CN108102111B - Cobalt ion doped metal organic framework material and preparation method thereof - Google Patents

Cobalt ion doped metal organic framework material and preparation method thereof Download PDF

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CN108102111B
CN108102111B CN201810089625.8A CN201810089625A CN108102111B CN 108102111 B CN108102111 B CN 108102111B CN 201810089625 A CN201810089625 A CN 201810089625A CN 108102111 B CN108102111 B CN 108102111B
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cobalt
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曹姣
杨朝晖
熊炜平
李鑫
徐锐
张燕茹
柯托
谢靓程
金佳慧
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Abstract

The invention discloses a cobalt ion doped metal organic framework material and a preparation method thereof, wherein the cobalt ion doped metal organic framework material comprises cobalt ions and UiO-66 (Zr), and the cobalt ions are doped in the UiO-66 (Zr). The preparation method comprises the following steps: mixing zirconium chloride, terephthalic acid, cobalt chloride hexahydrate and an organic solvent, and stirring to obtain a precursor solution; and carrying out hydrothermal reaction on the precursor solution to obtain the cobalt ion doped metal organic framework material. The cobalt ion doped metal organic framework material has the advantages of large specific surface area, good dispersibility, good stability, good adsorption performance, good photocatalytic performance and the like, can realize high-efficiency adsorption and degradation of antibiotics, and has good application prospect. The preparation method of the cobalt ion doped metal organic framework material has the advantages of convenient operation, simple synthesis, few raw material types, low cost, high yield and the like, and is suitable for large-scale preparation.

Description

Cobalt ion doped metal organic framework material and preparation method thereof
Technical Field
The invention belongs to the field of composite materials, relates to a metal organic framework material, and particularly relates to a cobalt ion doped metal organic framework material and a preparation method thereof.
Background
Metal Organic Frameworks (MOFs) are a class of highly crystalline, porous materials formed by self-assembly of metal ions or ion clusters with organic ligands. Compared with inorganic materials, the MOFs have ultrahigh porosity and specific surface area, and meanwhile, the MOFs have structural diversity and designability, so that the MOFs have great potential in the fields of adsorption and photocatalysis. UiO-66 (Zr) is a relatively stable MOFs, and has attracted much attention due to its excellent thermal stability and water stability, but UiO-66 (Zr) still has the problems of poor adsorption performance, poor photocatalytic activity and the like. In addition, the conventional process for synthesizing UiO-66 (Zr) is often complicated and has low yield, and the UiO-66 (Zr) material is difficult to produce on a large scale at low cost. Therefore, how to comprehensively improve the problems and the defects of the existing UiO-66 (Zr) and obtain a UiO-66 (Zr) material with good stability, good adsorption performance and good photocatalytic performance and a preparation method of the UiO-66 (Zr) material with convenient operation, simple synthesis, few raw material types, low cost and high yield has very important significance for improving the application range of the UiO-66 (Zr) material in wastewater treatment.
Disclosure of Invention
The invention aims to overcome the defects of the prior art, provides the cobalt ion doped metal organic framework material with good stability, good adsorption performance and good photocatalytic performance, and also provides the preparation method of the cobalt ion doped metal organic framework material with convenient operation, simple synthesis, less raw material types, low cost and high yield.
In order to solve the technical problems, the invention adopts the following technical scheme:
a cobalt ion doped metal organic framework material comprising cobalt ions and UiO-66 (Zr); the cobalt ions are doped in UiO-66 (Zr).
In the cobalt ion-doped metal organic framework material, the specific surface area is 815.178 m2/g～1024.709 m2/g。
As a general technical concept, the present invention also provides a preparation method of the cobalt ion doped metal organic framework material, comprising the following steps:
s1, mixing zirconium chloride, terephthalic acid, cobalt chloride hexahydrate and an organic solvent, and stirring to obtain a precursor solution;
s2, carrying out hydrothermal reaction on the precursor solution in the step S1 to obtain the cobalt ion doped metal organic framework material.
