CN110841679A - Flexible load type N-WO3/Ce2S3Photocatalyst and preparation method thereof - Google Patents

Flexible load type N-WO3/Ce2S3Photocatalyst and preparation method thereof Download PDF

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CN110841679A
CN110841679A CN201911037011.6A CN201911037011A CN110841679A CN 110841679 A CN110841679 A CN 110841679A CN 201911037011 A CN201911037011 A CN 201911037011A CN 110841679 A CN110841679 A CN 110841679A
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carbon fiber
nano
fiber fabric
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黄勇潮
郭忠杰
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Guangzhou University
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/24—Nitrogen compounds
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
    • B01J35/58—Fabrics or filaments
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam

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Abstract

The invention discloses a flexible load type N-WO3/Ce2S3A photocatalyst and a preparation method thereof. Flexible load type N-WO of the invention3/Ce2S3The photocatalyst consists of carbon fiber fabric and nano N-WO supported on the carbon fiber fabric3And nano Ce2S3The preparation method comprises the following steps: 1) mixing the nano WO3Loading on carbon fiber fabric to obtain nanometer WO3A loaded carbon fiber fabric; 2) mixing the nano WO3Conversion to nano-N-WO3To obtain nano N-WO3A loaded carbon fiber fabric; 3) nano Ce2S3Loading on carbon fiber fabric to obtain nano N-WO3And nano Ce2S3A loaded carbon fiber fabric. Flexible load type N-WO of the invention3/Ce2S3The photocatalyst has excellent photocatalytic performance, is convenient to recover, is suitable for reactors with different shapes, has a simple preparation process and easily-obtained raw materials, and is suitable for large-scale production and application.

Description

Flexible load type N-WO3/Ce2S3Photocatalyst and preparation method thereof
Technical Field
The invention relates to a flexible load type N-WO3/Ce2S3A photocatalyst and a preparation method thereof, belonging to the technical field of photocatalysis.
Background
The semiconductor photocatalysis has the advantages of simple operation, high efficiency, low energy consumption and the like, and has wide application prospect in the aspect of restoring environmental pollution (for example, removing organic pollutants in the environment). However, the conventional semiconductor photocatalyst is in a powder shape, and generally has the problems of high carrier recombination rate, low light energy utilization efficiency, low light energy conversion efficiency and the like, and also has the problems of high separation and recovery difficulty, high cost, secondary environmental pollution and the like, so that the requirements of practical application cannot be well met.
In recent years, supported semiconductor photocatalysts become a hot point of research, researchers develop some supported semiconductor photocatalysts, but the existing supported semiconductor photocatalysts are supported and fixed on a rigid surface (such as a glass drill, a glass slide, a glass reactor, stainless steel and the like), are limited in practical application (for example, are not beneficial to being installed in reactors with different shapes), and have common practical use effects.
Therefore, there is a need to develop a flexible supported photocatalyst which has excellent photocatalytic performance, is convenient to recover and is suitable for reactors with different shapes.
Disclosure of Invention
The invention aims to provide a flexible load type N-WO3/Ce2S3A photocatalyst and a preparation method thereof.
The technical scheme adopted by the invention is as follows:
flexible load type N-WO3/Ce2S3The photocatalyst consists of carbon fiber fabric and nano N-WO supported on the carbon fiber fabric3And nano Ce2S3And (4) forming.
The flexible load type N-WO3/Ce2S3The preparation method of the photocatalyst comprises the following steps:
1) mixing Na2WO4·2H2Dissolving O and NaCl in water to obtain a mixed solution, adjusting the pH value of the mixed solution to 1-3, adding the mixed solution and the carbon fiber fabric into a reaction kettle, carrying out hydrothermal reaction, and separating out the carbon fiber fabricWashing, drying and annealing the material to obtain the nano WO3A loaded carbon fiber fabric;
2) mixing the nano WO3The loaded carbon fiber fabric is placed in ammonia atmosphere for annealing to obtain the nano N-WO3A loaded carbon fiber fabric;
3) adding Ce (NO)3)3Dissolving hexamethylenetetramine and thioacetamide in ethanol solution to obtain mixed solution, and adding nano N-WO3Fully reacting the loaded carbon fiber fabric, separating the carbon fiber fabric, washing and drying to obtain the nano N-WO3And nano Ce2S3Loaded carbon fibre fabrics, i.e. flexible loaded N-WO3/Ce2S3A photocatalyst.
