CN111495431A - Photocatalyst and preparation method thereof - Google Patents
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- CN111495431A CN111495431A CN202010383477.8A CN202010383477A CN111495431A CN 111495431 A CN111495431 A CN 111495431A CN 202010383477 A CN202010383477 A CN 202010383477A CN 111495431 A CN111495431 A CN 111495431A
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 22
- 238000002360 preparation method Methods 0.000 title description 4
- OYFRNYNHAZOYNF-UHFFFAOYSA-N 2,5-dihydroxyterephthalic acid Chemical compound OC(=O)C1=CC(O)=C(C(O)=O)C=C1O OYFRNYNHAZOYNF-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 19
- 239000000463 material Substances 0.000 claims abstract description 18
- 230000001699 photocatalysis Effects 0.000 claims abstract description 15
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 claims abstract description 5
- 229910001431 copper ion Inorganic materials 0.000 claims abstract description 5
- 239000011259 mixed solution Substances 0.000 claims description 40
- 239000000243 solution Substances 0.000 claims description 38
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 18
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 16
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 12
- 239000003054 catalyst Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 12
- 229910021641 deionized water Inorganic materials 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical group Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 10
- 239000002244 precipitate Substances 0.000 claims description 10
- 238000009777 vacuum freeze-drying Methods 0.000 claims description 9
- 229910021592 Copper(II) chloride Inorganic materials 0.000 claims description 8
- 238000009210 therapy by ultrasound Methods 0.000 claims description 8
- 150000001879 copper Chemical class 0.000 claims description 6
- 238000004090 dissolution Methods 0.000 claims description 6
- 239000007787 solid Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 238000007710 freezing Methods 0.000 claims description 4
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- 230000006798 recombination Effects 0.000 abstract 1
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- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 4
- KKEYFWRCBNTPAC-UHFFFAOYSA-N Terephthalic acid Chemical compound OC(=O)C1=CC=C(C(O)=O)C=C1 KKEYFWRCBNTPAC-UHFFFAOYSA-N 0.000 description 4
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- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2204—Organic complexes the ligands containing oxygen or sulfur as complexing atoms
- B01J31/2208—Oxygen, e.g. acetylacetonates
- B01J31/2213—At least two complexing oxygen atoms present in an at least bidentate or bridging ligand
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/007—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols by irradiation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8671—Removing components of defined structure not provided for in B01D53/8603 - B01D53/8668
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- B01J35/39—
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/41—Preparation of salts of carboxylic acids
- C07C51/418—Preparation of metal complexes containing carboxylic acid moieties
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/50—Carbon oxides
- B01D2257/504—Carbon dioxide
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/802—Visible light
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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
- Y02A—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE
- Y02A50/00—TECHNOLOGIES FOR ADAPTATION TO CLIMATE CHANGE in human health protection, e.g. against extreme weather
- Y02A50/20—Air quality improvement or preservation, e.g. vehicle emission control or emission reduction by using catalytic converters
Abstract
Embodiments of the present application relate to CO2The technical field of reduction, in particular to a method for catalyzing CO2Reduced photocatalysts and methods of making the same. The photocatalyst is Cu-DHTP prepared from copper ions and 2, 5-dihydroxy terephthalic acid, and the Cu-DHTP is a nano flaky material with an amorphous structure. The photocatalyst provided by the embodiment of the application has a large number of active sites and is used for treating CO2The catalytic performance has obvious promotion effect, the band gap is reduced, the electron transmission effect is accelerated, the electron-hole recombination is inhibited, the utilization rate of sunlight can be improved, and the photocatalytic CO is improved2The CO production efficiency is high.
Description
Technical Field
Embodiments of the present application relate to CO2The technical field of reduction, in particular to a method for catalyzing CO2Reduced photocatalysts and methods of making the same.
