CN111875031A - Method for synchronously denitrifying and degrading organic pollutants by coupling photocatalytic electrode with denitrifying microbial fuel cell - Google Patents

Method for synchronously denitrifying and degrading organic pollutants by coupling photocatalytic electrode with denitrifying microbial fuel cell Download PDF

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CN111875031A
CN111875031A CN202010704921.1A CN202010704921A CN111875031A CN 111875031 A CN111875031 A CN 111875031A CN 202010704921 A CN202010704921 A CN 202010704921A CN 111875031 A CN111875031 A CN 111875031A
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bivo
denitrifying
photocatalytic
fuel cell
organic pollutants
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胡晓钧
陶子豪
张宏波
邢海波
田富箱
张洪慎
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Shanghai Institute of Technology
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Abstract

The invention relates to a method for synchronously denitrifying and degrading organic pollutants by coupling a photocatalytic electrode with a denitrifying microbial fuel cell, which uses BiVO4And g-C3N4The precursor is prepared into BiVO by a simple hydrothermal method4/g‑C3N4Compounding a photocatalytic material and hydrothermal reaction of BiVO4/g‑C3N4The composite photocatalyst and the nano-sheet MOFs are loaded on a carbon cloth material and used as a photoanode, anaerobic denitrifying bacteria with strong adhesiveness are domesticated at the other end of the carbon cloth material, a carbon rod is inserted into the carbon cloth material and used as a microbial cathode, an electric circuit is formed through chemical potential difference, and a nitrate denitrification system is constructed to be coupled and promote BiVO4/g‑C3N4/MOFs photoelectrocatalytic degradation of organic pollutant systems. Compared with the prior art, the BiVO in the invention4/g‑C3N4The MOFs photoelectrocatalysis electrode is coupled with denitrifying microorganisms to realize the synchronous degradation of nitrate and organic pollutants, and an efficient method is provided for the combined denitration and organic pollutant treatment.

Description

Method for synchronously denitrifying and degrading organic pollutants by coupling photocatalytic electrode with denitrifying microbial fuel cell
Technical Field
The invention relates to the technical field of denitration, water body organic matter degradation and energy-saving resource utilization, in particular to a method for synchronously denitration and degrading organic pollutants by coupling a photocatalytic electrode with a denitrification microbial fuel cell.
Background
With the increase of urban population, the increase of material demand has led to the rise of modern synthetic chemical industry, improper treatment of organic pollutants and harm to environment. Such as plastics, synthetic fibers, synthetic rubber, dyes, paints, pesticides, drugs, etc. in soil and water, and in addition, part of hydrocarbons and olefins can generate photochemical reaction with substances with strong oxidizing property, etc. after being irradiated by the sun, secondary pollutants such as ester, aldehyde, ketone, etc. are generated. The photocatalysis technology is always regarded as an environment treatment technology without secondary pollution. Researchers have found that some chemical energy can be recovered in the form of electric energy in the process of degrading organic pollutants.
The existing photocatalytic pollutant removal technology is singleThe photocatalytic technology, in which a single photocatalyst is used for catalytic treatment of organic pollutants, still has the following problems to be solved: such as BiVO4The spectral response range of the catalyst is narrow, and only the ultraviolet part in sunlight can be utilized. The photocatalytic reaction speed is low, and the activity of photocatalytic oxidation of organic pollutants is not high; under the gas phase condition, the photocatalytic degradation intermediate product is easy to accumulate on the surface of the catalyst, and the deactivation of the photocatalyst is fast; the electron-hole separation efficiency is low, and the defects that some organic pollutants are completely mineralized, the degradation is not complete, the speed is slow, the catalyst is easy to lose efficacy and the like cannot be guaranteed.
Disclosure of Invention
The invention aims to overcome the defects of the prior art and provide a method for synchronously denitrifying and degrading organic pollutants by coupling a photocatalytic electrode with a denitrifying microbial fuel cell4/g-C3N4Construction of MOFs photocatalytic electrode coupled denitrification microbial fuel cell system, synchronous denitration and organic pollutant degradation, specifically BiVO4/g-C3N4The preparation of the MOFs composite visible light catalytic anode and the denitrification of nitrate are utilized as the cathode, and the degradation of organic pollutants is completed at the same time, so that an efficient method is provided for combined denitration and organic pollutant treatment.
