CN111996613A - Preparation method of cerium dioxide-graphite phase carbon nitride photocatalyst fiber - Google Patents

Preparation method of cerium dioxide-graphite phase carbon nitride photocatalyst fiber Download PDF

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CN111996613A
CN111996613A CN202010831866.2A CN202010831866A CN111996613A CN 111996613 A CN111996613 A CN 111996613A CN 202010831866 A CN202010831866 A CN 202010831866A CN 111996613 A CN111996613 A CN 111996613A
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carbon nitride
phase carbon
graphite phase
powder
cerium dioxide
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CN111996613B (en
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卢定泽
曾宜梅
吴琼
张勃宇
张育豪
潘玖存
秦成
汪昊
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Xian Polytechnic University
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Xian Polytechnic University
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    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/88—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds
    • D01F6/92—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from mixtures of polycondensation products as major constituent with other polymers or low-molecular-weight compounds of polyesters
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01D—MECHANICAL METHODS OR APPARATUS IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS
    • D01D5/00—Formation of filaments, threads, or the like
    • D01D5/0007—Electro-spinning
    • D01D5/0015—Electro-spinning characterised by the initial state of the material
    • D01D5/003—Electro-spinning characterised by the initial state of the material the material being a polymer solution or dispersion
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F1/00—General methods for the manufacture of artificial filaments or the like
    • D01F1/02—Addition of substances to the spinning solution or to the melt
    • D01F1/10—Other agents for modifying properties

Abstract

The invention discloses a preparation method of cerium dioxide-graphite phase carbon nitride photocatalyst fiber, which comprises the step of preparing CeO2Nanoparticles of urea reagent with CeO2Uniformly stirring nano particles, grinding the nano particles into powder, heating the powder to 450-650 ℃ for calcination treatment, cooling the powder to room temperature, grinding the powder to obtain cerium dioxide-graphite phase carbon nitride, adding polyethylene glycol terephthalate and the cerium dioxide-graphite phase carbon nitride which are in a mass ratio of 0.1-10: 0.01-1 into hexafluoroisopropanol together, ultrasonically dispersing the mixture to prepare photocatalyst emulsion, carrying out electrostatic spinning by adopting the photocatalyst emulsion, putting the product into an aqueous solution formed by NaOH and CTAB for water bath heating, washing the product after the water bath heating by using deionized water and absolute ethyl alcohol, and finally drying the product, namely the prepared dioxideThe cerium dioxide-graphite phase carbon nitride photocatalyst fiber prepared by the method has larger specific surface area and visible light utilization rate.

Description

Preparation method of cerium dioxide-graphite phase carbon nitride photocatalyst fiber
Technical Field
The invention belongs to the technical field of textile engineering, and relates to a preparation method of cerium dioxide-graphite phase carbon nitride photocatalyst fibers.
Background
With the rapid development of global science and technology and the rapid progress of society, people rely on the exploitation of earth energy and the utilization of resources to create unequally economic wealth for the human society. While bringing wealth to human beings, with the increasing demand of society for energy, increasingly serious environmental pollution and energy crisis come after. Environmental pollution and energy crisis become important problems to be solved urgently all over the world, so that the method is a high-efficiency, rapid, economic and environment-friendly treatment method, and the semiconductor photocatalysis technology is generated at the same time. Compared with the common treatment method, the technology has the advantages of rich material sources, simple preparation process, no secondary pollution to the environment and the like, and the technology is rapidly in the fields of sewage treatment and new energy development. g-C as a modern novel highly efficient visible light responsive photocatalytic material3N4The star material in the field of photocatalysis has the unique advantages of being capable of being excited under visible light to carry out photocatalytic hydrogen production by virtue of excellent positions of a Valence Band (VB) and a Conduction Band (CB), simple and green preparation process, stable in physicochemical property, wide in precursor source, free of secondary pollution and the like. But, in the same way, g-C3N4The material has the defects of small specific surface area, rapid recombination of photon-generated carriers, low quantum efficiency, low utilization rate of visible light, difficult recovery and the like, and also seriously influences the research prospect of the material in the field of photocatalysis.
Disclosure of Invention
The invention aims to provide a preparation method of a cerium dioxide-graphite phase carbon nitride photocatalyst fiber, and the prepared cerium dioxide-graphite phase carbon nitride photocatalyst fiber has larger specific surface area and visible light utilization rate and is convenient to recycle.
