CN107626335B - Bismuth-based/carbon nitride composite catalyst and preparation method and application thereof - Google Patents
Bismuth-based/carbon nitride composite catalyst and preparation method and application thereof Download PDFInfo
- Publication number
- CN107626335B CN107626335B CN201710860808.0A CN201710860808A CN107626335B CN 107626335 B CN107626335 B CN 107626335B CN 201710860808 A CN201710860808 A CN 201710860808A CN 107626335 B CN107626335 B CN 107626335B
- Authority
- CN
- China
- Prior art keywords
- bioi
- powder
- bismuth
- mixture
- composite catalyst
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Abstract
The invention discloses a bismuth system/carbon nitride composite catalyst and a preparation method and application thereof, wherein the preparation method comprises the following steps: (1) c3N4Precursor and Bi2O3Mixing the precursors in proportion to prepare Bi2O3/C3N4Powder; (2) taking the obtained Bi2O3/C3N4Mixing the powder and KI according to a ratio, dispersing the mixture in water, continuously stirring the mixture after the mixture is uniformly mixed, dripping dilute sulfuric acid solution, and sequentially centrifuging, washing, drying and grinding the mixture after the reaction to obtain Bi2O3‑BiOI/C3N4Powder; (3) taking Bi2O3‑BiOI/C3N4Dispersing the powder in methanol, performing ultraviolet irradiation under the anaerobic condition, and then sequentially performing centrifugation, water washing, drying and grinding to obtain Bi @ Bi2O3‑BiOI/C3N4. The invention is preparing Bi2O3In-process synchronous introduction of C3N4To obtain Bi2O3/C3N4(ii) a Bi is prepared under the etching action of KI2O3‑BiOI/C3N4Then, in order to further broaden the visible light responsiveness, a part of Bi plasma is reduced by in-situ ultraviolet light to form Bi @ Bi2O3‑BiOI/C3N4。
Description
Technical Field
The invention relates to the technical field of high-efficiency visible light photocatalytic materials, in particular to bismuth-based/C3N4A composite catalyst, a preparation method and application thereof.
Background
In recent years, with the continuous development and progress of science and technology, people enjoy many conveniences and simultaneously have a severe development trend of environmental pollution and energy shortage, so that people in all circles have attracted extensive attention. On the one hand, under the tide of developing technology and industry vigorously, the three industrial wastes (waste water, waste gas, solid waste) are generated in the industrial and agricultural production process and discharged into the environment in large quantities, and migrate along with the circulation of the natural environment. On the other hand, the continuous consumption of traditional non-renewable resources such as coal and oil makes high-quality energy sources increasingly in short supply, so that the development of efficient sustainable energy sources becomes a great hot spot. Water pollution, one of the major problems of environmental pollution, is one of the key points of environmental management at present. For example, the treatment of wastewater pollution generated in the printing and dyeing industry and the pharmaceutical industry is performed because a large amount of organic pollutants, such as chlorophenol, exist in the wastewater, which not only harm human health, but also have severe influence on the ecological environment. At present, scientists mainly adopt physical and chemical methods such as an electrolysis method, a chemical flocculation method, an adsorption method, a membrane filtration method, a reduction precipitation method and the like aiming at the wastewater, but the problems of high residue, high cost, secondary pollution and the like exist.
Therefore, how to remove organic pollutants in sewage by adopting an energy-saving and efficient method becomes a key point of the research of sewage treatment technology in recent years. Semiconductor photocatalysis technology, as a novel advanced catalytic oxidation technology, can play a significant role in degrading various organic pollutants to enter the visual field of people and is developed rapidly.
Under the condition of taking sunlight as a driving force, the semiconductor photocatalyst can perform catalytic reaction, and is applied to hydrogen production, organic matter degradation and the like. However, the conventional photocatalyst generally has the problems of weak visible light response, low photocatalytic efficiency and the like. Therefore, the high-efficiency semiconductor photocatalyst with strong visible light responsiveness is very important for solving the organic pollution in the current wastewater.