Preferably, said Na of step 1)2WO4·2H2O, NaCl is in a molar ratio of 1: (4.5-5.0).
Preferably, said Na of step 1)2WO4·2H2The mass-volume ratio of O to water is 1 g: (20-40) mL.
Preferably, hydrochloric acid with the concentration of 2-4 mol/L is adopted in the step 1) to adjust the pH value of the mixed solution.
Preferably, the size specification of the carbon fiber fabric in the step 1) is (2-4) cm x (3-5) cm.
Preferably, the hydrothermal reaction in the step 1) is carried out at 170-190 ℃, and the reaction time is 20-30 h.
Preferably, the drying in step 1) is carried out at 50-70 ℃.
Preferably, the annealing in the step 1) is carried out at 400-500 ℃, and the annealing time is 0.5-1.5 h.
Preferably, the annealing in the step 2) is carried out at 300-500 ℃, and the annealing time is 0.5-1.5 h.
Preferably, the flow rate of the ammonia gas in the step 2) is 180-220 sccm.
Preferably, step 3) said Ce (NO)3)3The molar ratio of the hexamethylene tetramine to the thioacetamide is (3-5): (1-3): 1.
preferably, the volume ratio of ethanol to water in the ethanol solution in the step 3) is 1: 1.
Preferably, the concentration of thioacetamide in the mixed solution of step 3) is 4 × 10-3～6×10-3mol/L。
Preferably, the reaction in the step 3) is carried out at 70-80 ℃, and the reaction time is 8-15 h.
Preferably, the drying in the step 3) is carried out at 50-70 ℃.
The invention has the beneficial effects that: flexible load type N-WO of the invention3/Ce2S3The photocatalyst has excellent photocatalytic performance, is convenient to recover, is suitable for reactors with different shapes, has a simple preparation process and easily-obtained raw materials, and is suitable for large-scale production and application.
1) Flexible load type N-WO of the invention3/Ce2S3The photocatalyst has a three-dimensional layered structure and a large reaction area, can provide a larger interface area and a shorter diffusion path for a photon-generated carrier, and can further show excellent photocatalytic performance;
2) flexible load type N-WO of the invention3/Ce2S3WO in photocatalyst3And Ce2S3Can form a z-type heterostructure and is beneficial to WO3Photoinduced electron transport in conduction band and with Ce2S3The holes in the valence band are combined, so that the recombination of photon-generated carriers can be effectively hindered, and the catalytic efficiency of organic pollutant degradation is improved;
3) flexible load type N-WO of the invention3/Ce2S3The photocatalyst is convenient to separate and recover, so that the practical application cost can be reduced, and secondary environmental pollution cannot be caused;
4) flexible load type N-WO of the invention3/Ce2S3The photocatalyst takes carbon fiber fabric as a carrier, has good flexibility and is easy to be arranged in reactors with different shapes.
Drawings
FIG. 1 shows N-WO3SEM image of (d).
FIG. 2 shows N-WO3/Ce2S3SEM image of (d).
FIG. 3 shows N-WO3/Ce2S3A TEM image of (a).
FIG. 4 shows N-WO3/Ce2S3EDS element distribution map of.
FIG. 5 shows WO3、N-WO3And N-WO3/Ce2S3XRD pattern of (a).
FIG. 6 is WO3、N-WO3And N-WO3/Ce2S3High resolution W4f XPS spectra.
FIG. 7 is WO3、N-WO3And N-WO3/Ce2S3High resolution N1s XPS spectra.
FIG. 8 shows N-WO3/Ce2S3High resolution Ce 3d XPS spectra.
FIG. 9 shows N-WO3/Ce2S3High resolution S2 p XPS spectra of (a).
FIG. 10 shows WO3、N-WO3、N-WO3/Ce2S3And N-WO3/Ce2S3The formaldehyde degradation effect test result.
FIG. 11 shows N-WO3/Ce2S3The photocatalytic degradation stability test result.