The technical scheme adopted by the invention is that the preparation method of the cerium dioxide-graphite phase carbon nitride photocatalyst fiber comprises the following steps:
step 1, CeO preparation2A nanoparticle;
step 2, mixing urea reagent with CeO2Uniformly stirring the nano particles, grinding the nano particles into powder, heating the powder to 450-650 ℃, calcining, cooling to room temperature, and grinding the powder to obtain cerium dioxide-graphite phase carbon nitride;
step 3, adding polyethylene glycol terephthalate and cerium dioxide-graphite phase carbon nitride into hexafluoroisopropanol in a mass ratio of 0.1-10: 0.01-1, and preparing a photocatalyst emulsion after ultrasonic dispersion;
and 4, performing electrostatic spinning by using the photocatalyst emulsion, putting the product into an aqueous solution formed by NaOH and CTAB for water bath heating, washing the product after the water bath heating by using deionized water and absolute ethyl alcohol, and finally drying to obtain the cerium dioxide-graphite phase carbon nitride photocatalyst fiber.
The present invention is also technically characterized in that,
the specific process of step 1 is as follows:
step 1.1, preparing NaOH solution with the concentration of 0.1 g/mL-0.3 g/mL;
step 1.2, taking Ce (NO)3)3·6H2Adding O into the NaOH solution prepared in the step 1.1, stirring for 1-5 h, then putting the solution into a drying oven for drying, and finally taking out and grinding into powder;
step 1.3, washing the powder prepared in the step 1.2 to be neutral by using deionized water and alcohol, and drying the washed powder at 50-70 ℃;
step 1.4, placing the dried powder in an alumina crucible, placing the alumina crucible in a muffle furnace, heating to 500-600 ℃, calcining, cooling to room temperature, taking out and grinding to obtain the powderNano-scale particles to obtain CeO2And (3) nanoparticles.
In step 1.2, Ce (NO)3)3·6H2The mass ratio of O to NaOH solid in the NaOH solution is 1.74: 12.
in the step 1.2, the solution is placed into an oven to be dried, the drying temperature is 110-130 ℃, and the drying time is 2-30 h.
In the step 1.4, the heating rate during the calcination treatment is 3 ℃/min to 6 ℃/min, and the calcination treatment time is 1.5h to 2.5 h.
In step 2, urea reagent and CeO2The mass ratio of the nano particles is 30: 0004-0.036.
In the step 2, the heating rate during the calcination treatment is 3-6 ℃/min, and the calcination treatment time is 1.5-2.5 h.
In the step 3, the solid-to-liquid ratio of the polyethylene terephthalate to the hexafluoroisopropanol in the photocatalyst emulsion is 0.5-50 g: 3-300 mL.
In step 4, the electrostatic spinning parameters are as follows: the voltage is 10-15 kV, the spinning speed is 0.1-2 mL/h, and the receiving distance is 10-50 cm.
And step 4, putting the product into an aqueous solution formed by NaOH and CTAB for water bath heating, wherein the concentration of NaOH in the aqueous solution is 0.4-40 g/L, the concentration of CTAB in the aqueous solution is 0.04-4 g/L, the temperature of the water bath is 60-70 ℃, and the time of the water bath is 0.5-5 hours.
The invention has the beneficial effect that the CeO2The nano particles are combined with a urea reagent to generate the cerium oxide-graphite phase carbon nitride heterojunction photocatalyst, so that the migration and separation efficiency of a photon-generated carrier of a compound system is improved, the rapid recombination of photon-generated electron hole pairs is reduced, and the bulk phase g-C is further improved3N4The quantum efficiency and the visible light utilization rate of the quantum are overcome, and the pure phase g-C is overcome3N4The prepared cerium oxide-graphite phase carbon nitride heterojunction photocatalyst fiber has larger specific surface area and quantum efficiency and is easy to recycle.
Drawings
FIG. 1 is a low power transmission electron microscope image of cerium oxide nanotubes (CeNT);
FIG. 2 is a high transmission electron microscope image of cerium oxide nanotubes (CeNT);
FIG. 3 is a low power transmission electron microscope photograph of the ceria-graphite phase carbon nitride prepared in example 1 of the present invention;
FIG. 4 is a high-power transmission electron microscope photograph of the ceria-graphite phase carbon nitride prepared in example 1 of the present invention;
FIG. 5 is a graph showing the degradation activity of the cerium oxide-graphite phase carbon nitride prepared in examples 1 to 5 of the present invention against rose bengal B under visible light irradiation;
FIG. 6 is a graph of a first order kinetic fit of the degradation of rose bengal B under visible light irradiation by the ceria-graphite phase carbon nitride prepared in examples 1-5 of the present invention;
FIG. 7 is a graph showing the degradation rate of rose bengal B under visible light irradiation by the ceria-graphite phase carbon nitride prepared in examples 1 to 5 of the present invention.
