CN113694910A - CuS-ZIF-8-TiO2Preparation method and application of NTAs photoelectrode - Google Patents

CuS-ZIF-8-TiO2Preparation method and application of NTAs photoelectrode Download PDF

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CN113694910A
CN113694910A CN202110779367.8A CN202110779367A CN113694910A CN 113694910 A CN113694910 A CN 113694910A CN 202110779367 A CN202110779367 A CN 202110779367A CN 113694910 A CN113694910 A CN 113694910A
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tio
ntas
cus
zif
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徐迈
王凤武
张媛
方文彦
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Huainan Normal University
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Abstract

The invention relates to CuS-ZIF-8-TiO2The preparation method and the application of the NTAs photoelectrode comprise the following steps: step (1), preparing a titanium dioxide nanotube; step (2), CuS-ZIF-8-TiO2Manufacture of NTAs photoelectrodesPreparing, loading CuS hollow nanospheres on black TiO2NTAs to obtain black CuS-TiO2NTAs, and then loading ZIF-8 particles to the black CuS-TiO by adopting a layer-by-layer self-assembly method2NTAs, preparation of Black CuS-ZIF-8-TiO2The invention provides an NTAs photoelectrode, and provides CuS-ZIF-8-TiO2The preparation method of the NTAs photoelectrode and the product obtained by the application have large specific surface area, can provide more catalytic active sites, and in addition, the black CuS-ZIF-8-TiO2The NTAs can combine the advantages of photocatalysis and electrocatalysis to realize the synergistic effect of the two, and the research is carried out by the research of the black CuS-ZIF-8-TiO2Experiment of NTAs on photoelectrocatalysis degradation of rhodamine B solution, black CuS-ZIF-8-TiO2The degrading efficiency of the NTAs on the rhodamine B reaches 98.1%, the mineralization efficiency is 82%, the catalytic process stability is good, the photoelectric catalytic performance is high, and the application prospect is wide.

Description

CuS-ZIF-8-TiO2Preparation method and application of NTAs photoelectrode
Technical Field
The invention relates to the technical field of photoelectrocatalysis, in particular to CuS-ZIF-8-TiO2A preparation method and application of an NTAs photoelectrode.
Background
The photoelectrocatalysis refers to the action of accelerating photoelectrochemical reaction by selecting semiconductor photoelectrode (or powder) materials and/or changing the surface state of electrodes (surface treatment or surface modification catalyst) under the condition of adding illumination and proper bias voltage, the photoelectrocatalysis technology has the characteristics of low energy consumption, complete degradation and no secondary pollution, and is widely applied to the fields of photoelectrocatalysis organic dye wastewater and the like, the photoelectrocatalysis technology combines the advantages of photocatalysis and electrocatalysis, the synergistic action of the photocatalysis and the electrocatalysis can be realized, and the catalytic degradation efficiency is further improved.
Organic dye wastewater is one of the main industrial pollution sources recognized in the world, often contains non-degradable toxic organic pollutants, and causes great harm to ecological environment and drinking water, RhB is one of the most commonly used dyes in textile industry, the discharge of aqueous solution of RhB into the environment can generate harmful effects on aquatic animals and plants, and can also generate effects on human health, and in addition, rhodamine B has the characteristics of high non-degradability, easy accumulation and the like, so that the exploration of a method for efficiently degrading rhodamine B is a popular subject researched by experts and scholars.
TiO2The material has the advantages of stable material property, safety, no toxicity, strong anti-light corrosion performance, low price and the like, is one of the hottest nanometer photocatalyst materials, is widely applied to the technical field of photocatalysis, and aims to further improve TiO2Photocatalytic activity of (A) TiO2Gold of different species was performedIs doped, but there are various TiO2The photocatalyst has a large forbidden band width (3.2eV), cannot well utilize sunlight, and mostly adopts a single photocatalytic degradation mode, so that the catalysis efficiency is low and the mineralization efficiency is low.
Disclosure of Invention
The invention aims to provide CuS-ZIF-8-TiO2A preparation method and application of NTAs photoelectrode, aiming at solving the problem that in the prior art, various TiO photoelectrodes2The photocatalyst has large forbidden band width, and most of the photocatalysts adopt a single catalytic degradation mode, so that the photocatalyst has the problems of low catalytic efficiency and low mineralization efficiency.
In order to achieve the purpose, the invention provides the following technical scheme: CuS-ZIF-8-TiO2The preparation method of the NTAs photoelectrode comprises the following steps:
step (1), preparing the titanium dioxide nanotube:
placing the pretreated titanium sheet as an anode and the copper sheet with the same size as the titanium sheet as a cathode in an electrolyte for anodic oxidation, and preparing amorphous TiO by an anodic oxidation method at room temperature2NTs, then placing in absolute ethyl alcohol, ultrasonic cleaning, removing amorphous TiO2Residual electrolyte solution and surface impurities in NTs, followed by Na2SO4To TiO in solution2Reducing the NTAs electrode to partially Ti in the nanotube4+Reduction to Ti3+Finally in N2Annealing treatment is carried out under the atmosphere, the annealing temperature is 500-550 ℃, and heat preservation is carried out for 2 hours to obtain black TiO of anatase2An NT electrode;
step (2), CuS-ZIF-8-TiO2Preparation of NTAs photoelectrode:
adding 0.8mL of glacial acetic acid into 30mL of methanol solution, then adding 1.24mmol of copper acetate, adding 1.24mmol of thiourea after the copper acetate is completely dissolved, gradually changing the color of the solution from the initial blue to the final yellow-green color, aging the solution at room temperature for 24 hours, generating yellow precipitate at the bottom of the solution after the aging is completed, transferring the aged solution into a 18mL high-temperature high-pressure reaction kettle, and adding a piece of black TiO into the reaction solution2NTAs oneReact to load the CuS nano hollow sphere on the black TiO2NTAs, dried in a vacuum oven at 50 ℃ overnight to give black CuS-TiO2The NTAs electrode adopts a layer-by-layer self-assembly method to load ZIF-8 particles to CuS-TiO2Adding 0.1833g of zinc nitrate hexahydrate into 25mL of methanol, stirring and dissolving, then adding 0.405g of 2-methylimidazole to prepare 2-methylimidazole solution for later use, and adding prepared CuS-TiO to NTAs2Soaking the NTAs in a zinc nitrate solution for 6h, gradually adding a 2-methylimidazole solution into the solution, stirring at a proper speed for 30 minutes, gradually whitening the solution, finally cleaning the surface of the photoelectrode by using ethanol, carrying out the whole experimental process at room temperature, and obtaining black CuS-ZIF-8-TiO after the operation is finished2NTAs photoelectrodes.
Preferably, the anodic oxidation electrolyte in the step (1) is prepared from 97 vol% of ethylene glycol, 3 vol% of distilled water and 0.5 wt% of NH in mass fraction4F, preparing the product.
Preferably, the voltage of the anodic oxidation in the step (1) is 60V, and the oxidation time is 4 h.
Preferably, in the step (2), the CuS hollow nanospheres are loaded with black TiO2The reaction temperature of NTAs was 100 ℃ and the reaction time was 8 hours.
CuS-ZIF-8-TiO2Application of NTAs photoelectrode, black CuS-ZIF-8-TiO2The NTAs photoelectrode has larger specific surface area, can be used for photoelectrocatalytic degradation of organic dye, and is prepared by using black CuS-ZIF-8-TiO2The experimental research of the NTAs photoelectrode on the photoelectrocatalysis degradation of the rhodamine B solution shows that the black CuS-ZIF-8-TiO2The catalytic process stability of the NTAs photoelectrode is good, the degradation efficiency of rhodamine B reaches 98.1%, and the mineralization efficiency is 82%.
The invention has at least the following beneficial effects:
the invention provides CuS-ZIF-8-TiO2The preparation method and the application of the NTAs photoelectrode are characterized in that the CuS nano hollow sphere can be loaded on the black TiO2NTAs to obtain black CuS-TiO2NTAs, then by layer-by-layer self-assembly methodZIF-8 particles loaded to Black CuS-TiO2NTAs to prepare black CuS-ZIF-8-TiO2The NTAs shows that CuS and ZIF-8 particles are successfully loaded on the black TiO through a series of tests2On NTAs, for black CuS-ZIF-8-TiO2The specific surface area of the NTAs is measured, and the result shows that the black CuS-ZIF-8-TiO2The specific surface area of the NTAs is larger than that of the black TiO2NTAs and Black CuS-TiO2The NTAs has larger specific surface area, can provide more catalytic active sites and is beneficial to the black CuS-ZIF-8-TiO2The NTAs are more efficiently contacted with organic contaminant molecules, and in addition, the black CuS-ZIF-8-TiO2The NTAs can combine the advantages of photocatalysis and electrocatalysis to realize the synergistic effect of the two, and the research is carried out by the research of the black CuS-ZIF-8-TiO2The experiment results of the photoelectrocatalysis degradation experiments of the rhodamine B solution by the NTAs show that the black CuS-ZIF-8-TiO2The degrading efficiency of the NTAs to the rhodamine B reaches 98.1 percent, the mineralizing efficiency is 82 percent, and the degrading and mineralizing efficiency is equal to that of the black TiO before being loaded2Compared with the NTAs photoelectrode, the NTAs photoelectrode is greatly improved, has good stability in the catalytic process and high photoelectrocatalysis performance, can be used for photoelectrocatalysis degradation of organic dyes, and has wide application prospect.
Detailed Description
The technical solutions in the embodiments of the present invention are clearly and completely described below, and it is obvious that the described embodiments are only a part of the embodiments of the present 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.
Examples
CuS-ZIF-8-TiO2The preparation method of the NTAs photoelectrode comprises the following steps:
step (1), preparing the titanium dioxide nanotube:
taking a titanium sheet for pretreatment, shearing the titanium sheet into a titanium sheet with the length of 3cm, the width of 1cm and the thickness of 0.5cm, putting the sheared titanium sheet on a polishing machine, fully polishing the titanium sheet by 600-mesh abrasive paper until the surface is smooth, polishing the polished titanium sheet by 4000-mesh polishing paste until the surface is smooth, then sequentially cleaning the polished titanium sheet by absolute ethyl alcohol, acetone and deionized water for ten minutes under the ultrasonic condition, then putting the cleaned titanium sheet into 100ml of mixed solution of ethylene glycol, deionized water and hydrofluoric acid for corrosion for a period of time, then putting the titanium sheet into the absolute ethyl alcohol for ultrasonic treatment to remove residual corrosive liquid, and finally putting the titanium sheet into the ethyl alcohol for storage for later use;
wherein, the volume fraction ratio of the glycol to the deionized water to the hydrofluoric acid in 100ml of mixed solution of the glycol to the deionized water to the hydrofluoric acid is 6: 2: 1;
taking out the corroded titanium sheet from absolute ethyl alcohol and airing, adopting a two-electrode system in the oxidation process, taking the corroded and cleaned titanium sheet as an anode, taking a copper sheet with the same size as the titanium sheet as a cathode, placing the titanium sheet into electrolyte for anodic oxidation, wherein the electrolyte comprises 97 vol% of ethylene glycol, 3 vol% of distilled water and 0.5 wt% of NH4F, preparing amorphous TiO by anodic oxidation at room temperature2NTs, controlling the oxidation voltage to be 60V and the oxidation time to be 4h, then placing the mixture in absolute ethyl alcohol for ultrasonic cleaning, and removing amorphous TiO2Residual electrolyte solution and surface impurities in NTs, followed by Na2SO4To TiO in solution2Reducing the NTAs electrode to partially Ti in the nanotube4+Reduction to Ti3+Finally in N2Annealing treatment is carried out under the atmosphere, the annealing temperature is 500-550 ℃, and heat preservation is carried out for 2 hours to obtain black TiO of anatase2An NT electrode;
step (3), CuS-ZIF-8-TiO2Preparation of NTAs photoelectrode:
adding 0.8mL of glacial acetic acid into 30mL of methanol solution, then adding 1.24mmol of copper acetate, adding 1.24mmol of thiourea after the copper acetate is completely dissolved, gradually changing the color of the solution from the initial blue to the final yellow-green color, aging the solution at room temperature for 24 hours, generating yellow precipitate at the bottom of the solution after the aging is completed, transferring the aged solution into a 18mL high-temperature high-pressure reaction kettle, and adding a piece of black TiO into the reaction solution2Reacting together with NTAs to load CuS hollow nanospheres toBlack TiO2NTAs, controlling the reaction temperature at 100 ℃ and the reaction time at 8 hours, and drying in a vacuum drying oven at 50 ℃ overnight to obtain black CuS-TiO2The NTAs electrode adopts a layer-by-layer self-assembly method to load ZIF-8 particles to the black CuS-TiO2Adding 0.1833g zinc nitrate hexahydrate into 25mL methanol, stirring for dissolving, then adding 0.405g 2-methylimidazole to obtain 2-methylimidazole solution for later use, and adding prepared black CuS-TiO2Soaking the NTAs in a zinc nitrate solution for 6h, gradually adding a 2-methylimidazole solution into the solution, stirring at a proper speed for 30 minutes, gradually whitening the solution, finally cleaning the surface of the photoelectrode by using ethanol, carrying out the whole experimental process at room temperature, and obtaining black CuS-ZIF-8-TiO after the operation is finished2NTAs photoelectrodes.
CuS-ZIF-8-TiO2Application of NTAs photoelectrode, black CuS-ZIF-8-TiO2The NTAs photoelectrode has larger specific surface area, can be used for photoelectrocatalytic degradation of organic dye, and is prepared by using black CuS-ZIF-8-TiO2The experimental research of the NTAs photoelectrode on the photoelectrocatalysis degradation of the rhodamine B solution shows that the black CuS-ZIF-8-TiO2The catalytic process of the NTAs photoelectrode has good stability, the degradation efficiency of rhodamine B reaches 98.1 percent, the mineralization efficiency is 82 percent, and the degradation and mineralization efficiencies are equal to those of black TiO before being loaded2The NTAs photoelectrode is greatly improved.
For the product prepared in the above embodiment, the physicochemical properties such as the surface morphology, the phase structure, the element composition, the valence state and the like of the modified electrode are deeply analyzed by the characterization means such as a scanning electron microscope, X-ray diffraction, an energy dispersion X-ray spectrum, an X-ray photoelectron spectrum, an ultraviolet-visible diffusion spectrum, a nitrogen adsorption/desorption isotherm and the like, and in addition, the photoelectrochemical properties of the modified photoelectrode are also explored by testing the photocurrent, the mott schottky curve, the electrochemical impedance and the like, and the results are as follows:
the highly ordered nano-tube stands vertically on the titanium substrate, the average pore diameter of the nano-tube is about 145nm, the thickness of the nano-tube is about 10nm, and black TiO is obtained by a hydrothermal method2NTs are still maintainedThe surface of the original tubular structure, flower-shaped CuS hollow sphere, is composed of a plurality of interconnected nano-sheets with the thickness of about 10nm, and is subjected to layer-by-layer self-assembly ZIF-8 and then is subjected to black TiO2The position of the NTAs pipe orifice and the surface of the CuS sphere are provided with ZIF-8 nano particles with the size of about 20nm, CuS-TiO2The specific surface area of the NTAs is 0.557m2/g，TiO2The specific surface area of the NTAs is 0.310m2/g，CuS-TiO2The specific surface area of NTAs is larger than that of TiO2Specific surface area of NTAs, and CuS-TiO2Compared with an NTAs photoelectrode, the CuS-ZIF-8-TiO modified by ZIF-82The specific surface area of the NTAs photoelectrode is greatly increased, and the CuS-ZIF-8-TiO2The specific surface area of the NTAs photoelectrode is 2.440m2The catalyst has a large specific surface area, can provide more catalytic active sites, enables the catalytic active sites to be in more effective contact with organic pollutant molecules, further enhances the photoelectrocatalysis activity, and also has CuS-ZIF-8-TiO2The forbidden band width of the NTAs photoelectrode is 2.43eV, which is lower than 2.58eV of CuS-TiO2NTAs and 3.16eV of TiO2NTAs, and the electron transition generation reaction requires less energy and is easier to catalyze.
In the photoelectric performance test process, CuS-ZIF-8-TiO2The transient photocurrent density of the NTAs photoelectrode is 0.59mA/cm3Respectively being CuS-TiO2NTAs and TiO21.86 times and 8.2 times of NTAs photoelectrode, CuS-ZIF-8-TiO2The diameter of the Nyquist plot for the NTAs photoelectrode is the smallest, indicating a lower charge transfer resistance, and it has been found that the impedance of the photoelectrode is reduced after illumination, due to the efficient separation of the photo-induced electron holes, and the calculation of the TiO using the Mott-Schotty equation2NTAs、CuS-TiO2NTAs and CuS-ZIF-8-TiO2The electron carrier densities of the NTAs photoelectrodes were calculated to be 4.2 × 1019cm-3，1.17×1020cm-3And 4.76X 1020cm-3。
While there have been shown and described what are at present considered the fundamental principles and essential features of the invention and its advantages, it will be apparent to those skilled in the art that the invention is not limited to the details of the foregoing exemplary embodiments, but is capable of other specific forms without departing from the spirit or essential characteristics thereof. The present embodiments are therefore to be considered in all respects as illustrative and not restrictive, the scope of the invention being indicated by the appended claims rather than by the foregoing description, and all changes which come within the meaning and range of equivalency of the claims are therefore intended to be embraced therein.
Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