The invention develops BiVO4/g-C3N4A method for synchronously denitrifying and degrading organic pollutants by coupling MOFs photocatalytic electrodes with denitrifying microbial fuel cells. Adopts a certain proportion of BiVO4And g-C3N4The BiVO is prepared by a simple hydrothermal method4/g-C3N4A composite binary photocatalytic material. The prepared composite photocatalyst, and the sheet MOFs and the carbon cloth synthesized by the micro-fluidic technology are prepared into BiVO through hydrothermal reaction4/g-C3N4The MOFs composite photocatalyst is used as a photo-anode. The other end domesticates nontoxic denitrifying bacteria with strong adhesiveness as a system cathode. Controlling the system to room temperature by a condensed water circulator, adding a certain amount of carbon, nitrogen and phosphorus elements to provide nutrition for microorganisms, and connecting the microorganisms by a leadThe cathode is inserted into a carbon rod to form an electric loop, and BiVO is constructed4/g-C3N4The MOFs photocatalysis electrode is coupled with a denitrification microbial fuel cell system. Finally, the denitrification of nitrate and the degradation of organic pollutants are completed by only utilizing sunlight.
The purpose of the invention can be realized by the following technical scheme:
the method for synchronously denitrifying and degrading organic pollutants by coupling the photocatalytic electrode with the denitrifying microbial fuel cell is characterized by comprising the following steps of:
S1、BiVO4/g-C3N4preparing a composite binary photocatalytic material:
respectively adding the precursor NH4VO3And Bi (NO)3)3·5H2Dissolving O in nitric acid solution, adding urea, stirring, adjusting pH with ammonia solution under stirring until precipitate is formed, standing, adding the precipitate and liquid at the bottom into a reactor, performing hydrothermal reaction, and collecting the precipitate and supernatant to obtain BiVO4/g-C3N4A mixture of a composite binary photocatalytic material and a reaction solution;
S2、BiVO4/g-C3N4preparing a MOFs composite photocatalytic material:
adding polymer sheet MOFs material and carbon cloth into BiVO4/g-C3N4The mixture of the composite binary photocatalytic material and the reaction solution is stirred uniformly and transferred into a reaction kettle for hydrothermal reaction to obtain BiVO4/g-C3N4MOFs composite photocatalytic materials;
S3、BiVO4/g-C3N4establishing and applying an MOFs photocatalytic electrode coupling active microbial fuel cell:
selecting nontoxic and easily-attached denitrifying bacteria to inoculate to the cathode, inserting a carbon rod, and using BiVO4/g-C3N4The composite photocatalytic material is a photoanode and is connected by a lead to form a loop, and the BiVO is formed by generating electric energy through the chemical potential difference of the system4/g-C3N4The MOFs photocatalytic electrode is coupled with a denitrification microbial fuel cell, and organic pollutants are used as an anode solution, so that the pollutants are denitrated and degraded at the same time.
Further, BiVO prepared in S14/g-C3N4BiVO in composite binary photocatalytic material4And g-C3N4The mass ratio of (A) to (B) is 1: 99-1: 9.
Further, BiVO prepared in S14/g-C3N4BiVO in composite binary photocatalytic material4And g-C3N4In a mass ratio of 5: 95.
Further, in S1, the pH of the mixed solution is adjusted to 2.0 by 25% -28% ammonia water under the stirring condition until an orange precipitate is formed, and then the mixed solution is kept stand for 2-2.5 hours.
Further, the hydrothermal reaction time of S1 was 12 hours, and the hydrothermal reaction temperature was 180 ℃.
Further, the high molecular sheet-like MOFs material in S2 is synthesized by a microfluidic technology.
Further, in S2, adding polymer sheet MOFs material and carbon cloth into BiVO4/g-C3N4After the mixture of the composite binary photocatalytic material and the reaction solution is stirred for 12-24 hours, the mixture is transferred to a reaction kettle.
Further, in S2, the hydrothermal reaction time in the reaction vessel was 12 hours, and the hydrothermal reaction temperature was 120 ℃.
Furthermore, in S3, carbon, nitrogen and phosphorus elements are added into the catholyte to provide nutrition for microorganisms;
controlling the temperature of the reaction system by using a condensate water circulator, wherein the temperature control range is as follows: 2-10 ℃, preventing the temperature from being overhigh and killing microorganisms.
Further, the contaminants include nitrates and organic contaminants.
g-C in the invention3N4The (graphite phase carbon nitride) can perform a photocatalytic reaction under visible light, has good photocatalytic performance, and becomes a popular material with prospect in the field of photocatalysis.