Detailed Description
The present invention will be described in detail below with reference to the accompanying drawings and specific embodiments.
The invention relates to a preparation method of cerium dioxide-graphite phase carbon nitride photocatalyst fiber, which comprises the following steps:
step 1, CeO preparation2Nanoparticles
Step 1.1, preparing NaOH solution with the concentration of 0.1 g/mL-0.3 g/mL;
step 1.2, taking Ce (NO)3)3·6H2Adding O into the NaOH solution prepared in the step 1.1, and stirring for 0.5-5 h, wherein Ce (NO) is3)3·6H2The mass ratio of O to NaOH in the NaOH solution is 1.74: 12, then putting the solution into an oven for drying at the drying temperature of 110-130 ℃ for 2-30 h, and finally taking out and grinding the solution into powder;
step 1.3, washing the powder prepared in the step 1.2 to be neutral by using deionized water and alcohol, and drying the washed powder at 50-70 ℃;
step 1.4, placing the dried powder in an alumina crucible, and then placing the alumina crucible in a muffle furnace at a heating rate of 3-6 ℃/minHeating the mixture to 500-600 ℃ at room temperature, calcining the mixture for 1.5-2.5 h, cooling the mixture to room temperature, taking the cooled mixture out, grinding the cooled mixture into nano-scale particles to obtain CeO2And (3) nanoparticles.
Step 2, mixing a urea reagent and CeO according to the mass ratio of 30: 0004-0.0362Uniformly stirring the nano particles, grinding the nano particles into powder, heating the powder to 450-650 ℃ at a heating rate of 3-6 ℃/min, calcining for 1.5-2.5 h, cooling to room temperature, and grinding the powder to obtain cerium dioxide-graphite phase carbon nitride;
step 3, adding polyethylene glycol terephthalate and cerium dioxide-graphite phase carbon nitride into hexafluoroisopropanol in a mass ratio of 0.1-10: 0.01-1, and preparing a photocatalyst emulsion after ultrasonic dispersion;
the solid-to-liquid ratio of the polyethylene terephthalate to the hexafluoroisopropanol in the photocatalyst emulsion is 0.5-50 g: 3-300 mL.
And 4, carrying out electrostatic spinning by adopting the photocatalyst emulsion, wherein the electrostatic spinning parameters are as follows: the voltage is 10-15 kV, the spinning speed is 0.1-2 mL/h, and the receiving distance is 10-50 cm; then putting the electrostatic spinning product into an aqueous solution formed by NaOH and CTAB (cetyl trimethyl ammonium bromide) for water bath heating, wherein the concentration of NaOH in the aqueous solution is 0.4-40 g/L, the concentration of CTAB is 0.04-4 g/L, the temperature of the water bath is 60-70 ℃, and the time of the water bath is 0.5-5 h; and washing the product after water bath heating by using deionized water and absolute ethyl alcohol, and finally drying to obtain the cerium dioxide-graphite phase carbon nitride photocatalyst fiber.
Example 1
The preparation method of the cerium dioxide-graphite phase carbon nitride photocatalyst fiber comprises the following steps:
step 1, CeO preparation2Nanoparticles
Step 1.1, putting 12g of flake NaOH into 60mL of deionized water, and stirring to completely dissolve the NaOH to prepare NaOH solution;
step 1.2, 1.74g of Ce (NO) is taken3)3·6H2Adding O into the NaOH solution prepared in the step 1.1, stirring for 2h, then putting the beaker containing the solution into an oven for drying, heating to 120 ℃ at the speed of 2.3 ℃/min, and then heatingKeeping the temperature for 24h, finally taking out the solid in the beaker, and grinding the solid into powder;
step 1.3, washing the powder prepared in the step 1.2 to be neutral by using deionized water and alcohol, and drying the washed powder at 60 ℃ for 12 hours;
step 1.4, placing the dried powder in an alumina crucible, placing the alumina crucible in a muffle furnace, heating the alumina crucible to 550 ℃ from room temperature at the heating rate of 4.6 ℃/min, calcining the alumina crucible for 2 hours, cooling the alumina crucible to the room temperature, taking out the alumina crucible and grinding the alumina crucible into nano-scale particles to obtain CeO2And (3) nanoparticles.