Disclosure of Invention
The invention provides a catalyst, a preparation method and application thereof, and Bi is prepared by adopting the method2O3In-process synchronous introduction of C3N4To obtain Bi2O3/C3N4(ii) a Bi is prepared under the etching action of KI2O3-BiOI/C3N4Then, in order to further broaden the visible light responsiveness, a part of Bi plasma is obtained by in-situ ultraviolet light reduction so as to become Bi @ Bi2O3-BiOI/C3N4。
Bismuth series/C3N4The preparation method of the composite catalyst comprises the following steps:
(1) with C3N4Precursor and Bi2O3Mixing the precursors in proportion to prepare Bi2O3/C3N4Powder;
(2) taking the obtained Bi2O3/C3N4Mixing the powder and KI according to a ratio, dispersing the mixture in water, continuously stirring the mixture after the mixture is uniformly mixed, dripping dilute sulfuric acid solution, and sequentially centrifuging, washing, drying and grinding the mixture after the reaction to obtain Bi2O3-BiOI/C3N4Powder;
(3) taking Bi2O3-BiOI/C3N4Dispersing the powder in methanol, performing ultraviolet irradiation under the anaerobic condition, and then sequentially performing centrifugation, water washing, drying and grinding to obtain Bi @ Bi2O3-BiOI/C3N4。
The invention is preparing Bi2O3In-process synchronization of introducing C3N4On the basis, KI is used for etching to prepare Bi2O3-BiOI/C3N4A ternary heterojunction with purple for further broadening its visible light responsivityPreparing Bi @ Bi by reducing with an outer lamp2O3-BiOI/C3N4。
Preferably, the Bi in step (1)2O3The precursor is bismuth nitrate pentahydrate, C3N4The precursor is melamine, dicyandiamide or urea; c is to be3N4Precursor and Bi2O3Grinding the precursor in a mixed agate mortar for half an hour, and calcining the ground precursor in a muffle furnace at the temperature of 300 ℃ and 700 ℃ for 1.5 to 2.5 hours to obtain the composite material; more preferably, the catalyst is obtained by semi-anaerobic calcination in a muffle furnace at 500 ℃ for 2 hours.
Most preferably, said C3N4The precursor is melamine.
The invention respectively adopts melamine, dicyandiamide and urea as C3N4The precursor of (1).
In the invention C3N4Because of the unique structural morphology and the electronic energy band structure, the catalyst can be used as a carrier of various catalysts; bi2O3As the catalyst which is most widely applied in bismuth series catalysts, the bismuth series catalyst has the advantages of simple preparation method, adjustable band gap, certain visible light activity and the like, however, Bi2O3The visible light catalytic activity is not high, and a certain method is needed for modification. BiOX (X ═ Cl, Br, I) vs. Bi2O3The BiOCl, BiOBr and BiOI have sequentially reduced band gaps, and pure BiOX has better photocatalytic performance, but the pure BiOX has no good stability, so that the practical application of the BiOX is limited. The visible light responsiveness of the metal plasma effect can be effectively widened, and the invention innovatively uses ultraviolet to reduce the metal plasma in one step, which is a relatively innovative place. In order to combine the advantages of the above products, Bi is used in the patent2O3And C3N4Is taken as a basis. In the preparation of Bi2O3In-process synchronization of introducing C3N4On the basis, KI is used for etching to prepare Bi2O3-BiOI-C3N4Ternary heterojunction, see for further broadeningPhotoresponsiveness, and preparing Bi @ Bi by reduction with an ultraviolet lamp2O3-BiOI-C3N4。
Preferably, step (1) is C3N4Precursor and Bi2O3Precursor is expressed as Bi2O3The molar ratio of the C to the C is 1: 1-1: 5. Further preferably Bi2O3The molar ratio of the C to the C is 1: 1-1: 3; most preferably Bi2O3The molar ratio of the C to the C is 1: 2.
Preferably, the concentration of the dilute sulfuric acid in the step (2) is 0.8-1.2 mol/L; respectively reacting for 10min, 30min, 60min and 100min, and dripping Bi in each dripping amount2O3/C3N4The total volume of the powder, KI and water is 0.04 percent. The acid is added to better promote the etching of KI, and the acid is added at intervals to prevent the pH from changing suddenly and prevent excessive acid from influencing the catalyst.
Preferably, Bi in step (2)2O3/C3N4The ratio of the powder to KI is 0.5 to 0.5gBi2O3/C3N4Mixing with 0.3-0.5 gKI. More preferably, the amount of the organic solvent is 0.5gBi per unit2O3/C3N4Etch with 0.4 gKI.
When KI is less, the generated BiOI is less, and the promotion effect on the catalyst is not obvious; more KI can improve the yield of the BiOI, but the relative stability of the catalyst is poor; the visible light responsiveness and the stability of the catalyst are combined, and 0.5gBi is selected2O3/C3N4Etching with 0.4gKI is the most preferred formulation.
Preferably, the ultraviolet light irradiation in step (2) is: and (3) irradiating for 20-300 min under full-wavelength illumination of an ultraviolet iodine lamp. More preferably, the irradiation is performed for 150 to 200min, and most preferably for 200 min.
A most preferred method of preparation:
(1) preparation of Bi2O3In-process isotopic introduction of C3N4：
1) 0.368g of melamine (melamine) was mixed with 485g bismuth nitrate pentahydrate (Bi (NO)3).5H2Purity of O is 99.0 percent) is put in an agate mortar to be mixed evenly, the mixture is ground and finely crushed by force, 4 to 5 drops of deionized water are dripped by a dropper, and then the mixture is ground continuously, and finally, viscous white paste is presented.