In the preparation method, the molar ratio of the cobalt chloride hexahydrate to the zirconium chloride is further improved to be 1: 1-8.
In the preparation method, the molar ratio of the zirconium chloride to the terephthalic acid to the organic solvent is 1: 162.
In the preparation method, the organic solvent is N, N-dimethylformamide.
In the above preparation method, further improvement is provided, in step S1, the rotation speed of the stirring is 300r/min to 400 r/min; the stirring time is 1 h.
In a further improvement of the preparation method, in step S2, the temperature of the hydrothermal reaction is 120 ℃; the time of the hydrothermal reaction is 24 hours.
In a further improvement of the above preparation method, in step S2, the method further includes the following steps after the hydrothermal reaction is completed: and centrifuging, washing and drying a reaction product obtained after the hydrothermal reaction is finished.
The preparation method is further improved, and the rotating speed of the centrifugation is 3000 r/min-5000 r/min.
In the preparation method, the washing is carried out by adopting N, N-dimethylformamide and ethanol; the number of washing times is 6 to 8.
In the preparation method, the drying is carried out under vacuum condition; the drying temperature is 60 ℃; the drying time is 8-12 h.
Compared with the prior art, the invention has the advantages that:
(1) the invention provides a cobalt ion doped metal organic framework material, which comprises cobalt ions and UiO-66 (Zr), wherein the cobalt ions are doped in the UiO-66 (Zr). In the invention, cobalt ions are doped in the metal organic framework material (UiO-66 (Zr)), the pore structure and the specific surface area of the metal organic framework material (UiO-66 (Zr)) can be changed by doping the cobalt ions, and the cobalt ions can contribute valence band electrons carried by the cobalt ions in the UiO-66 (Zr), thereby enhancing the adsorption performance of the metal organic framework material (UiO-66 (Zr)). Meanwhile, the light absorption of the UiO-66 (Zr) in an ultraviolet region can be enhanced by doping cobalt ions, and the generation and transmission of valence band electrons can be promoted, so that the UiO-66 (Zr) semiconductor can respond to photons with longer wavelength, and the utilization region of light is widened, therefore, the doping of the cobalt ions is beneficial to enhancing the light absorption efficiency of the UiO-66 (Zr) and the utilization rate of photon-generated carriers, and is beneficial to enhancing the photocatalytic performance of the material. Compared with the prior art, the cobalt ion doped metal organic framework material has the advantages of large specific surface area, good dispersibility, good stability, good adsorption property, good photocatalytic property and the like, can realize high-efficiency adsorption on antibiotics and high-efficiency degradation on the antibiotics under visible light, and has good application prospect.
(2) The cobalt ion doped metal organic framework material can be applied to treatment of antibiotic wastewater, and can be used for stirring, adsorbing and photocatalytic degradation of the cobalt ion doped metal organic framework material and the antibiotic wastewater, so that the cobalt ion doped metal organic framework material can efficiently adsorb and photocatalytic degrade antibiotics in the wastewater, has the advantages of high treatment efficiency, good removal effect, high recycling rate, cleanness, no pollution and the like, is a photocatalytic adsorbent which can be widely used and can efficiently remove the antibiotics in water, and has very high application value and commercial value.
(3) The invention also provides a preparation method of the cobalt ion doped metal organic framework material, which synthesizes the cobalt ion doped metal organic framework material with good adsorption performance, good photocatalysis performance and good stability for the first time, has the advantages of convenient operation, simple synthesis, less raw material types, low cost, high yield and the like, and is suitable for large-scale preparation.
