CN108439567B - Transition metal chlorophyll derivative Fenton reaction reagent and application thereof - Google Patents

Transition metal chlorophyll derivative Fenton reaction reagent and application thereof Download PDF

Info

Publication number
CN108439567B
CN108439567B CN201810274621.7A CN201810274621A CN108439567B CN 108439567 B CN108439567 B CN 108439567B CN 201810274621 A CN201810274621 A CN 201810274621A CN 108439567 B CN108439567 B CN 108439567B
Authority
CN
China
Prior art keywords
fenton
transition metal
reaction
ion
chlorophyll derivative
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
Application number
CN201810274621.7A
Other languages
Chinese (zh)
Other versions
CN108439567A (en
Inventor
胡敬平
张鹏
潘可亮
杨小容
赵晓娜
李星吾
陈思静
侯慧杰
刘冰川
杨家宽
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Huazhong University of Science and Technology
Original Assignee
Huazhong University of Science and Technology
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Huazhong University of Science and Technology filed Critical Huazhong University of Science and Technology
Priority to CN201810274621.7A priority Critical patent/CN108439567B/en
Publication of CN108439567A publication Critical patent/CN108439567A/en
Application granted granted Critical
Publication of CN108439567B publication Critical patent/CN108439567B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Images

Classifications

    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00—Treatment of water, waste water, or sewage
    • C02F1/72—Treatment of water, waste water, or sewage by oxidation
    • C02F1/722—Oxidation by peroxides
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00—Nature of the contaminant
    • C02F2101/30—Organic compounds
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/023—Reactive oxygen species, singlet oxygen, OH radical
    • C—CHEMISTRY; METALLURGY
    • C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00—Use of specific compounds during water treatment
    • C02F2305/02—Specific form of oxidant
    • C02F2305/026—Fenton's reagent

Landscapes

  • Life Sciences & Earth Sciences (AREA)
  • Hydrology & Water Resources (AREA)
  • Engineering & Computer Science (AREA)
  • Environmental & Geological Engineering (AREA)
  • Water Supply & Treatment (AREA)
  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment Of Water By Oxidation Or Reduction (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)

Abstract

The invention discloses a Fenton-like reagent for degrading organic pollutants and application thereof, and belongs to the field of water pollution treatment. The TMCD can react with various oxidants in aqueous solution, and can efficiently degrade various persistent pollutants without illumination conditions. Has good degradation effect in the range of pH more than 3. The method can rapidly and efficiently degrade various pollutants which are difficult to degrade, and the effect is obviously superior to that of the existing Fenton and Fenton-like water treatment technology.