Background
Excessive consumption of fossil fuels not only can cause energy crisis, but can also lead to significant carbon dioxide emissions and can lead to climate change. The concentration of carbon dioxide in the atmosphere has been reported to increase from 280ppm prior to industrialization to 400 ppm. CO 22Reduction not only solves the greenhouse effect, but also brings clean fuel and more valuable carbon 1(C1) and carbon 2 (C2) (Z.Sun, et. al. Angew Chem Int Ed 2018,57, 7610-. Utilizing solar energy to convert CO under natural environmental conditions2The photocatalytic conversion into value-added products is considered to be one of the best ways to solve the future renewable energy sources. However, photocatalytic CO2The conversion includes photoelectric conversion, charge separation and migration, CO2Various physical and chemical processes such as adsorption and reduction greatly limit CO2Conversion efficiency and product selectivity (H.Zhang, et. al. appl Catal B2018,220, 126-. Therefore, how to improve the utilization rate of sunlight, increase the separation of photon-generated carriers and develop photocatalytic CO with high conversion rate and high selectivity2The catalyst is of great importance for the successful commercialization of these economic energy sources.
Metal Organic Frameworks (MOFs) have been developed in the last two decades and are a kind of inorganic-organic hybrid materials with porous structure formed by coordination of metal ions (clusters) and organic ligands. MOFs exhibit a broad UV-visible absorption spectrum with absorption edges falling within the typical semiconductor band gap range. The absorption can be due to local ligand-to-metal charge transfer or metal-to-ligand charge transfer, or pi-pi transition of the aromatic linker (t.zhang, et.al.chem Soc Rev 2014,43, 5982-. By adjusting the metal nodes and organic linkers, the charge transfer and light absorption ranges can be modified to design efficient MOF-based photocatalysts. MOFs and their derivatives have been extensively studied in the field of photocatalysis.
Most of the currently studied MOFs photocatalysts are crystalline catalysts, but the crystalline catalysts have the following disadvantages:
1. the number of surface active sites is small;
2. the heterojunction composed of the crystalline catalyst has lattice mismatch at the interface, which is not beneficial to the transfer of photo-generated charges at the interface, and limits the commercial application process.
Disclosure of Invention
In view of the above problems, embodiments of the present application provide a photocatalyst and a method for preparing the same.
In a first aspect, embodiments of the present application provide a photocatalytic CO2The photocatalyst is Cu-DHTP prepared from copper ions and 2, 5-dihydroxy terephthalic acid, and the Cu-DHTP is a nano flaky material with an amorphous structure.
In one possible implementation, the molar ratio of copper ions to 2,5 dihydroxy terephthalic acid in the Cu-DHTP is 1: 1.
In a second aspect, embodiments of the present application provide a method for preparing a photocatalyst according to the first aspect, including the following steps:
(1) mixing N, N-dimethylformamide, absolute ethyl alcohol and deionized water to obtain a first mixed solution;
(2) adding 2, 5-dihydroxyterephthalic acid (DHTP) into the first mixed solution, and ultrasonically dissolving to obtain a second mixed solution;
(3) adding a soluble copper salt into the second mixed solution, and performing ultrasonic dissolution to obtain a third mixed solution;
(4) injecting triethylamine into the third mixed solution, and shaking to obtain a brown gel solution;
(5) carrying out ultrasonic treatment on the brown gel solution to promote substances in the brown gel solution to carry out chemical reaction to obtain a reacted solution containing suspended granular Cu-DHTP;
(6) and extracting Cu-DHTP from the reacted solution to obtain the photocatalyst.
In one possible implementation, the soluble copper salt is copper chloride.
In one possible implementation manner, in the step (2), the ultrasonic power of ultrasonic dissolution is 40kHz, and the ultrasonic time is 8 h;
and/or the presence of a gas in the gas,
in the step (3), the ultrasonic power of ultrasonic dissolution is 40kHz, and the ultrasonic time is 8 h;
and/or the presence of a gas in the gas,
in the step (5), the ultrasonic power of the ultrasonic treatment is 40kHz, and the ultrasonic time is 8 h.
In one possible implementation, in the step (3), the shaking time is 5 min.
In one possible implementation, the amounts of soluble copper salt and 2,5 dihydroxy terephthalic acid material are equal.