FIG. 12 shows N-WO3/Ce2S3In N2、O2And the result of the photocatalytic degradation performance test on HCHO under the air condition.
FIG. 13 shows N-WO3/Ce2S3The results of the photocatalytic degradation performance test on HCHO in normal and bent states.
FIG. 14 shows WO3、N-WO3And N-WO3/Ce2S3The phenol degradation effect test result.
FIG. 15 shows WO3、N-WO3And N-WO3/Ce2S3And (5) simulating a first order reaction kinetic constant test result.
FIG. 16 is WO3、N-WO3And N-WO3/Ce2S3Test results for TOC degradation effect.
FIG. 17 shows WO3、N-WO3And N-WO3/Ce2S3And testing the photocatalytic degradation stability of phenol.
FIG. 18 is WO3、N-WO3And N-WO3/Ce2S3Electron spin resonance spectroscopy (low intensity).
FIG. 19 is WO3、N-WO3And N-WO3/Ce2S3Electron spin resonance spectroscopy (high intensity).
FIG. 20 shows WO3、N-WO3And N-WO3/Ce2S3EIS map of (a).
FIG. 21 is WO3、N-WO3And N-WO3/Ce2S3The photocurrent response test results.
FIG. 22 shows WO3、N-WO3And N-WO3/Ce2S3The photoluminescence test results of (a).
FIG. 23 is WO3、N-WO3And N-WO3/Ce2S3Time resolved photoluminescence spectroscopy test results.
FIG. 24 is WO3、N-WO3And N-WO3/Ce2S3The ultraviolet-visible diffuse reflection spectrum test result.
FIG. 25 shows WO3、N-WO3And N-WO3/Ce2S3The ultraviolet-visible diffuse reflection spectrum of (a) to (b).
FIG. 26 is WO3、N-WO3And N-WO3/Ce2S3The result of the density of states calculation.
FIG. 27 shows WO3、N-WO3And N-WO3/Ce2S3The charge redistribution calculation result of (1).
FIG. 28 shows N-WO3/Ce2S3Schematic diagram of the Z-type heterojunction charge separation and migration process.
FIG. 29 shows WO3、N-WO3-300、N-WO3400 and N-WO3-500 photocatalytic degradation performance test results on HCHO.
Detailed Description
The invention will be further explained and illustrated with reference to specific examples.
Example 1:
flexible load type N-WO3/Ce2S3The preparation method of the photocatalyst comprises the following steps:
1) 1.056g of Na2WO4·2H2Dissolving O and 0.9g NaCl in 30mL of water, stirring for 0.5h to prepare a mixed solution, adjusting the pH value of the mixed solution to 2 by using hydrochloric acid with the concentration of 3mol/L, stirring for 3h, adding the mixed solution and carbon fiber fabrics (the size specification: 3cm multiplied by 4cm) into an autoclave (the lining: polytetrafluoroethylene), reacting for 24h at 180 ℃, separating out the carbon fiber fabrics, washing with water, drying at 60 ℃ and annealing at 450 ℃ for 1h to obtain the nano WO3Supported carbon fiber fabrics (abbreviated as "WO)3”)；
2) Mixing the nano WO3Placing the loaded carbon fiber fabric in an ammonia gas atmosphere (pure ammonia, the flow rate is 200sccm), and annealing at 400 ℃ for 1h to obtain the nano N-WO3Supported carbon fiber fabrics (abbreviated as "N-WO)3”)；
3) Adding Ce (NO)3)3Adding hexamethylenetetramine and thioacetamide into an ethanol solution (the volume ratio of ethanol to water is 1:1) to prepare Ce (NO)3)3The concentration is 2X 10-2mol/L, the concentration of hexamethylene tetramine is 8 multiplied by 10-2mol/L, thioacetamide concentration 5X 10-3Adding the mixed solution of mol/L and then adding nano N-WO3Reacting the loaded carbon fiber fabric for 12 hours at 75 ℃, separating the carbon fiber fabric, washing with water and drying at 60 ℃ to obtain the nano N-WO3And nano Ce2S3Loaded carbon fibre fabrics, i.e. flexible loaded N-WO3/Ce2S3Photocatalyst (abbreviated as' N-WO3/Ce2S3”)。
And (3) performance testing:
N-WO3(i.e. nano)Rice N-WO3A loaded carbon fiber fabric) is shown in fig. 1.