The MOFs has a highly porous and crystalline structure, so that the transport distance from a current carrier to the surface of a reaction hole is shortened, the recombination between a photon-generated electron and a photon-generated hole is inhibited, the good crystallinity has excellent stability, a recombination center generated by possible structural defects can be avoided, and an enriched substrate can be easily close to a high-density catalytic site in an ordered pore channel structure due to the large specific surface area of the MOFs. MOFs materials also behave like semiconductors.
BiVO is used in the invention4/g-C3N4the/MOFs composite material is used as a photo-anode, denitrifying bacteria are used as microbial cathodes, carbon rods are inserted, and the carbon rods are connected through a lead to form a conductive loop, so that a photocatalytic microbial fuel cell system is formed. Finally, denitrification of nitrate and degradation of organic pollutants are realized under the condition of simulated illumination.
Compared with the prior art, the invention has the following advantages:
1) comparing the single photocatalyst for catalytic treatment of organic pollutants, g-C3N4、BiVO4And the heterojunction structure formed after the MOFs are compounded not only effectively inhibits the recombination of photo-generated electrons and holes and promotes the transmission of photo-generated charges, but also effectively improves the stability and the activity of the catalyst. And the MOFs have a structure with high porosity and crystallinity, so that the conveying distance from a carrier to the surface of a reaction hole is shortened, and BiVO4/g-C3N4the/MOFs composite photoelectric catalytic material can prevent recombination centers generated by possible structural defects.
2)BiVO4/g-C3N4The development of the method for synchronously denitrifying and degrading organic pollutants by coupling the MOFs photocatalytic electrode with the denitrifying microbial fuel cell realizes an integrated removal mode of two water pollutants, and the technology is green, has no secondary pollution, and has a very wide application value in the fields of environmental pollution control, solar energy utilization and the like.
Drawings
FIG. 1 shows the investigation of different BiVO using phenol as the target pollutant4/g-C3N4BiVO under the condition of load ratio4/g-C3N4A comparison graph of phenol degrading effects of a method for synchronously denitrifying and degrading organic pollutants by coupling MOFs photocatalytic electrodes with denitrifying microbial fuel cells. In the figure, the abscissa represents time (h), and the ordinate represents the degradation efficiency (%) of phenol.
FIG. 2 is a graph of the degradation efficiency of phenol by the method of simultaneous denitration and degradation of organic pollutants by coupling different active components/MOFs photocatalytic electrodes with a denitrification microbial fuel cell. In the figure, the abscissa represents time (h), and the ordinate represents the degradation efficiency (%) of phenolics.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
BiVO in the invention4/g-C3N4A method for synchronously denitrifying and degrading organic pollutants by coupling MOFs photocatalytic electrodes with denitrifying microbial fuel cells is summarized as the following steps:
step 1, BiVO4/g-C3N4Preparing a composite binary photocatalytic material: all the chemicals are analytically pure, and BiVO with different combination ratios is synthesized by a hydrothermal method4/g-C3N4A composite binary photocatalyst. First, 0.1mmol NH of the precursor respectively4VO3(0.01178g) and 0.1228mmol of Bi (NO)3)3·5H2Dissolving O (0.05957g) in 50mL of 2.0M nitric acid solution, adding 4.2768g of urea and BiVO as precursors4And g-C3N4At a mass ratio of 1:99 (corresponding to a loading of 1% in fig. 1); respectively adding 0.6mmol NH of the precursor4VO3(0.0702g) and 0.7368mmol of Bi (NO)3)3·5H2Dissolving O (0.35741g) in 50mL of 2.0M nitric acid solution, adding 3.6936g of urea and BiVO as precursors4And g-C3N4Is 5:95 (corresponding to a loading of 5% in fig. 1); respectively adding 1.2mmol NH of the precursor4VO3(0.14075g) and 1.4736mmol of Bi (NO)3)3·5H2Dissolving O (0.71482g) in 50mL of 2.0M nitric acid solution, adding 3.4992g of urea and BiVO as precursors4And g-C3N4Is 1:9 (corresponding to a loading amount of 10% in fig. 1).
It can be seen that x BiVO in the invention4/y g-C3N4And the value range of x to y is not more than 1:9 and not less than 1:99, so that a more ideal degradation effect can be realized. Then, the pH of the mixed solution is adjusted to 2.0 by 25% -28% ammonia water under the stirring condition until an orange precipitate is formed, the mixed solution is kept stand for 2-2.5 hours, then the solution and the precipitate at the bottom of the beaker are transferred to a polytetrafluoroethylene lining of a stainless steel autoclave with the capacity of 150mL, and the hydrothermal treatment is carried out for 12 hours at 180 ℃.
Step 2, BiVO4/g-C3N4Preparing a MOFs composite photocatalytic material: preparing a high-molecular sheet MOFs material, and putting the MOFs material into the BiVO prepared in the step 14/g-C3N4Mixing and stirring a binary composite material solution, a precipitate, a high-molecular sheet MOFs material synthesized by a microfluidic technology and a carbon cloth at the bottom of a beaker for 12-24 hours, transferring the mixture into a polytetrafluoroethylene lining of a stainless steel autoclave with the capacity of 150mL, carrying out hydrothermal reaction at 120 ℃ for 12 hours, and cooling the autoclave to room temperature to obtain BiVO4/g-C3N4the/MOFs composite photoelectrocatalysis electrode.
Step 3, BiVO4/g-C3N4Establishing a MOFs photocatalytic electrode coupling active microbial fuel cell system: selecting non-toxic and easily-attached denitrifying bacteria to inoculate the cathode, and inserting a carbon rod. With BiVO4/g-C3N4The composite photocatalytic material is used as a system cathode and is connected by using a lead to form a loop, a xenon lamp is used for providing a light source for simulating visible light, and electric energy is generated through the chemical potential difference of the system to form BiVO4/g-C3N4The MOFs photocatalytic electrode is coupled with a denitrification microbial fuel cell, so that the denitrification is realized, and the degradation of organic pollutants is completed at the same time. A certain amount of carbon, nitrogen and phosphorus elements are required to be added to the cathode to provide nutrition for microorganisms; controlling the temperature of the reaction system by using a condensate water circulator, wherein the temperature control range is as follows: 2-10 deg.c to prevent over high temperature and kill microbe.
Examples 1 to 3
Different BiVO4/g-C3N4BiVO of load ratio4/g-C3N4Phenol degradation effect of/MOFs photocatalytic electrode as anode (1%, 5% and 10%, respectively)
Using BiVO4And g-C3N4The precursor is prepared into different BiVO by a simple hydrothermal method4/g-C3N4BiVO of load ratio4/g-C3N4the/MOFs photocatalysis electrode is used as an anode, the other end of the electrode domesticates denitrifying bacteria with strong adhesiveness, and a carbon rod is inserted into the electrode as a cathode. And a conductive circuit is formed by connecting wires, and a visible light source is simulated by a xenon lamp. And (3) turning off a xenon lamp power supply before the reaction, turning on the xenon lamp power supply after dark reaction for 30min, carrying out light reaction for 1h, taking a sample every 1.0h after the reaction starts, carrying out light reaction for 7h, detecting the content of phenol in the sample by using HPLC (high performance liquid chromatography), and calculating the degradation efficiency.
In FIG. 1, 5% BiVO in examples 1 to 34/95％g-C3N4The MOFs photo-anode has the best degradation effect, and the degradation efficiency is 97.30%.
1％BiVO4/95％g-C3N4MOFs photo anode and 10% BiVO4/95％g-C3N4The degrading effect of the MOFs photo-anode is the second time, and the larger or smaller loading capacity can not achieve the better degrading effect.
Comparative examples 1 to 3
BiVO respectively corresponds to the comparative examples4/g-C3N4、BiVO4、g-C3N4And (3) testing the phenol degrading effect of the three active component and inactive component systems.
Using BiVO4And g-C3N4The precursor is prepared into BiVO with the same quality by a simple hydrothermal method4/g-C3N4Composite active component and BiVO4Photocatalytic Material g-C3N4Photocatalytic material, active components, flaky MOFs and carbon cloth are prepared by using polytetrafluoroethylene lining and hydrothermal reaction kettle through hydrothermal methodCombining to prepare a photoanode; the other end domesticates the denitrifying bacteria with strong adhesiveness, and a carbon rod is inserted as a cathode. The conductive circuits are formed by connecting wires respectively, and a group of control groups without photocatalyst is made. Adding a xenon lamp to simulate visible light to provide a light source, turning off a xenon lamp power supply before reaction, turning on the xenon lamp power supply after dark reaction for 30min, carrying out light reaction for 1h, sampling every 1.0h after the reaction starts, carrying out light reaction for 7h, detecting the content of phenol in the sample by using HPLC (high performance liquid chromatography), and calculating the degradation efficiency.
In FIG. 2, BiVO 5% in comparative examples 1 to 34/g-C3N4The degradation effect of the/MOFs is optimal, and the degradation efficiency of the photocatalytic reaction for 7 hours is 97.30 percent and is far higher than that of BiVO4/MOFs、BiVO4And the degradation efficiency of the MOFs for degrading the organic pollutant phenol is 78.21%, 70.84% and 58.31% respectively.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.