In one possible implementation, in the step (6), the extracting Cu-DHTP from the post-reaction solution includes:
centrifuging the reacted solution;
washing the precipitate obtained by the centrifugal treatment;
and drying the washed precipitate to obtain the Cu-DHTP.
In one possible implementation, the rotation speed of the centrifugal treatment is 8000 r/min;
the washing is to use acetone and deionized water to wash in sequence;
the drying treatment is vacuum freeze drying, wherein the vacuum degree is 11Pa, and the freezing temperature is-48 ℃.
In one possible implementation manner, in the step (1), 32ml of N, N dimethylformamide, 2ml of absolute ethanol and 2ml of deionized water are added into a 50ml glass bottle to obtain the first mixed solution;
in the step (2), 0.75mmol of p-2, 5-dihydroxyterephthalic acid (DHTP) is added into the first mixed solution, and the 2, 5-dihydroxyterephthalic acid is dissolved by ultrasonic waves to obtain a second mixed solution;
in the step (3), 0.75mmol of CuCl2·2H2Adding O into the second mixed solution, and ultrasonically treating the CuCl2·2H2Dissolving O to obtain a third mixed solution;
in the step (4), 0.8m L triethylamine is injected into the third mixed solution, and the third mixed solution is shaken for 5min to obtain the brown gel solution;
in the step (5), performing continuous ultrasonic treatment on the brown gel solution for 8 hours by using an ultrasonic device to perform chemical reaction on substances in the brown gel solution to obtain a reacted solution, wherein the reacted solution comprises solid Cu-DHTP;
and (6) centrifuging the reacted solution, taking the precipitate, washing the precipitate by using acetone and deionized water in sequence, and performing vacuum freeze drying to obtain the catalyst.
The photocatalyst prepared by the embodiment of the application has the following beneficial effects:
1. the Cu-DHTP prepared by the embodiment of the application has a two-dimensional nanosheet structure, can provide abundant active sites, and can provide rapid mass transfer and charge transfer to CO2The catalytic performance has obvious promotion effect.
2. The application example uses-OH-containing 2, 5-dihydroxyterephthalic acid (DHTP) as an organic ligand, and the introduction of-OH increases the CO2The adsorption capacity of the catalyst is improved2Efficiency of catalytic reduction.
3. The Cu-DHTP prepared by the embodiment of the application is of an amorphous structure, and an amorphous material is rich in a large number of active sites, so that the possibility of rapid transmission of photo-generated charges is provided.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present application, the drawings needed to be used in the description of the embodiments are briefly introduced below, and it is obvious that the drawings in the following description are only some embodiments of the present application, and it is obvious for those skilled in the art to obtain other drawings based on these drawings without creative efforts.
FIG. 1 shows SEM curves of Cu-DHTP prepared in examples of the present application;
FIG. 2 shows XRD patterns of Cu-DHTP prepared in examples of the present application;
FIG. 3 shows Cu-DHTP prepared in examples of the present application and comparative examplesExample prepared Cu-BDC photocatalytic CO under simulated sunlight2Reduction performance diagram.
Detailed Description
It is to be understood that the scope of the present application is not limited to the particular embodiments described below; it is also to be understood that the terminology used in the examples herein is for the purpose of describing particular embodiments only, and is not intended to limit the scope of the present application; in the specification and claims of this application, the singular forms "a", "an" and "the" include plural referents unless the context clearly dictates otherwise.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected from the group consisting of the endpoints unless otherwise indicated herein. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the present application, in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and the description of the present application.
Compared with crystalline materials, amorphous materials have a large number of active sites, rich band structures, and the band tail state and electrons on the valence band of amorphous nanomaterials can be excited under illumination conditions, and the isotropic characteristics of amorphous materials also provide the possibility of rapid transmission of photogenerated charges (Kang Y, et al. advanced materials,2015,27(31): 4572-4577.). These characteristics of the amorphous material are advantageous for promoting the photocatalytic reaction.
The Cu-DHTP catalyst material synthesized by the ultrasonic synthesis method has obvious amorphous property and is beneficial to photocatalysis of CO2And (4) carrying out a reduction reaction.
Next, the scheme provided in the present application will be specifically described with reference to different embodiments.
