CN113171739A - Method for generating superoxide anion free radical by catalytically activating bromate and application of superoxide anion free radical generated by method - Google Patents

Method for generating superoxide anion free radical by catalytically activating bromate and application of superoxide anion free radical generated by method Download PDF

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CN113171739A
CN113171739A CN202110450231.2A CN202110450231A CN113171739A CN 113171739 A CN113171739 A CN 113171739A CN 202110450231 A CN202110450231 A CN 202110450231A CN 113171739 A CN113171739 A CN 113171739A
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bromate
superoxide anion
catalyst
reaction
anion free
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CN113171739B (en
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丁耀彬
潘聪
唐和清
雷鸣
吕康乐
王成俊
孙杰
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South Central Minzu University
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South Central University for Nationalities
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • 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
    • 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
    • C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • 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
    • C02F2101/10—Inorganic compounds
    • C02F2101/12—Halogens or halogen-containing compounds
    • 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

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Abstract

The invention relates to the technical field of inorganic chemistry and environmental chemistry, and particularly discloses a method for generating superoxide anion free radicals by catalyzing and activating bromate and application of the superoxide anion free radicals generated by the method, namely transition metal or a compound thereof is used as a catalyst to catalyze the bromate to generate the superoxide anion free radicals; the method can regulate the generation amount of superoxide anion free radicals by controlling the concentration of bromate, the reaction pH, the concentration and the type of catalyst; the method can be applied to the conversion and elimination of organic pollutants, can also be used for the treatment of bromate and organic compound polluted wastewater, and has the advantages of simple principle, simple and convenient operation, wide pH application range and the like.

Description

Method for generating superoxide anion free radical by catalytically activating bromate and application of superoxide anion free radical generated by method
Technical Field
The invention relates to the field of inorganic chemistry, in particular to a method for generating superoxide anion free radicals by catalytically activating bromate and application of the superoxide anion free radicals generated by the method.
Background
Bromate is a carcinogen whose emission concentrations are subject to strict regulatory standards both in surface water and groundwater. Meanwhile, as a non-metal oxysalt, the oxidation-reduction potential of the non-metal oxysalt is 1.52V (BrO)3 -+6H++5e-→1/2Br2+3H2O), which can react with ammonium salts (R.Hofmann, R.C.Andrews, Water Research,2006,40, 3343-. Shen et al at Fe @ Fe2O3During the reduction of bromate, radicals such as superoxide radical are generated, but the radicals are derived from Fe @ Fe2O3Activation of dissolved oxygen, not from decomposition of bromate (W.Shen, F.Lin, X.Jiang, H.Li, Z.ai, L.Zhang, Chemical Engineering Journal,2017,308, 880-888). Nie et Al report beta-FeOOH/Al2O3Bromate can be reduced to bromide, but they do not report that the hydroxyl and superoxide radicals in the system are derived from the decomposition of bromate. Instead, they found that these radicals are generated by the catalytic decomposition of ozone (Y.Nie, C.Hu, N.Li, L.Yang, J.Qu, Applied Catalysis B: Environmental,2014,147, 287-292). Qiao et al generate sulfite radicals by reaction of bromate with sulfite. Under aerobic conditions, other radicals such as sulfate radicals may be further generated by the reaction of sulfite radicals with molecular oxygen. It is noted, however, that the source of these free radicals is sulfite and dissolved oxygen, but not bromate (j.qiao, l.feng, h.dong, z.zhao, x.guan, Environmental science)&technology,2019,53,10320 and 10328). Therefore, how to add other oxidant or dissolved oxygen is not neededThe catalytic production of superoxide anion radicals by catalysts using bromate as the oxidant is an important part of the present study.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a method for generating superoxide anion free radicals by catalytically activating bromate and application of the superoxide anion free radicals generated by the method, and the method can generate the superoxide anion free radicals by only taking the bromate as an oxidant and catalyzing the bromate by a metal catalyst without adding other oxidants or dissolved oxygen; the superoxide anion free radical generated by the invention can be applied to the conversion and elimination of organic pollutants and can also be used for the treatment of bromate and organic composite polluted wastewater; the invention has the advantages of simple principle, simple and convenient operation, wide pH application range and the like.