Step 2, putting 30g of urea reagent into the crucible, and adding 0.004g of CeO into the crucible2Uniformly stirring the nano particles, grinding the nano particles into powder in a grinding bowl, heating the powder to 550 ℃ in a muffle furnace at the heating rate of 4 ℃/min, calcining for 2 hours, cooling to room temperature, and grinding the powder to obtain cerium dioxide-graphite phase carbon nitride;
step 3, adding polyethylene terephthalate and cerium dioxide-graphite phase carbon nitride in a mass ratio of 0.1:0.01 into hexafluoroisopropanol, and performing ultrasonic dispersion to prepare photocatalyst emulsion, wherein the solid-to-liquid ratio of the polyethylene terephthalate to the hexafluoroisopropanol in the photocatalyst emulsion is 0.5 g: 6 mL;
and 4, carrying out electrostatic spinning by adopting the photocatalyst emulsion, wherein the electrostatic spinning parameters are as follows: the voltage is 10kV, the spinning speed is 1mL/h, and the receiving distance is 10 cm; putting the product into an aqueous solution formed by NaOH and CTAB for water bath heating, wherein the concentration of NaOH in the aqueous solution is 0.5g/L, the concentration of CTAB is 0.04g/L, the temperature of the water bath is 60 ℃, and the time of the water bath is 1 h; and washing the product after water bath heating by using deionized water and absolute ethyl alcohol, and finally drying to obtain the cerium dioxide-graphite phase carbon nitride photocatalyst fiber.
Fig. 1 and 2 are low-power and high-power transmission electron microscope images of cerium oxide nanotubes (CeNT), respectively, and clear morphology of the cerium oxide nanotubes can be clearly seen from fig. 1 and 2. FIG. 3 is a low transmission electron microscope photograph of the ceria-graphite phase carbon nitride prepared in example 1 of the present invention, in which CeO is shown as a black region in FIG. 32Nanoparticles with grey areas of g-C3N4NanoparticlesAs can be seen from FIG. 3, CeO is contained in the ceria-graphite phase carbon nitride prepared in example 12The particle size of the nanoparticles is about 20nm, CeO2And g-C3N4The surfaces of the nano particles are tightly connected together to form a semiconductor heterojunction structure, and the surfaces of the nano particles are tightly connected, so that the charge transfer efficiency is accelerated, and the photocatalytic activity of the material is improved. FIG. 4 is a high-power transmission electron microscope photograph of the ceria-graphite phase carbon nitride prepared in example 1 of the present invention, and it can be seen from FIG. 4 that CeO is contained in the ceria-graphite phase carbon nitride2The internal lattice structure is measured at the position with clear image, and the interplanar spacing d is 0.31nm corresponding to CeO2The (111) crystal plane of (a).
Example 2
The preparation method of the cerium dioxide-graphite phase carbon nitride photocatalyst fiber comprises the following steps:
step 1, CeO preparation2Nanoparticles
Step 1.1, putting 10g of flake NaOH into 50mL of deionized water, and stirring to completely dissolve the NaOH to prepare NaOH solution;
step 1.2, 1.45g of Ce (NO) is taken3)3·6H2Adding O into the NaOH solution prepared in the step 1.1, stirring for 0.5h, then putting the beaker containing the solution into an oven for drying, heating to 110 ℃ at the speed of 2.5 ℃/min, then preserving heat for 20h, finally taking out the solid in the beaker, and grinding into powder;
step 1.3, washing the powder prepared in the step 1.2 to be neutral by using deionized water and alcohol, and drying the washed powder at 50 ℃ for 12 hours;
step 1.4, placing the dried powder in an alumina crucible, placing the alumina crucible in a muffle furnace, heating the alumina crucible from room temperature to 500 ℃ at the heating rate of 3 ℃/min, calcining the alumina crucible for 2 hours, cooling the alumina crucible to the room temperature, taking out the alumina crucible and grinding the alumina crucible into nano-scale particles to obtain CeO2And (3) nanoparticles.