(4) In the preparation method of the cobalt ion doped metal organic framework material, the molar ratio of cobalt chloride hexahydrate to zirconium chloride is optimized, and the prepared cobalt ion doped metal organic framework material contains cobalt ions with proper doping amount by optimizing the molar ratio of the cobalt chloride hexahydrate to the zirconium chloride to be 1: 1-8, so that the cobalt ions and the metal organic framework material generate stronger adsorption strength and photocatalytic activity, and the cobalt ion doped metal organic framework material with better adsorption effect and photocatalytic effect is obtained. Particularly, when the adding molar ratio of the cobalt chloride hexahydrate to the zirconium chloride is 1: 1, the best adsorption effect and photocatalysis effect are achieved. Therefore, the invention optimizes the molar ratio of the cobalt chloride hexahydrate and the zirconium chloride to obtain the proper cobalt ion doping amount, and has important significance for improving the adsorption performance and the photocatalytic performance of the cobalt ion doped metal organic framework material.
Drawings
In order to make the objects, technical solutions and advantages of the embodiments of the present invention clearer, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention.
FIG. 1 is a scanning electron micrograph of a cobalt ion-doped metal-organic framework material (CoUiO-1) prepared in example 1 of the present invention and UiO-66 (Zr) prepared in comparative example 1, wherein (a) is UiO-66 (Zr) and (b) is CoUiO-1.
FIG. 2 shows X-ray diffraction patterns of cobalt ion-doped metal organic framework materials (CoUiO-1, CoUiO-2, CoUiO-4, and CoUiO-8) prepared in examples 1 to 4 of the present invention and UiO-66 (Zr) prepared in comparative example 1.
FIG. 3 is an X-ray photoelectron spectrum of the cobalt ion-doped metal organic framework material (CoUiO-1) prepared in example 1 of the present invention.
FIG. 4 is a UV-VISIBLE diffuse reflectance spectrum of a cobalt ion-doped metal organic framework material (CoUiO-1) prepared in example 1 of the present invention and UiO-66 (Zr) prepared in comparative example 1.
FIG. 5 is a photoluminescence spectrum of a cobalt ion-doped metal organic framework material (CoUiO-1) prepared in example 1 of the present invention and UiO-66 (Zr) prepared in comparative example 1.
FIG. 6 is a graph showing the adsorption and photocatalytic effects of cobalt ion-doped metal organic framework materials (CoUiO-1, CoUiO-2, CoUiO-4, and CoUiO-8) prepared in examples 1 to 4 of the present invention and UiO-66 (Zr) prepared in comparative example 1 on tetracycline.
FIG. 7 shows X-ray diffraction patterns of cobalt ion-doped metal organic framework material (CoUiO-1) before and after treatment with tetracycline in example 5 of the present invention.
Detailed Description
The invention is further described below with reference to the drawings and specific preferred embodiments of the description, without thereby limiting the scope of protection of the invention.
The starting materials and equipment used in the following examples are commercially available. In the following examples, unless otherwise specified, the data obtained are the average of three or more repeated experiments.
Example 1
A cobalt ion doped metal organic framework material comprising cobalt ions and UiO-66 (Zr), wherein the cobalt ions are doped in the UiO-66 (Zr).
In this example, the specific surface area of the cobalt ion-doped metal-organic framework material is 815.178 m2/g。
The preparation method of the cobalt ion-doped metal organic framework material of the embodiment is to prepare the cobalt ion-doped metal organic framework material by taking zirconium chloride, terephthalic acid and cobalt chloride hexahydrate as raw materials and adopting a hydrothermal synthesis method, and comprises the following steps of:
(1) according to the molar ratio of 1: 162 of zirconium chloride, terephthalic acid and N, N-dimethylformamide and the molar ratio of 1: 1 of cobalt chloride hexahydrate and zirconium chloride, dispersing the zirconium chloride, the terephthalic acid and the cobalt chloride hexahydrate in the N, N-dimethylformamide, and stirring for 1h at the rotating speed of 300r/min to obtain a precursor solution.
(2) And (2) putting the precursor solution obtained in the step (1) into a reaction kettle, and carrying out hydrothermal reaction for 24 hours at the temperature of 120 ℃. After the reaction is finished, centrifuging the reaction product obtained after the hydrothermal reaction at the rotating speed of 5000 r/min, respectively washing the obtained centrifugal product by adopting N, N-dimethylformamide and ethanol for three times, and then drying the product in vacuum at the temperature of 60 ℃ for 12 hours to obtain the cobalt ion doped metal organic framework material named as CoUiO-1.
