CN111889121B - Application of tungsten trioxide/graphite phase carbon nitride composite material in degradation CIP - Google Patents
Application of tungsten trioxide/graphite phase carbon nitride composite material in degradation CIP Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 108
- 238000006731 degradation reaction Methods 0.000 title claims abstract description 86
- 230000015556 catabolic process Effects 0.000 title claims abstract description 71
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 18
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 title abstract description 111
- 229910002804 graphite Inorganic materials 0.000 title abstract description 6
- 239000010439 graphite Substances 0.000 title abstract description 6
- JMANVNJQNLATNU-UHFFFAOYSA-N oxalonitrile Chemical compound N#CC#N JMANVNJQNLATNU-UHFFFAOYSA-N 0.000 title abstract description 6
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- 230000000593 degrading effect Effects 0.000 claims abstract description 10
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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
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J35/33—Electric or magnetic properties
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- 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
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- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
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- C02F1/30—Treatment of water, waste water, or sewage by irradiation
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- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/46—Treatment of water, waste water, or sewage by electrochemical methods
- C02F1/461—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis
- C02F1/467—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction
- C02F1/4672—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation
- C02F1/4674—Treatment of water, waste water, or sewage by electrochemical methods by electrolysis by electrochemical disinfection; by electrooxydation or by electroreduction by electrooxydation with halogen or compound of halogens, e.g. chlorine, bromine
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Abstract
The invention discloses an application of a tungsten trioxide/graphite phase carbon nitride composite material in degrading CIP, and a preparation method of the tungsten trioxide/graphite phase carbon nitride composite material comprises the following steps: mixing tungstate and distilled water, stirring at room temperature to obtain a solution A, adding dicyandiamide into the solution A, stirring at room temperature to obtain a solution B, adding glucose into the solution B, stirring at room temperature to obtain a solution C, carrying out hydrothermal reaction on the solution C at 180-200 ℃ for 18-20 h, naturally cooling to room temperature, centrifuging, washing, and drying to obtain a solid; calcining the solid at 400-550 ℃ for 3-5 h, and naturally cooling to room temperature to obtain WO3/g‑C3N4A composite material. The degradation is a photoelectric Fenton-like system degradation, and WO is added within 2 hours of the degradation3/g‑C3N4The composite material improves the degradation rate of CIP to 100%.
Description
Technical Field
The invention belongs to the technical field of organic pollutant wastewater treatment, and particularly relates to an application of a tungsten trioxide/graphite phase carbon nitride composite material in CIP degradation.
Background
Ciprofloxacin (CIP) is a typical fluoroquinolone antibiotic and is widely used not only in agriculture and aquaculture, but also in animal and human medicine. CIP is reported to be widely detected in aquatic ecosystems including sewage, rivers, groundwater, and drinking water because it is chemically stable and difficult to biodegrade. In addition, CIP residues have been shown to lead to the formation of new antibiotic resistance genes and bacteria, which cause a tremendous panic to public health and ecosystems. Therefore, there is an urgent need to find a method for efficiently removing CIP, which is very beneficial to create a green and harmonious ecological environment.
Electrochemical Advanced Oxidation Processes (EAOPs) are widely used to remove persistent organic pollutants. The type and yield of active radicals are key factors for EAOPs. The main reactive free radicals or intermediates include e-,h+,·OH,O2,H2O2And O2 -. The electro-Fenton (EF) process is to generate a large amount of H through the continuous electricity generation of a two-electron reduction reaction of oxygen at a cathode2O2This in turn gives a good source of OH, but the yield is low and the organic contaminants which are difficult to degrade cannot be completely degraded. e.g. of the type-,h+,·O2 -Can be generated by a semiconductor in a photocatalysis process, but after a single semiconductor catalyst is excited by light, the photocatalysis efficiency is low due to the rapid reunion of photo-generated electron-hole pairs. The heterojunction composite photocatalyst is designed to effectively avoid the defect. In addition, in the conventional electro-Fenton system, Fe must be added2+(if Fenton's reaction does not occur without addition of iron, no hydroxyl radical is generated), and Fe (OH) is generated when the pH of the solution is increased3Precipitation, resulting in a decrease in degradation efficiency. Therefore, the design of an iron-free photoelectricity concerted catalysis system is very important.
Disclosure of Invention
Aiming at the defects of the prior art and the problem that CIP is difficult to biodegrade, the invention aims to provide WO3/g-C3N4Preparation method of composite material, taking tungstate as WO3The precursor of (A) dicyandiamide is g-C3N4The precursor of (graphite phase carbon nitride) is prepared into WO by a method of firstly carrying out hydrothermal synthesis and then drying and calcining3/g-C3N4A composite material.
Another object of the present invention is to provide WO obtained by the above-mentioned preparation method3/g-C3N4A composite material.