Example 1 preparation of catalytic CO2Reduced photocatalyst Cu-DHTP
In this example, the photocatalyst Cu-DHTP was prepared as follows.
(1) 32ml of N, N-dimethylformamide, 2ml of ethanol and 2ml of deionized water were put into a 50ml glass bottle to obtain a mixed solution.
(2) 0.75mmol of p-2, 5-dihydroxyterephthalic acid (DHTP) was added to the above mixed solution, and DHTP was dissolved by sonication to obtain a mixed solution A. Wherein the ultrasonic power is 40kHz, and the ultrasonic time is 8 h.
(3) 0.75mmol of CuCl2·2H2Adding O into the mixed solution A, and ultrasonically treating the CuCl2·2H2Dissolving the O to obtain a mixed solution B. Wherein the ultrasonic power is 40kHz, and the ultrasonic time is 8 h.
(4) 0.8m L triethylamine was quickly injected into the mixed solution B, and shaken for 5min to give a brown gel solution.
(5) And carrying out ultrasonic treatment on the gel solution by an ultrasonic device to enable the mixed solution to carry out chemical reaction to obtain a reacted solution, wherein the reacted solution comprises solid Cu-DHTP. Wherein the ultrasonic power is 40kHz, and the ultrasonic time is 8 h. The solid Cu-DHTP in the solution after the reaction is in a suspended particle shape.
(6) And centrifuging the solution after reaction, wherein the rotating speed of the centrifugation is 8000r/min, and the time is 5 min. After centrifugation was completed, the supernatant was removed. The resulting centrifuged product (precipitate) was washed with acetone and then with deionized water. The washed centrifugal product is subjected to vacuum freeze drying to obtain photocatalytic CO2The catalyst material Cu-DHTP is reduced. Wherein the vacuum degree of vacuum freeze drying is 11Pa, and the freezing temperature is-48 deg.C.
Example 2
1. Scanning electron microscopy is used for shooting the Cu-DHTP prepared in example 1 to obtain an SEM image, and as shown in FIG. 1, the Cu-DHTP material is shown to be in the shape of a nanosheet.
Example 3
XRD measurement was carried out on the centrifuged product after vacuum freeze-drying in step (6) in example 1 to obtain the XRD profile shown in FIG. 2, and analysis of the XRD profile revealed that the centrifuged product (Cu-DHTP prepared in example 1) had an amorphous structure.
Comparative example 1 preparation of catalytic CO2Reduced photocatalyst Cu-BDC
In this comparative example, the photocatalyst Cu-BDC was prepared by the following procedure.
(1) 32ml of N, N-dimethylformamide, 2ml of ethanol and 2ml of deionized water were put into a 50ml glass bottle to obtain a mixed solution.
(2) 0.75mmol of terephthalic acid (BDC) was added to the above mixed solution, and BDC was dissolved by sonication to obtain a mixed solution A. Wherein the ultrasonic power is 40kHz, and the ultrasonic time is 8 h.
(3) 0.75mmol of CuCl2·2H2Adding O into the mixed solution A, and ultrasonically treating the CuCl2·2H2Dissolving the O to obtain a mixed solution B. Wherein the ultrasonic power is 40kHz, and the ultrasonic time is 8 h.
(4) 0.8m L triethylamine was quickly injected into the mixed solution B, and shaken for 5min to obtain a blue gel solution.
(5) And carrying out ultrasonic treatment on the gel solution by an ultrasonic device, so that the mixed solution reacts to obtain a reacted solution, wherein the reacted solution comprises solid Cu-BDC. Wherein the ultrasonic power is 40kHz, and the ultrasonic time is 8 h.
(6) And centrifuging the solution after reaction, wherein the rotating speed of the centrifugation is 8000r/min, and the time is 5 min. After centrifugation was completed, the supernatant was removed. The resulting centrifuged product (precipitate) was washed with acetone and then with deionized water. The washed centrifugal product is subjected to vacuum freeze drying to obtain photocatalytic CO2The catalyst material Cu-BDC is reduced. Wherein the vacuum degree of vacuum freeze drying is 11Pa, and the freezing temperature is-48 deg.C.
