CN110064437B - Surface-regularly-loaded Ag/BiOBr nanosheet cellulose-based fabric and preparation and application thereof - Google Patents

Surface-regularly-loaded Ag/BiOBr nanosheet cellulose-based fabric and preparation and application thereof Download PDF

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CN110064437B
CN110064437B CN201910279868.2A CN201910279868A CN110064437B CN 110064437 B CN110064437 B CN 110064437B CN 201910279868 A CN201910279868 A CN 201910279868A CN 110064437 B CN110064437 B CN 110064437B
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biobr
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徐红
周培文
毛志平
吕景春
王雅梅
张琳萍
陈支泽
钟毅
隋晓锋
王碧佳
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Donghua University
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J31/00Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • BPERFORMING OPERATIONS; TRANSPORTING
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    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
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    • B01J35/30Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/306Pesticides
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/308Dyes; Colorants; Fluorescent agents
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
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    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/38Organic compounds containing nitrogen
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/10Photocatalysts

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Abstract

The invention relates to a surface-regularly-loaded Ag/BiOBr nano-sheet cellulose-based fabric and preparation and application thereof.

Description

Surface-regularly-loaded Ag/BiOBr nanosheet cellulose-based fabric and preparation and application thereof
Technical Field
The invention belongs to the field of photocatalytic materials and preparation and application thereof, and particularly relates to a surface-regularly-loaded Ag/BiOBr nanosheet cellulose-based fabric and preparation and application thereof.
Background
With the rapid development of industry, the purification treatment of organic pollutants (dyes, antibiotics, chemical pesticides) and pathogenic bacteria in industrial sewage is a troublesome concern. In recent years, semiconductor photocatalysis technology is considered to be an effective way for removing organic pollutants, but because traditional photocatalysts such as titanium dioxide, zinc oxide, cadmium sulfide and the like have the problems of wide forbidden bandwidth, high recombination rate of photon-generated carriers and the like, the application of the traditional photocatalysts in the aspects of environment and energy is greatly limited. Meanwhile, in the practical application process, the photocatalyst is often suspended in the wastewater in the form of solid particles, the recovery and separation process of the photocatalyst after the pollutant treatment is finished is time-consuming and labor-consuming, and the photocatalyst powder inevitably has partial loss in the recovery process. Therefore, the activity of the photocatalyst is improved, and a proper loading method is selected, so that the method has practical significance for the effective utilization of the photocatalyst.
In the aspect of improving the activity of the photocatalyst, researchers mainly improve the photocatalytic efficiency from three directions of constructing a heterogeneous photocatalytic system, modifying a carbon-based material and modifying the surface of a metal nanoparticle: (1) the heterogeneous photocatalytic system is a heterogeneous structure formed by utilizing various semiconductor photocatalysts of different types, and according to the forbidden band structure and the electronic energy level of a semiconductor, the multi-component semiconductor heterogeneous photocatalytic system can be divided into five types, including: an energy band spanning heterostructure, an energy band alternating heterostructure, a p-n heterojunction structure, a homojunction structure and a Z-type heterostructure; (2) carbon-based material modification is generally to compound a carbon material with better electron conduction and transfer performance with a photocatalyst, and a photogenerated electron on a semiconductor conduction band can be rapidly transferred to the carbon-based material, so that separation of the photogenerated electron and a hole is promoted, and current research focuses on two types of carbon-based materials, namely Graphene (Graphene) and Carbon Quantum Dots (CQDs); (3) the metal nanoparticle surface modification mainly utilizes the characteristic that the Fermi level of the metal nanoparticle is generally lower than that of a semiconductor photocatalyst, and promotes the migration of photo-generated electrons of the semiconductor photocatalyst to the metal nanoparticle through Schottky contact. The modification mode usually adopts rare noble metals such as Pt, Pd, Au, Ag, Rh and the like to deposit on the surface of the photocatalyst, and compared with the construction of a heterogeneous photocatalytic system and the modification of a carbon-based material, the surface modification of the metal nanoparticles has the characteristics of simple method and obvious improvement efficiency.
