CN113634285A - Preparation method of supermolecule self-assembly PDI nano material - Google Patents
Preparation method of supermolecule self-assembly PDI nano material Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
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- B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
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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
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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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
- C02F2101/30—Organic compounds
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
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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
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Abstract
The invention belongs to the technical field of energy and material preparation, and particularly relates to a preparation method of a supermolecule self-assembled PDI nano material, which is used for photocatalytic degradation of pollutants. According to the invention, transition metal monoatomic anchor is used on aza-graphene as a cocatalyst, so that the separation efficiency of a PDI material photon-generated carrier is accelerated, and the performance of the PDI material in photocatalytic degradation of environmental water phenol pollutants is improved.
Description
Technical Field
The invention belongs to the technical field of energy and material preparation, and particularly relates to a preparation method of a supermolecule self-assembled PDI nano material, which is used for photocatalytic degradation of pollutants.
Background
In recent years, the degradation of pollutants using environmentally friendly, economical photocatalytic techniques has been considered as a promising strategy in the field of environmental science. At present, the traditional inorganic semiconductor photocatalyst has the defects of high cost, high environmental toxicity, poor structure controllability, low efficiency and the like, and the practical application of the traditional inorganic semiconductor photocatalyst is greatly limited. Therefore, it is important to develop a novel photocatalyst having high efficiency, low cost and no toxicity.
Organic materials are receiving wide attention due to their chemically tunable optical and electronic properties, diverse structural flexibility, low cost and diverse and simple synthetic methods. Among organic materials, perylene bisimide (PDI) and its derivatives, as a classical n-type organic semiconductor, have been widely noticed by scholars at home and abroad due to their unique photoelectric properties and excellent photo-thermal stability, and have been widely used in the directions of pollutant degradation, oxygen generation, cancer treatment, etc. Recent studies have shown that PDI-based photocatalytic materials have a higher HOMO level and a strong oxidizing active species (· O)2–，1O2，h+) Therefore, the method has wide application prospect in the field of purification of environmental organic pollutants. However, the photocatalytic activity of PDI is greatly limited due to its low specific surface area and high recombination rate of photo-generated electron-hole pairs. The cocatalyst is introduced in the PDI self-assembly process, so that the migration efficiency of a photon-generated carrier can be effectively improved, and the photocatalytic performance of the PDI is improved.
Currently, Pt and Pt-based are considered the most effective promoters, but their high cost and low earth reserves severely limit their practical application. Therefore, there is an urgent need to search for non-noble metal promoters having excellent properties. To date, a number of high performance and low cost non-noble metal promoters have been constructed. Among them, transition metals have proven to be the most promising non-noble metal promoters due to their abundant earth reserves (Fe, Co, Ni). However, transition metal nanoparticles are prone to aggregation, thereby severely affecting their performance. Recent work proves that the aza-graphene can effectively avoid metal agglomeration, and the anchoring of a metal single atom on the aza-graphene is regarded as a promoter which can be compared with Pt base.
Therefore, the PDI is subjected to in-situ self-assembly on the monoatomic anchored aza-graphene by a rapid and simple solvent dispersion method to form the composite photocatalyst, and the capability of the composite photocatalyst for degrading pollutants by photocatalysis is further researched.
Disclosure of Invention
The invention relates to a preparation method of a transition metal monoatomic modification supermolecule self-assembly PDI nano material, which accelerates the separation efficiency of photon-generated carriers of the PDI material by anchoring the transition metal monoatomic modification on aza-graphene as a cocatalyst, and further improves the performance of the PDI material in photocatalytic degradation of environmental water phenol pollutants.
The invention provides a preparation method of a transition metal monoatomic modification supermolecule self-assembly PDI nano material, which comprises the following steps:
(1) adding graphene oxide into deionized water, carrying out ultrasonic mixing uniformly to obtain a mixed solution 1, adding a transition metal salt solution, carrying out ultrasonic mixing until the transition metal salt is uniformly dispersed in the mixed solution 1, rapidly freezing the solution in liquid nitrogen, and carrying out freeze-drying treatment in a freeze-dryer.