Example 2
A method for preparing a cobalt ion-doped metal-organic framework material, which is substantially the same as the preparation method in example 1, except that: the molar ratio of cobalt chloride hexahydrate to zirconium chloride in example 2 was 1: 2.
The cobalt ion-doped metal organic framework material prepared in example 2 was named CoUiO-2.
Example 3
A method for preparing a cobalt ion-doped metal-organic framework material, which is substantially the same as the preparation method in example 1, except that: the molar ratio of cobalt chloride hexahydrate to zirconium chloride in example 3 was 1: 4.
The cobalt ion-doped metal organic framework material prepared in example 3 was named CoUiO-4.
Example 4
A method for preparing a cobalt ion-doped metal-organic framework material, which is substantially the same as the preparation method in example 1, except that: the molar ratio of cobalt chloride hexahydrate to zirconium chloride in example 4 was 1: 8.
The cobalt ion-doped metal organic framework material prepared in example 4 was named CoUiO-8.
Comparative example 1
A method of producing UiO-66 (Zr) substantially the same as in example 1 except that: in comparative example 1, cobalt chloride hexahydrate was not added.
FIG. 1 is a scanning electron micrograph of a cobalt ion-doped metal-organic framework material (CoUiO-1) prepared in example 1 of the present invention and UiO-66 (Zr) prepared in comparative example 1, wherein (a) is UiO-66 (Zr) and (b) is CoUiO-1. As can be seen from FIG. 1, UiO-66 (Zr) exhibits an agglomerated morphology and is poorly dispersed. The CoUiO-1 has a cubic appearance and is relatively dispersed. Therefore, the cobalt ion-doped UiO-66 (Zr) has more uniform and dispersed appearance, and the size of the cobalt ion-doped UiO-66 (Zr) particles becomes smaller, and the particle size is about 180 nm.
FIG. 2 shows X-ray diffraction patterns of cobalt ion-doped metal organic framework materials (CoUiO-1, CoUiO-2, CoUiO-4, and CoUiO-8) prepared in examples 1 to 4 of the present invention and UiO-66 (Zr) prepared in comparative example 1. As shown in fig. 2, all samples have sharp and prominent peaks, indicating that the crystallinity of the samples is better. The cobalt ion doped metal organic framework materials (CoUiO-1, CoUiO-2, CoUiO-4 and CoUiO-8) doped with different amounts of cobalt ions are similar to the X-ray diffraction pattern of pure UiO-66 (Zr), and no other impurity peak appears, which indicates that the topological structure of the UiO-66 (Zr) is not changed due to the doping of the cobalt ions.
FIG. 3 is an X-ray photoelectron spectrum of the cobalt ion-doped metal organic framework material (CoUiO-1) prepared in example 1 of the present invention. Wherein, FIG. 3 is a Co 2p spectrum. As can be seen from FIG. 3, the Co 2p spectrum is disordered in peak shape and still presents Co 2p3/2And Co 2p1/2Two peaks, indicating that the doped cobalt bonds well with the O in the UiO-66 (Zr) and forms Co-O bonds, and no cobalt oxide peak was found in the Co 2p spectrum, indicating that no cobalt oxide was present and that cobalt ions could be successfully doped into the UiO-66 (Zr) lattice. As can be seen from the two peaks fitted with Co, the Co element exhibits Co in UiO-66 (Zr)2+And Co3+Two states, wherein Co3+Predominate.