The invention provides a method for generating superoxide anion free radicals by catalytically activating bromate, which is generated by catalyzing bromate reaction by using a transition metal or a compound of the transition metal as a catalyst.
Preferably, the present invention comprises the steps of: adding a catalyst into the solution containing bromate, adjusting the pH value to a preset value, and stirring for reaction to generate superoxide anion free radicals.
Preferably, the bromate is sodium bromate (NaBrO)3) Potassium bromate (KBrO)3) Sodium bromite (NaBrO)2) And potassium hypobromite (KBrO)2) Any one or more of them.
Preferably, the concentration of bromate in the bromate solution is 0.05 mmol/L-0.1 mol/L.
Further, the bromate solution and the transition metal compound solution may be aqueous solutions or alcoholic solutions.
Preferably, the catalyst is iron, copper, manganese, molybdenum, silver and/or nickel elementary substance or any one or a mixture of several of oxide, hydroxide, sulfide, phosphate, chloride, carbonate, sulfate and nitrate of the above metals.
Preferably, the catalyst is an iron-based catalyst having a molar concentration of 0.01 to 10 times that of the bromate, and the catalyst is not an iron-based catalyst having a molar concentration of 0.1 to 100 times that of the bromate.
When the catalyst is a transition metal compound, the catalyst is added directly or added in the form of a transition metal compound solution;
preferably, the pH preset value is 2.5-10.
The invention also provides application of the superoxide anion radical generated by the method for generating the superoxide anion radical by catalytically activating bromate.
Further, the superoxide anion radical is applied to sewage treatment (the sewage is sewage containing organic pollutants, or the sewage is sewage containing organic pollutants and bromate).
According to the method for producing superoxide anion free radicals by catalytically activating bromate, provided by the invention, other oxidizing agents or dissolved oxygen are not required to be added, and the superoxide anion free radicals can be produced only by taking the bromate as the oxidizing agent and catalyzing the bromate by using a metal catalyst. The method uses a catalyst as an electron donor to catalyze and reduce bromate, and promotes oxygen atoms in the bromate to be released in the form of superoxide anion free radicals. The process not only converts bromate into bromide ions and reduces the environmental hazard of the bromate, but also provides superoxide anion free radicals with oxidizing capability, and can be applied to the oxidation conversion and elimination of organic pollutants. The method has the advantages of simple principle, simple and convenient operation, wide pH application range and the like, can be applied to the conversion and elimination of organic pollutants, and can also be applied to the treatment of bromate and organic compound polluted wastewater.
Drawings
FIG. 1 is FeSO according to example 1 of the present invention4ESR signal profile for catalytically activated bromate systems;
FIG. 2 FeSO concentrations in example 2 of the invention4ESR signal diagram and ESR signal intensity of catalytic activation bromate in reaction for 10 min;
FIG. 3 shows FeSO obtained in example 3 of the present invention4ESR signal of bromate in different concentrations in reaction for 10min by catalytic activationGraph and ESR signal intensity (the linear correlation coefficient in the right graph is R)2，R2＝0.98)；
FIG. 4 shows FeCl in example 4 of the present invention2ESR signal graphs and ESR signal strengths of the catalytic activated bromate at different pH values;
FIG. 5 is a graph of ESR signals for bromate/bromite catalyzed by iron-based catalysts in examples 5-9 of the present invention;
FIG. 6 shows zero-valent molybdenum, CuCl and Mn in examples 10, 11 and 12 of the present invention2O3ESR signal plot of catalytically activated bromate;
FIG. 7 shows FeSO obtained in example 13 of the present invention4Kinetics of catalytic activation of bromate degradation of phenol.
Detailed Description
The present invention is further described below in conjunction with specific examples to provide those skilled in the art with a further understanding of the present invention, but the following examples should not be construed or interpreted as limiting the scope of the invention as claimed in the claims.
Example 1
In this example, commercial chemical purity FeSO was selected4As a catalyst, the bromate is catalytically activated to produce superoxide anion radicals. According to the method for producing superoxide anion free radicals by catalytically activating bromate, 0.5mL of FeSO with the concentration of 0.18mol/L is added into 49.5mL of aqueous solution of sodium bromate4Aqueous solution of 0.1mol/L HClO4Adjusting the pH value of the aqueous solution and 0.1mol/L NaOH aqueous solution to 4 to obtain reaction liquid, and stirring and reacting for 10-180 min. Sodium bromate and FeSO4The initial concentrations in the reaction solution were 0.5mmol/L and 1.8mmol/L, respectively. In order to demonstrate the generation of superoxide anion free radical, 1mL of the reaction solution was sampled at different times, 0.1mL of a methanol solution of 5, 5-dimethyl-1-pyrroline-N-oxide having a concentration of 100mmol/L was added, the reaction was carried out for 1min, and the ESR spectrum of the adduct of superoxide anion free radical and 5, 5-dimethyl-1-pyrroline-N-oxide was measured using an electron spin resonance spectrometer (ESR, Bruk EMX nano type), and the results are shown in FIG. 1.
As can be seen from FIG. 1, this signal is compared withThe ESR signal of a typical superoxide anion radical coincides with the ESR signal of the 5, 5-dimethyl-1-pyrroline-N-oxide adduct, indicating the production of a superoxide anion radical. FeSO4When the sodium bromate is reacted for 10min, the ESR signal intensity of the superoxide anion free radical is 0.57a.u.
In this example, when FeSO4In reaction with sodium bromate, Fe2+The reduction of the bromate ion by one electron leads to the production of superoxide anion radical and hypobromate ion, the reaction principle of which is shown in equation (1):
Fe2++BrO3 -→BrO-+Fe3++O2 ·- (1)
example 2
In this example, by changing FeSO4Initial concentration of catalyst, the effect on superoxide anion radical generation was investigated. The procedure of example 1 was followed, with only FeSO being adjusted4Initial concentration in the reaction solution. FeSO4The initial concentrations of the catalyst were 0.018mmol/L, 0.18mmol/L, 1.8mmol/L, 3.5mmol/L and 5mmol/L, respectively; the initial concentration of sodium bromate is 0.5 mmol/L; the initial pH of the reaction was 4.
The signal of superoxide anion radical at 10min of reaction was measured using the method in example 1. As can be seen from FIG. 2, when FeSO4At an initial concentration of 1.8mmol/L, the ESR signal of the superoxide anion radical is strongest, indicating that the FeSO with a proper concentration4The bromate can be decomposed with high efficiency to generate superoxide anion radical.
Example 3
In this example, the initial concentration change of sodium bromate versus FeSO was studied4The effect of catalytically activating bromate to generate superoxide anion radicals. The procedure of the experiment was as in example 1, only the initial concentration of sodium bromate in the reaction solution was adjusted. The initial concentration of the sodium bromate in the reaction liquid is 0mmol/L, 0.1mmol/L, 0.3mmol/L, 0.4mmol/L, 0.5mmol/L and 1.0mmol/L respectively; FeSO4The initial concentration is 1.8 mmol/L; the initial pH of the reaction was 4.
The signal of superoxide anion radical at 10min of reaction was measured using the method in example 1. As can be seen from FIG. 3, as the initial concentration of the sodium bromate solution increases, the ESR signal of the superoxide anion radical increases linearly, indicating that the superoxide anion radical is generated from the reductive decomposition of sodium bromate.
Example 4
In this example, the effect of the initial pH of the reaction on the production of superoxide anion radicals was investigated. The procedure of example 1 was followed by adjusting the initial pH of the reaction mixture to different values and changing the catalyst to ferrous chloride. FeCl2And the initial concentrations of sodium bromate were 1.8mmol/L and 0.5mmol/L, respectively; the initial pH values were 2.5, 4, 5, 6, 7 and 8, respectively.
The signal of superoxide anion radical at 10min of reaction was measured using the method in example 1. As can be seen from FIG. 4, the ESR signal intensity of the superoxide anion radical decreases significantly with increasing initial pH, indicating that acidic pH conditions favor FeCl2Catalytic activation of the bromate generates superoxide anion radicals.