As can be seen from fig. 1: many voids are generated in the carbon nanotubes in the carbon fiber fabric.
N-WO3/Ce2S3(i.e., flexible load type N-WO)3/Ce2S3Photocatalyst) is shown in fig. 2, a TEM is shown in fig. 3, and an EDS elemental distribution is shown in fig. 4.
As can be seen from fig. 2: ce2S3Well grown in N-WO3Description of N-WO3Surface coating Ce2S3And (4) covering the nanodots.
As can be seen from fig. 3: ce2S3And N-WO3Are combined together.
As can be seen from fig. 4: N-WO3/Ce2S3N, W, O, Ce and S are present.
WO3、N-WO3And N-WO3/Ce2S3The XRD pattern of (A) is shown in FIG. 5, the high resolution W4f XPS spectrum is shown in FIG. 6, and the high resolution N1s XPS spectrum is shown in FIG. 7.
As can be seen from fig. 5: in the figure there is WO3Diffraction peak of (3) and Ce2S3Shows that Ce is successfully constructed2S3Modified N-WO3A heterostructure.
As can be seen from fig. 6: N-WO3/Ce2S3The W4f peak of (a) was shifted to lower binding energies, indicating that the bonding environment of W was changed.
As can be seen from fig. 7: only N-WO3And N-WO3/Ce2S3The existence of N can be detected in the photocatalyst, which indicates that N is successfully doped into N-WO3And N-WO3/Ce2S3In (1).
N-WO3/Ce2S3The high-resolution Ce 3d XPS spectrum of (a) is shown in fig. 8, and the high-resolution S2 p XPS spectrum is shown in fig. 9.
As can be seen from fig. 8 and 9: ce2S3Is coated on WO3The above.
WO3、N-WO3、N-WO3/Ce2S3(Nano N-WO)3And nano Ce2S3Simple combination of) and N-WO3/Ce2S3The results of the formaldehyde degradation effect test are shown in fig. 10.
As can be seen from fig. 10: under the irradiation of visible light, pure WO3After 120min, 40% of HCHO can be removed through NH3After gas treatment, the photocatalytic activity of the catalyst is obviously improved, which shows that the photocatalytic performance can be improved by proper amount of N doping; WO3/Ce2S3The photocatalytic performance of the photocatalyst is superior to that of pure WO3The heterostructure can improve the photocatalytic performance; under visible light irradiation, N-WO3/Ce2S3Can completely degrade HCHO after 80min, and has the photocatalytic activity about that of the original WO33 times of the total weight of the product.
N-WO3/Ce2S3The photocatalytic degradation stability test results of (1) are shown in fig. 11.
As can be seen from fig. 11: N-WO3/Ce2S3The excellent performance stability was demonstrated in a 5 cycle test.
N-WO3/Ce2S3In N2、O2And the results of the photocatalytic degradation performance test on HCHO under air conditions are shown in fig. 12.
As can be seen from fig. 12: N-WO3/Ce2S3The performance varies greatly under different gas environments, at O2Higher performance in gas than N2Gas, description of O2Plays an important role in the photocatalytic degradation of HCHO.
N-WO3/Ce2S3The results of the photocatalytic degradation performance test on HCHO in normal and bent states are shown in fig. 13.
As can be seen from fig. 13: N-WO3/Ce2S3The photocatalytic performance in the normal and bent states is substantially the same, indicating that N-WO3/Ce2S3Is a good flexible photocatalyst.
WO3、N-WO3And N-WO3/Ce2S3The test results of the phenol degradation effect of (2) are shown in fig. 14.
As can be seen from fig. 14: WO3、N-WO3And N-WO3/Ce2S3The adsorption capacity to phenol is good, which shows that the supported structure can provide larger surface area; under visible light irradiation, N-WO3/Ce2S3Complete degradation of phenol after 120min, and WO3The degradation rate of phenol is only 50 percent, which shows the doping of N and Ce2S3Can effectively improve WO3Photocatalytic activity of (1).
