific surface area and many active sites, so that heavy metal ions in sewage can be quickly removed, and the material has high saturated adsorption capacity and is obviously higher than the adsorption effect of an adsorbent in the prior art.
(2) The addition of the N- (4-carboxyphenyl) thiourea defect-causing agent can increase the pore diameter of the copper-based MOFs material, and realizes the regulation and control of the structure and the performance of the copper-based MOFs material.
(3) The functionalized copper-based MOFs material has excellent adsorption capacity, and the adsorption capacity to lead ions is about 700 mg/g.
Drawings
FIG. 1 is an X-ray diffraction pattern of a functionalized copper-based MOFs material prepared in example 3 of the present invention;
FIG. 2 is a scanning electron microscope image of the functionalized copper-based MOFs material prepared in example 3 of the present invention;
FIG. 3 is a graph showing the relationship between the adsorption amount Qe (mg/g) of the functionalized copper-based MOFs material prepared in example 3 of the present invention to lead ions under different pH values (pH values);
FIG. 4 is a graph showing the relationship between the equilibrium concentration Ce (mg/g) of the lead ion solution and the adsorption Qe (mg/g) of the lead ion solution for the functionalized copper-based MOFs material prepared in example 3 of the present invention;
FIG. 5 is a graph showing the relationship between the adsorption amount Qe (mg/g) of the functionalized copper-based MOFs material prepared in example 3 of the present invention and lead ions at different temperatures.
FIG. 6 is a reaction scheme of the present invention.
Detailed Description
The present invention will be described in further detail below with reference to examples. The present invention is implemented on the premise of the technology of the present invention, and the detailed embodiments and specific procedures are given to illustrate the inventive aspects of the present invention, but the scope of the present invention is not limited to the following embodiments.
Various modifications to the precise description of the invention will be readily apparent to those skilled in the art from the information contained herein without departing from the spirit and scope of the appended claims. It is to be understood that the scope of the invention is not limited to the procedures, properties, or components defined, as these embodiments, as well as others described, are intended to be merely illustrative of particular aspects of the invention. Indeed, various modifications of the embodiments of the invention which are obvious to those skilled in the art or related fields are intended to be covered by the scope of the appended claims.
For a better understanding of the invention, and not as a limitation on the scope thereof, all numbers expressing quantities, percentages, and other numerical values used in this application are to be understood as being modified in all instances by the term "about". At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.
The test methods used in the following examples are all conventional methods unless otherwise specified; the raw materials and reagents used are, unless otherwise specified, those commercially available from ordinary commercial sources.
The method of calculating the adsorption amount in the following application examples was as follows:
the adsorption amount (mg/g) ═ lead ion concentration before reaction-lead ion concentration after reaction x sewage volume/adsorbent addition amount.
In the above calculation method, the concentration of lead ions after reaction (i.e., the concentration of lead ions in the adsorbed sewage) can be measured by using a plasma emission spectrometer, and the concentration of lead ions before reaction (i.e., the concentration of lead ions in the sewage before adsorption) can also be measured by using a plasma emission spectrometer in practical applications.
Example 1
The preparation method of the functionalized copper-based MOFs material comprises the following steps:
(1) dissolving 1.13g of trimesic acid (organic ligand) in 35mL of absolute ethanol to obtain an organic ligand solution; then 0.0192g of N- (4-carboxyphenyl) thiourea (defect causing agent) is added into the organic ligand solution and mixed evenly to obtain a solution 1;
(2) dissolving 2.4g of copper nitrate trihydrate (soluble copper salt) in 35mL of ultrapure water to obtain a soluble salt water solution containing copper ions;
(3) uniformly mixing the soluble salt water solution containing copper ions in the step (2) with the solution 1 obtained in the step (1) to obtain a solution 2, transferring the solution 2 to a reaction kettle, sealing, heating the reaction kettle to 110 ℃, reacting for 5 hours at a constant temperature, after the reaction is finished, centrifugally separating generated blue particles, washing for 3 times by using absolute ethyl alcohol, and drying for 12 hours at 50 ℃ to obtain the functionalized copper-based MOFs material.