Step 2, 30g of urea reagent is put into a crucible, and 0.012g of CeO is added into the crucible2Grinding the nanoparticles in a grinding bowl to obtain powder, heating the powder in a muffle furnace at a temperature rise rate of 3 deg.C/minCalcining for 1.5h at 450 ℃, cooling to room temperature, and grinding to powder to obtain cerium dioxide-graphite phase carbon nitride;
and 3, adding polyethylene terephthalate and cerium dioxide-graphite phase carbon nitride into hexafluoroisopropanol in a mass ratio of 2:0.5, and performing ultrasonic dispersion to prepare a photocatalyst emulsion, wherein the solid-to-liquid ratio of the polyethylene terephthalate to the hexafluoroisopropanol in the photocatalyst emulsion is 8 g: 15 mL;
and 4, carrying out electrostatic spinning by adopting the photocatalyst emulsion, wherein the electrostatic spinning parameters are as follows: the voltage is 12kV, the spinning speed is 0.5mL/h, and the receiving distance is 20 cm; putting the electrostatic spinning product into an aqueous solution formed by NaOH and CTAB for water bath heating, wherein the concentration of NaOH in the aqueous solution is 10g/L, the concentration of CTAB is 2g/L, the temperature of the water bath is 65 ℃, and the time of the water bath is 0.5 h; and washing the product after water bath heating by using deionized water and absolute ethyl alcohol, and finally drying to obtain the cerium dioxide-graphite phase carbon nitride photocatalyst fiber.
Example 3
The preparation method of the cerium dioxide-graphite phase carbon nitride photocatalyst fiber comprises the following steps:
step 1, CeO preparation2Nanoparticles
Step 1.1, putting 10g of flake NaOH into 100mL of deionized water, and stirring to completely dissolve the NaOH to prepare NaOH solution;
step 1.2, 1.45g of Ce (NO) is taken3)3·6H2Adding O into the NaOH solution prepared in the step 1.1, stirring for 3h, then putting the beaker containing the solution into an oven for drying, heating to 120 ℃ at the speed of 2 ℃/min, then preserving heat for 24h, finally taking out the solid in the beaker, and grinding into powder;
step 1.3, washing the powder prepared in the step 1.2 to be neutral by using deionized water and alcohol, and drying the washed powder at 55 ℃ for 12 hours;
step 1.4, placing the dried powder in an alumina crucible, placing the alumina crucible in a muffle furnace, heating the alumina crucible from room temperature to 570 ℃ at the heating rate of 5 ℃/min, calcining the alumina crucible for 2 hours, cooling the alumina crucible to the room temperature, taking out the alumina crucible and grinding the alumina crucible into nano-scale particles to obtain CeO2And (3) nanoparticles.
Step 2, putting 30g of urea reagent into a crucible, and adding 0.02g of CeO into the crucible2Uniformly stirring the nano particles, grinding the nano particles into powder in a grinding bowl, heating the powder to 550 ℃ in a muffle furnace at the heating rate of 4 ℃/min, calcining for 2 hours, cooling to room temperature, and grinding the powder to obtain cerium dioxide-graphite phase carbon nitride;
and 3, adding polyethylene terephthalate and cerium dioxide-graphite phase carbon nitride into hexafluoroisopropanol in a mass ratio of 3:0.05, and performing ultrasonic dispersion to prepare a photocatalyst emulsion, wherein the solid-to-liquid ratio of the polyethylene terephthalate to the hexafluoroisopropanol in the photocatalyst emulsion is 15 g: 28 mL;
and 4, carrying out electrostatic spinning by adopting the photocatalyst emulsion, wherein the electrostatic spinning parameters are as follows: the voltage is 13kV, the spinning speed is 1.5mL/h, and the receiving distance is 20 cm; putting the product into an aqueous solution formed by NaOH and CTAB for water bath heating, wherein the concentration of NaOH in the aqueous solution is 10g/L, the concentration of CTAB is 2.5g/L, the temperature of the water bath is 65 ℃, and the time of the water bath is 3 h; and washing the product after water bath heating by using deionized water and absolute ethyl alcohol, and finally drying to obtain the cerium dioxide-graphite phase carbon nitride photocatalyst fiber.
Example 4
The preparation method of the cerium dioxide-graphite phase carbon nitride photocatalyst fiber comprises the following steps:
step 1, CeO preparation2Nanoparticles
Step 1.1, putting 30g of flake NaOH into 100mL of deionized water, and stirring to completely dissolve NaOH to prepare NaOH solution;
step 1.2, 43.5g of Ce (NO) is taken3)3·6H2Adding O into the NaOH solution prepared in the step 1.1, stirring for 4h, then putting the beaker containing the solution into an oven for drying, heating to 130 ℃ at the speed of 2.3 ℃/min, then preserving heat for 24h, finally taking out the solid in the beaker, and grinding into powder;
step 1.3, washing the powder prepared in the step 1.2 to be neutral by using deionized water and alcohol, and drying the washed powder for 15h at the temperature of 60 ℃;
step 1.4, drying the mixtureThe powder is put into an alumina crucible, then put into a muffle furnace to be calcined for 2.3 hours from room temperature to 580 ℃ at the heating rate of 5 ℃/min, cooled to room temperature, taken out and ground into nano-scale particles to obtain CeO2And (3) nanoparticles.