Test example 1 catalytic CO comparison of Cu-DHTP and Cu-BDC2Effect of reduction
In this test example, Cu-DHTP prepared in example 1 and Cu-BDC prepared in comparative example 1 were subjected to photocatalytic CO respectively under simulated sunlight2And (5) reduction testing.
Wherein both are subjected to photocatalytic CO2Reduction testThe light source of the reactor is a 300W xenon lamp, the volume of the reactor is 200m L, the addition amount of the catalyst is 10mg, and the gas-solid reaction is carried out.
Both of them are used for photocatalysis of CO2The results of the reduction test are shown in fig. 3. As can be seen from FIG. 3, the Cu-DHTP prepared in example 1 has very good photocatalytic CO compared to the Cu-BDC prepared in comparative example 12Reduction performance.
In summary, the Cu-DHTP prepared in the embodiments of the present application has the following beneficial effects:
1. the Cu-DHTP prepared by the embodiment of the application has a two-dimensional nanosheet structure, can provide abundant active sites, and can provide rapid mass transfer and charge transfer to CO2The catalytic performance has obvious promotion effect.
2. The application example uses-OH-containing 2, 5-dihydroxyterephthalic acid (DHTP) as an organic ligand, and the introduction of-OH increases the CO2The adsorption capacity of the catalyst is improved2Efficiency of catalytic reduction.
3. The Cu-DHTP prepared by the embodiment of the application is of an amorphous structure, and an amorphous material is rich in a large number of active sites, so that the possibility of rapid transmission of photo-generated charges is provided.
The above embodiments are merely illustrative of the principles and utilities of the present application and are not intended to limit the application. Any person skilled in the art can modify or change the above-described embodiments without departing from the spirit and scope of the present application. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical concepts disclosed in the present application shall be covered by the claims of the present application.
Claims (10)
1. Photocatalytic CO2The reduced photocatalyst is characterized in that the photocatalyst is Cu-DHTP prepared from copper ions and 2, 5-dihydroxy terephthalic acid, and the Cu-DHTP is a nano flaky material with an amorphous structure.
2. The photocatalyst as recited in claim 1, wherein the molar ratio of copper ions to 2, 5-dihydroxyterephthalic acid in the Cu-DHTP is 1: 1.
3. The method for preparing the photocatalyst according to claim 1 or 2, comprising the steps of:
(1) mixing N, N-dimethylformamide, absolute ethyl alcohol and deionized water to obtain a first mixed solution;
(2) adding 2, 5-dihydroxyterephthalic acid (DHTP) into the first mixed solution, and ultrasonically dissolving to obtain a second mixed solution;
(3) adding a soluble copper salt into the second mixed solution, and performing ultrasonic dissolution to obtain a third mixed solution;
(4) injecting triethylamine into the third mixed solution, and shaking to obtain a brown gel solution;
(5) carrying out ultrasonic treatment on the brown gel solution to promote substances in the brown gel solution to carry out chemical reaction to obtain a reacted solution containing suspended granular Cu-DHTP;
(6) and extracting Cu-DHTP from the reacted solution to obtain the photocatalyst.
4. The method according to claim 3, wherein the soluble copper salt is copper chloride.
5. The method of claim 3,
in the step (2), the ultrasonic power of ultrasonic dissolution is 40kHz, and the ultrasonic time is 8 h;
and/or the presence of a gas in the gas,
in the step (3), the ultrasonic power of ultrasonic dissolution is 40kHz, and the ultrasonic time is 8 h;
and/or the presence of a gas in the gas,
in the step (5), the ultrasonic power of the ultrasonic treatment is 40kHz, and the ultrasonic time is 8 h.
6. The method of claim 3, wherein in step (3), the shaking time is 5 min.
7. A method according to claim 3, characterized in that the amounts of soluble copper salt and 2,5 dihydroxyterephthalic acid are equal.
8. The method according to any one of claims 3 to 7, wherein in step (6), extracting Cu-DHTP from the post-reaction solution comprises:
centrifuging the reacted solution;
washing the precipitate obtained by the centrifugal treatment;
and drying the washed precipitate to obtain the Cu-DHTP.