In terms of the loading of the photocatalyst, various techniques have been invented, such as a thermal sintering method, a sol-gel method, a magnetron sputtering method, a chemical vapor deposition method, a liquid phase deposition method, an electrochemical deposition method, and the like. The thermal sintering method is relatively simple to operate, and the carrier is required to have certain temperature resistance. The sol-gel method is suitable for various carrier materials, and has low cost but poor appearance regularity. The magnetron sputtering method provides an effective way for loading the photocatalyst at low temperature, is suitable for glass and organic polymer carriers, and the photocatalyst loaded by the method has small particles and uniform particle size distribution, but needs special treatment equipment. The chemical vapor deposition method is also a method by which a photocatalyst can be deposited on any support in a short period of time, and the photocatalyst prepared by the method has a relatively high purity but requires high equipment.
CN101850263A discloses an Ag-doped BiOBr catalytic material, a preparation method and application thereof, the Ag-doped BiOBr nanosheet prepared by the patent is large and uneven in shape, reaction liquid needs to be stirred continuously in the catalytic process, agglomeration is easy to occur, and the catalyst is difficult to recover and recycle.
Disclosure of Invention
The invention aims to solve the technical problem of providing a surface-regularly-loaded Ag/BiOBr nanosheet cellulose-based fabric and preparation and application thereof, effectively solving the problems of dispersion and recycling of a nano catalyst and remarkably improving the catalytic efficiency and recycling performance of the BiOBr nanosheet.
The invention discloses a preparation method of an Ag/BiOBr nano sheet loaded cellulose-based fabric, which comprises the following steps:
(1) performing carboxylation modification on the surface of the cellulose fabric to obtain carboxymethylation modified cellulose fabric CMF;
(2) carboxymethylated fibresThe method for assembling BiOBr on CMF by using the cellulose fabric as a carrier and adopting an ion layer-by-layer adsorption method comprises the following steps: soaking the CMF in a bismuth nitrate aqueous solution for 10-120 s at room temperature, taking out and cleaning the CMF with ultrapure water until no Bi exists2O2 2+Dropping, soaking the membrane in a bromide ion solution for 10-120 s, finally, cleaning the CMF by using ultrapure water to prevent bromide ions from dropping, circulating the operation, washing and drying to obtain BiOBr-CMF;
(3) and soaking the BiOBr-CMF in a silver nitrate solution, and then carrying out photoreduction, washing and drying to obtain the Ag/BiOBr nanosheet cellulose-based fabric.
The preferred mode of the above preparation method is as follows:
the cellulose fabric in the step (1) is one of cotton fabric, viscose fabric and hemp fabric.
The step (1) of performing carboxylation modification on the surface of the cellulose fabric specifically comprises the following steps: adding a cellulose fabric into a sodium hydroxide solution, carrying out an alkalization reaction, adding chloroacetic acid after the alkalization is finished, heating to an etherification temperature for reaction, cooling to room temperature after the reaction is finished, adjusting the reaction to a pH value of 7-8, fishing out the fabric, washing with water, and drying; wherein the mass ratio of the chloroacetic acid to the cellulose-based fabric is 0.1-1: 1.
The mass fraction of the sodium hydroxide solution is 1-10%; the solvent of the sodium hydroxide solution is ethanol water solution with the mass fraction of 70-90%.
The alkalization reaction is as follows: alkalizing reaction for 10-60 min at 10-30 ℃; and (3) reaction at the etherification temperature: the etherification temperature is 50-70 ℃, and the reaction time is 60-300 min.
The reagent used for adjusting the pH to 7-8 is one of hydrochloric acid, sulfuric acid and nitric acid.
The drying is drying at 80 ℃.
And (3) the room temperature in the step (2) is 20-25 ℃.
The concentration of the bismuth nitrate aqueous solution in the step (2) is 0.5-10 mmol/L; the concentration of the bromide ion solution is 0.5-10 mmol/L.