Example 5
In this example, commercial chemical purity FeSO was selected4As a catalyst, the bromate is catalytically activated to produce superoxide anion radicals. According to the method for producing superoxide anion free radicals by catalytically activating bromate, 0.5mL of FeSO with the concentration of 5mmol/L is added into 49.5mL of sodium bromite in methanol4Methanol solution with 0.1mol/L HClO4Adjusting the pH value of the aqueous solution and 0.1mol/L NaOH aqueous solution to 4 to obtain reaction liquid, and stirring and reacting for 30 min. Sodium bromite and FeSO4The initial concentrations in the reaction solution were 5mmol/L and 0.05mmol/L, respectively.
The signal of the superoxide anion radical was detected using the method of example 1. As shown in FIG. 5, the ESR signal intensity of the superoxide anion radical was 0.17 a.u.at the time of reaction for 30 min.
In this example, when Fe2+In reaction with sodium bromite, Fe2+The reduction of the bromite ion by an electron leads to the production of superoxide anion radical and bromide ion, the reaction principle of which is shown in equation (2):
Fe2++BrO2 -→Br-+Fe3++O2 ·- (2)
example 6
In this example, commercial product nano-Fe was selected3O4As a catalyst, the bromate is catalytically activated to produce superoxide anion radicals. The method for producing superoxide anion free radical by catalyzing and activating bromate of the invention is adopted, and 4.6mg of nano Fe is added into 50mL of aqueous solution with the concentration of 2.5mmol/L potassium bromate3O4Using 0.1mol/L HClO4Adjusting the pH value of the aqueous solution and 0.1mol/L NaOH aqueous solution to 5 to obtain reaction liquid, and stirring and reacting for 20 min. Potassium bromate and nano Fe3O4The initial concentrations in the reaction solution were 2.5mmol/L and 0.4mmol/L, respectively.
The signal of the superoxide anion radical was detected using the method of example 1. As shown in FIG. 5, the ESR signal intensity of the superoxide anion radical was 0.13 a.u.at 20 min.
In this example, when nano Fe3O4When reacting with potassium bromate, nano Fe3O4Surface ferrous iron (≡ Fe)2+And, "≡ represents a solid catalyst surface, and hereinafter, will not be described) causes reduction of a bromate ion by one electron to produce a superoxide anion radical and a hypobromate ion, and the reaction principle is shown in reaction formula (3):
≡Fe2++BrO3 -→BrO-+≡Fe3++O2 ·- (3)
example 7
In this example, a commercial product FeS is selected2As a catalyst, the bromate is catalytically activated to produce superoxide anion radicals. According to the method for producing superoxide anion free radicals by catalytically activating bromate, 6mg of FeS is added into 50mL of aqueous solution with the concentration of 0.1mmol/L potassium bromate2Solid particles, using 0.1mol/LHClO4Adjusting the pH value of the aqueous solution and 0.1mol/L NaOH aqueous solution to 7 to obtain reaction liquid, and stirring and reacting for 10 min. Potassium bromate and FeS2The initial concentrations in the reaction solutions were 0.1mmol, respectivelyand/L and 1 mmol/L.
The signal of the superoxide anion radical was detected using the method of example 1. As shown in FIG. 5, the ESR signal intensity of the superoxide anion radical was 0.15a.u. at 10min of the reaction.
In this example, when FeS2FeS upon reaction with potassium bromate2Surface ferrous iron (≡ Fe)2+) The reduction of the bromate ion by one electron leads to the production of superoxide anion radical and hypobromate ion, the reaction principle of which is shown in the reaction formula (3).
Example 8
In this example, a commercial product FeS is selected2As a catalyst, the bromate is catalytically activated to produce superoxide anion radicals. According to the method for producing superoxide anion free radicals by catalytically activating bromate, 6mg of FeS is added into 50mL of aqueous solution with the concentration of 0.1mmol/L sodium bromite2Solid particles, using 0.1mol/LHClO4Adjusting the pH value of the aqueous solution and 0.1mol/L NaOH aqueous solution to 7 to obtain reaction liquid, and stirring and reacting for 30 min. Sodium bromite and FeS2The initial concentrations in the reaction solution were 0.1mmol/L and 1mmol/L, respectively.
The signal of the superoxide anion radical was detected using the method of example 1. As shown in FIG. 5, the ESR signal intensity of the superoxide anion radical was 0.12 a.u.at 30 min.
In this example, when FeS2FeS upon reaction with sodium bromite2Surface ferrous iron (≡ Fe)2+) The reduction of the bromite ion by an electron leads to the production of superoxide anion radical and bromide ion, the reaction principle of which is shown in equation (4):
≡Fe2++BrO2 -→Br-+≡Fe3++O2 ·- (4)
example 9
In this example, commercial FeSO was selected4And Ni (NO)3)2As a catalyst, the bromate is catalytically activated to produce superoxide anion radicals. Method for generating superoxide anion free radical by using bromate catalytically activated by the inventionIn the method, 0.5mL of FeSO with the concentration of 10mmol/L is added into 49mL of sodium bromate aqueous solution4Aqueous solution and 0.5mL of Ni (NO) with a concentration of 100mmol/L3)2Aqueous solution of 0.1mol/L HClO4Adjusting the pH value of the aqueous solution and 0.1mol/L NaOH aqueous solution to 2.5 to obtain a reaction solution, and stirring and reacting for 60 min. Sodium bromate, FeSO4And Ni (NO)3)2The initial concentrations in the reaction solution were 0.1mmol/L, 0.1mmol/L and 1mmol/L, respectively.
The signal of the superoxide anion radical was detected using the method of example 1. As shown in FIG. 5, the ESR signal intensity of the superoxide anion radical was 0.21 a.u.at 60 min.
Example 10
In this example, commercial zero-valent molybdenum (i.e., molybdenum metal) was selected as the catalyst to catalytically activate the bromate to generate superoxide anion radicals. The method for generating superoxide anion free radical by catalytically activating bromate comprises the steps of adding 4.8mg of zero-valent molybdenum solid particles into 50mL of aqueous solution with the concentration of 0.05mmol/L sodium bromate, and adopting 0.1mol/L HClO4Adjusting the pH value of the aqueous solution and 0.1mol/L NaOH aqueous solution to 5, and stirring and reacting for 90 min. The initial concentrations of sodium bromate and zero-valent molybdenum in the reaction solution are 0.05mmol/L and 1mmol/L respectively.
The generation of superoxide anion radicals was detected using the method of example 1. As shown in FIG. 6, the ESR signal intensity of the superoxide anion radical was 0.2a.u. at 90min of reaction.
In this example, zero-valent molybdenum (≡ Mo) was reacted with sodium bromate0) The released electrons reduce bromate ions to generate superoxide anion free radicals and hypobromate ions, and the reaction principle is shown as the reaction formula (5):
≡Mo0+4BrO3 -→≡Mo4++4BrO-+4O2 ·- (5)
example 11
In this example, commercial CuCl was selected as the catalyst to catalytically activate bromate to generate superoxide anion radicals. Production of superoxide anion radical using the catalytically activated bromate of the present inventionThe method is that 49.5mg of CuCl solid is added into 50mL of aqueous solution with the concentration of 0.1mmol/L potassium bromate, and 0.1mol/LHClO is adopted4Adjusting the pH value of the aqueous solution and 0.1mol/L NaOH aqueous solution to 7 to obtain reaction liquid, and stirring and reacting for 10 min. The initial concentrations of potassium bromate and CuCl in the reaction solution were 0.1mmol/L and 10mmol/L, respectively.
The generation of superoxide anion radicals was detected using the method of example 1. As shown in FIG. 6, the ESR signal intensity of the superoxide anion radical was 0.34a.u. at 10min of the reaction.
In this example, Cu in CuCl was reacted with potassium bromate+The reduction of the bromate ion by one electron leads to the production of superoxide anion radical and hypobromate ion, the reaction principle of which is shown in equation (6):
Cu++BrO3 -→BrO-+Cu2++O2 ·- (6)
example 12
In this example, commercial Mn is selected2O3As a catalyst, the bromate is catalytically activated to produce superoxide anion radicals. By adopting the method for generating superoxide anion free radicals by catalytically activating bromate, 79mg of Mn is added into 50mL of aqueous solution with the concentration of 0.1mol/L sodium bromate2O3Solid, using 0.1mol/LHClO4Adjusting the pH value of the aqueous solution and 0.1mol/L NaOH aqueous solution to 10 to obtain reaction liquid, and stirring and reacting for 10 min. Sodium Bromide and Mn2O3The initial concentrations in the reaction solution were 0.1mol/L and 10mmol/L, respectively.