Claims (5)

1. CuS-ZIF-8-TiO2The preparation method of the NTAs photoelectrode is characterized by comprising the following steps:
step (1), preparing the titanium dioxide nanotube:
placing the pretreated titanium sheet as an anode and the copper sheet with the same size as the titanium sheet as a cathode in an electrolyte for anodic oxidation, and preparing amorphous TiO by an anodic oxidation method at room temperature2NTs, then placing in absolute ethyl alcohol, ultrasonic cleaning, removing amorphous TiO2Residual electrolyte solution and surface impurities in NTs, followed by Na2SO4To TiO in solution2Reducing the NTAs electrode to partially Ti in the nanotube4+Reduction to Ti3+Finally in N2Annealing treatment is carried out under the atmosphere, the annealing temperature is 500-550 ℃, and heat preservation is carried out for 2 hours to obtain black TiO of anatase2An NT electrode;
step (2), CuS-ZIF-8-TiO2Preparation of NTAs photoelectrode:
adding 0.8mL of glacial acetic acid into 30mL of methanol solution, then adding 1.24mmol of copper acetate, adding 1.24mmol of thiourea after the copper acetate is completely dissolved, gradually changing the color of the solution from initial blue to green and finally yellow-green, aging the solution at room temperature for 24 hours, and after the aging is finished, generating yellow precipitate at the bottom of the solution,transferring the aged solution to a 18mL high-temperature high-pressure reaction kettle, and putting a piece of black TiO into the reaction solution2Reacting with NTAs together to load CuS nano hollow sphere on black TiO2NTAs, dried in a vacuum oven at 50 ℃ overnight to give black CuS-TiO2The NTAs electrode adopts a layer-by-layer self-assembly method to load ZIF-8 particles to CuS-TiO2Adding 0.1833g of zinc nitrate hexahydrate into 25mL of methanol, stirring and dissolving, then adding 0.405g of 2-methylimidazole to prepare 2-methylimidazole solution for later use, and adding prepared CuS-TiO to NTAs2Soaking the NTAs in a zinc nitrate solution for 6h, gradually adding a 2-methylimidazole solution into the solution, stirring at a proper speed for 30 minutes, gradually whitening the solution, finally cleaning the surface of the photoelectrode by using ethanol, carrying out the whole experimental process at room temperature, and obtaining black CuS-ZIF-8-TiO after the operation is finished2NTAs photoelectrodes.
2. The CuS-ZIF-8-TiO of claim 12The preparation method of the NTAs photoelectrode is characterized in that the anode oxidation electrolyte in the step (1) is prepared by 97 vol% of ethylene glycol, 3 vol% of distilled water and 0.5 wt% of NH in mass fraction4F, preparing the product.
3. The CuS-ZIF-8-TiO of claim 12The preparation method of the NTAs photoelectrode is characterized in that the voltage of anode oxidation in the step (1) is 60V, and the oxidation time is 4 h.
4. The CuS-ZIF-8-TiO of claim 12The preparation method of the NTAs photoelectrode is characterized in that in the step (2), the CuS hollow nanospheres load black TiO2The reaction temperature of NTAs was 100 ℃ and the reaction time was 8 hours.
5. The CuS-ZIF-8-TiO of any one of claims 1 to 42The application of the NTAs photoelectrode is characterized in that the black CuS-ZIF-8-TiO2NTAs photoelectrodeHas large specific surface area, can be used for photoelectrocatalytic degradation of organic dye by using black CuS-ZIF-8-TiO2The experimental research of the NTAs photoelectrode on the photoelectrocatalysis degradation of the rhodamine B solution shows that the black CuS-ZIF-8-TiO2The catalytic process stability of the NTAs photoelectrode is good, the degradation efficiency of rhodamine B reaches 98.1%, and the mineralization efficiency is 82%.
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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105951154A (en) * 2016-04-27 2016-09-21 中国计量大学 Anodic oxidation preparation method for titanium dioxide nanotube array photocatalyst for degrading rhodamine B
CN111547822A (en) * 2020-05-14 2020-08-18 淮南师范学院 High-catalytic-activity electrode and method for photoelectrocatalytic degradation of active red 195 by using same
CN112266055A (en) * 2020-10-22 2021-01-26 淮南师范学院 Preparation method and application of novel photoelectrode with high catalytic activity

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105951154A (en) * 2016-04-27 2016-09-21 中国计量大学 Anodic oxidation preparation method for titanium dioxide nanotube array photocatalyst for degrading rhodamine B
CN111547822A (en) * 2020-05-14 2020-08-18 淮南师范学院 High-catalytic-activity electrode and method for photoelectrocatalytic degradation of active red 195 by using same
CN112266055A (en) * 2020-10-22 2021-01-26 淮南师范学院 Preparation method and application of novel photoelectrode with high catalytic activity

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