WO3、N-WO3And N-WO3/Ce2S3The results of the first order reaction kinetics constants test are shown in FIG. 15.
As can be seen from fig. 15: WO3、N-WO3And N-WO3/Ce2S3The pseudo first-order reaction kinetic constants are respectively 0.0026min-1、0.012min-1And 0.045min-1。
WO3、N-WO3And N-WO3/Ce2S3The results of the TOC degradation effect test are shown in fig. 16.
As can be seen from fig. 16: WO3、N-WO3And N-WO3/Ce2S3The COD removal rates for phenol were 32%, 45% and 94%, respectively, indicating that most of the phenol was completely converted to CO during the degradation process2And H2O。
WO3、N-WO3And N-WO3/Ce2S3The test results of the photocatalytic degradation stability test on phenol are shown in fig. 17.
As can be seen from fig. 17: N-WO3/Ce2S3The excellent performance stability was demonstrated in a 5 cycle test.
WO3、N-WO3And N-WO3/Ce2S3The electron spin resonance spectrum is shown in fig. 18 and 19.
As can be seen from FIGS. 18 and 19：N-WO3/Ce2S3The peak intensity of (A) is far higher than that of WO3And N-WO3Description of N-WO3/Ce2S3More O can be generated in the photocatalysis process2-(ii) a The ESR result for the DMPO-and. OH adduct has four peaks, typical of. OH; N-WO3/Ce2S3The peak intensity of (A) is far higher than that of WO3And N-WO3Description of N-WO3/Ce2S3More OH can be generated in the photocatalysis process.
WO3、N-WO3And N-WO3/Ce2S3The EIS map of (A) is shown in FIG. 20.
As can be seen from fig. 20: N-WO3/Ce2S3Arc ratio of WO3And N-WO3Smaller, which indicates a higher separation efficiency of photogenerated carriers; enhanced charge separation and migration significantly improves N-WO3/Ce2S3Photocatalytic properties of the heterostructure.
WO3、N-WO3And N-WO3/Ce2S3The photocurrent response test results of (a) are shown in fig. 21.
As can be seen from fig. 21: N-WO3/Ce2S3The photocurrent density of (a) is the greatest, indicating that three-dimensional heterostructures have inherent advantages in facilitating photon-generated carrier separation.
WO3、N-WO3And N-WO3/Ce2S3The photoluminescence test results of (a) are shown in fig. 22.
As can be seen from fig. 22: N-WO3/Ce2S3The photoluminescence spectral intensity of the compound is far lower than that of WO3And N-WO3Description of N-WO3/Ce2S3The heterostructure has strong charge separation and migration capability.
WO3、N-WO3And N-WO3/Ce2S3The results of the time-resolved photoluminescence spectroscopy test are shown in fig. 23.
As can be seen from fig. 23: N-WO3/Ce2S3(17ns) ratio WO3(8ns) and N-WO3The lifetime of (12ns) is longer, which indicates that the heterostructure can improve the separation efficiency of the photoinduced carrier.
WO3、N-WO3And N-WO3/Ce2S3The test results of the ultraviolet-visible diffuse reflectance spectrum of (a) are shown in fig. 24.
As can be seen from fig. 24: N-WO3/Ce2S3The absorption edge of (A) is shifted to longer wavelength and the absorption intensity is higher than that of N-WO3Enhancement of N-WO3Bound Ce2S3After that, the absorption of light is enhanced.
WO3、N-WO3And N-WO3/Ce2S3The optical bandgap test results determined by the uv-vis diffuse reflectance spectrum of (a) are shown in fig. 25.
As can be seen from fig. 25: WO3、N-WO3And N-WO3/Ce2S3Have band gaps of 2.6eV, 2.1eV and 1.6eV, respectively, indicating that N-WO3Bound Ce2S3The back band gap decreases, increasing the separation of electron-hole pairs.
WO3、N-WO3And N-WO3/Ce2S3The result of the state density calculation of (2) is shown in fig. 26.
As can be seen from fig. 26: WO3、N-WO3And N-WO3/Ce2S3The calculated result of the density of states is basically consistent with the experimental result.
WO3、N-WO3And N-WO3/Ce2S3The charge redistribution (DFT) calculation result of (2) is shown in fig. 27.