FIG. 4 is a UV-VISIBLE diffuse reflectance spectrum of a cobalt ion-doped metal organic framework material (CoUiO-1) prepared in example 1 of the present invention and UiO-66 (Zr) prepared in comparative example 1. As can be seen from FIG. 4, the light absorption edge of the cobalt ion-doped metal organic framework material of the present invention is not significantly red-shifted compared to the UiO-66 (Zr) monomer, but the light absorption in the UV region becomes stronger and there is additional light absorption in the visible region. The doping of cobalt ions may create a doping level that extends the light absorption range of UiO-66 (Zr). The ICP-AES result shows that the mass content of Co in the CoUiO-1 is only 0.45%, metal ions are difficult to dope into crystal lattices, and the bulk of the doped product is still UiO-66 (Zr), so that the forbidden bandwidth of the UiO-66 (Zr) is not changed by the doping of the cobalt ions. From this result, it was found that the photoresponse range of UiO-6 (Zr) 6 can be improved by doping cobalt ions.
FIG. 5 is a photoluminescence spectrum of a cobalt ion-doped metal organic framework material (CoUiO-1) prepared in example 1 of the present invention and UiO-66 (Zr) prepared in comparative example 1. The photoluminescence spectrogram can reflect the influence of metal doping on the electronic performance of the material, and in general, the photoluminescence spectrogram is related to the recombination rate of photon-generated carriers, and the higher the photoluminescence spectrum intensity is, the higher the recombination rate of the photon-generated carriers is. As shown in FIG. 5, the photoluminescence spectral intensity of the UiO-66 (Zr) monomer is much higher than that of the CoUiO-1, which shows that the cobalt ion doping greatly reduces the recombination of photo-generated carriers, and the high photo-generated carrier utilization rate is helpful for the photocatalytic reaction.
The specific surface areas of UiO-66 (Zr) and CoUiO-1 were calculated analytically to be 584.44 and 815.178 m, respectively2The specific surface area of the cobalt ion doped metal organic framework material is obviously increased after the cobalt ion doping, and the increase of the specific surface area is beneficial to increasing the contact area of the catalyst and pollutants and increasing reaction sites.
Example 5
The method is used for investigating the treatment effect of the cobalt ion doped metal organic framework material on the antibiotic wastewater, and specifically is used for treating the tetracycline wastewater by adopting the cobalt ion doped metal organic framework material with different cobalt ion doping amounts, and comprises the following steps:
weighing CoUiO-1 (example 1), CoUiO-2 (example 2), CoUiO-4 (example 3), CoUiO-8 (example 4) and UiO-66 (Zr) (comparative example 1), respectively adding 20mg of the above components into 100mL of tetracycline wastewater with a concentration of 20 mg/L, magnetically stirring for 1h in a dark place at a rotation speed of 300r/min to reach adsorption balance, then turning on a light source, and irradiating under simulated sunlight to perform a photocatalytic reaction to complete the treatment of tetracycline.
After the magnetic stirring was completed, 4mL of the sample was taken and centrifuged. And (3) measuring absorbance of the supernatant obtained by centrifugation by using an ultraviolet-visible spectrophotometer, and determining the adsorption removal rate of the tetracycline, so as to obtain the adsorption effect of different materials on the tetracycline, wherein the result is shown in fig. 6.
In the process of the photocatalytic reaction, 4mL of samples are taken at intervals (when the photocatalytic reaction is carried out for 0min, 15min, 30min, 45min and 60 min), and the samples are centrifuged. And (3) measuring absorbance of the supernatant obtained by centrifugation by an ultraviolet-visible spectrophotometer, and determining the photocatalytic removal rate of tetracycline, so as to obtain the photocatalytic effect of different materials on tetracycline, wherein the result is shown in fig. 6.
FIG. 6 is a graph showing the adsorption and photocatalytic effects of cobalt ion-doped metal organic framework materials (CoUiO-1, CoUiO-2, CoUiO-4, and CoUiO-8) prepared in examples 1 to 4 of the present invention and UiO-66 (Zr) prepared in comparative example 1 on tetracycline. As can be seen from FIG. 6, the total removal rate of CoUiO-1 is the highest and reaches 94%, while the total removal rate of the UiO-66 (Zr) monomer is only 20%, which indicates that after doping cobalt ions, the adsorption performance and the photocatalytic performance of the UiO-66 (Zr) are both greatly improved. In addition, the effect of different cobalt ion doping amounts on the adsorption and photocatalytic performance of UiO-66 (Zr) was different, and as shown in FIG. 6, the total removal rates of CoUiO-2, CoUiO-4, CoUiO-8 and UiO-66 (Zr) were 84.3%, 81.4%, 78.9% and 20.7%, respectively. Therefore, in the preparation of the cobalt ion doped metal organic framework material, when the molar ratio of the cobalt chloride hexahydrate to the zirconium chloride is 1: 1-8, better adsorption effect and photocatalysis effect can be obtained, wherein when the molar ratio of the cobalt chloride hexahydrate to the zirconium chloride is 1: 1, the adsorption performance and the photocatalysis performance of the cobalt ion doped metal organic framework material are the best, so that the proper cobalt ion doping amount has great significance for improving the adsorption performance and the photocatalysis performance of the cobalt ion doped metal organic framework material.
X-ray diffraction analysis was performed on the cobalt ion-doped metal-organic framework material (CoUiO-1) before and after treatment of tetracycline, and the results are shown in FIG. 7. FIG. 7 shows X-ray diffraction patterns of cobalt ion-doped metal organic framework material (CoUiO-1) before and after treatment with tetracycline in example 5 of the present invention. As shown in fig. 7, the X-ray diffraction patterns before and after the reaction of the cobalt ion-doped metal-organic framework material of the present invention remain unchanged and the peak shape is sharp, which indicates that the structure before and after the reaction remains unchanged and the crystallinity is good, and the cobalt ion-doped metal-organic framework material has good stability.
The above examples are merely preferred embodiments of the present invention, and the scope of the present invention is not limited to the above examples. All technical schemes belonging to the idea of the invention belong to the protection scope of the invention. It should be noted that modifications and embellishments within the scope of the invention may be made by those skilled in the art without departing from the principle of the invention, and such modifications and embellishments should also be considered as within the scope of the invention.

Claims (7)

1. A cobalt ion doped metal organic framework material, comprising cobalt ions and UiO-66 (Zr); the cobalt ions are doped in UiO-66 (Zr); the specific surface area of the cobalt ion doped metal-organic framework material is 815.178 m2(ii)/g; the mass content of Co in the cobalt ion doped metal organic framework material is 0.45%.
2. A method for preparing a cobalt ion doped metal organic framework material according to claim 1, comprising the steps of:
s1, mixing zirconium chloride, terephthalic acid, cobalt chloride hexahydrate and an organic solvent, and stirring to obtain a precursor solution; the molar ratio of the cobalt chloride hexahydrate to the zirconium chloride is 1: 1; the molar ratio of the zirconium chloride to the terephthalic acid to the organic solvent is 1: 162;
s2, carrying out hydrothermal reaction on the precursor solution in the step S1 to obtain the cobalt ion doped metal organic framework material.
3. The method according to claim 2, wherein the organic solvent is N, N-dimethylformamide.
4. The production method according to claim 2 or 3, wherein in step S1, the rotation speed of the stirring is 300r/min to 400 r/min; the stirring time is 1 h.
5. The method according to claim 2 or 3, wherein the hydrothermal reaction is carried out at 120 ℃ in step S2; the time of the hydrothermal reaction is 24 hours.
6. The method according to claim 2 or 3, wherein the step S2 further comprises the following steps after the hydrothermal reaction is completed: and centrifuging, washing and drying a reaction product obtained after the hydrothermal reaction is finished.
7. The method according to claim 6, wherein the rotation speed of the centrifugation is 3000 r/min to 5000 r/min;
the washing adopts N, N-dimethylformamide and ethanol; the washing times are 6-8 times;
the drying is carried out under vacuum conditions; the drying temperature is 60 ℃; the drying time is 8-12 h.
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