The bromide ion solution is one of potassium bromide or sodium bromide.
The cycle number in the step (2) is 10-60.
The washing in the step (2) is water washing and ethanol washing; the drying is carried out at the temperature of 80 ℃.
The concentration of the silver nitrate solution in the step (3) is 0.2-3 g/L.
In the step (3), the photoreduction is as follows: the ultraviolet wavelength is 235nm, and the photoreduction time is 1-60 min.
The washing in the step (3) is water washing and ethanol washing; the drying is carried out at the temperature of 80 ℃.
The Ag/BiOBr nanosheet cellulose-based fabric prepared by the method is provided.
The invention provides application of the Ag/BiOBr nano sheet loaded cellulose-based fabric in photodegradation of organic pollutants in sewage.
The light degradation is carried out by using sunlight or a xenon lamp as a light source.
The organic pollutants are one or more of dyes, antibiotics and pesticides, and the concentration of degradation products is 1-200 mg/L.
According to the invention, the BiOBr nano-sheets are assembled on the surface of the carboxylated modified cellulose-based fabric layer by adopting ions, and the silver ions adsorbed on the surface of the BiOBr micro-sheets are reduced by ultraviolet light, so that the BiOBr nano-sheets modified by silver particles are constructed on the surface of the cellulose-based fabric, and the capability of degrading organic pollutants by visible light of the Ag/BiOBr nano-sheet cellulose fabric is obviously improved. Under the irradiation of a xenon lamp, the degradation rate (20mg/l) of rhodamine B can reach more than 99% in 90 minutes, and the degradation rate (20mg/l) of herbicide isoproturon reaches more than 95% in 180 minutes, and meanwhile, the composite fabric is convenient to recycle and good in catalytic stability, and can degrade more than 90% of rhodamine B in 180 minutes after 5 times of recycling.
The preparation method of the cellulose-based fabric loaded with the BiOBr nanosheets is simple, effective compounding of the silver particles and the BiOBr nanosheets is achieved, and catalytic degradation efficiency of the photocatalyst is remarkably improved.
Drawings
FIG. 1 is an XRD spectrum of CMF and BiOBr-CMF in example 1 and Ag/BiOBr-CMF in example 3; wherein the inset is a partial magnified view of Ag/BiOBr-CMF (S2);
FIGS. 2 (a) and (e) are digital photographs of BiOBr-CMF in example 1 and Ag/BiOBr-CMF in example 3 (S2), respectively, and (b-d) and (f-h) are field emission electron micrographs of BiOBr-CMF in example 1 and Ag/BiOBr-CMF in example 3 (S2), respectively;
FIG. 3 shows the UV diffuse reflectance absorption spectrum (a) and the fluorescence spectrum (b) of CMF, BiOBr-CMF in example 1 and Ag/BiOBr-CMF (S2) F in example 3;
FIG. 4 shows the test results of cyclic degradation of rhodamine B by Ag/BiOBr-CMF (S2) under irradiation of visible light
FIG. 5 is a high performance liquid chromatography of isoproturon degradation raffinate under visible light irradiation with Ag/BiOBr-CMF (S2) as a photocatalyst.
Detailed Description
The invention will be further illustrated with reference to the following specific examples. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention. Further, it should be understood that various changes or modifications of the present invention may be made by those skilled in the art after reading the teaching of the present invention, and such equivalents may fall within the scope of the present invention as defined in the appended claims.
Example 1
(1) Weighing 2g of sodium hydroxide, dissolving in 100g of ethanol water solution (mass fraction 85%), adding 2g of cotton fabric, transferring to a conical flask, shaking for 30min, adding 0.45g of chloroacetic acid, heating to 70 ℃, keeping the temperature for 3h, cooling to below 40 ℃, neutralizing, washing and drying to obtain the carboxymethyl modified cotton fabric (CMF), wherein the carboxyl content is 1.35 mmol/g.
(2) Soaking carboxymethylated cotton fabric in a bismuth nitrate aqueous solution with the concentration of 4mmol/L for 30s, fishing out and cleaning with ultrapure water, soaking the carboxymethylated cotton fabric in a potassium bromide solution with the concentration of 4mmol/L for 30s, finally cleaning with ultrapure water, circulating for 15 times according to the steps, washing with water and ethanol, and drying at 80 ℃ to obtain BiOBr-CMF.
