CN112850914A - Application of rhodium complex in promoting photosynthetic bacteria to degrade azo dye and method for promoting photosynthetic bacteria to degrade azo dye - Google Patents

Application of rhodium complex in promoting photosynthetic bacteria to degrade azo dye and method for promoting photosynthetic bacteria to degrade azo dye Download PDF

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CN112850914A
CN112850914A CN202110228859.8A CN202110228859A CN112850914A CN 112850914 A CN112850914 A CN 112850914A CN 202110228859 A CN202110228859 A CN 202110228859A CN 112850914 A CN112850914 A CN 112850914A
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photosynthetic bacteria
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degrade
rhodium complex
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CN112850914B (en
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张新颖
林暮雪
王永净
刘明华
刘璐
赵少宏
黄彦琦
张禹城
周亚
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Fuzhou University
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    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F3/00Biological treatment of water, waste water, or sewage
    • C02F3/34Biological treatment of water, waste water, or sewage characterised by the microorganisms used
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    • C07F15/00Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
    • C07F15/0006Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
    • C07F15/0073Rhodium compounds

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Abstract

The invention provides application of a rhodium complex in promoting photosynthetic bacteria to degrade azo dyes and a method for promoting photosynthetic bacteria to degrade azo dyes, belonging to the field of degrading azo dyes by biological bacteria. The method accelerates the degradation rate of the photosynthetic bacteria to the azo dyes by adding an electron medium. Firstly, preparing intermediate precipitate by using rhodium metal polymer, dissolving the intermediate precipitate in water, hydrolyzing the intermediate precipitate to generate rhodium metal complex serving as an electronic medium, taking azo dye as a target pollutant, and adding a proper amount of photosynthetic bacteria into the solution. After the rhodium metal complex is added, the decolorization of the azo dye and the degradation efficiency of COD by the photosynthetic bacteria are higher.

Description

Application of rhodium complex in promoting photosynthetic bacteria to degrade azo dye and method for promoting photosynthetic bacteria to degrade azo dye
Technical Field
The invention relates to the field of degrading azo dyes by biological bacteria, in particular to application of a rhodium complex in promoting photosynthetic bacteria to degrade azo dyes and a method for promoting photosynthetic bacteria to degrade azo dyes.
Background
China is the largest textile production and export country in the world, and the amount of textile wastewater generated each year accounts for 11% of the total discharge amount of industrial wastewater. The annual dye yield worldwide is about 100 million t, with azo dyes being the most produced and extremely difficult to handle. The high utilization rate of azo dyes leads to the continuous increase of organic wastewater. Azo dyes are characterized by the presence of one or more azo (-N ═ N-) groups, and usually from 1 to 4 groups, linked to phenyl and naphthyl groups. These aromatic groups are usually combined with substituents, such as hydroxy (-OH), methyl (-CH)3) Nitro (-NO)2) Sulfonic acid (-SO)3H) And sodium salt (-SO)3Na), and the like. The azo dye has high chroma, is difficult to degrade in natural environment and has biotoxicity, so the azo dye has serious influence on the ecological balance of the water body. In addition, the azo dye is an aniline organic compound, and can be decomposed to generate more than twenty carcinogenic aromatic amine substances to cause canceration of human bodies under certain special conditions, thereby influencing the health of human beings.
The treatment means of the printing and dyeing wastewater are mainly divided into three major categories, namely a physical method, a chemical method and a biological method, wherein the biological method is the most widely applied method at present. The biological method for treating the dye wastewater refers to that microorganisms take organic pollutants as a carbon source, utilize the self life metabolic activity to separate the dye from the wastewater or convert the dye into an intermediate product or a simple inorganic substance, and further realize sewage purification. However, the dye wastewater has high concentration and complex water quality, and the biological treatment method has certain limitation. Practice shows that the traditional biological method for treating the printing and dyeing wastewater by the wastewater treatment plant cannot effectively degrade organic dyes in the wastewater. However, researches in recent years show that the photosynthetic bacteria have better degradation performance on azo dyes, and the decolorization rate of 12 dyes reaches over 75 percent. Compared with common activated sludge or microbial communities, the photosynthetic bacteria have better adaptability to pH, temperature and salinity, are wider in adaptability and easy to control, can tolerate high-concentration and high-salinity organic wastewater, have certain degradation capability on toxic substances, and cannot generate secondary pollution. Therefore, the photosynthetic bacteria are suitable for degrading azo dye wastewater. As a biological treatment method, the problems of long treatment time, low degradation efficiency and the like still need to be solved.
In the existing multiple coenzyme regeneration technology, Methyl Viologen (MV) is often used2+) And rhodium complex [ CpRh (bpy) (H)2O)]2+As an electronic medium. However, methyl viologen is a toxic substance, easily causes secondary pollution, has strong reducibility and has no selectivity. And [ Cp Rh (bpy) (H)2O)]2+Is the most suitable electronic medium in the enzymatic redox reaction and the regeneration process of various coenzymes at present, can keep activity under a wide range of pH values and temperatures and can maintain stable chemical properties even under extreme conditions, and the prior researches are used for nicotinoyl coenzyme NADH and reduced flavin dinucleotide FADH2And (4) regeneration. But directly adds electronic medium [ Cp Rh (bpy) (H) in complex biological system2O)]2+Studies that promote biological activity are rarely reported.
Disclosure of Invention
The invention aims to provide application of a rhodium complex in promoting photosynthetic bacteria to degrade azo dyes and a method for promoting photosynthetic bacteria to degrade azo dyes.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides an application of a rhodium complex in promoting photosynthetic bacteria to degrade azo dyes, wherein the rhodium complex contains an electron medium [ CpRh (bpy) ((H))2O)]2+
The invention provides a method for promoting photosynthetic bacteria to degrade azo dyes, which comprises the following steps:
and mixing the photosynthetic bacteria suspension, the organic carbon source, the azo dye solution and the rhodium complex solution.
Further, the photosynthetic bacteria are rhodospirillum; the absorbance value of the photosynthetic bacteria suspension is 1.2-1.6.
Further, the azo dye is one or more of reactive red, methyl orange, congo red, acid orange and Sudan red, and the concentration of the azo dye solution is 45-55 mg/L.
Furthermore, the concentration of the rhodium complex solution is 2.5-3.5 mM.
Further, the organic carbon source is glucose with the concentration of 850-950 mg/L.
Further, the volume ratio of the photosynthetic bacteria suspension to the organic carbon source to the rhodium complex solution to the azo dye solution is 10-15: 450-500: 0.5-2: 200 to 300.
The invention has the beneficial effects that:
the invention adds electron medium [ Cp Rh (bpy) (H) into dye solution containing photosynthetic bacteria2O)]2+The rhodium complex and the rhodium complex are matched with each other, so that the reaction process of the photosynthetic bacteria for degrading the azo dye is accelerated. Compared with the photosynthetic bacteria without the rhodium complex, the photosynthetic bacteria added with the rhodium complex has the dye removal efficiency as high as 82.2 percent and the COD removal efficiency as high as 59 percent.
Drawings
FIG. 1 is a schematic diagram of the effect of the photosynthetic bacteria with added rhodium complex and the photosynthetic bacteria without added rhodium complex on dye decolorization and degradation in example 1.
FIG. 2 is a schematic diagram showing the effect of the photosynthetic bacteria to remove COD in example 1, wherein the rhodium complex is added, and the photosynthetic bacteria are not added with the rhodium complex.
Detailed Description
The invention provides an application of a rhodium complex in promoting photosynthetic bacteria to degrade azo dyes.
In the present invention, the rhodium complex comprises an electron mediator [ CpRh (bpy) (H)2O)]2+
In the present invention, the rhodium complex is preferably [ Cp × rh (bpy) Cl ] Cl.
The invention provides a method for promoting photosynthetic bacteria to degrade azo dyes, which comprises the following steps:
and mixing the photosynthetic bacteria suspension, the organic carbon source, the azo dye solution and the rhodium complex solution.
In the present invention, the photosynthetic bacteria are preferably rhodospirillum; the absorbance value of the photosynthetic bacteria bacterial suspension is 1.2-1.6, and preferably 1.4.
In the invention, the azo dye is preferably one or more of reactive red, methyl orange, congo red, acid orange and Sudan red, and the reactive red is preferably reactive red 2; the concentration of the azo dye solution is preferably 45-55 mg/L, and more preferably 50 mg/L.
In the invention, the preparation method of the rhodium complex solution comprises the following steps: adding a solvent and 2,2' -bipyridyl into a rhodium metal polymer in sequence to react to obtain a metal complex solution, heating and crystallizing the metal complex solution in a water bath to obtain an intermediate, and mixing the intermediate with water to obtain a rhodium complex solution;
in the present invention, in the above preparation method, the solvent is preferably anhydrous methanol, wherein the volume-to-mass ratio of the solvent, the 2,2' -bipyridine and the rhodium metal polymer is preferably (3 to 5) mL: (9-11) mg: (15-25) mg, more preferably 4 mL: 10.1 mg: 20 mg.
In the present invention, in the above production method, the rhodium metal polymer is preferably [ Cp + RhCl ]2]2
In the preparation method, the reaction temperature of the 2,2' -bipyridyl and the rhodium metal polymer is 20-30 ℃, and preferably 25 ℃.
In the present invention, in the above preparation method, the temperature for heating the metal complex solution in a water bath is 55 to 65 ℃, preferably 60 ℃; the heating time is 1.5-2.5h, preferably 2 h.
In the present invention, the concentration of the rhodium complex solution is preferably 2.5 to 3.5mM, and more preferably 3.0 mM.
In the invention, the organic carbon source is preferably glucose with the concentration of 850-950 mg/L, more preferably glucose with the concentration of 880-920 mg/L, and even more preferably glucose with the concentration of 900 mg/L.
In the invention, the volume ratio of the photosynthetic bacteria suspension, the organic carbon source, the rhodium complex solution and the azo dye solution is preferably 10-15: 450-500: 0.5-2: 200 to 300, more preferably 11 to 14: 470-480: 1-1.8: 220 to 280, more preferably 13: 475: 1.5: 250.
the technical solutions provided by the present invention are described in detail below with reference to examples, but they should not be construed as limiting the scope of the present invention.
Example 1
1. 20.00mg of [ Cp + RhCl ] was taken2]2Placing into a beaker, adding 4mL of anhydrous methanol, red [ Cp + RhCl2]2Insoluble and suspended in methanol. To the suspension was added 10.10mg of 2,2' -bipyridine and the mixture was reacted with [ Cp + RhCl ] at 25 deg.C2]2The reaction lasts for 2h to form a metal complex, and the red suspended substance gradually disappears to generate an orange solution. The solution was heated in a water bath at 55 ℃ for 2h to evaporate the methanol and the solution was concentrated to 1 mL. At 4 deg.C, dropwise adding anhydrous diethyl ether to the concentrated solution to make [ Cp Rh (bpy) Cl]Cl gradually precipitated. The precipitate was collected and dissolved in water to prepare a 3mM solution, which was stored at 4 ℃. [ Cp + Rh (bpy) Cl]Cl is immediately hydrolyzed in water to generate [ Cp Rh (bpy) ((H))2O)]2+
2. Taking 2 erlenmeyer flasks, and marking as an erlenmeyer flask 1 and an erlenmeyer flask 2;
the conical flask 1: 250mL of active red 2 solution with the concentration of 50mg/L, bacterial suspension prepared by rhodospirillum with the wet weight of 3g and 0.225g of glucose; the absorbance of the rhodospirillum suspension measured at OD660 was 1.2.
The conical flask 2: 250mLActivated Red 2 solution with concentration of 50mg/L, suspension prepared from Rhodospirillum with wet weight of 3g, glucose 0.225g, and 1mL of prepared suspension containing [ Cp Rh (bpy) ((H))2O)]2+The solution of (1);