Claims (10)

1. A method for synchronously denitrifying and degrading organic pollutants by coupling a photocatalytic electrode with a denitrifying microbial fuel cell is characterized by comprising the following steps:
S1、BiVO4/g-C3N4preparing a composite binary photocatalytic material:
respectively adding the precursor NH4VO3And Bi (NO)3)3·5H2Dissolving O in nitric acid solution, adding urea, stirring, adjusting pH with ammonia solution under stirring until precipitate is formed, standing, adding the precipitate and liquid at the bottom into a reactor, performing hydrothermal reaction, and collecting the precipitate and supernatant to obtain BiVO4/g-C3N4A mixture of a composite binary photocatalytic material and a reaction solution;
S2、BiVO4/g-C3N4preparing a MOFs composite photocatalytic material:
adding polymer sheet MOFs material and carbon cloth into BiVO4/g-C3N4The mixture of the composite binary photocatalytic material and the reaction solution is stirred uniformly and transferred into a reaction kettle for hydrothermal reaction to obtain BiVO4/g-C3N4MOFs composite photocatalytic materials;
S3、BiVO4/g-C3N4establishing and applying an MOFs photocatalytic electrode coupling active microbial fuel cell:
selecting nontoxic and easily-attached denitrifying bacteria to inoculate to the cathode, inserting a carbon rod, and using BiVO4/g-C3N4The composite photocatalytic material is a photoanode and is connected by a lead to form a loop, and the BiVO is formed by generating electric energy through the chemical potential difference of the system4/g-C3N4The MOFs photocatalytic electrode is coupled with a denitrification microbial fuel cell, and organic pollutants are used as an anode solution to denitrate nitrate and degrade the organic pollutants at the same time.
2. The method for synchronously denitrifying and degrading organic pollutants by coupling a photocatalytic electrode with a denitrifying microbial fuel cell as claimed in claim 1, wherein BiVO prepared in S14/g-C3N4BiVO in composite binary photocatalytic material4And g-C3N4The mass ratio of (A) to (B) is 1: 99-1: 9.
3. The method for synchronously denitrifying and degrading organic pollutants by coupling a photocatalytic electrode with a denitrifying microbial fuel cell as claimed in claim 2, wherein the BiVO prepared in S14/g-C3N4BiVO in composite binary photocatalytic material4And g-C3N4In a mass ratio of 5: 95.
4. The method for synchronously denitrifying and degrading organic pollutants by using the photocatalytic electrode coupled denitrification microbial fuel cell as claimed in claim 1, wherein the pH of the mixed solution is adjusted to 2.0 by using 25% -28% ammonia water under the stirring condition in S1 until an orange precipitate is formed, and then the mixed solution is kept stand for 2-2.5 hours.
5. The method for synchronously denitrifying and degrading organic pollutants by coupling the photocatalytic electrode with the denitrification microbial fuel cell as claimed in claim 1, wherein the hydrothermal reaction time in S1 is 12 hours, and the hydrothermal reaction temperature is 180 ℃.
6. The method for synchronously denitrifying and degrading organic pollutants by coupling the photocatalytic electrode with the denitrification microbial fuel cell as claimed in claim 1, wherein the macromolecular flaky MOFs material in S2 is synthesized by a microfluidic technology.
7. The method for synchronously denitrating and degrading organic pollutants by coupling a photocatalytic electrode with a denitrifying microbial fuel cell as claimed in claim 1, wherein in S2, macromolecular flaky MOFs material and carbon cloth are added into BiVO4/g-C3N4After the mixture of the composite binary photocatalytic material and the reaction solution is stirred for 12-24 hours, the mixture is transferred to a reaction kettle.
8. The method for synchronously denitrating and degrading organic pollutants by the photocatalytic electrode coupled denitrification microbial fuel cell as claimed in claim 1, wherein the hydrothermal reaction time in the reaction kettle in S2 is 12h, and the hydrothermal reaction temperature is 120 ℃.
9. The method for synchronously denitrating and degrading organic pollutants by coupling the photocatalytic electrode with the denitrification microbial fuel cell as claimed in claim 1, wherein in S3, carbon, nitrogen and phosphorus elements are added into catholyte to provide nutrients for microbes;
controlling the temperature of the reaction system by using a condensate water circulator, wherein the temperature control range is as follows: 2-10 ℃, preventing the temperature from being overhigh and killing microorganisms.
10. The method of claim 1, wherein the contaminants comprise nitrates and organic contaminants.
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