(3) Photocatalytic activity characterization: taking the BiOBr-CMF (8cm multiplied by 8cm) prepared in the step (2), flatly paving the BiOBr-CMF in a square polyethylene box with the diameter of 9cm, respectively adding 50ml of solution containing 20mg/L rhodamine B and isoproturon, placing the solution in a BL-GHX-II type photochemical reaction instrument, taking a certain amount of reaction liquid at regular intervals under the irradiation of a 300W xenon lamp, analyzing the concentration of the rhodamine B degradation liquid by using a visible light spectrophotometer, and analyzing the concentration of the isoproturon degradation liquid by using liquid chromatography, wherein the result shows that: the degradation rate of rhodamine B is 77.5% (visible light irradiation for 90min), and the degradation rate of isoproturon is 70.5% (visible light irradiation for 180 min).
Example 2
(1) The BiOBr-CMF prepared in the example 1 is soaked in 200mL of silver nitrate solution with the concentration of 0.5g/L, is taken out after being shaken for 1 hour, is placed in a surface dish containing ultrapure water, the distance between the fabric and the liquid level is 1cm, and is irradiated for 1min by adopting an ultraviolet lamp with the luminous wavelength of 235nm, so that the Ag/BiOBr-CMF is obtained (S1).
(2) Photocatalytic activity characterization: adding the Ag/BiOBr-CMF prepared in the step (1) into a solution containing 50ml of 20mg/L rhodamine B and isoproturon respectively, placing the solution into a BL-GHX-II type photochemical reaction instrument, taking a certain amount of reaction liquid at regular intervals under the irradiation of a 300W xenon lamp, analyzing the concentration of the rhodamine B degradation liquid by using a visible light spectrophotometer, and analyzing the concentration of the isoproturon degradation liquid by using liquid chromatography, wherein the result shows that: the degradation rate of rhodamine B is 85.3% (visible light irradiation for 90min), and the degradation rate of isoproturon is 86.7% (visible light irradiation for 180 min).
Example 3
(1) The BiOBr-CMF prepared in the example 1 is soaked in 200ml of silver nitrate solution with the concentration of 1g/L, is taken out after being vibrated for 1 hour, is placed in a surface dish containing ultrapure water, the distance between the fabric and the liquid surface is 1cm, and an ultraviolet lamp with the light-emitting wavelength of 235nm is adopted for irradiation for 10min, so that the Ag/BiOBr-CMF is obtained (S2).
(2) Photocatalytic activity characterization: adding the Ag/BiOBr-CMF prepared in the step (1) into a solution containing 50ml of 20mg/L rhodamine B and isoproturon respectively, placing the solution into a BL-GHX-II type photochemical reaction instrument, taking a certain amount of reaction liquid at regular intervals under the irradiation of a 300W xenon lamp, analyzing the concentration of the rhodamine B degradation liquid by using a visible light spectrophotometer, and analyzing the concentration of the isoproturon degradation liquid by using liquid chromatography, wherein the result shows that: the degradation rate of rhodamine B is more than 99% (visible light irradiation for 90min), and the degradation rate of isoproturon is more than 95% (visible light irradiation for 180 min).
The XRD spectra of CMF and BiOBr-CMF in example 1 and Ag/BiOBr-CMF in example 3 are shown in FIG. 1, and the spectra show: the diffraction peak of the catalyst prepared by adopting the layer-by-layer self-assembly method and the photoreduction method is completely consistent with the BiOBr and Ag standard diffraction peak.
In the field emission electron microscope images of BiOBr-CMF in example 1 and Ag/BiOBr-CMF in example 3, as shown in FIG. 2, BiOBr is a nanosheet with a thickness of about 40nm as seen in FIG. 2(d), and the surface of the BiOBr nanosheet is full of small nanoparticles as seen in FIG. 2 (h).
The UV diffuse reflectance absorption spectra and fluorescence spectra of CMF, BiOBr-CMF in example 1 and Ag/BiOBr-CMF in example 3 are shown in FIG. 3. compared with BiOBr-CMF, Ag/BiOBr-CMF (S2) has stronger absorption in the visible light region and the photoluminescence intensity is also significantly reduced.
TABLE 1 comparison of the degradation rate of rhodamine B at 90min under visible light irradiation
Catalyst and process for preparing same Effective mass Degradation rate (rhodamine B)
TiO2 25mg 5%
BiOBr 25mg 60.5%
BiOBr-CMF 25mg 77.5%
Ag/BiOBr-CMF (photo-reduction 1min) 25mg 85.3%
Ag/BiOBr-CMF (photo-reduction 5min) 25mg 93.4%
Ag/BiOBr-CMF (photo-reduction 10min) 25mg >99%
Ag/BiOBr-CMF (photoreduction 20min) 25mg 97.2%
Note: BiOBr-CMF in Table 1 referring to example 1, the BiOBr-CMF in Table 1 was immersed in 1g/L silver nitrate solution and shaken for 1 hour, and then placed in a petri dish containing ultrapure water with the fabric being spaced from the liquid surface by 1cm, irradiated with an ultraviolet lamp having a luminescence wavelength of 235nm for 1min, 5min, 10min and 20min, respectively, to prepare different photo-reduced Ag/BiOBr-CMF samples.