Description

Transition metal chlorophyll derivative Fenton reaction reagent and application thereof
Technical Field
The invention belongs to the field of environmental water pollution treatment, and particularly relates to a transition metal chlorophyll derivative Fenton reaction reagent and application thereof in degradation of organic pollutants.
Background
With the rapid development of printing and dyeing, pharmacy, chemical industry and other industries and the large use of pesticides in agriculture, the discharge amount of various organic wastewater difficult to degrade is increasing day by day. The pollutants which are difficult to degrade are accumulated in soil and water for a long time, and some pollutants even have carcinogenic, teratogenic and mutagenic effects, thereby causing great influence on the ecological environment and human health.
These organic pollutants such as pesticides, drugs, dyes, etc. have very high chemical stability and very poor biodegradability, which makes them difficult to remove by conventional biological treatment methods, so that the need for developing a new method to degrade these organic pollutants which are difficult to degrade is urgent. Advanced oxidation techniques have good results for these poorly biodegradable contaminants. Wet oxidation, electro-Fenton, ultrasound, photocatalytic technologies, etc., can degrade various pollutants to a certain extent. Among all advanced oxidation technologies, the fenton technology has received extensive attention from researchers due to its characteristics of simple operation, high degradation efficiency, environmental friendliness, and the like.
The classical Fenton system is carried out by reacting ferrous iron with H2O2The reaction of (2) generates hydroxyl free radicals and superoxide free radicals, has very high oxidation-reduction potential, and can oxidize most organic matters without selectivity. However, the classical Fenton reaction also has some disadvantages, such as Fe (II) and H2O2The rate of reaction to hydroxyl radicals is greater than the rate of reaction of Fe (III) with H2O2The rate of Fe (II) formation by the reaction is several orders of magnitude higher, resulting in a large accumulation of Fe (III), which in turn precipitates due to hydrolysis, preventing Fe (III)/Fe (II) cycling during the reaction. The classical fenton reaction requires strict control of pH conditions below 3 to prevent precipitation of Fe (III), thereby greatly increasing the cost of the process.
To achieve a more efficient Fe (III)/Fe (II) cycle, the classical Fenton reaction can be modified by: (1) the introduction of ultraviolet irradiation in the fenton system to promote the regeneration of Fe (II) also causes problems of excessive energy consumption and cost. (2) With nano-Fe3O4The heterogeneous Fenton system replaces the traditional homogeneous Fenton system, and Fe in a solid phase3O4The catalyst solves the problem that Fe (III) is easy to precipitate, so that the degradation of pollutants can be carried out under the neutral pH condition. But because the leaching of Fe ions is slow and the heterogeneous catalytic reaction rate of the interface is slow, the efficiency of degrading pollution is higher than that of classical FentonThe reaction is much smaller.
Recent studies have found that organic complexes of iron, such as aminocarboxylates, overcome these disadvantages of the classical fenton reaction, allowing contaminant degradation to proceed under neutral pH conditions. The carboxylic acid groups in these materials are attached to tertiary nitrogen atoms therein, the metal cations are centered and coordinate to confine the nitrogen and oxygen atoms, and unlike typical ligands, these chelating agents can form multiple bonds with a single metal ion, firmly immobilizing the metal ion in the middle. Although ligands such as EDTA, NTA, EDDS, oxalic acid, citric acid, tartaric acid, succinic acid and the like can enable Fenton reaction to proceed under neutral conditions and can promote the effect of Fenton reaction under neutral conditions to some extent, the efficiency of pollution degradation is much smaller than that of the classical Fenton reaction.
Further improvements and improvements are needed in the art to find a highly efficient ligand to meet the need for the degradation of a variety of recalcitrant contaminants by fenton-like reactions under broad pH conditions.
Disclosure of Invention
In view of the above defects or improvement needs of the prior art, the present invention provides a transition metal chlorophyll derivative fenton-like reaction reagent and an application thereof in degrading organic pollutants, and the purpose of the present invention is to use a transition metal chlorophyll derivative as a fenton-like reagent, to act on organic pollutants together with a traditional fenton-like or fenton-like oxidant, and to generate a high-valence metal-oxygen complex as an active intermediate, so as to achieve efficient degradation of a plurality of refractory organic pollutants in a wide pH range, thereby solving the technical problems of low degradation efficiency and narrow suitable pH range of the organic pollutants of the fenton-like reaction reagent in the prior art.