The proportion of the graphene oxide to the deionized water and the transition metal salt solution is as follows: 80-100 mg; 40-50mL:1-3mL, and the concentration of the transition metal salt solution is 1-5 mg/mL. The temperature of the freeze drying treatment is-10 to-50 ℃, the time of the freeze drying treatment is 24 to 48 hours, and the pressure is 1.3 to 13 Pa.
(2) And (2) putting the sample obtained by the freeze drying treatment in the step (1) into a tube furnace, calcining for 1h at 750 ℃ in the atmosphere of argon and ammonia gas, and heating up at a rate of 12 ℃/min to obtain the nitrogen-doped graphene anchored by the transition metal monoatomic group.
The flow rate of the argon is 160-170mL/min, and the flow rate of the ammonia is 60-70 mL/min.
(3) Dissolving PDI in an absolute ethyl alcohol solution to obtain a mixed solution 2, transferring triethanolamine by using a liquid transfer gun, adding the triethanolamine into the mixed solution 2, performing ultrasonic treatment to uniformly dissolve the PDI, adding the nitrogen-doped graphene anchored by the transition metal monoatomic group obtained in the step (2) into the mixed solution under the ultrasonic condition, performing ultrasonic treatment to uniformly mix the PDI and the nitrogen-doped graphene anchored by the transition metal monoatomic group, dropwise adding hydrochloric acid, and stirring until a sample is separated out.
The proportion of the absolute ethyl alcohol, the triethanolamine, the nitrogen-doped graphene anchored by the transition metal monoatomic group and the PDI is controlled to be 100-200 mL: 400-600 μ L: 0.002-0.02 g: 0.02-0.2 g; the concentration of the hydrochloric acid is 1-4mol/L, the ultrasonic treatment time is 1-2h, the ultrasonic power is 160W, and the stirring time is 4-5 h.
(4) And (4) centrifuging the mixed solution obtained in the step (3), washing the obtained sample to be neutral, quickly freezing the sample by using liquid nitrogen, and then freezing and drying the sample to obtain the transition metal monoatomic modification supermolecule self-assembly PDI catalyst.
The freeze drying time is 24-48h, the freeze drying temperature is-10 to-50 ℃, and the pressure is 1.3-13Pa under high vacuum.
Transition metal is a typical non-noble metal cocatalyst, transition metal monoatomic dispersion nitrogen-doped graphene oxide attracts wide attention as an effective photocatalyst in recent years, PDI is used as a novel organic semiconductor, a modification method of the PDI is mainly focused on introducing functional groups, and a composite material of the PDI and the transition metal anchored on the nitrogen-doped graphene oxide is only reported.
Drawings
Figure 1 is an XRD pattern of Graphene Oxide (GO), aza-graphene (NG), and cobalt-anchored aza-graphene (Co-NG). GO can be seen via NH3After treatment, the XRD patterns of NG and Co-NG showed broad peaks at 2 θ 10.6 ° where the peak disappeared at 2 θ 26.6 °, indicating NH3In the treatment process, the functional group of the graphene oxide is removed, and the aza-graphene is successfully prepared.
Fig. 2 is a scanning electron microscope image of a PDI monomer, a self-assembled PDI, a cobalt-anchored aza-graphene (Co-NG), a composite material of a cobalt-anchored aza-graphene and a supramolecular self-assembled PDI (Co-NG/PDI), as can be seen in fig. 2(a, b), the PDI undergoes self-assembly, and compared with the PDI monomer, the PDI after self-assembly is more regular and ordered, as can be seen in fig. 2(c, d), the cobalt-anchored aza-graphene is successfully loaded on the supramolecular self-assembled PDI, and the supramolecular PDI material with the cobalt monoatomic modified graphene surface in-situ self-assembly is formed.
FIG. 3 is an activity diagram of the prepared sample for degrading BPA, and compared with a PDI monomer, the PDI modified by the single atom modification of the transition metal effectively improves the performance of degrading phenolic pollutants by photocatalysis. Within three hours, the degradation rate of BPA (bisphenol A) degraded by 7 wt% of Co-NG/PDI (cobalt monoatomic-anchored aza graphene accounts for 7% of the mass of the supermolecule self-assembled PDI nano material) can reach 99%.