Claims (10)

1. A preparation method of an Ag/BiOBr nanosheet cellulose-based fabric comprises the following steps:
(1) performing carboxylation modification on the surface of the cellulose fabric to obtain carboxymethylation modified cellulose fabric CMF;
(2) soaking the CMF in a bismuth nitrate aqueous solution for 10-120 s at room temperature, taking out and cleaning, soaking the CMF in a bromide ion solution for 10-120 s, cleaning again, circulating the above operation, washing and drying to obtain BiOBr-CMF;
(3) and soaking the BiOBr-CMF in a silver nitrate solution, and then carrying out photoreduction, washing and drying to obtain the Ag/BiOBr nanosheet cellulose-based fabric.
2. The preparation method according to claim 1, wherein the cellulose fabric in the step (1) is one of cotton fabric, viscose fabric and hemp fabric.
3. The preparation method according to claim 1, wherein the surface of the cellulose fabric is subjected to carboxylation modification in the step (1) specifically: adding a cellulose fabric into a sodium hydroxide solution, carrying out an alkalization reaction, adding chloroacetic acid after the alkalization is finished, heating to an etherification temperature for reaction, cooling to room temperature after the reaction is finished, adjusting the reaction to a pH value of 7-8, fishing out the fabric, washing with water, and drying; wherein the mass ratio of the chloroacetic acid to the cellulose-based fabric is 0.1-1: 1.
4. The preparation method according to claim 3, wherein the mass fraction of the sodium hydroxide solution is 1-10%; the solvent of the sodium hydroxide solution is ethanol water solution with the mass fraction of 70-90%.
5. The method according to claim 3, wherein the alkalization reaction is: alkalizing reaction for 10-60 min at 10-30 ℃; and (3) reaction at the etherification temperature: the etherification temperature is 50-70 ℃, and the reaction time is 60-300 min.
6. The preparation method according to claim 1, wherein the concentration of the aqueous bismuth nitrate solution in the step (2) is 0.5 to 10 mmol/L; the concentration of the bromide ion solution is 0.5-10 mmol/L.
7. The method according to claim 1, wherein the concentration of the silver nitrate solution in the step (3) is 0.2 to 3 g/L.
8. The method according to claim 1, wherein the photoreduction in the step (3) is: the ultraviolet wavelength is 235nm, and the photoreduction time is 1-60 min.
9. An Ag/BiOBr nanosheet cellulose-based fabric prepared by the method of claim 1.
10. Use of the Ag/BiOBr nanosheet loaded cellulose-based fabric of claim 9 in photodegradation of organic contaminants in sewage.
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CN101850263A (en) * 2010-06-17 2010-10-06 江西理工大学 Ag doped BiOBr catalytic material and preparation method and application thereof
CN106978715A (en) * 2017-04-20 2017-07-25 武汉工程大学 A kind of weaving cloth composite with photocatalysis and anti-microbial property and preparation method thereof

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CN101850263A (en) * 2010-06-17 2010-10-06 江西理工大学 Ag doped BiOBr catalytic material and preparation method and application thereof
CN106978715A (en) * 2017-04-20 2017-07-25 武汉工程大学 A kind of weaving cloth composite with photocatalysis and anti-microbial property and preparation method thereof

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Title
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