2) Placing the mixture into a 50ml crucible, and then transferring the mixture into a hot constant-temperature air-blast drying oven to dry the mixture for 3 hours at a constant temperature of 80 ℃.
3) Calcining the mixture for 2 hours in a muffle furnace at a constant temperature of 500 ℃ to obtain powder.
(2) Potassium iodide (KI) is used as Bi2O3-BiOI/C3N4The source of the I element(s) of (2):
1) respectively take 0.5gBi2O3/C3N4The powder was placed in a 25ml beaker and 0.4gKI was weighed into the beaker, followed by 25ml of water and an appropriately sized rotor.
2) After the mixture is stirred evenly on a magnetic stirrer, the stirring is kept continuously started and the rotating speed is kept unchanged, and 20 microliter of 1mol/L concentrated H is transferred by a liquid transfer gun2SO4The solution was placed in a beaker.
3) Sequentially separating 10min, 20min, 30min and 40min, and transferring 10 microliters of 1mol/L concentrated H by using a liquid transfer gun each time2SO4The solution was placed in a beaker.
4) Stirring for 20min, turning off the stirrer, taking out the rotor, transferring the solution to a 50ml centrifuge tube, centrifuging, pouring off the supernatant, washing with water for 2-3 times, and oven drying at 80 deg.C for 3 hr.
5) Taking out the centrifuge tube, putting the powder into an agate mortar for grinding to obtain 3 Bi sources with different carbon nitride sources2O3-BiOI/C3N4。
(3) Using an ultraviolet light source to Bi2O3-BiOI/C3N4Reduction to Bi @ Bi2O3-BiOI/C3N4：
1) 0.5g of prepared Bi is taken2O3-BiOI/C3N4The powder was placed in a 50ml photochemical reaction flask, the rotor was added, 50ml of 100% methanol was added, and the flask was capped and sealed.
2) Under the action of nitrogen (N)2) Squeeze awayWith the air remaining in the bottle, the stirrer was kept working continuously with nitrogen flushing, under full wavelength illumination with UV iodine lamp for 3 hours.
3) Bi @ Bi of different carbon nitride sources2O3-BiOI/C3N4Are prepared according to the method. And (4) after the rotor is taken out, transferring the substances in the bottle to a centrifugal tube for centrifugation, recovering methanol supernatant, washing precipitates in the bottle with water for multiple times, and then placing the bottle in an oven for drying at the constant temperature of 30 ℃ for 8 hours.
4) Taking out the centrifuge tube, putting the powder into an agate mortar for grinding to obtain the optimal Bi @ Bi2O3-BiOI/C3N4。
The invention also provides bismuth-system/C prepared by the preparation method3N4And (3) compounding a catalyst.
The invention also provides the bismuth-series/C3N4The application of the composite catalyst in the treatment of organic polluted wastewater. Namely, a bismuth-based compound using the bismuth-based compound/C3N4A method for treating organic polluted wastewater by using a composite catalyst. The method comprises the following steps:
the bismuth system/C3N4The composite catalyst is added into organic polluted wastewater, and the reaction is carried out by visible light irradiation.
Preferably, the organic contaminated wastewater is phenol contaminated wastewater. Preferably, bismuth-based/C3N4The adding amount of the composite catalyst is 0.8-1.2 g/L. Further preferably 1 g/L.
Preferably, the illumination intensity is 100mW/m2～160mW/m2. The illumination time is 55-65 min; further preferably, the light is irradiated for 60 min. The pH value of the wastewater is not required to be adjusted, and the original pH value is 5-6.
The photocatalytic activity of the prepared catalyst is investigated by taking phenol degradation as a model. Under the irradiation of visible light, after reacting for a certain time, the residual concentration of phenol was monitored by a liquid chromatograph, and the removal efficiency of phenol was determined.
The experiment carries out degradation on the simulated target pollutant phenol under the light adding condition, and filters light by adopting an optical filter of 420 nanometers in an ultraviolet light source. Firstly 0.05gThe prepared catalyst powder is put into 50mL of phenol solution with the concentration of 5mg/L for adsorption for 40min, so that the reaction substrate reaches adsorption-desorption balance. Then, the light source is turned on, and the corresponding catalytic reaction is carried out, and a sample is taken at regular time (the sampling amount is about 2 ml). The intensity of the light (UV-visible light) applied in the photocatalytic reactor was measured to be 100mW/m2And in the catalytic oxidation degradation process of 105min, collecting a sample at 0min, 15 min, 30min, 45 min, 60min, 75 min, 90 min and 105min respectively, and measuring the content of phenol at different degradation times by using high performance liquid chromatography. All reactions were carried out in a glass instrument with 50ml of a 5mg/L solution of phenol as the target contaminant.