after the mixture is uniformly mixed, the mixed solution in the two conical flasks is irradiated for 12 hours under a halogen lamp light source of 300W, then sampling is respectively carried out, and the concentration of the azo dye and the removal rate of COD in the two conical flasks are calculated, wherein the sampling time interval is 24 hours.
Example 1 of the invention will determine whether to add [ Cp Rh (bpy) (H)2O)]2+As experimental variables, the effect of adding or not adding rhodium complex on the degradation of dye by photosynthetic bacteria was compared. The sampling time interval was 24 hours, and the decolorization of the dye and the removal of COD were analyzed. As can be seen from FIG. 1, the rate of decolorization is much faster after the addition of the rhodium complex to the dye solution than when the rhodium complex solution is not added. As can be seen from fig. 2, the removal rate of COD in the dye solution by the photosynthetic bacteria was always higher than that of the solution without the rhodium complex added. From this, it was found that the addition of rhodium complex in the dye solution can promote the degradation of the photosynthetic bacteria.
Example 2
1. 25.00mg of [ Cp + RhCl ] was taken2]2Placing into a beaker, adding 3mL of anhydrous methanol, red [ Cp + RhCl2]2Insoluble and suspended in methanol. To the suspension was added 15.00mg of 2,2' -bipyridine and the mixture was reacted with [ Cp + RhCl ] at 30 ℃2]2The reaction is carried out for 1.5h to form a metal complex, and the red suspended substance gradually disappears to generate an orange solution. The solution was heated in a water bath at 60 ℃ for 1.5h to evaporate the methanol and the solution was concentrated to 1 mL. At 4 deg.C, dropwise adding anhydrous diethyl ether to the concentrated solution to make [ Cp Rh (bpy) Cl]Cl gradually precipitated. The precipitate was collected and dissolved in water to prepare a 4mM solution and stored at 4 ℃. [ Cp + Rh (bpy) Cl]Cl is immediately hydrolyzed in water to generate [ Cp Rh (bpy) ((H))2O)]2+
2. Taking a conical flask, and preparing 250mL of active red 2 solution with the concentration of 50 mg/L;
and (3) preparing rhodospirillum with wet weight of 3g into bacterial suspension, and adding the rhodospirillum bacterial suspension into the prepared active red 2 solution for mixing. The absorbance of the rhodospirillum suspension measured at OD660 was 1.4.
3. 0.225g of glucose is used as an organic carbon source required by growth of rhodospirillum, and the initial carbon source concentration is 900mg/L when the solution prepared in the step 2 is added.
4. 1.5mL of the prepared solution containing [ Cp Rh (bpy) (H)2O)]2+And (3) adding the solution in the step (2) into the mixed solution, uniformly stirring, and irradiating the mixed solution for 12 hours under a 300W halogen lamp light source.
By verification, the treatment method obtained in example 2 has the removal rate of 88% for the reactive red 2 dye solution and the removal rate of COD of 55%.
Example 3
1. 20.00mg of [ Cp + RhCl ] was taken2]2Placing into a beaker, adding 5mL of anhydrous methanol, red [ Cp + RhCl2]2Insoluble and suspended in methanol. To the suspension was added 10.10mg of 2,2' -bipyridine and the mixture was reacted with [ Cp + RhCl ] at 20 deg.C2]2The reaction lasts for 2h to form a metal complex, and the red suspended substance gradually disappears to generate an orange solution. The solution was heated in a water bath at 65 ℃ for 2h to evaporate the methanol and the solution was concentrated to 1 mL. At 4 deg.C, dropwise adding anhydrous diethyl ether to the concentrated solution to make [ Cp Rh (bpy) Cl]Cl gradually precipitated. The precipitate was collected and dissolved in water to prepare a 4mM solution and stored at 4 ℃. [ Cp + Rh (bpy) Cl]Cl is immediately hydrolyzed in water to generate [ Cp Rh (bpy) ((H))2O)]2+
2. Taking a conical flask, and preparing 250mL of active red 2 solution with the concentration of 50 mg/L;
and (3) preparing rhodospirillum with wet weight of 3g into bacterial suspension, and adding the rhodospirillum bacterial suspension into the prepared active red 2 solution for mixing. The absorbance of the rhodospirillum suspension measured at OD660 was 1.6.
3. 0.225g of glucose is used as an organic carbon source required by growth of rhodospirillum, and the initial carbon source concentration is 900mg/L when the solution prepared in the step 2 is added.
4. 0.8mL of the prepared solution containing [ Cp Rh (bpy) (H)2O)]2+And (3) adding the solution in the step (2) into the mixed solution, uniformly stirring, and irradiating the mixed solution for 12 hours under a 300W halogen lamp light source.
By verification, the treatment method obtained in example 2 has the removal rate of 86.7% for the reactive red 2 dye solution and the removal rate of COD of 56%.
From the above embodiments, the present invention provides an application of rhodium complex in promoting photosynthetic bacteria to degrade azo dyes and a method for promoting photosynthetic bacteria to degrade azo dyes. The invention relates to an electron mediator [ Cp + Rh (bpy) (H) with excellent enzyme activity2O)]2+The method is added into a biological bacteria system, greatly accelerates the speed of the photosynthetic bacteria degrading azo dyes and the removal rate of COD, and is safe, environment-friendly, simple to operate and high in feasibility.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.