To achieve the above objects, according to one aspect of the present invention, there is provided a fenton-like reaction reagent for degrading organic pollutants, comprising a water-soluble transition metal chlorophyll derivative, which is a chlorophyll derivative having a porphyrin ring as a ligand and forming a coordinate bond with a central transition metal ion, and an oxidizing agent; the oxidant is used for degrading organic pollutants by utilizing Fenton-like reaction or Fenton reaction; the water-soluble transition metal chlorophyll derivative and the oxidant are used for generating Fenton-like reaction with organic pollutants together to realize the degradation of the organic pollutants.
Preferably, the transition metal chlorophyll derivative has a structural formula shown as formula (I) or formula (II):
Figure BDA0001613359890000031
wherein, the metal ion M is a metal ion of Fe element, Cu element, Mn element, Co element, Mg element, Zn element, Pd element, Sn element, Ni element or Cr element; substituent R1Is CH3-or CHO-; r2、R3And R4Each independently is a K ion, a Ca ion or a Na ion.
Preferably, the oxidant is H2O2One or more of persulfate, m-CPBA m-chloroperoxybenzoic acid, cumene hydroperoxide MPPH and tert-butyl hydroperoxide.
Preferably, the organic contaminant is a pesticide, herbicide, fungicide, antibiotic or environmental hormone.
Preferably, the molar ratio of the transition metal chlorophyll derivative to the organic pollutant to the oxidant is (0.1-2): (0.1-10): (10-200).
According to another aspect of the present invention, there is provided a use of a transition metal chlorophyll derivative for degrading organic pollutants by fenton-like reaction.
Preferably, after the transition metal chlorophyll derivative and the organic pollutant are mixed, the pH value of the system is controlled to be more than 3, and then an oxidizing agent is added to generate Fenton-like reaction to degrade the organic pollutant.
Preferably, the transition metal chlorophyll derivative has a structural formula shown as formula (I) or formula (II):
Figure BDA0001613359890000041
wherein, the metal ion M is a metal ion of Fe element, Cu element, Mn element, Co element, Mg element, Zn element, Pd element, Sn element, Ni element or Cr element; substituent R1Is CH3-or CHO-; r2、R3And R4Each independently is a K ion, a Ca ion or a Na ion.
Preferably, the oxidant is H2O2One or more of persulfate, m-CPBA m-chloroperoxybenzoic acid, cumene hydroperoxide MPPH and tert-butyl hydroperoxide.
Preferably, the molar ratio of the transition metal chlorophyll derivative to the organic pollutant to the oxidant is (0.1-2): (0.1-10): (10-200).
In general, compared with the prior art, the above technical solution contemplated by the present invention can achieve the following beneficial effects:
1. the invention provides a Fenton-like reagent which comprises a water-soluble transition metal chlorophyll derivative and a Fenton-like or Fenton-like oxidant, and realizes efficient degradation of organic pollutants by generating a high-valence metal-oxygen complex as an active intermediate.
2. The porphyrin ring of the chlorophyll derivative is used as a ligand, and can be tightly combined with metal ions in the reaction process, so that the metal ions are prevented from precipitating due to the rise of pH in the reaction process, the generation of precipitates is reduced, and the circulation of the metal ions is promoted.
3. Chlorophyll is widely present in nature, and the extraction method is very simple. The chlorophyll derivative obtained by simple modification treatment can greatly improve the stability, compared with the traditional method of FeSO4As the Fenton reagent, the Fenton reagent is more beneficial to the storage and transportation of the reaction reagent.
4. Chlorophyll derivatives and conventional Fenton reagent FeSO4Compared with the prior art, the Fenton reagent can stably exist in neutral and alkaline solutions, the step that the pH needs to be adjusted in advance before the Fenton reagent is added in the traditional Fenton reaction is omitted, the reagent cost is greatly saved, and the operation steps are simplified.
5. The transition metal chlorophyll derivative is applied to Fenton-like reaction for degrading organic pollutants, and due to the characteristics of the transition metal chlorophyll derivative, the transition metal chlorophyll derivative and an oxidant react in the reaction to form an active intermediate of a non-hydroxyl radical, so that the transition metal chlorophyll derivative is a high-valence metal-oxygen complex with better pollutant degradation performance, and the pollutant degradation efficiency is greatly improved.
6. The invention optimizes TMCD, the optimal molar ratio range between the pollutants and the oxidant, and improves the performance of the method, thereby achieving the high-efficiency degradation of various pollutants under the condition of saving cost.
7. The Fenton-like reagent can degrade pollutants in the dark without additional illumination conditions like other photocatalytic materials.
Drawings
FIG. 1 is a graph of the percent concentration versus time for bisphenol A degradation over a wide pH range using Transition Metal Chlorophyll Derivatives (TMCD) as Fenton-like reagents in accordance with example 1 of the present invention;
FIG. 2 shows TMCD and H in different molar ratios2O2As a graph of percent concentration of fenton's reagent degrading bisphenol a at pH 7 versus time;