Step 2, putting 30g of urea reagent into the crucible, and adding 0.028g of CeO into the crucible2Uniformly stirring the nano particles, grinding the nano particles into powder in a grinding bowl, heating the powder to 600 ℃ in a muffle furnace at the heating rate of 4 ℃/min, calcining for 2.2h, cooling to room temperature, and grinding the powder to obtain cerium dioxide-graphite phase carbon nitride;
and 3, adding polyethylene terephthalate and cerium dioxide-graphite phase carbon nitride into hexafluoroisopropanol in a mass ratio of 8:0.08, and performing ultrasonic dispersion to prepare a photocatalyst emulsion, wherein the solid-to-liquid ratio of the polyethylene terephthalate to the hexafluoroisopropanol in the photocatalyst emulsion is 20 g: 100 mL;
and 4, carrying out electrostatic spinning by adopting the photocatalyst emulsion, wherein the electrostatic spinning parameters are as follows: the voltage is 14kV, the spinning speed is 1.8mL/h, and the receiving distance is 40 cm; putting the product into an aqueous solution formed by NaOH and CTAB for water bath heating, wherein the concentration of NaOH in the aqueous solution is 25g/L, the concentration of CTAB is 3g/L, the temperature of the water bath is 68 ℃, and the time of the water bath is 4 h; and washing the product after water bath heating by using deionized water and absolute ethyl alcohol, and finally drying to obtain the cerium dioxide-graphite phase carbon nitride photocatalyst fiber.
Example 5
The preparation method of the cerium dioxide-graphite phase carbon nitride photocatalyst fiber comprises the following steps:
step 1, CeO preparation2Nanoparticles
Step 1.1, putting 12g of flake NaOH into 60mL of deionized water, and stirring to completely dissolve the NaOH to prepare NaOH solution;
step 1.2, 1.74g of Ce (NO) is taken3)3·6H2Adding O into the NaOH solution prepared in the step 1.1, stirring for 2h, then putting the beaker containing the solution into an oven for drying, heating to 120 ℃ at the speed of 2.3 ℃/min, then preserving heat for 24h, finally taking out the solid in the beaker, and grinding into powder;
step 1.3, washing the powder prepared in the step 1.2 to be neutral by using deionized water and alcohol, and drying the washed powder at 60 ℃ for 12 hours;
step 1.4, placing the dried powder in an alumina crucible, placing the alumina crucible in a muffle furnace, heating the alumina crucible to 550 ℃ from room temperature at the heating rate of 4.6 ℃/min, calcining the alumina crucible for 2 hours, cooling the alumina crucible to the room temperature, taking out the alumina crucible and grinding the alumina crucible into nano-scale particles to obtain CeO2And (3) nanoparticles.
Step 2, putting 30g of urea reagent into a crucible, and adding 0.036g of CeO into the crucible2Uniformly stirring the nano particles, grinding the nano particles into powder in a grinding bowl, heating the powder to 650 ℃ in a muffle furnace at the heating rate of 6 ℃/min, calcining for 2.5h, cooling to room temperature, and grinding the powder to obtain cerium dioxide-graphite phase carbon nitride;
and 3, adding polyethylene glycol terephthalate and cerium dioxide-graphite phase carbon nitride into hexafluoroisopropanol in a mass ratio of 5:1, and performing ultrasonic dispersion to prepare a photocatalyst emulsion, wherein the solid-to-liquid ratio of the polyethylene glycol terephthalate to the hexafluoroisopropanol in the photocatalyst emulsion is 5 g: 6 mL;
and 4, carrying out electrostatic spinning by adopting the photocatalyst emulsion, wherein the electrostatic spinning parameters are as follows: the voltage is 10kV, the spinning speed is 1mL/h, and the receiving distance is 50 cm; putting the product into an aqueous solution formed by NaOH and CTAB for water bath heating, wherein the concentration of NaOH in the aqueous solution is 40g/L, the concentration of CTAB is 4g/L, the temperature of the water bath is 70 ℃, and the time of the water bath is 5 h; and washing the product after water bath heating by using deionized water and absolute ethyl alcohol, and finally drying to obtain the cerium dioxide-graphite phase carbon nitride photocatalyst fiber.
