CN115739192A - Photocatalytic material based on aminobenzoic acid compound, preparation method and application - Google Patents
Photocatalytic material based on aminobenzoic acid compound, preparation method and application Download PDFInfo
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Images
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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
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
Abstract
The invention discloses a photocatalytic material based on aminobenzoic acid compounds, a preparation method and application thereof, and successfully screens out a ligand with stronger photocatalytic oxidation TMB capacity: 2-amino isophthalic acid (2-AIA), 2-AIA has photosensitive activity, and 2-AIA is used as a photosensitizer to synthesize a nano material for photocatalytic oxidation, so that the method has a great prospect. Based on the reaction of 2-AIA and MOFs (UiO-66), the heterogeneous catalyst UiO-66@2-AIA with higher photocatalytic activity is obtained. Under the condition of short irradiation time, uiO-66@2-AIA can obviously catalyze 1,5-DHN to obtain the juglone. The photocatalytic material based on the aminobenzoic acid compound provides possibility for the development of novel photocatalysts.
Description
Technical Field
The invention particularly relates to a photocatalytic material based on an aminobenzoic acid compound, a preparation method and application.
Background
Photocatalysis is a promising ideal technology for energy regeneration and environmental remediation by utilizing solar energy. The photocatalytic material can be used for decomposing organic compounds, partial inorganic compounds, bacteria, viruses and the like. In daily life, the photocatalytic material can effectively degrade toxic and harmful gases in the air, such as formaldehyde and the like, and efficiently purify the air; meanwhile, various bacteria can be effectively killed, and toxin released by the bacteria or fungi can be decomposed and harmlessly treated.
However, the catalytic activity of the existing photocatalytic material needs to be improved, and the development of a catalytic material with higher photocatalytic activity is urgently needed.
Disclosure of Invention
Aiming at the situation, in order to overcome the defects of the prior art, the invention provides a photocatalytic material based on an aminobenzoic acid compound, a preparation method and application.
In order to achieve the above object, the present invention provides the following technical solutions:
the photocatalytic material based on the aminobenzoic acid compound is prepared by adopting the following steps:
adding a ligand into a DMF (dimethyl formamide) solution of UiO-66, wherein the mass ratio of the ligand to the UiO-66 is 0.2-1.5, stirring at normal temperature overnight, washing the obtained reactant with DMF until a supernatant does not have an ultraviolet absorption characteristic peak of the ligand, centrifuging, collecting a solid, and drying to obtain a photocatalytic material;
the ligand is 2-amino isophthalic acid, 2-amino terephthalic acid, 5-amino isophthalic acid and 2-hydroxy terephthalic acid.
Further, the stirring time is 2-24 h.
Furthermore, the stirring speed is 300-1000 rpm/min.
Furthermore, the centrifugal rotating speed is 6000 to 10000rmp/min.
Further, drying for 12-24 h to obtain the photocatalytic material.
The application of the photocatalytic material in the synthesis of the juglone comprises the photocatalytic material.
The synthesis method of the juglone comprises the following steps that:
(1) Adding the aqueous dispersion of the photocatalytic material into a mixed solvent of acetonitrile and water;
(2) Adding 1,5-DHN to obtain a mixed solution; in the mixed solution, the mass concentrations of the photocatalytic material and 1,5-DHN are respectively 20-1000 mg/L and 50-200 mug/mL;
(3) Irradiating with xenon lamp to obtain juglone;
further, the xenon lamp power is 50-300W.
Further, in the mixed solvent of acetonitrile and water, the volume ratio of acetonitrile to water is 4:1.
Further, the xenon lamp irradiation time is 1-30 min.
The beneficial effects of the invention are:
(1) The invention screens a series of aminobenzoic acid compounds, uses TMB as a substrate to evaluate the photocatalytic performance of the ligand, successfully screens out the ligand with stronger photocatalytic oxidation TMB performance, namely 2-amino isophthalic acid (2-AIA), wherein the 2-AIA has photosensitive activity, and has larger prospect for synthesizing nano materials for photocatalytic oxidation by using the 2-AIA as a photosensitizer.