FIG. 3 shows the use of TMCD, Fe (II) -EDTA as a Fenton-like reagent and Fe (II) ions as a Fenton-like reagent, with H2O2A graph comparing the effect of degrading bisphenol a as an oxidizing agent with pH 9 when TMCD was used as a fenton-like reagent, pH 7 when Fe (II) -EDTA was used as a fenton-like reagent, and pH 2.7 when Fe (II) ion was used as a fenton-like reagent;
FIG. 4 shows TMCD and H2O2When the Fenton-like reagent is used for degrading bisphenol A, no free radical quencher, hydroxyl radical quencher Isopropanol (IPA) and superoxide radical quencher (CHCl) are added3) Degradation of bisphenol a;
FIG. 5 shows the results of the reaction between Fe (II) and H2O2When used as Fenton reagent for degrading bisphenol A, no free radical quencher, hydroxyl radical quencher Isopropanol (IPA) and superoxide radical quencher (CHCl) are added3) Degradation of bisphenol A.
Detailed Description
In order to make the objects, technical solutions and advantages of the present invention more apparent, the present invention is described in further detail below with reference to the accompanying drawings and embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention. In addition, the technical features involved in the embodiments of the present invention described below may be combined with each other as long as they do not conflict with each other.
Chlorophyll is a natural complex, widely exists in nature, can be extracted from silkworm excrement and plant leaves, and is simple and easy to obtain. The chlorophyll takes a porphyrin ring as a ligand and forms a coordination bond with a central magnesium ion. However, chlorophyll is poor in stability and is easily decomposed and deteriorated under conditions of high temperature, light and the like, and various chlorophyll derivatives can be obtained by modifying chlorophyll to replace central magnesium ions with other metal ions such as iron, copper and the like and saponifying the metal ions to change the water solubility of the chlorophyll, and the chlorophyll is widely applied to the fields of food pigments and the like. In the chlorophyll derivatives, metal ions such as iron and the like in the center form a coordination bond with a porphyrin ring, and the iron ions can stably exist in the solution under neutral or alkaline pH conditions, so that a reaction reagent can stably exist before the reaction is started in the advanced oxidation process, and the service life of the chlorophyll derivatives is prolonged. In addition, with H2O2The iron ions with higher valence state after the reaction can not be precipitated due to pH, thereby reducing the generation of iron mud, promoting the circulation of Fenton reaction and being a potential catalytic material. The method can quickly and efficiently degrade various pollutants which are difficult to degrade, and the effect is obviously superior to that of the prior Fenton-like water treatment technology.
The invention provides a Fenton-like reaction reagent for degrading organic pollutants, which comprises a water-soluble Transition Metal Chlorophyl Derivatives (TMCD) and an oxidant, wherein the Transition Metal Chlorophyll Derivatives are Chlorophyll Derivatives which take porphyrin rings as ligands and form coordination bonds with central Transition Metal ions; the transition metal chlorophyll derivative has a structural formula shown as a formula (I) or a formula (II):
Figure BDA0001613359890000071
wherein, the metal ion M is the metal ion of each valence state of Fe, Cu, Mn, Co, Mg, Zn, Pd, Sn, Ni or Cr; substituent R1Is CH3-or CHO-; r2、R3And R4Each independently is potassium K, calcium Ca or sodium Na ion, and the oxidant is used in Fenton-like reaction or Fenton reaction for degrading organic pollutants and can be H2O2Persulfates, m-CPBA, cumene hydroperoxide MPPH, t-butyl hydroperoxide or other types of oxidizing agents; the water-soluble transition metal chlorophyll derivatives and the oxidant jointly generate Fenton-like reaction with the organic pollutants, so that the degradation of the organic pollutants is realized. The organic contaminants can be, but are not limited to, pesticides (e.g., carbaryl), herbicides (e.g., atrazine), fungicides (e.g., trichlorophenol) antibiotics (e.g., cephalexin), environmental hormones (e.g., bisphenol a), and the like.
The molar ratio of the transition metal chlorophyll derivative to the organic pollutant to the oxidant is (0.1-2): (0.1-10): (10-200).
The Fenton-like reaction reagent is applied to degradation of organic pollutants, the pH value of a system is controlled to be larger than 3 after the transition metal chlorophyll derivatives and the organic pollutants are mixed, then the oxidizing agent is added, the water-soluble transition metal chlorophyll derivatives and the oxidizing agent jointly generate the Fenton-like reaction with the organic pollutants, and high-valence metal-oxygen complexes are generated to serve as active intermediates, so that degradation of the organic pollutants is realized. Since the living life of such reactive intermediates is short, the resulting reactive intermediates can act to degrade organic contaminants by first mixing TMCD with the organic contaminants and then adding the oxidizing agent. On the other hand, in order to ensure the water solubility of TMCD, it is necessary to control the pH of the system to be more than 3, and TMCD has poor water solubility under strongly acidic conditions.