As can be seen from fig. 27: compared with the original WO3And Ce2S3The positive charge of W decreases, the positive charge of Ce increases, and the negative charge of O decreases. The results show that N-WO3And Ce2S3The electronic interaction between the samples is advantageous for enhancing WO3Can improve the photocatalytic performance.
N-WO3/Ce2S3The Z-type heterojunction charge separation and migration process is schematically shown asAs shown in fig. 28.
As can be seen from fig. 28: WO3Photoinduced electron transport in conduction band and with Ce2S3Hole bonding in valence band to Ce2S3The remaining electrons in the CBM of (1) and WO3The remaining holes in the VBM of (1) are well separated from each other.
Example 2:
flexible load type N-WO3/Ce2S3The preparation method of the photocatalyst comprises the following steps:
1) 1.056g of Na2WO4·2H2Dissolving O and 0.9g NaCl in 30mL of water, stirring for 0.5h to prepare a mixed solution, adjusting the pH value of the mixed solution to 2 by using hydrochloric acid with the concentration of 3mol/L, stirring for 3h, adding the mixed solution and carbon fiber fabrics (the size specification: 3cm multiplied by 4cm) into an autoclave (the lining: polytetrafluoroethylene), reacting for 24h at 180 ℃, separating out the carbon fiber fabrics, washing with water, drying at 60 ℃ and annealing at 450 ℃ for 1h to obtain the nano WO3A loaded carbon fiber fabric;
2) mixing the nano WO3Placing the loaded carbon fiber fabric in an ammonia gas atmosphere (pure ammonia, the flow rate is 200sccm), and annealing at 300 ℃ for 1h to obtain the nano N-WO3A loaded carbon fiber fabric;
3) adding Ce (NO)3)3Adding hexamethylenetetramine and thioacetamide into an ethanol solution (the volume ratio of ethanol to water is 1:1) to prepare Ce (NO)3)3The concentration is 2X 10-2mol/L, the concentration of hexamethylene tetramine is 8 multiplied by 10-2mol/L, thioacetamide concentration 5X 10-3Adding the mixed solution of mol/L and then adding nano N-WO3Reacting the loaded carbon fiber fabric for 12 hours at 75 ℃, separating the carbon fiber fabric, washing with water and drying at 60 ℃ to obtain the nano N-WO3And nano Ce2S3Loaded carbon fibre fabrics, i.e. flexible loaded N-WO3/Ce2S3Photocatalyst (abbreviated as' N-WO3/Ce2S3”)。
Through testing, the prepared flexible load type N-WO3/Ce2S3Photocatalyst and the photocatalyst of example 1Sex-loaded N-WO3/Ce2S3The photocatalyst has equivalent performance and excellent performance.
Example 3:
flexible load type N-WO3/Ce2S3The preparation method of the photocatalyst comprises the following steps:
1) 1.056g of Na2WO4·2H2Dissolving O and 0.9g NaCl in 30mL of water, stirring for 0.5h to prepare a mixed solution, adjusting the pH value of the mixed solution to 2 by using hydrochloric acid with the concentration of 3mol/L, stirring for 3h, adding the mixed solution and carbon fiber fabrics (the size specification: 3cm multiplied by 4cm) into an autoclave (the lining: polytetrafluoroethylene), reacting for 24h at 180 ℃, separating out the carbon fiber fabrics, washing with water, drying at 60 ℃ and annealing at 450 ℃ for 1h to obtain the nano WO3A loaded carbon fiber fabric;
2) mixing the nano WO3Placing the loaded carbon fiber fabric in an ammonia gas atmosphere (pure ammonia, the flow rate is 200sccm), and annealing at 500 ℃ for 1h to obtain the nano N-WO3A loaded carbon fiber fabric;
3) adding Ce (NO)3)3Adding hexamethylenetetramine and thioacetamide into an ethanol solution (the volume ratio of ethanol to water is 1:1) to prepare Ce (NO)3)3The concentration is 2X 10-2mol/L, the concentration of hexamethylene tetramine is 8 multiplied by 10-2mol/L, thioacetamide concentration 5X 10-3Adding the mixed solution of mol/L and then adding nano N-WO3Reacting the loaded carbon fiber fabric for 12 hours at 75 ℃, separating the carbon fiber fabric, washing with water and drying at 60 ℃ to obtain the nano N-WO3And nano Ce2S3Loaded carbon fibre fabrics, i.e. flexible loaded N-WO3/Ce2S3Photocatalyst (abbreviated as' N-WO3/Ce2S3”)。
Through testing, the prepared flexible load type N-WO3/Ce2S3Photocatalyst and Flexible Supported N-WO of example 13/Ce2S3The photocatalyst has equivalent performance and excellent performance.