FIG. 5 is a graph showing the degradation activity of the ceria-graphite phase carbon nitride prepared in examples 1 to 5 of the present invention under visible light irradiation on Rose Bengal B, which is an organic contaminant RhB, and it can be seen from the graph that the degradation rate and the final degradation efficiency of the ceria-graphite phase carbon nitride prepared in the present application on the organic contaminant RhB are much higher than those of pure CeO after 120min degradation2(i.e., ceria nanotubes CeNT).
FIG. 6 is a preparation of examples 1 to 5 of the present inventionA first order kinetic fit graph of the degradation of rose bengal B under visible light irradiation of the ceria-graphite phase carbon nitrides of (1-5) can be seen from the graph, where-ln (C/C) of the ceria-graphite phase carbon nitrides prepared in examples 1-50) Linear with illumination time, -ln (C/C)0) Is an equation of reaction kinetics, showing that the photocatalytic reaction of the ceria-graphite phase carbon nitride prepared in examples 1-5 conforms to a first order kinetic model.
FIG. 7 is a graph showing the degradation rate of rose bengal B under visible light irradiation for the ceria-graphite phase carbon nitride prepared in examples 1 to 5 of the present invention, in which a represents pure CeO2B represents the ceria-graphite phase carbon nitride prepared in example 1, c represents the ceria-graphite phase carbon nitride prepared in example 2, d represents the ceria-graphite phase carbon nitride prepared in example 3, e represents the ceria-graphite phase carbon nitride prepared in example 4, and f represents the ceria-graphite phase carbon nitride prepared in example 5, from which it can be seen that pure CeO2The degradation rate of rose bengal B under visible light irradiation was about 9%, the degradation rate of the ceria-graphite phase carbon nitride prepared in example 1 under visible light irradiation was about 83%, the degradation rate of the ceria-graphite phase carbon nitride prepared in example 2 under visible light irradiation was about 91%, the degradation rate of the ceria-graphite phase carbon nitride prepared in example 3 under visible light irradiation was about 100%, the degradation rate of the ceria-graphite phase carbon nitride prepared in example 4 under visible light irradiation was about 75%, and the degradation rate of the ceria-graphite phase carbon nitride prepared in example 5 under visible light irradiation was about 62%. CeO is clearly shown therein2/g-C3N4The degradation rate is faster than that of pure CeO2Among them, the ceria-graphite phase carbon nitride prepared in example 3 has the fastest degradation rate, the highest degradation efficiency, and the best photocatalytic activity. The ceria-graphite phase carbon nitride prepared in example 3 exhibited the highest degradation rate with a degradation rate constant of: k is 0.035min-1Is pure CeO2The reagent degradation rate constant was 21 times, showing the highestPhotocatalytic activity of (1).

Claims (10)

1. A preparation method of cerium dioxide-graphite phase carbon nitride photocatalyst fiber is characterized by comprising the following steps:
step 1, CeO preparation2A nanoparticle;
step 2, mixing urea reagent with CeO2Uniformly stirring the nano particles, grinding the nano particles into powder, heating the powder to 450-650 ℃, calcining, cooling to room temperature, and grinding the powder to obtain cerium dioxide-graphite phase carbon nitride;
step 3, adding polyethylene glycol terephthalate and cerium dioxide-graphite phase carbon nitride into hexafluoroisopropanol in a mass ratio of 0.1-10: 0.01-1, and preparing a photocatalyst emulsion after ultrasonic dispersion;
and 4, performing electrostatic spinning by using the photocatalyst emulsion, putting the product into an aqueous solution formed by NaOH and CTAB for water bath heating, washing the product after the water bath heating by using deionized water and absolute ethyl alcohol, and finally drying to obtain the cerium dioxide-graphite phase carbon nitride photocatalyst fiber.
2. The method as claimed in claim 1, wherein the step 1 comprises the following steps:
step 1.1, preparing NaOH solution with the concentration of 0.1 g/mL-0.3 g/mL;
step 1.2, taking Ce (NO)3)3·6H2Adding O into the NaOH solution prepared in the step 1.1, stirring for 1-5 h, then putting the solution into a drying oven for drying, and finally taking out and grinding into powder;
step 1.3, washing the powder prepared in the step 1.2 to be neutral by using deionized water and alcohol, and drying the washed powder at 50-70 ℃;
step 1.4, placing the dried powder in an alumina crucible, placing the alumina crucible in a muffle furnace, heating to 500-600 ℃, calcining, cooling to room temperature, taking out and grinding into nano-scale particles to obtain CeO2Nano-particlesAnd (4) granulating.