Experiments show that the Fenton-like reagent provided by the invention can achieve a good pollutant degradation effect in a wide pH range, particularly when the pH value is more than 8, the degradation efficiency is higher, and the degradation rate of organic pollutants in half a minute can reach 95%.
Through comparison experiments, the Fenton-like reagent, namely TMCD (thermal mechanical control decomposition) and an oxidizing agent are mixed to serve as the Fenton-like reagent, different from the traditional Fenton reaction reagent and other neutral chelate Fenton-like reagents such as EDTA (ethylene diamine tetraacetic acid), the Fenton-like reagent generates a high-valence metal-oxygen complex instead of a hydroxyl radical and a superoxide radical in the Fenton-like reaction process, and the Fenton-like reagent generates the high-valence metal-oxygen complex, so that the Fenton-like reagent has excellent performance in degrading various pollutants difficult to degrade, probably because the Fenton-like reagent generates the high-valence metal-oxygen complex2O2After the transition metal chlorophyll derivative is added in the axial direction, an O-O bond is broken, and a remaining O atom and a central metal ion form a metal ═ oxygen atom (M ═ O) covalent bond, so that the interaction between the d orbital, the O atom orbital and the porphyrin ring molecular orbital of the central transition metal is caused, the properties of the LUMO and HOMO orbital of the complex are changed, and the complex has stronger electron-gaining oxidation capability, and therefore, the Fenton-like reagent disclosed by the invention shows a completely different degradation mechanism from the traditional Fenton reaction and the Fenton-like reaction dominated by ligands such as EDTA and the like.
The following are examples:
example 1
(1) Preparing 2mM transition metal chlorophyll derivative (TMCD, its structural formula is shown in formula I, wherein metal ion M is ferrous ion; and substituent R1Is CH3-；R2、R3And R4Both Na ions) stock solution, at which point the solution is alkaline.
(2) 0.0456g of bisphenol A were weighed out and dissolved in 1L of water to give a stock solution of bisphenol A at a concentration of 0.2 mM. With KMnO4Determination of 30% H by titration2O2Diluting by a certain multiple to prepare H with the concentration of 400mM2O2A stock solution;
(3) 40mL of bisphenol A stock solution, 4.8mL of TMCD stock solution and 33.2mL of water were added to a 250mL Erlenmeyer flask and the mixture was adjustedTo different pH and finally adding H2O21mL of the stock solution was started, at which time TMCD contaminant: H in the reaction solution2O2Is 1.2:1: 50.
(4) 3mL samples were taken at regular intervals, and the concentration of bisphenol A in the samples was measured by liquid chromatography to plot the percentage of bisphenol A concentration as a function of time at various pHs, as shown in FIG. 1. As can be seen from FIG. 1, when the Fenton-like reagent of the present embodiment is used for degrading bisphenol A, the good degradation effect is achieved within the range of pH 4-10, and the degradation efficiency is particularly prominent when the pH is greater than 8.
Example 2:
(1) preparing 2mM transition metal chlorophyll derivative (TMCD, its structural formula is shown in formula I, wherein metal ion M is ferrous ion; and substituent R1Is CH3-；R2、R3And R4Both Na ions) stock solution, at which point the solution is alkaline.
(2) 0.0456g of bisphenol A were weighed out and dissolved in 1L of water to give a stock solution of bisphenol A at a concentration of 0.2 mM. With KMnO4Determination of 30% H by titration2O2Diluting by a certain multiple to prepare H with the concentration of 400mM2O2A stock solution;
(3) to a 250mL Erlenmeyer flask was added 40mL of bisphenol A stock solution, a volume of TMCD stock solution and water, the pH of the solution was adjusted to 7 and finally H was added2O21mL of the stock solution was started, and the contaminant in the reaction solution was H2O2In a molar ratio of 1: 50.
(4) 3mL of samples were taken at regular intervals, and the concentration of bisphenol A in the samples was measured by liquid chromatography to plot the percentage concentration of bisphenol A as a function of time at different TMCD concentrations, as shown in FIG. 2. As can be seen from FIG. 2, when bisphenol A is degraded with the Fenton-like reagent of this example, the degradation effect gradually increases as the molar ratio of TMCD is increased from 0.1 to 2. Even at very low TMCD concentrations, rapid removal of contaminants can be achieved.
Example 3
(1) Configuration ofTransition metal chlorophyll derivative (TMCD with a structural formula shown as formula II) and a concentration of 2mM, wherein the metal ion M is ferrous ion, and the substituent R1Is CHO-; r2、R3And R4Both K ions), a Fe (II) -EDTA stock solution at a concentration of 2mM and a Fe (II) stock solution at a concentration of 2 mM.
(2) 0.0456g of bisphenol A were weighed out and dissolved in 1L of water to give a stock solution of bisphenol A at a concentration of 0.2 mM. With KMnO4Determination of 30% H by titration2O2Diluting by a certain multiple to prepare H with the concentration of 400mM2O2A stock solution;
