CN114618594B - Ti atom pyridine coordination carbon-based three-dimensional nano-framework material and preparation method and application thereof - Google Patents

Ti atom pyridine coordination carbon-based three-dimensional nano-framework material and preparation method and application thereof Download PDF

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CN114618594B
CN114618594B CN202210426675.7A CN202210426675A CN114618594B CN 114618594 B CN114618594 B CN 114618594B CN 202210426675 A CN202210426675 A CN 202210426675A CN 114618594 B CN114618594 B CN 114618594B
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沈意
刘莎莎
张海忠
朱超
杨靖依
沈义新
许俊杰
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Zhejiang University of Technology ZJUT
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Abstract

The invention discloses a Ti atom pyridine coordination carbon-based three-dimensional nano-skeleton material, a preparation method and application thereof. Under the ultrasonic condition of normal temperature and normal pressure, the pyridine carbon nitrogen skeleton is used as an adsorption substrate, ti atoms are used as a photocatalyst to be doped on the substrate, the pyridine carbon nitrogen skeleton and the Ti atoms in the composite material are respectively used as the adsorption substrate and a photocatalytic site, the organic pollutant has better adsorption and photocatalytic degradation rate, and the adsorption and photocatalytic performance of the composite material can be regulated and controlled by regulating the doping rate of the Ti atoms. According to the properties, the Ti-atom pyridine ligand carbon-based three-dimensional nano-skeleton material is synthesized by adopting an environment-friendly method, has higher catalytic performance on pollutants, and can be used in the fields of environmental remediation, chemical industry and the like.

Description

Ti atom pyridine coordination carbon-based three-dimensional nano-framework material and preparation method and application thereof
Technical Field
The invention belongs to the field of material preparation, and particularly relates to a Ti atom pyridine coordination carbon-based three-dimensional nano-skeleton material, and a preparation method and application thereof.
Background
The heterogeneous semiconductor catalyst technology is a green approach to solve the environmental pollution problem by using solar energy. Among inorganic semiconductor materials, titanium dioxide (TiO 2 ) The photocatalyst has the advantages of good photocatalytic activity, stable chemical property, low cost and the like, and becomes one of the most widely applied photocatalytic materials. Organic semiconductors such as Covalent Organic Frameworks (COFs), metal Organic Frameworks (MOFs), etc., generally have a narrower forbidden band width and excellent electron and hole separation ability compared to inorganic semiconductors, and thus will be TiO 2 Coupling with organic semiconductors to increase photocatalytic activity is a popular research object. The photocatalytic performance of pyridine coordinated Covalent Triazine Frameworks (CTFs) is remarkably improved, because the unique n- & gtpi electron transition mode of pyridine is beneficial to transfer of photogenerated electrons, and the surface of the pyridine coordinated CTFs can generate more pore channel structures so as to be beneficial to absorption of pollutants, but the degradation efficiency and sustainable utilization rate of the pyridine coordinated CTFs are still required to be improved. In order to further improve the adsorption and photocatalysis performance, a pyridine carbon nitrogen framework with a layered structure doped with pyridine is taken as a matrix, and TiO is prepared 2 The three-dimensional composite structure is built by doping the three-dimensional composite structure into pyridine carbon nitrogen skeleton layers to enhance the specific surface area and the catalytic performance of the three-dimensional composite structure. In addition, the three-dimensional structure can enable photo-generated electrons and holes to be transferred not only on the pyridine carbon nitrogen skeleton layer, but also to move between layers through bridging actions of Ti-O and the like, so that recombination of electron-hole pairs is effectively inhibited, and the energy band structure is optimized to enable the energy band structure to have higher activity. In addition, ti atoms can also be used as adsorption sites of oxygen, promote the adsorption and protonation of oxygen, generate more free radicals, and provide a new way for the practical application of the Ti atoms in degrading organic pollutants.