(2) The invention obtains the heterogeneous catalyst UiO-66@2-AIA with higher photocatalytic activity based on the reaction of 2-AIA and MOFs (UiO-66). Under the condition of short irradiation time, uiO-66@2-AIA can obviously catalyze 1,5-DHN to obtain the juglone. The juglone, also named 5-5-hydroxynaphthoquinone, has the effects of relieving swelling and pain, dissipating heat, inhibiting bacteria, resisting tumors and the like, and has a very great prospect in the medical field; meanwhile, the compound can be used as a herbicide, a coloring agent and the like to be applied to the fields of agriculture, life and the like. The photocatalytic material based on the aminobenzoic acid compound provides possibility for the development of novel photocatalysts.
Drawings
FIG. 1 is a molecular structure diagram and abbreviations of screened aminobenzoic acid compounds and controls.
FIG. 2 is a photograph showing color development of TMB by photocatalytic oxidation of ligands of aminobenzoic acid compounds.
FIG. 3 is a photograph showing the color development of 2-AIA, ATA, 5-AIA and HTA at different concentrations under irradiation of ultraviolet lamps at 365nm and 395nm, respectively, by photocatalytic oxidation of TMB.
FIG. 4 is a graph showing the absorbance curves at 652nm of TMBox after photocatalytic TMB oxidation under 365nm and 395nm ultraviolet lamp irradiation at different concentrations of 2-AIA, ATA, 5-AIA and HTA, respectively.
FIG. 5 shows the absorbance values at 652nm of TMBox after photocatalytic oxidation of TMB by 5. Mu.M of 2-AIA, ATA, 5-AIA, HTA under 365nm UV irradiation.
FIG. 6 is a color development effect diagram of 2-AIA photocatalytic oxidation TMB at a concentration of 0-20 μ M and an absorbance curve diagram of an oxidation product TMBox at 652 nm.
FIG. 7 is a bar graph of absorbance values at 652nm for TMBox after addition of inhibitors of different reactive oxygen species.
FIG. 8 is a color photograph of UiO-66@2-AIA photocatalytically oxidized TMB and a bar graph of absorbance value at 652nm of an oxidized product TMBox.
FIG. 9 is a bar graph of absorbance values at 415nm of walnut ketone obtained by using UiO-66@2-AIA photocatalytic oxidation 1,5-DHN to synthesize Hu Taotong.
Detailed Description
In order to make the objects, technical solutions and advantages of the present application more apparent, the present application will be described and illustrated below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the present application and are not intended to limit the present application. All other embodiments obtained by a person of ordinary skill in the art based on the embodiments provided in the present application without any inventive step are within the scope of protection of the present application.
Reference in the specification to "an embodiment" means that a particular feature, structure, or characteristic described in connection with the embodiment can be included in at least one embodiment of the specification. The appearances of the phrase in various places in the specification are not necessarily all referring to the same embodiment, nor are separate or alternative embodiments mutually exclusive of other embodiments. It is to be expressly and implicitly understood by one of ordinary skill in the art that the embodiments described herein may be combined with other embodiments without conflict.
Unless otherwise defined, technical or scientific terms referred to herein should have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Reference to "a," "an," "the," and similar words throughout this application are not to be construed as limiting in number, and may refer to the singular or the plural. The use of the terms "including," "comprising," "having," and any variations thereof herein, is meant to cover a non-exclusive inclusion; reference to "connected," "coupled," and the like in this application is not limited to physical or mechanical connections, but may include electrical connections, whether direct or indirect. Reference herein to "a plurality" means greater than or equal to two. "and/or" describes the association relationship of the associated object, indicating that there may be three relationships, for example, "a and/or B" may indicate: a exists alone, A and B exist simultaneously, and B exists alone. Reference herein to the terms "first," "second," "third," and the like, are merely to distinguish similar objects and do not denote a particular ordering for the objects.
3,3',5,5' -Tetramethylbenzidine (TMB) is by far the most commonly used chromogenic substrate that can be oxidized to a colored product by a one-electron and two-electron pathway, losing one electron to give the blue oxidized product TMBox, and continuing to lose one electron to oxidize to a yellow product. The photosensitizer can also generate superoxide anion, singlet oxygen and hydroxyl radical by the energy released by electron transition and dissolved oxygen under the photocatalysis condition to enable TMB to lose one electron and develop color. When the photocatalyst is irradiated by light, electrons in the valence band are excited to jump to the conduction band, so that electrons (e) are generated - ) And a cavity (h) + ). The dissolved oxygen adsorbed on the surface traps electrons to form superoxide anions, and the holes oxidize the hydroxyl ions and water adsorbed on the surface of the catalyst to hydroxyl radicals to develop the TMB.