It is another object of the present invention to provide the above WO3/g-C3N4Use of composite materials for degrading CIP, as WO3/g-C3N4The composite material is a bifunctional catalyst (photo-electricity), the carbon felt is a cathode, the platinum sheet is an anode, CIP degradation is realized under the condition of an external power supply, and the degradation rate can reach 100%.
The purpose of the invention is realized by the following technical scheme.
WO (WO)3/g-C3N4The preparation method of the composite material comprises the following steps:
1) mixing tungstate and distilled water, stirring for 10-30 min at the room temperature of 20-25 ℃ to obtain a solution A, adding dicyandiamide to the solution A, stirring for 10-30 min at the room temperature of 20-25 ℃ to obtain a solution B, adding glucose to the solution B, and stirring for 10-30 min at the room temperature of 20-25 ℃ to obtain a solution C, wherein the ratio of the tungstate to the dicyandiamide to the glucose is 1: (4-10): (20-30);
in the step 1), the concentration of tungstate in the solution A is 0.01-0.05 mmol.L-1。
2) Carrying out hydrothermal reaction on the solution C at 180-200 ℃ for 18-20 h, naturally cooling to room temperature of 20-25 ℃, centrifuging, sequentially and respectively washing with distilled water and ethanol, and drying at 60-80 ℃ for 10-12 h to obtain a solid;
3) calcining the solid at 400-550 ℃ for 3-5 h, and naturally cooling to room temperature of 20-25 ℃ to obtain WO3/g-C3N4A composite material.
WO obtained by the above-mentioned preparation method3/g-C3N4A composite material.
In the above technical solution, the WO3/g-C3N4The particle size of the composite material is 50-100 nm.
In the above technical solution, the WO3/g-C3N4The average pore size of the composite was 15.38 nm.
WO mentioned above3/g-C3N4Use of a composite material for degrading CIP.
In the above technical scheme, the degradation is a quasi-photoelectric Fenton systemDegradation, within 2 hours of degradation, of said WO3/g-C3N4The composite material improves the degradation rate of CIP to 100%.
In the above technical scheme, within 15min of degradation, the WO3/g-C3N4The composite material improves the degradation rate of CIP to 92%; within 30min of degradation, the WO3/g-C3N4The composite material improves the degradation rate of CIP to 95%; within 60min of degradation, the WO3/g-C3N4The composite material improves the degradation rate of CIP to 97%; within 90min of degradation, the WO3/g-C3N4The composite material improves the degradation rate of CIP to 99%.
In the above technical scheme, the WO is applied within 2 hours of degradation3/g-C3N4The composite material enables the TOC removal rate to reach 80%.
In the above technical solution, the WO3/g-C3N4The composite material can be recycled as a catalyst. In the above technical solution, the conditions of the quasi-photoelectric fenton system are as follows: charging WO into CIP wastewater3/g-C3N4Adding carbon felt as cathode and platinum sheet as anode into CIP waste water, and introducing O2And irradiating the solution to degrade the CIP photoelectric Fenton system.
In the technical scheme, the CIP wastewater is kept stirred in the process of degrading the CIP photoelectric Fenton system.
In the technical scheme, the pH value of the CIP wastewater is 2-9, and preferably 3.
In the above technical solution, said O2The flow rate of (A) is 100 to 120 mL/min-1。
In the technical scheme, a xenon lamp is adopted for illumination, and the light intensity is 100-150 mW-cm-1。
In the above technical scheme, the WO is calculated according to parts by weight3/g-C3N4The ratio of the composite material to CIP in the CIP wastewater is (20-40): (4-5).
In the technical proposalIn a case, WO is put into3/g-C3N4The ratio of the mass parts of the composite material to the volume parts of the CIP wastewater is (20-40): (80-100), when the unit of the mass part is mg, the unit of the volume part is mL.
Compared with the prior art, the invention has the beneficial effects that:
(1) compared with electro-Fenton-like and photocatalytic processes, the method is described in WO3/g-C3N4The composite material is a photoelectric Fenton-like system of the bifunctional catalyst, can generate more OH, and is beneficial to the oxidation of CIP.
(2) The iron-free photoelectric Fenton system ensures that the CIP still keeps higher degradation efficiency in the pH range of 2-9, and makes up the defect of degradation efficiency reduction caused by iron mud generated by the increase of the pH value of the iron-containing catalyst.
(3)WO3/g-C3N4The composite material shows excellent photocatalytic and electrocatalytic activity, and realizes rapid and efficient degradation of CIP.
Drawings
FIG. 1 shows WO obtained in examples 1 to 43/g-C3N4CIP degradation rate (degradation efficiency) of the composite;
FIG. 2 is CIP degradation rates for examples 6 and 9;
FIG. 3 shows CIP degradation rates of examples 6, 10 to 13;
FIG. 4 shows CIP degradation rates of examples 6 and 14 to 15;
FIG. 5 production of H for examples 6 and 152O2The amount of (c);
FIG. 6 is WO3、g-C3N4And WO3/g-C3N4The composite material has CIP degradation rate in a photoelectric Fenton-like system;
FIG. 7 is WO3、g-C3N4And WO3/g-C3N4The TOC of the composite material changes in the CIP degradation process in the photoelectric Fenton-like system;
FIG. 8 shows the WO obtained in example 23/g-C3N4Detecting the stability of the composite material in a photoelectric Fenton-like system;
FIG. 9(a) is WO3SEM image of (a);
FIG. 9(b) shows g-C3N4SEM image of (a);
FIG. 9(c) is WO3/g-C3N4SEM images of the composite;
FIG. 9(d) is WO3/g-C3N4TEM images of the composite;
FIG. 9(e) is WO3/g-C3N4TEM images of the composite;
FIG. 9(f) is WO3/g-C3N4TEM images of the composite;
FIG. 9(g) is a Mapping diagram of the corresponding region of FIG. 9 (f);
FIG. 9(h) is a Mapping diagram of the corresponding region of FIG. 9 (f);
FIG. 9(i) is a Mapping diagram of the corresponding region of FIG. 9 (f);
FIG. 9(j) is a Mapping diagram of the corresponding region of FIG. 9 (f);
FIG. 10(a) is (in example 16) WO3(in example 17) g-C3N4And WO3/g-C3N4N of composite material2Adsorption-removal of attached figures;
FIG. 10(b) is (in example 16) WO3(in example 17) g-C3N4And WO3/g-C3N4Pore size distribution map of the composite;
FIG. 11 shows (in example 16) WO3(in example 17) g-C3N4And WO3/g-C3N4An infrared spectrum of the composite;
FIG. 12.1 shows (in example 16) WO3(in example 17) g-C3N4And WO3/g-C3N4XPS spectra of the composite;
FIG. 12.2(a) is WO3/g-C3N4XPS spectra of C1s in the composite; (b) as WO3/g-C3N4XPS spectrum of N1s in composite; (c) as WO3/g-C3N4XPS spectrum of O1s in composite;(d) as WO3/g-C3N4XPS spectrum of W4f in the composite;
FIG. 13.1 shows (in example 16) WO3(in example 17) g-C3N4And WO3/g-C3N4EIS spectrum of the composite material;
FIG. 13.2 shows (in example 16) WO3(in example 17) g-C3N4And WO3/g-C3N4Transient photocurrent response spectrum of the composite material;
FIG. 13.3 is (in example 16) WO3(in example 17) g-C3N4And WO3/g-C3N4Linear sweep voltammogram of the composite.
Detailed Description
The technical scheme of the invention is further explained by combining specific examples.
The purity and purchase of the pharmaceutical products referred to in the following examples are as follows:
molecular formula | Purity of | Reagent Co Ltd |
Na2WO4·2H2O | Analytical purity | Yueli chemical Co Ltd of Tianjin City |
C2H4N4 | Analytical purity | SHANGHAI ALADDIN BIOCHEMICAL TECHNOLOGY Co.,Ltd. |
C6H12O6 | Analytical purity | Yueli chemical Co Ltd of Tianjin City |
C17H18FN3O3 | ≥98% | BEIJING J&K SCIENTIFIC Ltd. |
Na2SO4 | Analytical purity | Tianjin Guang science and technology development Co Ltd |
FeSO4 | Analytical purity | Tianjin Guang science and technology development Co Ltd |
H2O2(30%) | Analytical purity | TIANJIN DAMAO CHEMICAL REAGENT FACTORY |
NaOH | Analytical purity | Jiangtian chemical technology Limited of Tianjin |
HCl | Analytical purity | Jiangtian chemical technology Limited of Tianjin |
H2SO4 | Analysis ofPure | Jiangtian chemical technology Limited of Tianjin |
The following examples refer to the following types and manufacturers of equipment:
examples 1 to 4
WO (WO)3/g-C3N4The preparation method of the composite material comprises the following steps:
1) mixing Na2WO4·2H2Uniformly dispersing O in distilled water, stirring at room temperature of 20-25 ℃ for 30min to obtain solution A, wherein Na is contained in the solution A2WO4·2H2The concentration of O is 0.02 mmol.L-1Adding dicyandiamide into the solution A, stirring for 30min at room temperature of 20-25 ℃ to obtain a solution B, adding glucose into the solution B, stirring for 30min at room temperature of 20-25 ℃ to obtain a solution C, and adding Na2WO4·2H2The amounts of O, dicyandiamide and glucose species are shown in Table 1.
2) Transferring the solution C into a 100mL reaction kettle, sealing, carrying out hydrothermal reaction at 200 ℃ for 20h, naturally cooling to room temperature of 20-25 ℃, centrifuging, sequentially and respectively washing with distilled water and ethanol, and drying at 80 ℃ for 12h to obtain a solid;
3) grinding the solid, putting the ground solid into a crucible, calcining the solid in a muffle furnace at 550 ℃ for 4 hours, and naturally cooling the calcined solid to room temperature of 20-25 ℃ to obtain WO3/g-C3N4A composite material.
TABLE 1
Examples 5 to 13
At room temperature of 20-25 ℃, in a 100mL cubic quartz electrolytic cellDegrading the CIP photoelectric Fenton system under the following degradation conditions: 80ml of simulated CIP wastewater is contained in the cubic quartz electrolytic cell, the substances in the CIP wastewater are shown in Table 2, and the pH of the CIP wastewater is controlled to be 0.5 mol.L-1NaOH aqueous solution or 0.5 mol. L-1H of (A) to (B)2SO4The aqueous solution was adjusted to pH shown in Table 2. The carbon felt as the cathode and the platinum sheet as the anode were put into the CIP wastewater, the size of the carbon felt was 3cm × 4cm × 0.6cm, the size of the platinum sheet was 1cm × 2cm × 0.01cm, and the distance between the cathode and the anode was 1 cm. Introduction of O2And performing light irradiation, wherein O2The flow rate of (2) is 100 mL/min-1The light source is a xenon lamp light source which provides visible light irradiation (wavelength)>420nm) with a light intensity of 100mW cm-1. WO prepared in example 1, 2,3 or 4 is charged3/g-C3N430mg of composite material, carrying out degradation of the CIP photoelectric Fenton system, continuously stirring CIP wastewater in the degradation process of the CIP photoelectric Fenton system so as to ensure the uniformity of the CIP wastewater in the degradation process of the CIP photoelectric Fenton system, and adding WO3/g-C3N4The composites are shown in table 2.
TABLE 2
The results of degrading CIP-based photo-Fenton systems of examples 5 to 8 when Na is contained therein are shown in FIG. 12WO4·2H2The ratio of the amount of O to dicyandiamide substance is from 1: 4 to 1: at 6, the degradation efficiency increased. Following WO3/g-C3N4g-C in the composite3N4The ratio of (a) to (b) is continuously increased, and the degradation efficiency is rather decreased. Example 2 preparation of the obtained WO3/g-C3N4The composite material has the highest degradation efficiency, the degradation efficiency is obviously improved in the first half hour, and finally the degradation efficiency reaches 100% in 2 hours.
By comparing example 6 with example 9, the addition or non-addition of Fe in a photo-Fenton-like system is investigated2+Effect on CIP degradation, degradation results of example 6 and example 9As shown in FIG. 2, in the absence of Fe2+In the case of CIP, the degradation efficiency and addition of Fe2+The process of (a) is very consistent and slightly improved. Based on the results of this experiment, W can be estimated5+And H2O2Between the electro-Fenton-like reaction successfully replaces Fe2+Function and function in the conventional electro-Fenton catalytic Process (Fe)2++H2O2+H+→Fe3++·OH+H2O,Fe3++e-→Fe2+). In addition, as a novel electro-Fenton-like catalyst, WO3/g-C3N4The composite material can effectively avoid Fe (OH) caused by pH value increase in the traditional electro-Fenton system3And (4) precipitating.
As shown in FIG. 3, the results of degradation of the CIP-based photo-Fenton systems of examples 6, 10 to 13 show that the CIP degradation efficiency fluctuates sharply within 15 minutes from the start of the reaction when the pH is changed from 2 to 9. This phenomenon is mainly due to O2Two electrons are generated into H2O2Reaction (O)2+2H++2e-→H2O2) It is advantageous under acidic conditions, especially in the initial stage of electrolysis. The reason why the degradation efficiency at pH 2 is lower than that at pH 3 is that H is+Obtaining electrons at pH 2 to produce H2This hinders the dissolution of O2Generation of H2O2Active site and catalytic rate. However, at pH 2,3, 5,7 and 9, CIP removal rates of 85.1%, 100%, 89.8%, 84.3% and 84.2% were achieved at two hours of reaction, possibly due to H2O2Accumulates as the reaction time increases. Therefore, the influence of the change of the pH value on the CIP degradation efficiency is small at the later stage of the photoelectric Fenton degradation process. Thus, the present invention WO3/g-C3N4The composite material Fenton-like catalyst effectively expands the applicable pH range of the photoelectric Fenton-like system.
Study of WO3/g-C3N4Stability of the composite. Using the same WO3/g-C3N4The composite material was subjected to five CIP-based photo-electro-fenton system degradations according to the method cycle of example 6, and the results are shown in fig. 8 and table 3, wherein,each time the method combines the carbon felt with WO3/g-C3N4Recovering the composite material, washing with distilled water, and drying at 60 deg.C for the next step.
Table 3 shows the efficiency of the CIP degradation in different times per procedure, WO3/g-C3N4The degradation efficiency of the composite material can still reach 94% after five times of CIP recycling, which indicates that the WO is used3/g-C3N4The photoelectric Fenton-like system of the composite material has good stability and feasibility.
TABLE 3
Example 14
And (2) carrying out CIP photocatalytic degradation in a 100mL cubic quartz electrolytic cell at the room temperature of 20-25 ℃, wherein the CIP photocatalytic degradation conditions are as follows: 80ml of simulated CIP wastewater is contained in the cubic quartz electrolytic cell, and the CIP wastewater contains 50 mg.L-1CIP and 0.05 mol. L-1Na of (2)2SO4(the solvent is water), the pH value of the CIP wastewater is 0.5 mol.L-1H of (A) to (B)2SO4The aqueous solution was adjusted to pH 3. Introduction of O2And performing light irradiation, wherein O2The flow rate of (2) is 100 mL/min-1The light source is a xenon lamp light source which provides visible light irradiation (wavelength)>420nm) with a light intensity of 100mW cm-1. WO prepared in example 23/g-C3N430mg of composite material, and carrying out CIP photocatalytic degradation, wherein CIP wastewater is continuously stirred in the CIP photocatalytic degradation process so as to ensure the uniformity of the CIP wastewater in the photocatalytic degradation process.
Example 15
And (2) degrading the CIP electro-Fenton system in a 100mL cubic quartz electrolytic cell at the room temperature of 20-25 ℃, wherein the degrading conditions of the CIP electro-Fenton system are as follows: 80ml of simulated CIP wastewater is contained in the cubic quartz electrolytic cell, and the CIP wastewater contains 50 mg.L-1CIP and 0.05 mol. L-1Na of (2)2SO4(the solvent is water),the pH value of the CIP wastewater is 0.5 mol.L-1H of (A) to (B)2SO4The aqueous solution was adjusted to pH 3. The carbon felt as the cathode and the platinum sheet as the anode were put into the CIP wastewater, the size of the carbon felt was 3cm × 4cm × 0.6cm, the size of the platinum sheet was 1cm × 2cm × 0.01cm, and the distance between the cathode and the anode was 1 cm. Introduction of O2Wherein O is2The flow rate of (2) is 100 mL/min-1. WO prepared in example 23/g-C3N430mg of composite material, and carrying out degradation of the CIP electro-Fenton-like system, wherein CIP wastewater is continuously stirred in the degradation process of the CIP electro-Fenton-like system so as to ensure the uniformity of the degradation process of the electro-Fenton-like system.
Examples 6, 14 and 15 were compared to investigate the effect of the electro-fenton-like system (example 15), the photocatalytic system (example 14) and the electro-fenton-like system on CIP degradation. The degradation result is shown in fig. 4, the degradation efficiency of CIP is obviously improved in the initial 30 minutes of the photocatalytic process, the degradation efficiency reaches 49.3%, but the trend is basically stable, and the degradation efficiency of the rest processes is kept at 49.3%. The efficiency of CIP degradation in the electro-fenton like process is significantly improved compared to the photocatalytic process and reaches 78.9% at the first 30 minutes. This is mainly due to W5+And H2O2More OH is generated by fenton-like reaction, and the degradation efficiency reaches 94.7% in 2 hours. Finally, under the irradiation of visible light, the efficiency of CIP is greatly improved in a quasi-photoelectric Fenton system, the degradation efficiency reaches 95.1% in the first 30 minutes, and finally reaches 100% in 2 hours. Accelerated removal of CIP is attributable to the generation of a greater abundance of active species by photoelectrocatalytic interactions, including OH generated by electro-Fenton-like reactions during electrocatalysis, and OH, O generated during photocatalysis2 –And h+。
Study of the Generation of H in the electro-Fenton-like System (example 15) and in the photo-Fenton-like System (example 6)2O2Influence of (b) on CIP degradation to form H2O2The results of the amounts are shown in FIG. 5, from which it is clear that O is present within 5 minutes from the start of the reaction2The reduction reaction of (A) results in H2O2And (4) accumulating remarkably. With the passage of reaction time, H2O2The concentration gradually decreases. H in the first 1 hour, photoelectric Fenton-like System2O2The concentration is lower than that of the electro-Fenton-like system, mainly because of H2O2Can be W by electro-Fenton-like reaction5+And (5) decomposing. Furthermore, g-C3N4The photo-generated electrons can also decompose H in the photo-electro-Fenton-like process2O2。
Examples 16 to 17
And (2) degrading the CIP photoelectric Fenton system in a 100mL cubic quartz electrolytic cell at the room temperature of 20-25 ℃, wherein the degrading conditions of the CIP photoelectric Fenton system are as follows: 80ml of simulated CIP wastewater is contained in the cubic quartz electrolytic cell, and the CIP wastewater contains 50 mg.L-1CIP and 0.05 mol. L-1Na of (2)2SO4The pH of the CIP wastewater is 0.5 mol.L-1H of (A) to (B)2SO4The aqueous solution was adjusted to pH 3. The carbon felt as the cathode and the platinum sheet as the anode were put into the CIP wastewater, the size of the carbon felt was 3cm × 4cm × 0.6cm, the size of the platinum sheet was 1cm × 2cm × 0.01cm, and the distance between the cathode and the anode was 1 cm. Introduction of O2And performing light irradiation, wherein O2The flow rate of (2) is 100 mL/min-1The light source is a xenon lamp light source which provides visible light irradiation (wavelength)>420nm) with a light intensity of 100mW cm-1. 30mg of materials are added into the CIP photoelectric Fenton system to degrade the CIP photoelectric Fenton system, and the CIP wastewater is continuously stirred in the degradation process of the CIP photoelectric Fenton system so as to ensure the uniformity of the CIP wastewater in the degradation process of the CIP photoelectric Fenton system.
TABLE 4
Examples | Charging material |
Example 16 | WO3 |
Example 17 | g-C3N4 |
WO in example 163The preparation method comprises the following steps:
1) mixing Na2WO4·2H2Dissolving O in distilled water, stirring at room temperature of 20-25 ℃ for 30min to obtain solution A, and adding Na in the solution A2WO4·2H2The concentration of O is 0.02 mmol.L-1. Adding glucose into the solution A, stirring for 30min at room temperature of 20-25 ℃ to obtain a solution D, wherein the glucose and Na are calculated according to the amount of substances2WO4·2H2The ratio of O is 25: 1.
2) transferring the D solution into a 100mL reaction kettle, sealing, carrying out hydrothermal reaction at 200 ℃ for 20h, naturally cooling to room temperature of 20-25 ℃, centrifuging, sequentially and respectively washing with distilled water and ethanol, drying at 80 ℃ for 12h, grinding, placing into a crucible, placing into a muffle furnace, calcining at 550 ℃ for 4h, naturally cooling to room temperature of 20-25 ℃ to obtain WO3。
Example 17 g-C3N4The preparation method comprises the following steps:
weighing 6g of dicyandiamide solid, grinding, putting into a crucible, putting into a muffle furnace, calcining for 4h at 550 ℃, naturally cooling to room temperature of 20-25 ℃ to obtain g-C3N4。
Degradation rates by comparative examples 6, 16 and 17, as shown in FIG. 6, with WO3Tendency to degrade CIP and g-C3N4Very similar and the degradation efficiency reached 82% and 78% within 30 minutes, respectively. Example 2 WO obtained3/g-C3N4Compounding of WO3And g-C3N4 combined, the degradation efficiency reached 95% within 30 minutes, significantly facilitating CIP removal. This result can explain WO3/g-C3N4The heterostructure of the composite material realizes effective separation of electron-hole pairsAlternatively, more active sites can be provided in contact with the CIP molecule. By WO3And g-C3N4The photoelectric synergistic effect between the two can generate more active substances including OH, O2 –And h+This accelerates the degradation efficiency of CIP.
Comparing the change of Total Organic Carbon (TOC) during the degradation of examples 6, 16 and 17, as shown in fig. 7, it was found that the TOC removal rate greatly increased in the initial stage of the reaction with the increase of time. At the beginning of 15 minutes, WO3/g-C3N4Composite material, WO3And g-C3N4The TOC removal rates reached 63.1%, 58.9% and 56.6%, respectively. This is associated with further decomposition of the active substance intermediate. Finally, WO3/g-C3N4Composite material, WO3And g-C3N4The TOC removal rates reached 80.3%, 70.5% and 66.5% within 2 hours, respectively. Apparently, WO3/g-C3N4The composite material shows a better than WO3And g-C3N4Higher TOC removal rate, probably due to more active species generated under visible light irradiation, thus promoting CIP mineralization.
WO in example 16 was tested using a Scanning Electron Microscope (SEM) model JEOL-6700FE and a Transmission Electron Microscope (TEM) model JEM-2100F3Example 17 g-C3N4And example 2 preparation of the obtained WO3/g-C3N4And SEM images, TEM images and mapping images of the composite material under different times represent the morphology and the crystal structure of the material. The results are shown in FIG. 9, WO in FIG. 9a3Shows a bulky irregular morphology with some particles aggregated, g-C in FIG. 9b3N4Showing a layered structure. FIG. 9c clearly shows that3In contrast, WO3/g-C3N4The composite exhibited smaller particles that looked like rice grains. FIG. 9d is WO3/g-C3N4TEM image of the composite, further showing WO3/g-C3N4The composite material has a particle morphology with an average diameter of 50nm to 100 nm. FIG. 9e is WO3/g-C3N4High resolution TEM images of the composite showing significant lattice fringes, and WO3Has a lattice spacing of 0.383nm, g-C in the (002) plane3N4The lattice spacing in the (002) plane of (2) was 0.335 nm. FIG. 9f is WO3/g-C3N4TEM image of composite material, FIG. 9g-j are element mapping maps, showing that C, N, O and W are uniformly distributed in WO3/g-C3N4Among the composite materials, the composite material was confirmed to be composed of WO3And g-C3N4And (4) forming.