Detailed Description
The invention provides a preparation method of a transition metal monoatomic modification supermolecule self-assembly PDI nano material, which comprises the following steps:
(1) adding graphene oxide into deionized water, carrying out ultrasonic mixing uniformly to obtain a mixed solution 1, adding a transition metal salt solution, carrying out ultrasonic treatment for 30min until the graphene oxide is uniformly dispersed in the mixed solution, rapidly freezing the solution in liquid nitrogen, and carrying out freeze-drying treatment in a freeze-dryer.
The proportion of the graphene oxide to the deionized water and the transition metal salt solution is as follows: 80-100 mg; 40-50mL and 1-3 mL. The concentration of the transition metal salt solution is 1-5 mg/mL. The temperature of the freeze drying treatment is-10 to-50 ℃, the time of the freeze drying treatment is 24 to 48 hours, and the pressure is 1.3 to 13 Pa.
(2) And (2) putting the sample obtained by the freeze drying treatment in the step (1) into a tube furnace, calcining for 1h at 750 ℃ in the atmosphere of argon and ammonia gas, and heating up at a rate of 12 ℃/min to obtain the nitrogen-doped graphene anchored by the transition metal monoatomic group.
The flow rate of the argon is 160-170 mL/min; the flow rate of the ammonia gas is 60-70 mL/min.
(3) Dissolving PDI in an absolute ethyl alcohol solution, adding triethanolamine by using a liquid-transferring gun, performing ultrasonic treatment to uniformly dissolve PDI, adding the PDI into the aza-graphene anchored by the transition metal monoatomic atom obtained in the step (2), mixing under the ultrasonic condition, and dropwise adding 80mL of hydrochloric acid; stirring until the sample precipitates.
The proportion of the absolute ethyl alcohol, the triethanolamine, the nitrogen-doped graphene anchored by the transition metal monoatomic group and the PDI is controlled to be 100-200 mL: 400-600 μ L: 0.002-0.02 g: 0.02-0.2 g; the concentration of the hydrochloric acid is 1-4mol/L, the ultrasonic treatment time is 1-2h, the ultrasonic power is 160W, and the stirring time is 4-5 h.
(4) And (4) centrifuging the mixed solution obtained in the step (3), washing the obtained sample to be neutral, quickly freezing the sample by using liquid nitrogen, and then freezing and drying the sample in a vacuum drier to obtain the transition metal monoatomic modification supermolecule self-assembly PDI catalyst.
The temperature of the freeze drying treatment is-10 to-50 ℃, the time of the freeze drying treatment is 24 to 48 hours, and the pressure is 1.3 to 13 Pa.
Example 1:
firstly, 0.1g of graphene oxide is weighed and added into 50mL of ionized water, 1mL of 3mg/mL cobalt chloride solution is added after ultrasonic homogenization, ultrasonic treatment is carried out for 30 minutes until uniform dispersion is achieved, liquid nitrogen freezing is carried out, and then a freeze dryer is used for freeze drying for 48 hours at the temperature of minus 45 ℃. And calcining the obtained sample in a tube furnace in a mixed gas of argon and ammonia at 750 ℃, the flow of argon is 160mL/min, the flow of ammonia is 60mL/min, and the heating rate is 12 ℃/min for 1h to obtain the cobalt monoatomic anchored aza-graphene. Measuring 100mL of absolute ethyl alcohol by using a measuring cylinder, weighing 0.05g of PDI by using a balance, adding the PDI into a beaker while stirring, transferring 400 mu L of triethanolamine by using a liquid transfer gun, adding the triethanolamine into the beaker, performing ultrasonic treatment for 30min until the PDI is fully dissolved, adding 0.0025g of the nitrogen-doped graphene anchored by using the cobalt monoatomic group under the ultrasonic condition, performing ultrasonic treatment for 1h again with the ultrasonic power of 160W, slowly dropwise adding 80mL of 4mol/L hydrochloric acid, stirring for 4h, collecting red solid insoluble substances by using a centrifugal machine, and washing by using deionized water. And (3) rapidly freezing by using liquid nitrogen, and then freeze-drying for 48h at-45 ℃ by using a freeze dryer under the high vacuum of 10Pa to obtain a sample, namely the Co-NG/PDI-5% nano material (the mass of the cobalt monoatomic anchored aza-graphene accounts for 5% of that of the supermolecule self-assembled PDI nano material).