And (3) performance testing:
WO3(i.e., nano WO)3Loaded carbon fiber fabrics), N-WO3300 (i.e.the nano N-WO in example 2)3Loaded carbon fiber fabrics), N-WO3400 (i.e.the nano N-WO of example 1)3Loaded carbon fiber fabrics) and N-WO3500 (i.e.NanoN-WO in example 3)3Supported carbon fiber fabric) for HCHO the results of the photocatalytic degradation performance test are shown in fig. 29.
As can be seen from fig. 29: WO3By passing over NH3After treatment, the photocatalytic activity is obviously improved, the treatment temperature of 400 ℃ is optimal, and the obtained catalyst has the best performance.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. Flexible load type N-WO3/Ce2S3A photocatalyst, characterized in that: consists of a carbon fiber fabric and nano N-WO loaded on the carbon fiber fabric3And nano Ce2S3And (4) forming.
2. The flexibly supported N-WO of claim 13/Ce2S3The preparation method of the photocatalyst is characterized by comprising the following steps: the method comprises the following steps:
1) mixing Na2WO4·2H2Dissolving O and NaCl in water to obtain a mixed solution, adjusting the pH value of the mixed solution to 1-3, adding the mixed solution and the carbon fiber fabric into a reaction kettle, carrying out hydrothermal reaction, separating out the carbon fiber fabric, washing, drying and annealing to obtain the nano WO3A loaded carbon fiber fabric;
2) mixing the nano WO3The loaded carbon fiber fabric is placed in ammonia atmosphere for annealing to obtain the nano N-WO3A loaded carbon fiber fabric;
3) will be provided withCe(NO3)3Dissolving hexamethylenetetramine and thioacetamide in ethanol solution to obtain mixed solution, and adding nano N-WO3Fully reacting the loaded carbon fiber fabric, separating the carbon fiber fabric, washing and drying to obtain the nano N-WO3And nano Ce2S3Loaded carbon fibre fabrics, i.e. flexible loaded N-WO3/Ce2S3A photocatalyst.
3. The method of claim 2, wherein: step 1) said Na2WO4·2H2O, NaCl is in a molar ratio of 1: (4.5-5.0).
4. The production method according to claim 2 or 3, characterized in that: step 1) said Na2WO4·2H2The mass-volume ratio of O to water is 1 g: (20-40) mL.
5. The production method according to claim 2 or 3, characterized in that: the size specification of the carbon fiber fabric in the step 1) is (2-4) cm x (3-5) cm.
6. The production method according to claim 2 or 3, characterized in that: the hydrothermal reaction in the step 1) is carried out at 170-190 ℃, and the reaction time is 20-30 h.
7. The production method according to claim 2 or 3, characterized in that: the annealing in the step 1) is carried out at 400-500 ℃, and the annealing time is 0.5-1.5 h; and 2) annealing at 300-500 ℃ for 0.5-1.5 h.
8. The method of claim 2, wherein: step 3) said Ce (NO)3)3The molar ratio of the hexamethylene tetramine to the thioacetamide is (3-5): (1-3): 1.
9. according to claim 2 or 3 orThe preparation method is characterized by comprising the following steps: the concentration of thioacetamide in the mixed solution in the step 3) is 4 multiplied by 10-3～6×10-3mol/L。
10. The production method according to claim 2, 3 or 8, characterized in that: and 3) carrying out the reaction at 70-80 ℃ for 8-15 h.
CN201911037011.6A 2019-10-29 2019-10-29 Flexible load type N-WO3/Ce2S3Photocatalyst and preparation method thereof Pending CN110841679A (en)

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