The content of phenol in the solution is measured by adopting a high performance liquid chromatograph for the phenol solution obtained at different sampling time, the content of phenol is represented by a peak area, and the chromatographic condition is a methanol solution with a mobile phase of 30%. Before sample introduction, a high-speed centrifuge is needed to carry out centrifugal treatment on a sample to prevent suspended substances (suspended catalyst powder) in a solution from damaging a chromatographic column, wherein the rotating speed during centrifugation is 10000r/min, and the centrifugation time is 5 min.
The core of the invention is to provide a bismuth system/C3N4The preparation method of the composite catalyst is applied to degrading organic pollutants in water, especially phenol. By preparing Bi2O3In-process synchronous introduction of C3N4To obtain Bi2O3/C3N4(ii) a Bi is prepared under the etching action of KI2O3-BiOI/C3N4Then, in order to further broaden the visible light responsiveness, a part of Bi plasma is reduced by in-situ ultraviolet light to form Bi @ Bi2O3-BiOI/C3N4. The catalyst has good visible light responsiveness, high-efficiency organic matter degradation performance and stability.
The invention has the beneficial effects that:
(1) prepared bismuth system/C3N4The composite catalyst has good organic matter degradation capability;
(2) the catalyst has good stability;
(3) visible light is utilized, and ultraviolet light is avoided;
(4) has extremely high visible light responsiveness.
Drawings
FIG. 1 is a bar graph comparing the degradation efficiency of various catalysts of example 1 to phenol over 60 min.
FIG. 2 shows Bi @ Bi prepared from different carbon nitride precursors of example 22O3-BiOI/C3N4Histogram of catalyst degradation efficiency to phenol over 60 min.
FIG. 3 is a histogram showing the ratio of 1:1 to 1:5 for different doping amounts of carbon nitride and the degradation efficiency of phenol within 60min for the corresponding catalyst performance in example 3 of the present invention.
FIG. 4 is a bar graph of the degradation efficiency of the catalyst to phenol within 60min for different UV reduction times in example 4 of the present invention.
FIG. 5 is a bar graph of the degradation efficiency of the catalyst on phenol within 60min under different pH conditions, acidic, basic and unadjusted pH conditions in example 5 of the present invention.
FIG. 6 shows that the molecular weight of the polymer is 40mW/m in example 6 of the present invention2，70mW/m2，100mW/m2，130mW/m2，160mW/m2The catalyst degradation efficiency in 60min for five kinds of illumination intensity is bar chart.
Detailed Description
The invention will now be further described with reference to the drawings and specific examples.
Bismuth system/C3N4The preparation method of the composite catalyst comprises the following steps:
(1)Bi2O3/C3N4preparation of
The catalyst adopts melamine, dicyandiamide and urea as C3N4The precursor of (1). To exclude carbon nitride (C)3N4) The influence of the doping amount of (C) on the catalyst performance (the molar ratio of the fixed element Bi to C, the initial ratio being 1:2, i.e., Bi: C being 1:2) is set to five ratios of 1:1 to 1: 5. The specific method is as follows (taking 1:2 as an example):
1) 0.526g of urea(urea) with 4.85g of bismuth nitrate pentahydrate (Bi (NO)3).5H2Purity of O is 99.0 percent) is put in an agate mortar to be mixed evenly, the mixture is ground and finely crushed by force, 4 to 5 drops of deionized water are dripped by a dropper, and then the mixture is ground continuously, and finally, viscous white paste is presented.
2) 0.368g of melamine (melamine) was mixed with 4.85g of bismuth nitrate pentahydrate (Bi (NO)3).5H2Purity of O is 99.0%) is put in an agate mortar and mixed evenly, and then the step 1 is repeated.
3) 0.368g of Dicyandiamide (Dicyandiamide) was mixed with 4.85g of bismuth nitrate pentahydrate (Bi (NO)3).5H2Purity of O is 99.0%) is put in an agate mortar and mixed evenly, and then the step 1 is repeated.
4) The three mixtures are respectively placed in a 50ml crucible, and then transferred to a hot constant temperature air drying oven for drying at a constant temperature of 80 ℃ for 3 hours.
5) And placing the three dried products in a muffle furnace respectively, and calcining at the constant temperature of 500 ℃ for 2 hours to obtain powder.
6) The obtained powders were put into 50ml centrifuge tubes, washed with distilled water by ultrasonic, centrifuged, and repeated 3 times. Pouring out the supernatant, drying in a hot constant-temperature blast drying oven at 80 ℃ for 3 hours, taking out, grinding in an agate mortar to obtain three Bi with different carbon nitride sources2O3/C3N4. Respectively denoted as u-type Bi2O3/C3N4(Urea) m-type Bi2O3/C3N4(Melamine) d-type Bi2O3/C3N4(dicyandiamide).