Claims (7)

1. The application of rhodium complex in promoting photosynthetic bacteria to degrade azo dye is characterized in that the rhodium complex contains electron medium [ CpRh (bpy) ((H))2O)]2+
2. A method for promoting photosynthetic bacteria to degrade azo dyes is characterized by comprising the following steps:
and mixing the photosynthetic bacteria suspension, the organic carbon source, the azo dye solution and the rhodium complex solution.
3. A method for promoting photosynthetic bacteria to degrade azo dyes according to claim 2 wherein the photosynthetic bacteria are rhodospirillum; the absorbance value of the photosynthetic bacteria suspension is 1.2-1.6.
4. The method for promoting photosynthetic bacteria to degrade azo dyes according to claim 3, wherein the azo dyes are one or more of reactive red, methyl orange, congo red, acid orange and Sudan red, and the concentration of the azo dye solution is 45-55 mg/L.
5. The method for promoting photosynthetic bacteria to degrade azo dyes of claim 4 wherein the concentration of the rhodium complex solution is 2.5-3.5 mM.
6. The method for promoting photosynthetic bacteria to degrade azo dyes of claim 5, wherein the organic carbon source is glucose with a concentration of 850-950 mg/L.
7. The method for promoting photosynthetic bacteria to degrade azo dyes according to any one of claims 2 to 6, wherein the volume ratio of the photosynthetic bacteria suspension, the organic carbon source, the rhodium complex solution and the azo dye solution is 10-15: 450-500: 0.5-2: 200 to 300.
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Citations (3)

* Cited by examiner, † Cited by third party
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DE10339790A1 (en) * 2003-08-28 2005-03-17 Umicore Ag & Co.Kg Rhodium (I) diene bis-aqua complexes, process for their preparation and their use
CN101050444A (en) * 2007-03-09 2007-10-10 重庆大学 Bacterial strain of photosynthetic bacterium possessing behavior of producing hydrogen
CN101948768A (en) * 2010-08-20 2011-01-19 沈阳大学 Method for preparing photosynthetic bacteria for degrading 2-chlorophenol

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10339790A1 (en) * 2003-08-28 2005-03-17 Umicore Ag & Co.Kg Rhodium (I) diene bis-aqua complexes, process for their preparation and their use
CN101050444A (en) * 2007-03-09 2007-10-10 重庆大学 Bacterial strain of photosynthetic bacterium possessing behavior of producing hydrogen
CN101948768A (en) * 2010-08-20 2011-01-19 沈阳大学 Method for preparing photosynthetic bacteria for degrading 2-chlorophenol

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
周汝利: "石墨烯改性TiO2光催化再生辅酶及[Cp*Rh(bpy)(H2O)]2+前体的固定化", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 *

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