Example 2:
firstly, weighing 0.1g of graphene oxide, adding the graphene oxide into 50mL of ionized water, carrying out ultrasonic treatment for 30 minutes to uniformly disperse after the graphene oxide is uniformly subjected to ultrasonic treatment, and carrying out freeze drying for 48 hours at-45 ℃ by using a freeze dryer after the graphene oxide is frozen by liquid nitrogen. And calcining the obtained sample in a tube furnace in a mixed gas of argon and ammonia at 750 ℃, the flow of argon is 160mL/min, the flow of ammonia is 60mL/min, and the heating rate is 12 ℃/min for 1h to obtain the cobalt monoatomic anchored aza-graphene. Measuring 100mL of absolute ethyl alcohol by using a measuring cylinder, weighing 0.05g of PDI by using a balance, adding the PDI into a beaker while stirring, transferring 400 mu L of triethanolamine by using a liquid transfer gun, adding the triethanolamine into the beaker, carrying out ultrasonic treatment for 30min until the PDI is fully dissolved, adding 0.007g of the cobalt monoatomic anchored aza-graphene, carrying out ultrasonic treatment for 1h again, slowly dropwise adding 80mL of 4mol/L hydrochloric acid with the ultrasonic power of 160W, stirring for 4h, collecting red solid insoluble substances by using a centrifugal machine, and washing by using deionized water. And (3) rapidly freezing by using liquid nitrogen, and then freeze-drying for 48h at-45 ℃ by using a freeze dryer under the high vacuum of 10Pa to obtain a sample, namely the Co-NG/PDI-7% nano material (the mass of the cobalt monoatomic anchored aza-graphene accounts for 7% of that of the supermolecule self-assembled PDI nano material).
Example 3:
firstly, weighing 0.1g of graphene oxide, adding the graphene oxide into 50mL of ionized water, carrying out ultrasonic treatment for 30 minutes to uniformly disperse after the graphene oxide is uniformly subjected to ultrasonic treatment, and carrying out freeze drying for 48 hours at-45 ℃ by using a freeze dryer after the graphene oxide is frozen by liquid nitrogen. And calcining the obtained sample in a tube furnace in a mixed gas of argon and ammonia at 750 ℃, the flow of argon is 160mL/min, the flow of ammonia is 60mL/min, and the heating rate is 12 ℃/min for 1h to obtain the cobalt monoatomic anchored aza-graphene. Measuring 100mL of absolute ethyl alcohol by using a measuring cylinder, weighing 0.05g of PDI by using a balance, adding the PDI into a beaker while stirring, transferring 400 mu L of triethanolamine by using a liquid transfer gun, adding the triethanolamine into the beaker, carrying out ultrasonic treatment for 30min until the PDI is fully dissolved, adding 0.02g of the cobalt monoatomic anchored aza-graphene, carrying out ultrasonic treatment for 1h again, slowly dropwise adding 80mL of 4mol/L hydrochloric acid with the ultrasonic power of 160W, stirring for 4h, collecting red solid insoluble substances by using a centrifugal machine, and washing by using deionized water. And (3) rapidly freezing by using liquid nitrogen, and then freeze-drying for 48h at-45 ℃ by using a freeze dryer under the high vacuum of 10Pa to obtain a sample, namely the Co-NG/PDI-10% nano material (the mass of the cobalt monoatomic anchored aza graphene accounts for 10% of that of the supermolecule self-assembled PDI nano material).