(3) to a 250mL Erlenmeyer flask was added 40mL of bisphenol A stock solution, 4.8mL of TMCD stock solution/Fe (II) -EDTA stock solution/Fe (II) stock solution, 33.2mL of water was added, the pH of the solution was adjusted to 9.0/7.0/2.7, and finally H was added2O21mL of the stock solution was started, at which time TMCD/Fe (II) -EDTA/Fe (II): contaminant H in the reaction solution2O2Is 1.2:1: 50.
(4) 3mL of samples were taken at regular intervals, and the concentration of bisphenol A in the samples was measured by liquid chromatography, and the percentage of bisphenol A concentration was plotted against time at different TMCD concentrations, as shown in FIG. 3.
As can be seen from fig. 3, when the fenton-like reagent of this embodiment is used to degrade bisphenol a, 100% removal of bisphenol a can be achieved within 5min, but neither the fenton-like reaction dominated by Fe (II) -EDTA at pH 7 nor the fenton-like reaction dominated by Fe (II) at pH 2.7 has a good effect on removal of bisphenol a as compared to the fenton-like reagent of the present invention, which means that the fenton-like reagent of the present invention has a better effect than the existing fenton-like reagents such as EDTA, is better than the conventional fenton-like reaction under acidic conditions, and has a lower requirement on pH.
The Fenton-like reaction reagent is superior to the existing Fenton-like reagents such as EDTA and the like and the traditional Fenton reagent, because the Fenton-like reagent in the invention generates a high-valence metal-oxygen complex as an active intermediate after reacting with an oxidizing agent, and the Fenton-like reagents such as EDTA and the like and the traditional Fenton reagent generate hydroxyl radicals and superoxide radicals after reacting with the oxidizing agentAnd (4) a base. Hydroxyl radicals and superoxide radicals with Isopropanol (IPA) and trichloromethane (CHCl)3) The reaction rate is fast, and can be respectively used as quenchers of hydroxyl free radicals and superoxide free radicals, if IPA or CHCl is added in the process of degrading pollutants3Then, if the degradation of the contaminant is inhibited, it indicates that the substance degrading the contaminant is a hydroxyl radical or a superoxide radical, and vice versa.
In addition, intensive research has been conducted in the fields of biology and chemistry with respect to organometallic complexes having a high valence state, and also by EPR, Mossbauer spectra,1the existence of this substance is confirmed by means of H-NMR, resonance Raman, etc. In addition, the higher valent metal-oxygen complexes can epoxidize olefins to specific epoxidized products, as opposed to reactions induced by hydroxyl or superoxide radicals generated during conventional fenton and fenton-like reactions. The inventors have also confirmed the above reaction mechanism by experimental characterization that in the fenton-like reagent of the present invention, the generated reactive intermediate is a high-valent metal-oxygen complex, not a hydroxyl radical or a superoxide radical.
A comparative example of the mechanism is shown below.
Comparative example 1
(1) Preparing 2mM transition metal chlorophyll derivative (TMCD, its structural formula is shown in formula I, wherein metal ion M is ferrous ion; and substituent R1Is CHO-; r2、R3And R4Both Na ions) stock solution, Fe (II) stock solution at a concentration of 2 mM.
(2) 0.0456g of bisphenol A were weighed out and dissolved in 1L of water to give a stock solution of bisphenol A at a concentration of 0.2 mM. With KMnO4Determination of 30% H by titration2O2Diluting by a certain multiple to prepare H with the concentration of 400mM2O2A stock solution;
(3) to a 250mL Erlenmeyer flask, 40mL of bisphenol A stock solution, 4.8mL of TMCD stock solution/Fe (II) stock solution, 32.2mL of water were added, the pH of the solution was adjusted to 9.0/2.7, and IPA or CHCl was added30.6mL, and finally H2O2Starting the reaction with 1mL of stock solution;
(4) 3mL of the sample was sampled at regular intervals, and the concentration of bisphenol A in the sample was measured by liquid chromatography, and the percentage concentration of bisphenol A was plotted as a function of time with different quenchers, as shown in FIGS. 4 and 5. As can be seen from FIGS. 4 and 5, when TMCD is used as the Fenton-like reagent, IPA or CHCl3Does not inhibit the degradation of bisphenol A, as in the conventional Fenton reaction, IPA or CHCl3The addition of the compound can inhibit the degradation of bisphenol A, and the inhibition effect is more obvious when IPA is added, which indicates that in the traditional Fenton reaction, the active species for degrading pollutants are mainly hydroxyl free radicals and then superoxide free radicals. In the Fenton-like reagent, neither hydroxyl radical nor superoxide radical is generated, for TMCD, the structure that porphyrin ring coordinates with central metal ion can generate high-valence metal-oxygen complex as an active intermediate to degrade pollutants after reacting with an oxidizing agent, and the effect of the Fenton-like reagent is better than that of hydroxyl radical and superoxide radical in Fenton-like reaction dominated by chelating agents such as EDTA and Fe (II) ion.
It will be understood by those skilled in the art that the foregoing is only a preferred embodiment of the present invention, and is not intended to limit the invention, and that any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the scope of the present invention.