Reagents, instruments, and the like used in the following embodiments are commercially available; in the following examples and comparative examples, the photocatalytic performance of the ligand was evaluated using TMB as a substrate, and 1m =1mol/L.
Example 1
The photocatalytic performance of the ligand is explored through an experiment of carrying out photocatalytic oxidation TMB (3,3 ',5,5' -tetramethylbenzidine) color development on the aminobenzoic acid ligand.
An experiment for photocatalytic oxidation of TMB was performed on 15 different ligands (the structures of the 15 ligands are shown in fig. 1), and ligand solution was prepared:
a mixed solution of 2-aminoisophthalic acid (2-AIA), 2-aminoterephthalic acid (ATA), 5-aminoisophthalic acid (5-AIA), 2-hydroxyterephthalic acid (HTA), benzoic Acid (BA), aniline (PAm), terephthalic acid (TPA), isophthalic acid (IPA), phthalic Acid (PA), 4-aminoisophthalic acid (4-AIA), p-aminobenzoic acid (ABA), 2,5-diaminoterephthalic acid (DTA), 3,5-diaminobenzoic acid (DBA), ethanol and water (the volume ratio of ethanol to water is 1:1), a DMF solution of 4-aminophthalic acid (APA), and a trimesic acid (TMA) aqueous solution were prepared, respectively.
Screening ligand photocatalytic oxidation TMB color development:
adding the ligand solution into 50mM buffer solution with pH 4.0HAc-NaAc, adding TMB DMSO solution, mixing the above solutions in a microporous plate uniformly, wherein the concentration of the ligand in the mixed solution is 0.15mM, and the concentration of TMB is 200mg/L; irradiating under 365nm ultraviolet lamp for 1min with irradiance of 20mM/cm 2 。
Control experimental group: the reaction was carried out for 1min in the absence of light, i.e., no light.
Blank control group: refers to HAc-NaAc buffer solution without ligand.
Finally, recording the developed photo; spectral scanning was performed with an ultraviolet-visible spectrophotometer (UV-Vis) and the absorbance value at 652nm of the TMB oxidation product (TMBox) was recorded.
The photo of ligand photocatalytic oxidation TMB color development is shown in figure 2; as can be seen from FIG. 2, 2-aminoisophthalic acid (2-AIA), 2-aminoterephthalic acid (ATA), 5-aminoisophthalic acid (5-AIA), and 2-hydroxyterephthalic acid (HTA) oxidized TMB to blue under 365nm UV light, and 2-AIA oxidized TMB photocatalytically more strongly than ATA, which is a ligand for synthesizing MOFs.
Example 2
Optimization experiments were performed for the concentrations and optimal absorption wavelengths of these 4 ligands (2-AIA, ATA, 5-AIA, HTA).
Optimizing the ligand concentration and irradiation wavelength of the photocatalytic oxidation TMB:
in the experimental process, 4 ligands for realizing the photocatalytic oxidation color development of TMB are optimized to have final concentrations of 0 mu M, 5 mu M, 10 mu M, 20 mu M and 50 mu M, other experimental conditions are unchanged, and a color development photo and the absorbance value of TMBox at 652nm are recorded after the TMB is irradiated for 1min under an ultraviolet lamp at 365 nm; comparison of the developed color after 1min of irradiation at 395nm UV and the absorbance value of TMBox at 652nm was recorded. No light group: the reaction was carried out for 1min under protection from light.
Comparing the color development intensity, and screening the ligand with the best photocatalytic activity.