In this example, the mass ratio of copper nitrate trihydrate, trimesic acid and N- (4-carboxyphenyl) thiourea was 1: 0.471: 0.008.
Example 2
The preparation method of the functionalized copper-based MOFs material of the present embodiment is substantially the same as the method of embodiment 1, except that: the mass ratio of copper nitrate trihydrate, trimesic acid and N- (4-carboxyphenyl) thiourea is 1: 0.467: 0.013.
example 3
The preparation method of the functionalized copper-based MOFs material of the present embodiment is substantially the same as the method of embodiment 1, except that: the mass ratio of copper nitrate trihydrate, trimesic acid and N- (4-carboxyphenyl) thiourea is 1: 0.463: 0.017.
fig. 1 is an XRD spectrum of the functionalized copper-based MOFs material prepared in example 3, and as can be seen from fig. 1, several diffraction peaks within a range of 2 θ ═ 5 to 40 ° are more evident, which illustrates that the functionalized copper-based MOFs material having a Cu-BTC crystal structure was successfully synthesized.
Fig. 2 is a scanning electron microscope image of the functionalized copper-based MOFs material prepared in example 3 of the present invention. From fig. 2 it can be seen that the functionalized copper-based MOFs materials have an octahedral structure, consistent with the results of XRD.
Example 4
The preparation method of the functionalized copper-based MOFs material of the present embodiment is substantially the same as the method of embodiment 1, except that: the mass ratio of copper nitrate trihydrate, trimesic acid and N- (4-carboxyphenyl) thiourea is 1: 0.458: 0.021.
example 5
The preparation method of the functionalized copper-based MOFs material of the present embodiment is substantially the same as the method of embodiment 3, except that: reacting for 10 hours in a polytetrafluoroethylene lining reaction kettle at a constant temperature of 110 ℃.
Example 6
The preparation method of the functionalized copper-based MOFs material of the present embodiment is substantially the same as the method of embodiment 3, except that: the soluble copper salt is copper acetate.
Application example 1
The application example relates to the study on the lead ion adsorption effect of the functionalized copper-based MOFs material prepared in the example 3 as an adsorbent under different temperature conditions.
10mL of 120mg/L lead ion solution with pH values of 3, 4, 5 and 6 was added to 4 sample bottles, and then 0.001g of the functionalized copper-based MOFs material prepared in example 3 was added to the 4 sample bottles. Putting into a shaking table, and oscillating at constant temperature for reaction for 12 h. Standing for 10-15 min, taking the supernatant for dilution, measuring the concentration of lead ions in the supernatant by using a plasma emission spectrometer, and calculating the adsorption capacity, wherein the specific result is shown in figure 3: the amino groups in the functionalized copper-based MOFs absorb Pb (II) through complexation, and when the pH is 3, the MOFs are dissolved and most of the amino groups are protonated, so that the content of free amino groups is low, and the adsorption capacity is small; when the pH value is 4-6, free amino groups on the surface of the adsorbent are gradually increased along with the gradual increase of the pH value, the adsorption capacity is increased, and the hydrolysis of carboxyl groups is promoted by the increase of the pH value to form-COO-Is present in such a form that the electrostatic effect on pb (ii) is enhanced, thereby increasing the adsorption capacity.
Application example 2
The application example relates to the study on the lead ion adsorption effect of the functionalized copper-based MOFs material prepared in the example 3 as an adsorbent under different temperature conditions.