The photocatalytic activity of Co-NG/PDI was tested with 10mg/L BPA as the target contaminant. 25mg of catalyst is added into a photocatalytic reactor, 50mL of 10mg/L of BPA is added, a degradation experiment is carried out in a photochemical reaction instrument with a 300W xenon lamp and an ultraviolet cut-off filter (>400nm), and a circulating water system is used for maintaining the temperature at 30 ℃ so as to avoid thermal catalysis. And before the irradiation of the xenon lamp, magnetically stirring the solution for 30min to ensure that the solution achieves adsorption-desorption balance on the surface of the material. Every 1h during the illumination period, 2mL of the solution was centrifuged to remove particles, filtered through a 0.45 μm polyamide syringe filter, and finally collected in a centrifuge tube for subsequent analysis. The change in the concentration of the target contaminant was measured by high performance liquid chromatography at an absorption wavelength of 220 nm.
The degradation rate (R) was calculated as follows, R ═ 1-C/C0) 100% of C0Is the initial concentration of BPA and C is the concentration at reaction time t (min).
Claims (6)
1. A preparation method of a supermolecule self-assembly PDI nano material is characterized by comprising the following specific steps:
(1) adding graphene oxide into deionized water, carrying out ultrasonic mixing uniformly to obtain a mixed solution 1, adding a transition metal salt solution, carrying out ultrasonic mixing until the transition metal salt is uniformly dispersed in the mixed solution 1, rapidly freezing the solution in liquid nitrogen, and carrying out freeze-drying treatment in a freeze-dryer;
(2) putting the sample obtained by the freeze drying treatment in the step (1) into a tube furnace, and calcining the sample in an argon and ammonia atmosphere to obtain the nitrogen-doped graphene anchored by the transition metal monoatomic group;
(3) dissolving PDI in an absolute ethyl alcohol solution to obtain a mixed solution 2, transferring triethanolamine by using a liquid transfer gun, adding the triethanolamine into the mixed solution 2, performing ultrasonic treatment to uniformly dissolve the PDI, adding the nitrogen-doped graphene anchored by the transition metal monoatomic group obtained in the step (2) into the mixed solution under the ultrasonic condition, performing ultrasonic treatment to uniformly mix the PDI and the nitrogen-doped graphene anchored by the transition metal monoatomic group, dropwise adding hydrochloric acid, and stirring until a sample is separated out;
(4) and (4) centrifuging the mixed solution obtained in the step (3), washing the obtained sample to be neutral, quickly freezing the sample by using liquid nitrogen, and then freeze-drying the sample to obtain the supermolecule self-assembly PDI nano material modified by the transition metal monoatomic modification.
2. The method for preparing supramolecular self-assembly PDI nano-material as claimed in claim 1, wherein in step (1), the ratio of graphene oxide to deionized water and transition metal salt solution is 80-100 mg; 40-50mL:1-3mL, wherein the concentration of the transition metal salt solution is 1-5 mg/mL; the temperature of the freeze drying treatment is-10 to-50 ℃, the time of the freeze drying treatment is 24 to 48 hours, and the pressure is 1.3 to 13 Pa.
3. The method for preparing supramolecular self-assembled PDI nanomaterial as claimed in claim 1, wherein in step (2), the flow rate of argon is 160-170mL/min, and the flow rate of ammonia is 60-70 mL/min; the calcining temperature is 750 ℃, the time is 1h, and the heating rate is 12 ℃/min.
4. The method for preparing supramolecular self-assembly PDI nanomaterial as claimed in claim 1, wherein in step (3), the ratio of anhydrous ethanol, triethanolamine, transition metal monoatomic anchored aza-graphene and PDI is controlled to be 100-200 mL: 400-600 μ L: 0.006-0.02 g: 0.02-0.2 g; the concentration of the hydrochloric acid is 1-4mol/L, the ultrasonic treatment time is 1-2h, the ultrasonic power is 160W, and the stirring time is 4-5 h.
5. The method for preparing supramolecular self-assembled PDI nanomaterial in claim 1, wherein in the step (4), the freeze-drying treatment time is 24-48h, the freeze-drying treatment temperature is-10 to-50 ℃, and the pressure is high vacuum 1.3 to 13 Pa.
6. Use of the supramolecular self-assembled PDI nanomaterials prepared by the preparation methods of any one of claims 1 to 5 as photocatalysts for photocatalytic degradation of phenolic contaminants.
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