Claims (7)

1. A Fenton-like reaction reagent for degrading organic pollutants is characterized by comprising a water-soluble transition metal chlorophyll derivative and an oxidizing agent, wherein the transition metal chlorophyll derivative is a chlorophyll derivative which takes a porphyrin ring as a ligand and forms a coordination bond with a central transition metal ion; the oxidant is used for degrading organic pollutants by utilizing Fenton-like reaction or Fenton reaction; the water-soluble transition metal chlorophyll derivative and the oxidant are used for generating Fenton-like reaction with organic pollutants together to realize the degradation of the organic pollutants;
the transition metal chlorophyll derivative has a structural formula shown as a formula (I) or a formula (II):
Figure FDA0002360442730000011
wherein, the metal ion M is a metal ion of Fe element, Cu element, Mn element, Co element, Mg element, Zn element, Pd element, Sn element, Ni element or Cr element; substituent R1Is CH3-or CHO-; r2、R3And R4Each independently is a K ion, a Ca ion or a Na ion.
2. Fenton-like reaction reagent according to claim 1, wherein the oxidizing agent is H2O2One or more of persulfate, m-CPBA m-chloroperoxybenzoic acid, cumene hydroperoxide MPPH and tert-butyl hydroperoxide.
3. A fenton-like reaction reagent according to claim 1, wherein the organic contaminant is a pesticide, a herbicide, a bactericide, an antibiotic or an environmental hormone.
4. Fenton-like reaction reagent according to claim 1, wherein the transition metal chlorophyll derivative, the organic contaminant and the oxidizing agent are present in a molar ratio of (0.1-2): (0.1-10): (10-200).
5. The application of the transition metal chlorophyll derivative is characterized in that the transition metal chlorophyll derivative is applied to Fenton-like reaction to degrade organic pollutants;
mixing the transition metal chlorophyll derivative with organic pollutants, controlling the pH value of a system to be more than 3, and then adding an oxidant to generate Fenton-like reaction to degrade the organic pollutants;
the transition metal chlorophyll derivative has a structural formula shown as a formula (I) or a formula (II):
Figure FDA0002360442730000021
wherein, the metal ion M is a metal ion of Fe element, Cu element, Mn element, Co element, Mg element, Zn element, Pd element, Sn element, Ni element or Cr element; substituent R1Is CH3-or CHO-; r2、R3And R4Each independently is a K ion, a Ca ion or a Na ion.
6. The use of claim 5, wherein the oxidant is H2O2One or more of persulfate, m-CPBA m-chloroperoxybenzoic acid, cumene hydroperoxide MPPH and tert-butyl hydroperoxide.
7. The use according to claim 5, wherein the transition metal chlorophyll derivative, the organic contaminant and the oxidizing agent are present in a molar ratio of (0.1-2): (0.1-10): (10-200).
CN201810274621.7A 2018-03-30 2018-03-30 Transition metal chlorophyll derivative Fenton reaction reagent and application thereof Active CN108439567B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201810274621.7A CN108439567B (en) 2018-03-30 2018-03-30 Transition metal chlorophyll derivative Fenton reaction reagent and application thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201810274621.7A CN108439567B (en) 2018-03-30 2018-03-30 Transition metal chlorophyll derivative Fenton reaction reagent and application thereof