10mL of 120mg/L lead ion solution was added to each of 4 sample bottles, and 0.001g of the functionalized copper-based MOFs material prepared in example 3 was added to each of the 3 sample bottles. Respectively placing into shaking tables with temperature of 15 deg.C, 25 deg.C, 35 deg.C and 45 deg.C, and performing oscillation reaction for 12 hr. Standing for 10-15 min, taking the supernatant for dilution, measuring the concentration of lead ions in the supernatant by using a plasma emission spectrometer, and calculating the adsorption capacity, wherein the specific result is shown in fig. 5: the adsorption efficiency of the adsorbent to lead ions increases with the increase of temperature, which shows that the adsorption of the adsorbent to lead ions is an endothermic reaction.
Application example 3
The application example relates to the study on the lead ion adsorption effect of the functionalized copper-based MOFs material prepared in the example 3 as an adsorbent under different temperature conditions.
10mL of lead ion solution was added to 8 sample bottles at concentrations of 50mg/L, 80mg/L, 100mg/L, 120mg/L, 150mg/L, 170mg/L, 200mg/L, and 230mg/L, respectively, and then 0.001g of the functionalized copper-based MOFs material prepared in example 3 was added to these 8 sample bottles, respectively. The reaction was shaken at room temperature for 12 h. Standing for 10-15 min, taking the supernatant for dilution, measuring the concentration of lead ions in the supernatant by using a plasma emission spectrometer, and calculating the adsorption quantity, wherein the specific result is shown in fig. 4, and experiments show that the adsorption of the functionalized copper-based MOFs material on the lead ions can reach 775 mg/g.
Claims (10)
1. A preparation method of a functionalized copper-based MOFs material is characterized by comprising the following steps: the method comprises the following steps:
(1) dissolving an organic ligand in absolute ethyl alcohol to obtain an organic ligand solution; then adding a defect-causing agent into the organic ligand solution according to the proportion, and uniformly mixing to obtain a solution 1;
(2) dissolving soluble copper salt in water to obtain soluble salt water solution containing copper ions;
(3) and (3) uniformly mixing the soluble salt water solution containing copper ions in the step (2) with the solution 1 obtained in the step (1) to obtain a solution 2, transferring the solution 2 into a reaction kettle, sealing, heating the reaction kettle to 50-200 ℃, reacting for 1-24 h at a constant temperature, and after the reaction is finished, centrifuging or filtering, washing and drying the product to obtain the functionalized copper-based MOFs material.
2. The method for preparing functionalized copper-based MOFs materials according to claim 1, wherein: the organic ligand in the step (1) is trimesic acid.
3. The method for preparing functionalized copper-based MOFs materials according to claim 1, wherein: the defect agent in the step (1) is N- (4-carboxyphenyl) thiourea.
4. The method for preparing functionalized copper-based MOFs materials according to claim 1, wherein: the soluble copper salt in the step (2) is any one of copper acetate, copper nitrate and copper sulfate.
5. The method for preparing functionalized copper-based MOFs materials according to claim 1, wherein: the molar ratio of the soluble copper salt, the organic ligand and the defect-causing agent is 1: 0.45-0.5: 0.007 to 0.025.
6. The functionalized copper-based MOFs material prepared by the preparation method of the functionalized copper-based MOFs material according to any one of claims 1 to 5.
7. The application of the functional copper-based MOFs material prepared by the method in any one of claims 1 to 5 as an adsorbent in removing heavy metal ions in sewage.
8. An adsorbent for removing heavy metal ions in sewage, which comprises the functionalized copper-based MOFs material prepared by the method of any one of claims 1 to 5.
9. The application method of the functionalized copper-based MOFs material in the removal of heavy metal ions in sewage, which is characterized in that: the method comprises the following steps:
adjusting the pH value of the sewage containing the heavy metal ions to be treated to 3-6, then adding the functional copper-based MOFs material into the sewage, carrying out constant-temperature oscillation adsorption for 5 min-12 h at the temperature of 15-45 ℃, filtering and separating after the adsorption is finished, and taking clear liquor to obtain the treated water body.
10. The application method of the functionalized copper-based MOFs materials in the removal of heavy metal ions in sewage according to claim 9, wherein: the adding amount of the functional copper-based MOFs material is 0.1-2 g per liter of sewage.
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