The results of color development of the photocatalytic oxidation TMB under the irradiation of ultraviolet lamps with 365nm and 395nm respectively for the 2-AIA, ATA, 5-AIA and HTA with different concentrations are shown in figure 3, and the absorbance curves of the TMBox after the photocatalytic oxidation of the TMB under the irradiation of ultraviolet lamps with 365nm and 395nm respectively for the 2-AIA, ATA, 5-AIA and HTA with different concentrations are shown in figure 4; the results of comparing the absorbance values at 652nm of TMBox after 5 μ M2-AIA, ATA, 5-AIA and HTA are subjected to photocatalytic oxidation TMB oxidation under the irradiation of an ultraviolet lamp at 365nm are shown in FIG. 5; as can be seen from FIG. 5, the 2-AIA ligand has the best performance in photocatalytic oxidation of TMB, and the oxidation product TMBox has stronger absorbance at the maximum absorption wavelength of 652 nm.
Example 3
Optimizing the concentration of 2-AIA photocatalytic oxidation TMB:
the 2-AIA has very strong photocatalytic oxidation activity of TMB, and is prepared into a solution with the final concentration of 0 μ M, 1 μ M, 2 μ M, 3 μ M, 5 μ M, 10 μ M and 20 μ M, and a chromogenic picture and an absorbance value of TMBox at 652nm are recorded after being irradiated for 1min under an ultraviolet lamp at 365 nm.
The color development effect of photocatalytic oxidation of TMB in 2-AIA solutions at concentrations of 0. Mu.M, 1. Mu.M, 2. Mu.M, 3. Mu.M, 5. Mu.M, 10. Mu.M and 20. Mu.M is shown in FIG. 6 (a), and the absorbance at 652nm of the oxidation product TMBox is shown in FIG. 6 (b). It can be seen from fig. 6 that 2-AIA also has very excellent photocatalytic oxidation properties for TMB at lower concentrations.
Example 4
The mechanism of photosensitivity of 2-AIA was explored:
inhibitors of different active oxygen substances (singlet oxygen inhibitor L-tryptophan, hydroxyl radical inhibitor mannitol, superoxide anion inhibitor superoxide dismutase) are respectively added into a system of 2-AIA for photocatalytic oxidation of TMB, after the inhibitors are added, the concentrations of L-tryptophan, mannitol and superoxide dismutase are respectively 16.4mM, 2.5mM and 140U, and the concentration of 2-AIA is 1 mu M. Other experimental conditions were unchanged and absorbance values at 652nm were recorded for TMBox. Blank control group: systems of TMB without any inhibitor added.
After addition of inhibitors of different reactive oxygen species, the absorbance values of TMBox at 652nm are shown in figure 7, as can be seen from FIG. 7, 2-AIA can generate singlet oxygen under 365nm UV light irradiation: ( 1 O 2 ) And superoxide anion (. O) 2 - ) Active oxygen species, and thus it has photosensitive activity.
Example 5
2-AIA with stronger photocatalytic activity is exchanged into the MOF material through ligand exchange, and the heterogeneous catalyst with strong photocatalytic activity is obtained.
The preparation method of the heterogeneous catalyst comprises the following steps: adding 2-AIA into a DMF solution of 0.1mg/mLUiO-66, wherein the mass ratio of the 2-AIA to the UiO-66 is 1:1, stirring at normal temperature for 12h at the rotation speed of 300rpm/min, washing the obtained reactant with DMF for several times until the supernatant has no characteristic ultraviolet absorption peak of 2-AIA, centrifuging at the rotation speed of 10000rmp/min, collecting the solid, and drying for 12h to obtain UiO-66@2-AIA.
Example 6
UiO-66@2-AIA photocatalytic oxidation of TMB:
weighing UiO-66@2-AIA water dispersion, adding into 50mM, pH 4.0HAc-NaAc buffer solution, adding TMB solution, mixing the above suspension in a microporous plate (UiO-66 @2-AIA final concentration is 60mg/L, TMB final concentration is 200 mg/L), irradiating under 365nm ultraviolet lamp for 1min with irradiance of 20mM/cm 2 . Centrifuging and recording a color development picture of the supernatant; the supernatant was subjected to spectral scanning using an ultraviolet-visible spectrophotometer (UV-Vis) and the absorbance value at 652nm of the TMB oxidation product (TMBox) was recorded.
FIG. 8 (a) shows a color photograph of UiO-66@2-AIA photocatalytic oxidation TMB, and FIG. 8 (b) shows the results of the absorbance at 652nm of the oxidation product TMBox, where the blank group in FIG. 8 (b) indicates: the non-lighting group, the others are consistent with the experimental group, and all contain UiO-66@2-AIA; uiO-66 refers to: contains UiO-66, does not contain UiO-66@2-AIA, and the others are consistent with the conditions of the experimental group. As can be seen from FIG. 8, uiO-66@2-AIA has high photocatalytic activity and can be used for photocatalytic oxidation of TMB. The presence of 2-AIA significantly increases the ability of UiO-66 to oxidize TMB, which is essentially devoid of photocatalytic activity.
Example 7
UiO-66@2-AIA photocatalytic oxidation 1,5-dihydroxy naphthalene (1,5-DHN) synthesis Hu Taotong: weighing UiO-66@2-AIA water dispersion, adding the water dispersion into a mixed solvent (4, V/V) of acetonitrile and water, and adding 1,5-DHN; in the mixed solution, the final concentrations of UiO-66@2-AIA and 1,5-DHN are 60mg/L and 100 mug/mL respectively; irradiating the mixed solution with 300W xenon lamp for 10min to obtain juglone; the characteristic uv absorption peak at 415nm of the walnut ketone produced was recorded.
The absorbance values of the walnut ketones at 415nm are shown in fig. 9, where in fig. 9 the no light group refers to: compared with the experimental group, the lighting is only lacked, and other conditions are the same as the experimental group.
The illumination group means: with light, but without the catalyst UiO-66@2-AIA, the rest being the same as the experimental groups.
The experimental group (UiO-66 @2-AIA + light group) refers to: there is both illumination and UiO-66@2-AIA.
As can be seen from FIG. 9, uiO-66@2-AIA can catalyze 1,5-DHN to obtain juglone in short irradiation time. Therefore, the 2-AIA is used as the photosensitizer for synthesizing the nano material to carry out photocatalytic oxidation, and has a great prospect.
It is to be understood that the described embodiments are merely a few embodiments of the invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Claims (10)
1. The photocatalytic material based on the aminobenzoic acid compound is characterized by being prepared by the following steps:
adding a ligand into a DMF (dimethyl formamide) solution of UiO-66, wherein the mass ratio of the ligand to the UiO-66 is 0.2-1.5, stirring at normal temperature overnight, washing the obtained reactant with DMF until a supernatant does not have an ultraviolet absorption characteristic peak of the ligand, centrifuging, collecting a solid, and drying to obtain a photocatalytic material;
the ligand is 2-amino isophthalic acid, 2-amino terephthalic acid, 5-amino isophthalic acid and 2-hydroxy terephthalic acid.
2. The photocatalytic material according to claim 1, wherein the stirring time is 2 to 24 hours.
3. The photocatalytic material according to claim 1, wherein the stirring speed is 300 to 1000rpm/min.
4. The photocatalytic material based on aminobenzoic acid-based compound according to claim 1, characterized in that the centrifugation speed is 6000 to 10000rmp/min.
5. The photocatalytic material based on aminobenzoic acid-based compound according to claim 1, characterized in that the photocatalytic material is obtained by drying for 12 to 24 hours.
6. Use of a photocatalytic material for the synthesis of walnut ketones, characterized in that it is a photocatalytic material according to any one of claims 1 to 5.
7. Method for the synthesis of juglone characterized in that said photocatalytic material is a photocatalytic material according to any one of claims 1 to 5, comprising the following steps:
(1) Adding the aqueous dispersion of the photocatalytic material into a mixed solvent of acetonitrile and water;
(2) Adding 1,5-DHN to obtain a mixed solution; in the mixed solution, the mass concentrations of the photocatalytic material and 1,5-DHN are respectively 20-1000 mg/L and 50-200 mug/mL;
(3) Irradiating with xenon lamp to obtain juglone.
8. A process for the synthesis of walnut ketones as claimed in claim 7 wherein the xenon lamp power is between 50 and 300W.
9. The method of claim 7, wherein the volume ratio of acetonitrile to water in the mixed solvent of acetonitrile and water is 4:1.
10. A process for the synthesis of walnut ketones as claimed in claim 7 wherein the xenon lamp irradiation time is from 1 to 30min.
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