Publications (2)

Publication Number Publication Date
CN108439567A CN108439567A (en) 2018-08-24
CN108439567B true CN108439567B (en) 2020-05-19

Family

ID=63198236

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201810274621.7A Active CN108439567B (en) 2018-03-30 2018-03-30 Transition metal chlorophyll derivative Fenton reaction reagent and application thereof

Country Status (1)

Country Link
CN (1) CN108439567B (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109912156A (en) * 2019-03-26 2019-06-21 华中科技大学 A kind of method that sodium-iron-chlorophyllin conditioning promotes excess sludge methane phase

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4469953B2 (en) * 2005-09-14 2010-06-02 独立行政法人産業技術総合研究所 Catalyst for electrochemical oxidation of oxalic acids
CN106927535B (en) * 2017-03-16 2020-06-05 南京师范大学 Method for photocatalytic degradation of phenolic pollutants based on stable porphyrin metal organic framework material

Also Published As

Publication number Publication date
CN108439567A (en) 2018-08-24

Similar Documents

Publication Publication Date Title
Zhou et al. Transition metal catalyzed sulfite auto-oxidation systems for oxidative decontamination in waters: A state-of-the-art minireview
Yan et al. Efficient degradation of sulfamethoxazole by the CuO@ Al2O3 (EPC) coupled PMS system: optimization, degradation pathways and toxicity evaluation
CN102173500B (en) Method for treating water by Fenton oxidization of activated molecular oxygen
Sheng et al. Pivotal roles of MoS2 in boosting catalytic degradation of aqueous organic pollutants by Fe (II)/PMS
Oyekunle et al. Heterogeneous activation of persulfate by metal and non-metal catalyst for the degradation of sulfamethoxazole: A review
Cieśla et al. Homogeneous photocatalysis by transition metal complexes in the environment
Mukherjee et al. Advancements in visible light responsive MOF composites for photocatalytic decontamination of textile wastewater: A review
Du et al. Insights into periodate oxidation of bisphenol A mediated by manganese
Wang et al. Transformation of tetracycline antibiotics and Fe (II) and Fe (III) species induced by their complexation
Pignatello et al. Advanced oxidation processes for organic contaminant destruction based on the Fenton reaction and related chemistry
Sun et al. Enhanced heterogeneous and homogeneous Fenton-like degradation of carbamazepine by nano-Fe3O4/H2O2 with nitrilotriacetic acid
Wen et al. Oxidative degradation of organic pollutants in aqueous solution using zero valent copper under aerobic atmosphere condition
CN102259993B (en) Water treatment method utilizing complex-ferrous-activated persulfate oxidation
Pagano et al. Peroxymonosulfate–Co (II) oxidation system for the removal of the non-ionic surfactant Brij 35 from aqueous solution
Sun et al. A novel discovery of a heterogeneous Fenton-like system based on natural siderite: A wide range of pH values from 3 to 9
Ma et al. Elucidating the role of Fe (IV) and radical species for CBZ degradation in FeS2/PS system
CN103708647B (en) Deep treatment method for industrial wastewater through natural pyrite catalyzed H2O2 oxidation
Hamd et al. Heterogeneous photo-Fenton reaction and its enhancement upon addition of chelating agents
Xu et al. Enhancing the degradation of bisphenol A by dioxygen activation using bimetallic Cu/Fe@ zeolite: Critical role of Cu (I) and superoxide radical
Jin et al. Structure activity relationship study of N-doped ligand modified Fe (III)/H2O2 for degrading organic pollutants
Han et al. A comparative study of iron-based PAN fibrous catalysts for peroxymonosulfate activation in decomposing organic contaminants
Chen et al. Degradation of dimethyl sulfoxide through fluidized-bed Fenton process: kinetic analysis
CN108439567B (en) Transition metal chlorophyll derivative Fenton reaction reagent and application thereof
Huang et al. Hydroxylamine promoted hydroxyl radical production and organic contaminants degradation in oxygenation of pyrite
Wei et al. Reactive oxygen species generated in iron sulfide mediated advanced oxidation systems: A critical review of mechanisms and implications for geochemistry and environmental remediation

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