3. The method of claim 2, wherein in step 1.2, Ce (NO) is added to the reaction mixture3)3·6H2The mass ratio of O to NaOH solid in the NaOH solution is 1.74: 12.
4. the method for preparing the ceria-graphite phase carbon nitride photocatalyst fiber according to claim 2, wherein in the step 1.2, the solution is dried in an oven, wherein the drying temperature is 110-130 ℃, and the drying time is 20-30 h.
5. The method for preparing a ceria-graphite phase carbon nitride photocatalyst fiber as claimed in claim 2, wherein in the step 1.4, the temperature rise rate during the calcination treatment is 3 ℃/min to 6 ℃/min, and the calcination treatment time is 1.5h to 2.5 h.
6. The method as claimed in claim 1, wherein in step 2, the urea reagent and CeO are added2The mass ratio of the nano particles is 30: 0004-0.036.
7. The method of claim 6, wherein in step 2, the temperature increase rate during the calcination treatment is 3 ℃/min to 6 ℃/min, and the calcination treatment time is 1.5h to 2.5 h.
8. The method as claimed in claim 7, wherein in step 3, the solid-to-liquid ratio of polyethylene terephthalate to hexafluoroisopropanol in the photocatalyst emulsion is 0.5-50 g: 3-300 mL.
9. The method of claim 8, wherein in step 4, the electrospinning parameters are as follows: the voltage is 10-15 kV, the spinning speed is 0.1-2 mL/h, and the receiving distance is 10-50 cm.
10. The method for preparing a ceria-graphite phase carbon nitride photocatalyst fiber as claimed in claim 8, wherein in the step 4, the product is put into an aqueous solution formed by NaOH and CTAB for heating in a water bath, wherein the concentration of NaOH in the aqueous solution is 0.4-40 g/L, the concentration of CTAB in the aqueous solution is 0.04-4 g/L, the temperature of the water bath is 60-70 ℃, and the time of the water bath is 0.5-5 hours.
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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106319673A (en) * 2016-08-19 2017-01-11 浙江理工大学 Composite photocatalytic fibers and preparation method thereof
CN107626336A (en) * 2017-09-22 2018-01-26 陕西科技大学 A kind of preparation method and application of carbon point/class graphite phase carbon nitride composite photo-catalyst
CN108823672A (en) * 2018-06-06 2018-11-16 浙江理工大学 A kind of coloured photocatalytic fiber and preparation method thereof
CN109794277A (en) * 2019-01-30 2019-05-24 扬州工业职业技术学院 A kind of ceria/graphite phase carbon nitride composite material and its application in photocatalysis
CN110694666A (en) * 2019-11-07 2020-01-17 江汉大学 C3N4@CeO2Supported low-content gold catalyst and preparation method and application thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN106319673A (en) * 2016-08-19 2017-01-11 浙江理工大学 Composite photocatalytic fibers and preparation method thereof
CN107626336A (en) * 2017-09-22 2018-01-26 陕西科技大学 A kind of preparation method and application of carbon point/class graphite phase carbon nitride composite photo-catalyst
CN108823672A (en) * 2018-06-06 2018-11-16 浙江理工大学 A kind of coloured photocatalytic fiber and preparation method thereof
CN109794277A (en) * 2019-01-30 2019-05-24 扬州工业职业技术学院 A kind of ceria/graphite phase carbon nitride composite material and its application in photocatalysis
CN110694666A (en) * 2019-11-07 2020-01-17 江汉大学 C3N4@CeO2Supported low-content gold catalyst and preparation method and application thereof

Non-Patent Citations (3)

* Cited by examiner, † Cited by third party
Title
Q QIAO ET AL.: "Facile in situ construction of mediator-free direct Zscheme g-C3N4/CeO2 heterojunctions with highly efficient photocatalytic activity", 《JOURNAL OF PHYSICS D: APPLIED PHYSICS》 *
S. ANSARI ET AL.: "CeO2/g-C3N4 Nanocomposite: A Perspective for Electrochemical Sensing of Anti-Depressant Drug", 《SENSORS AND ACTUATORS B》 *
YIBIN LIU ET AL.: "Pt@g-C3N4/CeO2 photocatalyst for the remediation of low concentration NOx at room temperature", 《PROGRESS IN NATURAL SCIENCE: MATERIALS INTERNATIONAL》 *

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