(2)Bi2O3-BiOI/C3N4Preparation of
Potassium iodide (KI) is used as Bi2O3-BiOI/C3N4The source of element I of (1). The specific operation scheme is as follows:
1) respectively take 0.5gBi2O3/C3N4The powder was placed in a 25ml beaker and 0.4gKI was weighed into the beaker, followed by 25ml of water and an appropriately sized rotor.
2) After the mixture is uniformly stirred on a magnetic stirrer, the mixture is keptContinuously starting stirring and keeping the rotating speed unchanged, and transferring 20 microliters of 1mol/L concentrated H by using a liquid transfer gun2SO4The solution was placed in a beaker.
3) Dripping at 10min, 30min, 60min, and 100min, and transferring 10 μ L of 1mol/L concentrated H with liquid-transferring gun each time2SO4The solution was placed in a beaker.
4) Stirring for 20min, turning off the stirrer, taking out the rotor, transferring the solution to a 50ml centrifuge tube, centrifuging, pouring off the supernatant, washing with water for 2-3 times, and oven drying at 80 deg.C for 3 hr.
5) Taking out the centrifuge tube, putting the powder into an agate mortar for grinding to obtain 3 Bi sources with different carbon nitride sources2O3-BiOI/C3N4。
Respectively denoted as u-type Bi2O3-BiOI/C3N4(Urea) m-type Bi2O3-BiOI/C3N4(Melamine) d-type Bi2O3-BiOI/C3N4(dicyandiamide).
(3)Bi@Bi2O3-BiOI/C3N4Preparation of
Using an ultraviolet light source to Bi2O3-BiOI/C3N4Reduction to Bi @ Bi2O3-BiOI/C3N4. The specific operation is as follows:
1) 0.5g of prepared Bi is taken2O3-BiOI/C3N4The powder was placed in a 50ml photochemical reaction flask, the rotor was added, 50ml of 100% methanol was added, and the flask was capped and sealed.
2) Under the action of nitrogen (N)2) And keeping the stirrer continuously working and continuously flushing nitrogen under the condition of squeezing out residual air in the bottle, and irradiating for 20-300 minutes under full-wavelength illumination under an ultraviolet iodine lamp.
3) Bi @ Bi of different carbon nitride sources2O3-BiOI/C3N4Are prepared according to the method. And (4) after the rotor is taken out, transferring the substances in the bottle to a centrifugal tube for centrifugation, recovering methanol supernatant, washing precipitates in the bottle with water for multiple times, and then placing the bottle in an oven for drying at the constant temperature of 30 ℃ for 8 hours.
4) Taking out the centrifuge tube, putting the powder into an agate mortar for grinding to obtain 3 different carbon nitride sources Bi @ Bi2O3-BiOI/C3N4。
Respectively marked as u-type Bi @ Bi2O3-BiOI/C3N4(Urea), m-type Bi @ Bi2O3-BiOI/C3N4(Melamine) d-type Bi @ Bi2O3-BiOI/C3N4(dicyandiamide)
Example 1
Catalysts containing 5 different components were selected and their effectiveness was determined by comparing their degradation performance. From FIG. 1, it can be found that the illumination intensity is 100mW/m2The tendency of phenol degradation over time was determined by adding 50 mg of catalyst to 50ml of 5mg per liter of phenol solution. Bi @ Bi2O3-BiOI/C3N4Has the best degradation effect, and phenol is completely degraded in 60 min.
Referring to fig. 1, it is found that the remaining four catalysts, although the degradation effect is not very good, some are relatively poor, but by comparison, it can be found that:
1) comparison of g/C3N4And Bi2O3/C3N4From the viewpoint of degradation efficiency of Bi, it can be found that Bi2O3The doping of the catalyst can improve the catalytic degradation effect of the catalyst to a certain extent.
2) Comparative Bi2O3-BiOI/C3N4And Bi2O3/C3N4From the viewpoint of degradation efficiency, it was found that doping of part of the BiOI can suitably improve the catalytic performance.
3)Bi@Bi2O3-BiOI and Bi @ Bi2O3-BiOI/C3N4Compared with the prior art, the method can obviously find that the degradation efficiency of the catalyst can be obviously improved by doping a proper amount of carbon nitride.
Example 2
And (3) investigating the influence of the catalysts prepared by different carbon nitride precursors on the phenol degradation performance.The experiment is carried out by selecting common precursors of three kinds of carbon nitride, namely melamine, dicyandiamide and urea; respectively marked as u-type Bi @ Bi2O3-BiOI/C3N4(Urea), m-type Bi @ Bi2O3-BiOI/C3N4(Melamine) d-type Bi @ Bi2O3-BiOI/C3N4(dicyandiamide).
From the degradation effect chart (figure 2), Bi @ Bi prepared by three different precursors can be found2O3-BiOI/C3N4Has good degradation effect on phenol, but takes m-type Bi @ Bi2O3-BiOI/C3N4The degradation rate of (melamine is used as a precursor of carbon nitride) is fastest, and phenol can be completely degraded. The other two prepared catalysts also have good effects.