9. The method of claim 8,
the rotating speed of the centrifugal treatment is 8000 r/min;
the washing is to use acetone and deionized water to wash in sequence;
the drying treatment is vacuum freeze drying, wherein the vacuum degree is 11Pa, and the freezing temperature is-48 ℃.
10. The method of claim 3,
in the step (1), 32ml of N, N-dimethylformamide, 2ml of absolute ethyl alcohol and 2ml of deionized water are added into a 50ml glass bottle to obtain the first mixed solution;
in the step (2), 0.75mmol of p-2, 5-dihydroxyterephthalic acid (DHTP) is added into the first mixed solution, and the 2, 5-dihydroxyterephthalic acid is dissolved by ultrasonic waves to obtain a second mixed solution;
in the step (3), 0.75mmol of CuCl2·2H2Adding O into the second mixed solution, and ultrasonically treating the CuCl2·2H2Dissolving O to obtain a third mixed solution;
in the step (4), 0.8m L triethylamine is injected into the third mixed solution, and the third mixed solution is shaken for 5min to obtain the brown gel solution;
in the step (5), performing continuous ultrasonic treatment on the brown gel solution for 8 hours by using an ultrasonic device to perform chemical reaction on substances in the brown gel solution to obtain a reacted solution, wherein the reacted solution comprises solid Cu-DHTP;
and (6) centrifuging the reacted solution, taking the precipitate, washing the precipitate by using acetone and deionized water in sequence, and performing vacuum freeze drying to obtain the catalyst.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105524117A (en) * | 2014-09-28 | 2016-04-27 | 中国科学院大连化学物理研究所 | Preparation method for nanometer organic metal framework by ultrasonic atomization |
| CN106492754A (en) * | 2016-09-30 | 2017-03-15 | 昆明理工大学 | A kind of preparation method of adsorbent, method of modifying and application |
| JP2017170383A (en) * | 2016-03-25 | 2017-09-28 | 新日鐵住金株式会社 | Carbon dioxide absorbent and carbon dioxide recovery method |
| CN110038540A (en) * | 2019-01-25 | 2019-07-23 | 北京理工大学 | A kind of sponge composite metal organic framework material for adsorbing separation |
| CN110314700A (en) * | 2018-03-28 | 2019-10-11 | 中国科学院理化技术研究所 | A kind of photocatalytic reduction of carbon oxide co-catalyst, photocatalytic system and its application |
| CN111068783A (en) * | 2019-12-05 | 2020-04-28 | 三峡大学 | Preparation method and application of metal MOF (Metal organic framework) based composite material |
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Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105524117A (en) * | 2014-09-28 | 2016-04-27 | 中国科学院大连化学物理研究所 | Preparation method for nanometer organic metal framework by ultrasonic atomization |
| JP2017170383A (en) * | 2016-03-25 | 2017-09-28 | 新日鐵住金株式会社 | Carbon dioxide absorbent and carbon dioxide recovery method |
| CN106492754A (en) * | 2016-09-30 | 2017-03-15 | 昆明理工大学 | A kind of preparation method of adsorbent, method of modifying and application |
| CN110314700A (en) * | 2018-03-28 | 2019-10-11 | 中国科学院理化技术研究所 | A kind of photocatalytic reduction of carbon oxide co-catalyst, photocatalytic system and its application |
| CN110038540A (en) * | 2019-01-25 | 2019-07-23 | 北京理工大学 | A kind of sponge composite metal organic framework material for adsorbing separation |
| CN111068783A (en) * | 2019-12-05 | 2020-04-28 | 三峡大学 | Preparation method and application of metal MOF (Metal organic framework) based composite material |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115041172A (en) * | 2022-06-02 | 2022-09-13 | 宁波工程学院 | Preparation method and application of solid solution micron rod photocatalyst |
| CN115041172B (en) * | 2022-06-02 | 2024-02-13 | 宁波工程学院 | Preparation method and application of solid solution micron rod photocatalyst |
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