WO in test example 163Example 17 g-C3N4And example 2 preparation of the obtained WO3/g-C3N4N of composite material2Adsorption-desorption performance. The specific surface area and pore size distribution of a sample are analyzed by a BJH and BET method by adopting a Quantachrome Autosorb iQ-MP analyzer in nitrogen adsorption-desorption isotherm determination. As shown in FIG. 10, the pressure range of 0.5 to 1 in FIG. 10a shows the IV isotherm and the H3 hysteresis loop, indicating that it has a mesoporous structure, however, similar to WO3/g-C3N4Comparison of composite materials, WO3And g-C3N4The hysteresis loop of H3 type is small. FIG. 10b shows the pore size distribution, WO3/g-C3N4The average pore size of the composite was 15.38nm, which is consistent with a mesoporous structure. WO3And g-C3N4Has an average pore diameter of 31.11 and 27.36nm, respectively, in comparison with WO3/g-C3N4The composite material is slightly larger.
WO measurement in example 16 by KBr pellet method using Nicolet iS50 type Fourier transform Infrared Spectroscopy3Example 17 g-C3N4And WO obtained in examples 1 to 43/g-C3N4Infrared absorption spectrum of the composite material. The result is shown in FIG. 11, the spectrum is at 815cm-1Shows a broad adsorption peak, which is associated with stretching vibration of the W-O-W bond. g-C3N4At 1242,1320,1410,1571 and 1637cm-1Shows a plurality of adsorption peaks due to the stretching vibration of the C-N heterocyclic ring, 808cm-1The characteristic peak of (A) is the vibration mode of the triazine unit, it being noted that, as WO follows3/g-C3N4g-C in the composite3N4Increase in the ratio, g-C3N4Gradually increasing the characteristic absorption peak of (a).
WO in test example 163Example 17 g-C3N4And example 2 preparation of the obtained WO3/g-C3N4XPS of composite material. WO is obtained by using an ESCA X PHI-1600 type X-ray photoelectron spectrometer by taking the peak of C1s at 284.6eV as reference3,g-C3N4And WO3/g-C3N4The elemental composition and chemical state of the composite, as shown in fig. 12.1, shows the broad scan spectra of the different materials. WO3/g-C3N4The measured spectrum of the composite showed elemental signals for C, N, O and W, confirming WO3And g-C3N4Successful combinations of (1). The XPS spectrum for C1s in FIG. 12.2a is divided into three peaks with binding energies of 284.5eV, 286.0eV and 288.9eV, respectively. The peak at 284.5eV corresponds to sp bonded to three adjacent N atoms2The peak at C, 286.0eV is from g-C3N4Sp of surface defect3Coordinated carbon, peak at 288.9eV is sp2C is bonded to N in the aromatic ring (NC ═ N). The spectrum of N1s is shown in fig. 12.2b, with three peaks observed with binding energies of 398.9eV, 399.5eV and 400.4eV, corresponding to sp in the triazine ring (C ═ N-C)2Aromatic nitrogen, sp3Hybrid triaza (N- (C)3) And a free amino function (C-N-H). The two peaks of the O1s spectrum in FIG. 12.2c correspond to binding energies of 530.0eV and 531.2eV, the first peak being associated with the W-O-W bond and the second peak being associated with the W-O-H bond. As shown in FIG. 12.2d, the XPS spectrum of W4f was divided into two double peaks, with peaks with binding energies of 35.2eV and 35.4eV being attributed to W6+W4f7/2And W4f5/2The peaks with binding energies of 34.4eV and 36.1eV are attributed to W5+W4f7/2And W4f5/2Shows WO3/g-C3N4(1: 6) the composite material contains W5+And W6+。
For WO in example 163Example 17 g-C3N4And example 2 preparation of the obtained WO3/g-C3N4The photoelectrochemical properties of the composite materials were studied: by using CHI 660D electrochemical workstation and three-electrode photochemical electrolytic cell, taking a platinum sheet as an auxiliary electrode, a saturated calomel electrode as a reference electrode, FTO conductive glass serving as a load material as a working electrode, and 0.5 mol.L of electrolyte-1Na2SO4Electrochemical Impedance Spectroscopy (EIS), transient photocurrent response and linear sweep voltammetry tests of different materials were performed in solution. The results are shown in FIG. 13, FIG. 13.1 is WO3,g-C3N4And WO3/g-C3N4EIS spectra of composite materials, and WO3And g-C3N4In contrast, WO3/g-C3N4The corresponding half circle radius of the composite is the smallest, indicating that the interfacial charge transfer resistance is the smallest, because of WO3And g-C3N4Recombination facilitates charge transfer and reduces the rate of repolymerization of electron-hole pairs. FIG. 13.2 is WO3,g-C3N4And WO3/g-C3N4Transient photocurrent response spectra of composite materials, WO3/g-C3N4The composite material shows purer WO3And g-C3N4Higher photocurrent response, proving WO3And g-C3N4The heterojunction between them facilitates the efficient separation of electron-hole pairs. FIG. 13.3 is WO3,g-C3N4And WO3/g-C3N4Linear sweep voltammogram of composite materials, WO3/g-C3N4The current density of the composite material is in the range of-0.6 to 1.5eV, the composite material has the lowest photocurrent initial potential, and the photocurrent density of the composite material is higher than that of WO3And g-C3N4Shows WO3/g-C3N4The composite material can capture more visible light.