Example 3
And (3) investigating the influence of the doping amount of the carbon nitride in the catalyst on the performance of the catalyst. According to the degradation tendency of the prepared five catalysts under the same condition, C can be seen3N4The influence of the doping amount on the performance of the catalyst is relatively large, and Bi @ Bi can be seen from the degradation trend of the curve shown in FIG. 32O3-BiOI/C3N4The catalytic performance of 1:2 is the best, namely the catalyst is prepared by uniformly mixing bismuth nitrate pentahydrate and melamine according to the proportion of 4.85g to 0.368 g.
TABLE 1 Bi @ Bi2O3-BiOI/C3N4In different proportions
By comparing the degradation efficiencies of different proportions, it can be found that the addition of a proper amount of carbon nitride can effectively improve the degradation performance (Bi @ Bi) of the catalyst2O3-BiOI/C3N41:0.5，Bi@Bi2O3-BiOI/C3N41:1，Bi@Bi2O3-BiOI/C3N41:2 for comparison); however, when the amount exceeds a certain limit, the catalyst performance is deteriorated by increasing the amount of carbon nitride (p.Bi @ Bi)2O3-BiOI/C3N41:2，Bi@Bi2O3-BiOI/C3N41:3，Bi@Bi2O3-BiOI/C3N41:4 for comparison).
Example 4
In order to compare the influence of ultraviolet reduction illumination time on the performance of the catalyst, under the condition of the same preparation conditions in the previous period, different illumination times are selected for 20min, 40min, 180min and 300 min; the four catalysts are prepared and degraded under the same illumination and phenol concentration conditions, the specific degradation effect is shown in fig. 4, and the catalysts have good degradation effect under the selected four illumination times, wherein the degradation efficiency of Bi20, Bi180 and Bi300 is relatively similar.
TABLE 2 Bi @ Bi2O3-BiOI/C3N4Selection of different ultraviolet illumination time
As can be seen from Table 2, the catalytic efficiency of the catalyst is improved to a certain extent with the increase of the illumination time, but when the reduction amount in the catalyst reaches a certain saturation value to a certain extent, the change of the catalytic efficiency is no longer obvious.
Example 5
In order to examine the optimal pH value of the catalyst in the degradation process, three conditions of acidic condition with pH 3, alkaline condition with pH 10 and original pH value of 5.41 without debugging are selected in the experimental process to examine the influence of the pH value on the performance of the catalyst. As can be seen from FIG. 5, under the conditions of pH values of 3 and 10, the degradation performance of the catalyst is inhibited to a certain extent, and the inhibition effect is obvious
Example 6
In the experiment for investigating the influence of illumination intensity on the performance of the catalyst, an irradiator is used as an instrument for measuring the illumination intensity, and the unit is mW/m2. 40mW/m is selected in the experimental process2，70mW/m2，100mW/m2，130mW/m2，160mW/m2Five illumination intensities, from fig. 6, the present invention can find the following points: 1) for you 40mW/m2，70mW/m2，100mW/m2The results of the comparison of the three groups of degradation effects are shown in fig. 6, and it can be found that when other conditions are consistent, the degradation rate of the catalyst is gradually increased along with the increase of the illumination intensity, which indicates that the light intensity has a certain effect on the degradation efficiency of the catalyst. 2) When the concentration is 100mW/m2，130mW/m2，160mW/m2When the degradation efficiency of the catalyst is compared as a control group, the invention finds that the degradation efficiency of the catalyst has little obvious change, which shows that when the illumination intensity exceeds a certain limit value, the influence of illumination on the efficiency of the catalyst is no longer a main factor.
The above description is only an embodiment of the present invention, but the technical features of the present invention are not limited thereto, and any person skilled in the relevant art can change or modify the present invention within the scope of the present invention.
Claims (5)
1. Bismuth series/C3N4The composite catalyst is characterized in that the preparation method comprises the following steps:
(1) mixing melamine and bismuth nitrate pentahydrate according to the mass ratio of 0.368:4.85 to prepare Bi2O3/C3N4Powder; mixing melamine and bismuth nitrate pentahydrate, grinding for 20-40 min by an agate mortar, and then placing in a muffle furnace at 500 ℃ for semi-anaerobic calcination for 2 hours to obtain the melamine-bismuth nitrate pentahydrate powder;
(2) taking the obtained Bi2O3/C3N4Mixing the powder and KI according to a ratio, dispersing the mixture in water, continuously stirring the mixture after the mixture is uniformly mixed, dripping dilute sulfuric acid solution, and sequentially centrifuging, washing, drying and grinding the mixture after the reaction to obtain Bi2O3-BiOI/C3N4Powder;
(3) taking Bi2O3-BiOI/C3N4Dispersing the powder in methanol, and irradiating for 20-300 min under full-wavelength illumination of an ultraviolet iodine lamp under an oxygen-free condition; then sequentially carrying out centrifugation, water washing, drying and grinding to obtain Bi @ Bi2O3-BiOI/C3N4。
2. The bismuth-based/C of claim 13N4The composite catalyst is characterized in that the concentration of the dilute sulfuric acid in the step (2) is 0.8-1.2 mol/L; dripping at intervals, wherein the dosage of each dripping is Bi2O3/C3N4The total volume of the powder, KI and water is 0.04 percent.