The generation of superoxide anion radicals was detected using the method of example 1. As shown in FIG. 6, the ESR signal intensity of the superoxide anion radical was 0.25 a.u.at 10 min.
In this example, when Mn2O3Mn in reaction with sodium bromate2O3Surface trivalent manganese (≡ Mn)3+) The reduction of the bromate ion by one electron leads to the production of superoxide anion radical and hypobromate ion, the reaction principle of which is shown in equation (7):
≡Mn3++BrO3 -→BrO-+≡Mn4++O2 ·- (7)
example 13
In this example, commercially available chemically pure FeSO was selected4As a catalyst, the bromate is catalytically activated to generate superoxide anion free radicals, so that the oxidative conversion of the coexisting organic pollutant phenol is realized. 49.72mL of mixed solution of sodium bromate and phenol is prepared, the method for generating superoxide anion free radical by catalyzing and activating bromate to generate superoxide anion free radical to degrade phenol is adopted, and 0.28mL of FeSO with the concentration of 0.18mol/L is added into 49.72mL of mixed solution prepared in the above way4Using 0.1mol/L HClO4Adjusting the pH value of the aqueous solution and 0.1mol/L NaOH aqueous solution to 4 to obtain reaction liquid, stirring and starting the reaction. Sodium bromate, phenol and FeSO4The initial concentrations of (A) were 0.1mmol/L, 0.05mmol/L and 1mmol/L, respectively. Sampling from the reaction solution at different reaction time, and analyzing the concentrations of phenol, bromate and bromide ions in the reaction solution; as shown in figure 7, after 120min of treatment, the removal efficiency of phenol is 100%, the removal efficiency of sodium bromate is 94%, and the selectivity of converting sodium bromate into bromide ions is 99.5%. For comparison, FeSO was not added4When the catalyst is used, the removal efficiency of phenol is 0% and the removal efficiency of sodium bromate is 0% after 120min of treatment. As can be seen, the FeSO of this example4The catalyst can catalyze and activate bromate to generate superoxide anion free radicals, and the obtained superoxide anion free radicals can effectively remove organic pollutants phenol.

Claims (10)

1. A method of catalytically activating a bromate to produce a superoxide anion radical, wherein the superoxide anion radical is produced by catalyzing a reaction of the bromate with a transition metal or a transition metal compound as a catalyst.
2. The method of claim 1, comprising the steps of: adding a catalyst into a solution containing bromate, adjusting the pH value to 2.5-10, and reacting the obtained reaction solution to generate superoxide anion free radicals.
3. The method according to claim 1 or 2, wherein the bromate is any one or more of sodium bromate, potassium bromate, sodium bromite and potassium bromite.
4. The method as claimed in claim 3, wherein the concentration of bromate in the reaction solution is 0.05 mmol/L-0.1 mol/L.
5. The method of claim 3, wherein the bromate solution is an aqueous or alcoholic bromate solution.
6. The method according to claim 1 or 2, wherein the transition metal is elemental iron, copper, manganese, molybdenum, silver and/or nickel metal; the transition metal compound is any one or more of oxides, hydroxides, sulfides, phosphates, chlorides, carbonates, sulfates and nitrates of the transition metal.
7. The method according to claim 6, wherein when the transition metal is iron, the molar concentration of the catalyst in the reaction solution is 0.01 to 10 times that of the molar concentration of the bromate; when the transition metal is not iron, the molar concentration of the catalyst in the reaction solution is 0.1-100 times of that of bromate.
8. Use of a superoxide anion radical generated by the process of any one of claims 1 to 7.
9. The use of claim 8, wherein the superoxide anion radical is used in wastewater treatment.
10. Use according to claim 9, characterized in that: the sewage is sewage containing organic pollutants; the method according to any one of claims 1 to 7 is applied to the treatment of sewage containing organic pollutants and bromate.
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