The invention has been described in an illustrative manner, and it is to be understood that any simple variations, modifications or other equivalent changes which can be made by one skilled in the art without departing from the spirit of the invention fall within the scope of the invention.
Claims (13)
1.WO3/g-C3N4Application of composite material in degrading CIP (CIP), characterized in that the degradation is degradation of a photoelectric Fenton-like system, and within 2 hours of degradation, WO3/g-C3N4The composite material improves the degradation rate of CIP to 100 percent, and WO3/g-C3N4The preparation method of the composite material comprises the following steps:
1) mixing tungstate and distilled water, stirring for 10-30 min at the room temperature of 20-25 ℃ to obtain a solution A, adding dicyandiamide to the solution A, stirring for 10-30 min at the room temperature of 20-25 ℃ to obtain a solution B, adding glucose to the solution B, and stirring for 10-30 min at the room temperature of 20-25 ℃ to obtain a solution C, wherein the ratio of the tungstate to the dicyandiamide to the glucose is 1: (4-10): (20-30);
2) carrying out hydrothermal reaction on the solution C at 180-200 ℃ for 18-20 h, naturally cooling to room temperature of 20-25 ℃, centrifuging, sequentially and respectively washing with distilled water and ethanol, and drying at 60-80 ℃ for 10-12 h to obtain a solid;
3) calcining the solid at 400-550 ℃ for 3-5 h, and naturally cooling to room temperature of 20-25 ℃ to obtain the WO3/g-C3N4A composite material;
the conditions of the photoelectric Fenton-like system are as follows: charging WO into CIP wastewater3/g-C3N4Adding carbon felt as cathode and platinum sheet as anode into CIP waste water, and introducing O2Illumination is carried out, and CIP photoelectric Fenton system degradation is carried out; the pH value of the CIP wastewater is 2-9.
2. Use according to claim 1, wherein said WO is applied within 2 hours of degradation3/g-C3N4The composite material enables the TOC removal rate to reach 80%.
3. Use according to claim 2, characterized in thatIn, the WO3/g-C3N4The composite material can be recycled as a catalyst.
4. Use according to claim 3, wherein the CIP wastewater is kept under agitation during the degradation of the CIP-like photo-Fenton system.
5. The use according to claim 4, wherein the pH of the CIP wastewater is pH = 3.
6. Use according to claim 5, wherein said O is2The flow rate of (A) is 100 to 120 mL/min-1。
7. The use according to claim 6, wherein the illumination is carried out with a xenon lamp at a light intensity of 100-150 mW-cm-1。
8. Use according to claim 7, wherein said WO is in parts by mass3/g-C3N4The ratio of the composite material to CIP in the CIP wastewater is (20-40): (4-5).
9. Use according to claim 8, characterized in that WO is dosed in3/g-C3N4The ratio of the mass parts of the composite material to the volume parts of the CIP wastewater is (20-40): (80-100), when the unit of the mass part is mg, the unit of the volume part is mL.
10. Use according to claim 1, wherein the WO is applied within 15min of degradation3/g-C3N4The composite material improves the degradation rate of CIP to 92%.
11. Use according to claim 1, wherein said WO is applied within 30min of degradation3/g-C3N4Composite for CIPThe degradation rate is improved to 95 percent.
12. Use according to claim 1, wherein the WO is applied within 60min of degradation3/g-C3N4The composite material improves the degradation rate of CIP to 97%.
13. Use according to claim 1, wherein the WO is applied within 90min of degradation3/g-C3N4The composite material improves the degradation rate of CIP to 99%.
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