3. The bismuth-based/C of claim 13N4A composite catalyst, characterized in that Bi in the step (2)2O3/C3N4The ratio of the powder to KI is 0.5 to 0.5gBi2O3/C3N4Mixing with 0.3-0.5 gKI.
4. Use of the bismuth-based/C of claim 13N4The method for treating organic polluted wastewater by using the composite catalyst is characterized by comprising the following steps of:
the bismuth system/C3N4Adding the composite catalyst into organic polluted wastewater, and irradiating the organic polluted wastewater with visible light for reaction; the organic polluted wastewater is phenol polluted wastewater.
5. The method according to claim 4, wherein the bismuth-based compound is represented by formula (I)/C3N4The adding amount of the composite catalyst is 0.8-1.2 g/L; the illumination intensity is 100mW/m2～160mW/m2The visible light illumination time is 55-65 min.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710860808.0A CN107626335B (en) | 2017-09-21 | 2017-09-21 | Bismuth-based/carbon nitride composite catalyst and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201710860808.0A CN107626335B (en) | 2017-09-21 | 2017-09-21 | Bismuth-based/carbon nitride composite catalyst and preparation method and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN107626335A CN107626335A (en) | 2018-01-26 |
| CN107626335B true CN107626335B (en) | 2020-09-18 |
Family
ID=61102157
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201710860808.0A Active CN107626335B (en) | 2017-09-21 | 2017-09-21 | Bismuth-based/carbon nitride composite catalyst and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN107626335B (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108295884A (en) * | 2018-02-14 | 2018-07-20 | 扬州工业职业技术学院 | A kind of nanocomposite capable of magnetic separating and its application in rhodamine B degradation |
| CN108525695B (en) * | 2018-04-04 | 2020-05-05 | 镇江市高等专科学校 | Graphene/carbon nitrogen alkene/bismuth oxybromide composite nano photocatalytic material with two-dimensional layered structure and preparation method and application thereof |
| CN108607591B (en) * | 2018-04-04 | 2020-05-01 | 镇江市高等专科学校 | Carbon-nitrogen alkene/silver bromide co-modified bismuth oxybromide composite nano photocatalytic material and preparation method and application thereof |
| CN108671951B (en) * | 2018-04-17 | 2020-10-30 | 浙江工商大学 | Carbon nitride composite photocatalyst and preparation method and application thereof |
| CN108654595A (en) * | 2018-05-17 | 2018-10-16 | 齐鲁工业大学 | A kind of co-catalyst of photocatalytic reduction of carbon oxide and the preparation method and application thereof |
| CN108772091A (en) * | 2018-06-06 | 2018-11-09 | 上海电力学院 | One kind being used for CO2It is catalyzed heterojunction photocatalyst and its preparation of reduction |
| CN108925578B (en) * | 2018-08-10 | 2021-01-08 | 西北农林科技大学 | Preparation method and application of multifunctional bismuth-cobalt-carbide-rich nano antibacterial agent |
| CN109651281B (en) * | 2018-12-18 | 2021-04-20 | 合肥学院 | Preparation method and application of melamine bismuth complex powder |
| CN109772423B (en) * | 2019-03-30 | 2021-12-31 | 湖北文理学院 | Phosphorus and bismuth co-doped porous graphite phase carbon nitride photocatalyst and application thereof |
| CN111468176B (en) * | 2020-05-15 | 2022-04-15 | 山东师范大学 | Composite catalyst and preparation method and application thereof |
| CN113101972A (en) * | 2021-04-09 | 2021-07-13 | 兰州大学 | Preparation method and application of BiOX/BCCN composite material on polyurethane foam sponge |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923211A (en) * | 2015-05-20 | 2015-09-23 | 中国科学院地球环境研究所 | Bi2O3/(BiO)2CO3 heterojunction catalyst with visible photocatalytic activity and preparation method for Bi2O3/(BiO)2CO3 heterojunction catalyst |
| CN106348383A (en) * | 2016-09-22 | 2017-01-25 | 浙江工商大学 | C3N4-Bi2O3-BiOI-TiO2NTs visible-light response photocatalysis electrode as well as preparation method and application thereof |
| CN106694016A (en) * | 2016-11-24 | 2017-05-24 | 陕西科技大学 | g-C3N4/Bi2O3 composite powder as well as preparation method and application thereof |
| CN106732715A (en) * | 2016-11-24 | 2017-05-31 | 陕西科技大学 | A kind of BiOCl/g C3N4/Bi2O3Composite granule and its preparation method and application |
-
2017