Disclosure of Invention
The invention aims to provide a Ti atom pyridine coordination carbon-based three-dimensional nano-framework material, a preparation method and application thereof, which not only avoid high temperature and high pressure, but also enable Ti atoms to be uniformly doped on a pyridine carbon nitrogen framework.
In order to combine the dual functions of adsorption and catalysis, the invention adopts a brand new idea: the pore canal structure is increased by combining pyridine with a carbon-nitrogen framework, and the unique n- & gt pi electron transition mode of the pyridine is beneficial to transfer of photogenerated electrons; the doping of Ti atoms enhances the generation of free radicals by utilizing the adsorption of oxygen, and further participates in photocatalytic degradation.
The Ti atom pyridine coordination carbon-based three-dimensional nano-framework material takes a pyridine carbon nitrogen framework as a substrate, and Ti atoms are doped on the substrate.
The method is realized by the following technical scheme:
the pyridine carbon nitrogen skeleton is prepared through the following steps:
(1) Adding terephthalonitrile and 2, 6-pyridine dimethyl nitrile into a quartz tube filled with trifluoromethane sulfonic acid under the protection of ice water bath and nitrogen atmosphere at the temperature of-5 to 5 ℃ and keeping stirring for 1 to 2 hours to obtain uniform viscous yellow liquid;
(2) Transferring the quartz tube into an electrothermal constant-temperature blast drying oven, maintaining at a certain temperature for a period of time, naturally cooling to obtain yellow solid substances, washing with ethanol and water for three times in sequence, and removing unreacted residues;
(3) And (3) putting the washed yellow solid substance into a vacuum drying oven at 60-80 ℃ for drying for 24-48 hours to obtain a yellow solid, and then grinding the yellow solid substance into powder in a mortar to obtain the pyridine carbon nitrogen skeleton.
Further, the total molar mass of the terephthalonitrile and the 2, 6-pyridine-dinitrile is 6-10 mmol, and the molar ratio is 0.5-2.
Further, in the step (2), the mixture is kept at the temperature of 80-120 ℃ for 10-30min, and then the yellow solid substance is obtained after natural cooling.
A preparation method of a Ti atom pyridine coordination carbon-based three-dimensional nano-framework material comprises the following steps: ultrasonic treatment is carried out on the pyridine carbon nitrogen skeleton to ensure that the sheet layer is uniformly dispersed; after uniform dispersion, adding titanium tetrachloride, stirring, drying and calcining to obtain the Ti atom pyridine coordinated carbon-based three-dimensional nano-skeleton material.
Further, the Ti atom doping ratio is 5 to 50%, and the concentration of titanium tetrachloride is 2 to 6mg/mL, preferably 4mg/mL.
Further, the drying process after stirring is to put the stirred mixture into a water bath kettle for water bath drying, and the temperature of the water bath drying is 80-100 ℃.
Further, the dried material is put into a tube furnace to be calcined for 1 to 3 hours at the temperature of 150 to 210 ℃ to obtain the Ti atom pyridine ligand carbon group three-dimensional nano-skeleton.
The Ti atom pyridine coordination carbon-based three-dimensional nano-skeleton material prepared by the preparation method takes a pyridine carbon-nitrogen skeleton as a substrate, ti atoms are doped on the pyridine carbon-nitrogen skeleton, and the size of the pyridine carbon-nitrogen skeleton is larger than 50 mu m.
The application of the Ti atom pyridine coordinated carbon based three-dimensional nano-skeleton material in adsorbing and photo-catalytically degrading organic pollutants including but not limited to Phenol (PHE), bisphenol A (BPA) or 2,2', 4' -tetrahydroxybenzophenone (BP-2).
The invention has the beneficial effects that: the invention provides a mode of uniformly doping Ti atoms into a pyridine carbon nitrogen skeleton, which is used as a high-activity material for adsorption and photocatalysis, and has the following advantages in implementation and use: compared with the traditional catalytic material, the material can realize the combination of adsorption and photocatalysis, can efficiently adsorb pollutants in water, and also improves the rate of degrading the pollutants by photocatalysis. The catalysis rate can be regulated and controlled by changing the doping rate of Ti atoms; the Ti atom pyridine coordination carbon-based three-dimensional nano-skeleton material has the characteristics of simple preparation and high catalytic efficiency, and has great application potential in the fields of chemical catalysis, environmental protection and the like.
Drawings
FIG. 1 is an electron microscope scan of the material prepared in example 2;
FIG. 2 is an electron microscope scan of the material prepared in example 4;
FIG. 3 is an electron microscope scan of the material prepared in example 5.
Detailed Description
The present invention is further described in conjunction with the drawings and examples below to provide a better understanding of the nature of the present invention to those skilled in the art. The reagents or materials of the invention, unless otherwise specified, are commercially available products.
Preparing a pyridine carbon nitrogen skeleton:
(1) Adding 4mmol of terephthalonitrile and 4mmol of 2, 6-pyridine dimethyl nitrile into a quartz tube filled with 5mL of trifluoromethanesulfonic acid under the protection of ice water bath and nitrogen atmosphere at 0 ℃ and keeping stirring for 1.5h to obtain a uniform viscous yellow liquid;
(2) Transferring the quartz tube into an electrothermal constant-temperature blast drying oven, maintaining at 100deg.C for 20min, naturally cooling to obtain yellow solid substances, washing with ethanol and water for three times, and removing unreacted residues;
(3) And (3) putting the washed yellow solid substance into a vacuum drying oven at 60 ℃ for drying for 48 hours to obtain a yellow solid, and then grinding the yellow solid substance into powder in a mortar to obtain the pyridine carbon nitrogen skeleton, wherein the size of the pyridine carbon nitrogen skeleton is larger than 50 mu m.
In the following examples, the pyridine carbon nitrogen skeleton was used to prepare three-dimensional nano-frameworks of Ti-atom pyridine ligand carbon groups. Of course, those skilled in the art will recognize that the preparation of the pyridine carbon nitrogen skeleton and the three-dimensional nano-skeleton of the Ti-atom pyridine ligand carbon group is only a preferred mode of the invention, and each parameter can be adjusted according to actual needs. Other carbon-nitrogen frameworks in the prior art can also be used for the pyridine carbon-nitrogen framework.
The Ti atoms are doped on the pyridine carbon nitrogen skeleton, and after the pyridine carbon nitrogen skeleton is uniformly dispersed by adopting ultrasonic, the Ti atoms are connected with each layer surface as a connector through the action of Ti-O bonds or Ti-N bonds and the pyridine carbon nitrogen. Specific examples are as follows.
Example 1
In this embodiment, the specific steps for preparing the Ti atom pyridine ligand carbon based three-dimensional nano-skeleton material are as follows:
(1) Ultrasonic treatment is carried out on 0.5g of pyridine carbon nitrogen skeleton for 2 hours, so that the sheet layer is uniformly dispersed;
(2) Then mixing 24.96mL of titanium tetrachloride aqueous solution with the concentration of 4mg/mL with the pyridine carbon nitrogen skeleton well dispersed by ultrasonic, and continuously stirring for 24 hours;
(3) Placing the mixture in a water bath kettle, and drying in water bath at 80 ℃;
(4) Drying and then placing the mixture into a tube furnace to calcine for 2 hours at 180 ℃ to obtain the Ti atom pyridine coordinated carbon-based three-dimensional nano skeleton with the Ti atom doping rate of 5%.
Example 2
In this embodiment, the specific steps for preparing the Ti atom pyridine ligand carbon based three-dimensional nano-skeleton material are as follows:
(1) Ultrasonic treatment is carried out on 0.5g of pyridine carbon nitrogen skeleton for 2 hours, so that the sheet layer is uniformly dispersed;
(2) Then mixing 49.53mL of titanium tetrachloride aqueous solution with the concentration of 4mg/mL with the pyridine carbon nitrogen skeleton well dispersed by ultrasonic, and continuously stirring for 24 hours;
(3) Placing the mixture in a water bath kettle, and drying in water bath at 80 ℃;
(4) Drying and then placing the mixture into a tube furnace to calcine for 2 hours at 180 ℃ to obtain the three-dimensional nano-skeleton of the pyridine coordinated carbon group with the Ti atom doping rate of 10 percent.
As shown in FIG. 1, the electron microscope scan of the prepared surface with 10% Ti atoms doped is slightly reduced in porous structure and slightly increased in interlayer spacing.
Example 3
In this embodiment, the specific steps for preparing the Ti atom pyridine ligand carbon based three-dimensional nano-skeleton material are as follows:
(1) Ultrasonic treatment is carried out on 0.5g of pyridine carbon nitrogen skeleton for 2 hours, so that the sheet layer is uniformly dispersed;
(2) Then mixing 99.06mL of titanium tetrachloride aqueous solution with the concentration of 4mg/mL with the pyridine carbon nitrogen skeleton well dispersed by ultrasonic, and continuously stirring for 24 hours;
(3) Placing the mixture in a water bath kettle, and drying in water bath at 80 ℃;
(4) And (3) drying, and then placing the dried material into a tube furnace to calcine for 2 hours at 180 ℃ to obtain the Ti atom pyridine coordinated carbon-based three-dimensional nano-skeleton material with the Ti atom doping rate of 20%.
Example 4
In this embodiment, the specific steps for preparing the Ti atom pyridine ligand carbon based three-dimensional nano-skeleton material are as follows:
(1) Ultrasonic treatment is carried out on 0.5g of pyridine carbon nitrogen skeleton for 2 hours, so that the sheet layer is uniformly dispersed;
(2) Then 148.59mL of titanium tetrachloride aqueous solution with the concentration of 4mg/mL is mixed with the pyridine carbon nitrogen skeleton with good ultrasonic dispersion, and stirring is continued for 24 hours;
(3) Placing the mixture in a water bath kettle, and drying in water bath at 80 ℃;
(4) And (3) drying, and then placing the dried material into a tube furnace to calcine for 2 hours at 180 ℃ to obtain the Ti atom pyridine coordinated carbon-based three-dimensional nano-skeleton material with the Ti atom doping rate of 30%.
As shown in FIG. 2, the electron microscope scan is shown, the porous structure of the 30% Ti atom doped surface is reduced, the interlayer spacing is increased, and a two-dimensional layered structure is formed.
Example 5
In this embodiment, the specific steps for preparing the Ti atom pyridine ligand carbon based three-dimensional nano-skeleton material are as follows:
(1) Ultrasonic treatment is carried out on 0.5g of pyridine carbon nitrogen skeleton for 2 hours, so that the sheet layer is uniformly dispersed;
(2) Then 247.65mL of titanium tetrachloride aqueous solution with the concentration of 4mg/mL is mixed with the pyridine carbon nitrogen skeleton with good ultrasonic dispersion, and stirring is continued for 24 hours;
(3) Placing the mixture in a water bath kettle, and drying in water bath at 80 ℃;
(4) And (3) drying, and then placing the dried material into a tube furnace to calcine for 2 hours at 180 ℃ to obtain the Ti atom pyridine coordinated carbon-based three-dimensional nano-skeleton material with the Ti atom doping rate of 50%.
As shown in FIG. 3, the electron microscope scanning chart prepared by the method has the advantages that the porous structure of the 50% Ti atom doped surface is obviously reduced, the interlayer spacing is obviously increased, and an obvious two-dimensional layered structure is formed.
Application example 1
And (3) respectively carrying out photocatalytic degradation tests on Phenol (PHE) under the irradiation of a metal halogen lamp by using the Ti atom pyridine ligand carbon-based three-dimensional nano-skeleton materials obtained in the examples 1-5.
The experimental conditions are as follows: 100mL of Phenol (PHE) solution with the concentration of 5ppm is measured in each group of experiments and is respectively put into a photoreactor, 20mg of the Ti atom pyridine ligand carbon-based three-dimensional nano-framework material prepared in the examples 1-5 is respectively added, the three-dimensional nano-framework material is magnetically stirred in the dark for 1h to reach adsorption-desorption balance, a metal halogen lamp is turned on to perform photocatalytic degradation reaction, and the PHE concentration in the solution is sampled at regular time and is detected by high performance liquid chromatography.
Application example 2
A photocatalytic degradation test was performed on bisphenol A (BPA) under the irradiation of a metal halide lamp by using the Ti atom pyridine ligand carbon-based three-dimensional nano-skeleton materials obtained in examples 1 to 5.
The experimental conditions are as follows: 100mL of bisphenol A (BPA) solution with the concentration of 5ppm is measured in each group of experiments and is put into a photoreactor, 20mg of the Ti atom pyridine ligand carbon based three-dimensional nano-framework material prepared in the examples 1-5 is added respectively, the solution is magnetically stirred in the dark for 1h to reach adsorption-desorption equilibrium, a metal halogen lamp is turned on to perform photocatalytic degradation reaction, regular sampling is carried out, and the concentration of the BPA in the solution is detected by high performance liquid chromatography.
Application example 3
And (3) respectively carrying out photocatalytic degradation tests on the 2,2', 4' -tetrahydroxybenzophenone (BP-2) under the irradiation of a metal halogen lamp by using the Ti atom pyridine ligand carbon-based three-dimensional nano-framework materials obtained in the examples 1-5.
The experimental conditions are as follows: 100mL of 2,2', 4' -tetrahydroxybenzophenone (BP-2) solution with the concentration of 5ppm is measured in each group of experiments and is respectively put in a photoreactor, 20mg of the Ti atom pyridine ligand carbon-based three-dimensional nano-framework material prepared in the examples 1-5 is respectively added, the mixture is magnetically stirred in the dark for 1h to reach adsorption-desorption balance, a metal halogen lamp is turned on to perform photocatalytic degradation reaction, and the concentration of BP-2 in the solution is sampled at regular time and is detected by high performance liquid chromatography.
The results after the photocatalytic reaction for 6 hours are shown in table 1, the three-dimensional nano-skeleton materials with different Ti atom doping amounts, namely, the Ti atom pyridine coordinated carbon-based three-dimensional nano-skeleton materials, have different adsorption-photocatalytic degradation rates on Phenol (PHE), bisphenol A (BPA) and 2,2', 4' -tetrahydroxybenzophenone (BP-2), wherein each example 4 has the highest adsorption-photocatalytic degradation efficiency on BP-2. In example 4, when the doping rate of Ti atoms is 30%, the synthesized Ti atom pyridine coordinated carbon-based three-dimensional nano-skeleton material has the highest degradation efficiency on PHE, BPA and BP-2, and the degradation rates after light irradiation for 6 hours are 90.3%, 96.6% and 98.7%, respectively. Therefore, when the doping rate of the Ti atoms is 30%, the adsorption-photocatalytic degradation rate of the Ti atom pyridine coordination carbon-based three-dimensional nano-skeleton material is higher, and the photocatalytic degradation rate of the Ti atoms can be adjusted by adjusting the doping rate of the Ti atoms. The material of the invention can efficiently adsorb and photo-catalytically degrade Phenol (PHE), bisphenol A (BPA) and 2,2', 4' -tetrahydroxybenzophenone (BP-2).
TABLE 1 degradation Rate (%)
Pollutant name Example 1 Example 2 Example 3 Example 4 Example 5
PHE 39.5 53.1 69.8 90.3 82.6
BPA 58.9 74.1 91.4 96.6 92.0
BP-2 83.2 91.9 95.0 98.7 94.0
The above embodiment is only a preferred embodiment of the present invention, but it is not intended to limit the present invention. For example, although the raw materials in the preparation process are terephthalonitrile and 2, 6-pyridine-dinitrile in the above examples, it is not necessarily meant to be all that is required, and the effect of the present invention can be achieved as long as polymerization to produce triazine skeleton and pyridine coordination is possible. For example, although in the above-described embodiment, only titanium tetrachloride is selected for the doping of Ti atoms, it does not mean that only titanium tetrachloride can be selected, and other substances capable of achieving the doping of Ti atoms, such as titanium acetate, titanium oxalate, titanium sulfate, and the like, can also achieve the technical effects of the present invention. For example, the above embodiment selects only Ti atoms for doping, but does not mean that only Ti atoms can be selected for doping, and other elements that can achieve actions similar to Ti atoms, such as transition metals, can also achieve the technical effects of the present invention. For another example, the above examples only show the case where the doping ratio of Ti atoms is 5 to 50%, but the technical effect of the present invention can be achieved by adjusting the doping ratio of Ti atoms before and after the above range, for example, 15%, 25% or even 50% or more.
It will thus be seen that various changes and modifications may be made by those skilled in the art without departing from the spirit and scope of the invention. Therefore, all the technical schemes obtained by adopting the equivalent substitution or equivalent transformation fall within the protection scope of the invention.

Claims (7)

1. The preparation method of the Ti atom pyridine coordination carbon-based three-dimensional nano-framework material is characterized by comprising the following steps: ultrasonic treatment is carried out on the pyridine carbon nitrogen skeleton to ensure that the sheet layer is uniformly dispersed; after uniform dispersion, adding titanium tetrachloride, wherein the doping ratio of Ti atoms is 5-50%, stirring, drying and calcining the titanium tetrachloride, wherein the drying process is to put the stirred mixture into a water bath kettle, the drying temperature of the water bath kettle is 80-100 ℃, and the dried material is put into a tubular furnace to be calcined for 1-3 hours at 150-210 ℃ to obtain a Ti atom pyridine coordination carbon-based three-dimensional nano skeleton;
the pyridine carbon nitrogen skeleton is prepared through the following steps:
(1) Adding terephthalonitrile and 2, 6-pyridine dimethyl nitrile into a quartz tube filled with trifluoromethanesulfonic acid under the protection of ice water bath and nitrogen atmosphere at the temperature of-5 ℃, and stirring for 1-2 hours to obtain uniform viscous yellow liquid;
(2) Transferring the quartz tube into an electrothermal constant temperature blast drying oven, maintaining at 80-120deg.C for 10-30min, naturally cooling to obtain yellow solid substance, washing with ethanol and water for three times, and removing unreacted residues;
(3) And (3) putting the washed yellow solid substance into a vacuum drying oven at 60-80 ℃ for drying for 24-48 hours to obtain a yellow solid, and then grinding the yellow solid substance into powder in a mortar to obtain the pyridine carbon nitrogen skeleton.
2. The method of claim 1, wherein the concentration of titanium tetrachloride is 2 to 6 mg/mL.
3. The method of claim 2, wherein the concentration of titanium tetrachloride is 4mg/mL.
4. The process according to claim 1, wherein the total molar mass of terephthalonitrile and 2, 6-pyridine-dinitrile is 6 to 10mmol and the molar ratio is 0.5 to 2.
5. The Ti atom pyridine ligand carbon based three-dimensional nano-skeleton material prepared by the preparation method of claim 1, which is characterized in that the material takes a pyridine carbon nitrogen skeleton as a substrate, and Ti atoms are doped on the pyridine carbon nitrogen skeleton.
6. The Ti atom pyridine coordinated carbon based three-dimensional nano-skeleton material according to claim 5, wherein the pyridine carbon nitrogen skeleton size is more than 50 μm.
7. Use of the Ti atom pyridine ligand carbon based three-dimensional nano-skeleton material according to claim 6 for adsorbing and photo-catalytically degrading organic pollutants.
CN202210426675.7A 2022-04-22 2022-04-22 Ti atom pyridine coordination carbon-based three-dimensional nano-framework material and preparation method and application thereof Active CN114618594B (en)

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