- 2017-09-21 CN CN201710860808.0A patent/CN107626335B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104923211A (en) * | 2015-05-20 | 2015-09-23 | 中国科学院地球环境研究所 | Bi2O3/(BiO)2CO3 heterojunction catalyst with visible photocatalytic activity and preparation method for Bi2O3/(BiO)2CO3 heterojunction catalyst |
| CN106348383A (en) * | 2016-09-22 | 2017-01-25 | 浙江工商大学 | C3N4-Bi2O3-BiOI-TiO2NTs visible-light response photocatalysis electrode as well as preparation method and application thereof |
| CN106694016A (en) * | 2016-11-24 | 2017-05-24 | 陕西科技大学 | g-C3N4/Bi2O3 composite powder as well as preparation method and application thereof |
| CN106732715A (en) * | 2016-11-24 | 2017-05-31 | 陕西科技大学 | A kind of BiOCl/g C3N4/Bi2O3Composite granule and its preparation method and application |
Non-Patent Citations (2)
| Title |
|---|
| "Plasmonic Bi nanoparticles and BiOCl sheets as cocatalyst depositedon perovskite-type ZnSn(OH)6 microparticle with facet-oriented polyhedron for improved visible-light-driven photocatalysis";Hou Wang et.al;《Applied Catalysis B: Environmental》;20170306;第209卷;第545页右栏第2段 * |
| "新型卤化氧铋BiOX（X=Cl、Br、I）光催化剂的合成、表征及催化性能研究";张喜;《中国博士学位论文全文数据 工程科技I辑》;20101215;摘要 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN107626335A (en) | 2018-01-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107626335B (en) | Bismuth-based/carbon nitride composite catalyst and preparation method and application thereof | |
| CN110026225B (en) | In-NH with visible light catalytic activity2/g-C3N4Composite material and use thereof | |
| CN104525226B (en) | A kind of photocatalyst Bi4o5br2synthesis and application process | |
| CN102068998B (en) | Preparation and application methods of BiOBr/BiOCl compound photocatalyst | |
| CN110624566B (en) | CuInS2Preparation method and application of quantum dot/NiAl-LDH composite photocatalyst | |
| CN109395761B (en) | Nitrogen-doped BiOIO3Preparation method and application of photocatalyst | |
| CN103464122B (en) | A kind of preparation method of graphene/chitosan adsorbent resin | |
| CN106552651B (en) | Bi12O17Br2Synthesis and application method of photocatalyst | |
| CN108246334A (en) | A kind of functionalization tri compound catalysis material and preparation method thereof and purposes | |
| CN103191725A (en) | BiVO4/Bi2WO6 composite semiconductor material as well as hydrothermal preparation method and application thereof | |
| CN105148972A (en) | Preparation method and application of novel catalyst for reducing nitrate nitrogen in water under visible light condition | |
| CN112340830A (en) | Application of catalyst taking waste adsorbent after adsorption-desorption as raw material in persulfate activation treatment of high-salt organic wastewater | |
| CN108671951A (en) | A kind of nitridation carbon composite photocatalyst and its preparation method and application | |
| CN110841672A (en) | Method for treating antibiotic wastewater by utilizing graphite alkyne modified silver phosphate composite photocatalyst | |
| CN113318771A (en) | Magnetic nano carbon nitride photocatalyst capable of removing algae and preparation method thereof | |
| CN111957345B (en) | 4-phenoxy phenol doped carbon nitride photocatalyst and preparation method and application thereof | |
| CN103212405B (en) | Cadmium-doped bismuth molybdate visible-light-induced photocatalyst and preparation method and application of cadmium-doped bismuth molybdate visible-light-induced photocatalyst | |
| CN113318768A (en) | Composite photocatalyst and preparation method thereof | |
| CN112044398A (en) | Application of graphene adsorption material in phenol wastewater treatment | |
| CN109896574B (en) | Carbon ferrite-titanium oxide multifunctional water purification material and preparation method thereof | |
| CN103272575B (en) | A kind of nanometer titanic oxide composite photochemical catalyst material and preparation method thereof | |
| CN102489291B (en) | Method for preparing expanded graphite load nanometer bismuth vanadate photochemical catalyst | |
| CN108355686A (en) | A kind of PtO/Pt4+- BiOCl photochemical catalysts and its preparation method and application | |
| CN112495400A (en) | SnS with S vacancy2Preparation of nanosheet and application thereof in photodegradation of Cr (VI) | |
| CN108144585B (en) | Ternary magnetic composite material for heavy metal and dye wastewater treatment and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |