CN113171739B - Method for producing superoxide anion free radical by catalytic activation of bromate and application of superoxide anion free radical produced by method - Google Patents

Method for producing superoxide anion free radical by catalytic activation of bromate and application of superoxide anion free radical produced by method Download PDF

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CN113171739B
CN113171739B CN202110450231.2A CN202110450231A CN113171739B CN 113171739 B CN113171739 B CN 113171739B CN 202110450231 A CN202110450231 A CN 202110450231A CN 113171739 B CN113171739 B CN 113171739B
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bromate
superoxide anion
reaction
anion free
catalyst
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CN113171739A (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

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, the superoxide anion free radicals are generated by catalyzing bromate by using transition metal or a compound thereof as a catalyst; 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 the catalyst; the method can be applied to the conversion and elimination of organic pollutants and the treatment of bromate and organic composite polluted wastewater, and has the advantages of simple principle, simplicity and convenience in operation, wide pH application range and the like.

Description

Method for producing superoxide anion free radical by catalytic activation of bromate and application of superoxide anion free radical produced 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 catalyzing and activating bromate and application of the superoxide anion free radicals generated by the method.
Background
Bromate is a carcinogen whose discharge concentration has strict control standards in both surface and groundwater. Meanwhile, as a non-metal oxyacid salt, the oxidation-reduction potential was 1.52V (BrO 3 - +6H + +5e - →1/2Br 2 +3H 2 O) can react with ammonium salts (R.Hofmann, R.C.Andrews, water Research,2006,40,3343-3348), zero valent iron (L.Xie, C.Shang, chemosphere,2007,66,1652-1659), and cuprous (P.Y.Chen, H.H.Yang, C.C.Huang, Y.H.Chen, Y.Shih, electrochimica Acta,2015,161,100-107), etc., but the generation of oxygen-containing radicals is not observed in these systems. Shen et al at Fe@Fe 2 O 3 Free radicals such as superoxide radicals are found to be generated during the reduction of bromates, but these radicals come fromFrom Fe@Fe 2 O 3 Activation of dissolved oxygen, rather than from decomposition of bromates (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/Al 2 O 3 Bromates can be reduced to bromide ions, but they do not report that hydroxyl radicals and superoxide radicals in the system originate from the decomposition of bromates. Instead, they found that these radicals resulted from 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 generated sulfite radicals by reaction of bromate with sulfite. Other radicals such as sulfate radicals may be further generated by reaction of sulfite radicals with oxygen molecules under aerobic conditions. It should be noted, however, that the sources of these radicals are sulphite and dissolved oxygen, rather than bromate (J.Qiao, L.Feng, H.Dong, Z.Zhao, X.Guan, environmental science&technology,2019,53,10320-10328). Therefore, how to catalyze and generate superoxide anion free radicals by using bromate as an oxidant through a catalyst without adding other oxidants or dissolved oxygen is an important content of the research of the invention.
Disclosure of Invention
Aiming at the defects existing in the prior art, the invention aims to provide 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, and the superoxide anion free radicals can be generated by catalyzing with a metal catalyst only by taking bromate as an oxidant 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 pollution 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, wherein the superoxide anion free radicals are generated by catalyzing bromate reaction by adopting 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 bromate-containing solution, 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 hydrobromic acid (NaBrO) 2 ) And potassium hypobromite (KBrO) 2 ) Any one or more of the following.
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 either aqueous or alcoholic solutions.
Preferably, the catalyst is iron, copper, manganese, molybdenum, silver and/or nickel metal simple substance or any one or a mixture of a plurality of oxides, hydroxides, sulfides, phosphates, chlorides, carbonates, sulfates and nitrates of the metals.
Preferably, the molar concentration of the catalyst is 0.01-10 times of that of bromate when the catalyst is an iron-based catalyst, and the molar concentration of the catalyst is 0.1-100 times of that of bromate when the catalyst is not an iron-based catalyst.
When the catalyst is a transition metal compound, the catalyst is added directly or in the form of a solution of the transition metal compound;
preferably, the pH is set to a value of 2.5 to 10.
The invention also provides an application of the superoxide anion free radical generated by the method for generating superoxide anion free radical by catalytically activating bromate.
Further, the superoxide anion radical is applied to sewage treatment (the sewage is sewage containing organic pollutants or sewage containing organic pollutants and bromate).
According to the method for generating the superoxide anion free radical by catalytically activating bromate, provided by the invention, other oxidants or dissolved oxygen are not required to be added, and the superoxide anion free radical can be generated by catalyzing only the bromate serving as the oxidant through a metal catalyst. The method takes a catalyst as an electron donor to catalyze and reduce bromate, so that oxygen atoms in the bromate are released in the form of superoxide anion free radicals. The process not only converts bromate into bromide ions and reduces the environmental hazard of bromate, but also provides superoxide anion free radicals with oxidizing capability, and can be applied to the oxidative 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, and can be applied to the conversion and elimination of organic pollutants and the treatment of bromate and organic composite pollution wastewater.
Drawings
FIG. 1 is a FeSO of example 1 of the present invention 4 ESR signal plot of the catalytically activated bromate system;
FIG. 2 FeSO at different concentrations in example 2 of the present invention 4 ESR signal diagram and ESR signal intensity of catalytic activated bromate in 10min reaction;
FIG. 3 is a FeSO in example 3 of the present invention 4 ESR signal diagram and ESR signal intensity (linear correlation coefficient R in right diagram) of catalytic activation of bromates with different concentrations in reaction for 10min 2 ，R 2 ＝0.98)；
FIG. 4 is FeCl in example 4 of the present invention 2 ESR signal diagram and ESR signal intensity of the catalytic activation bromate at different pH values;
FIG. 5 is a graph of ESR signals for the iron-based catalyst catalyzed activation of bromate/bromate 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 invention 2 O 3 ESR signal plot of catalytically activated bromate;
FIG. 7 is a FeSO in example 13 of the present invention 4 Kinetics of catalytic activation of bromate degradation of phenol.
Detailed Description
The present invention is further described below in conjunction with the specific embodiments so that those skilled in the art may further understand the present invention, but the following embodiments should not be construed or interpreted in any way as limiting the scope of the present invention as claimed.
Example 1
In this example, commercially available chemically pure FeSO was selected 4 As a catalyst, catalytically activating bromates generates superoxide anion radicals. By adopting the method for generating superoxide anion free radical by catalytically activating bromate, 0.5mL FeSO with the concentration of 0.18mol/L is added into 49.5mL sodium bromate aqueous solution 4 Aqueous solution, using 0.1mol/L HClO 4 The pH value of the aqueous solution and 0.1mol/L NaOH aqueous solution is regulated to 4, so as to obtain a reaction solution, and the reaction solution is stirred and reacted for 10-180min. Sodium bromate and FeSO 4 The initial concentrations in the reaction solution were 0.5mmol/L and 1.8mmol/L, respectively. To demonstrate the generation of superoxide anion radicals, 1mL of a solution of 5, 5-dimethyl-1-pyrroline-N-oxide in methanol was sampled from the reaction mixture at various times of the reaction, and 0.1mL of the solution was added at a concentration of 100mmol/L, and the reaction was carried out for 1min, and ESR spectra of the adduct of superoxide anion radicals and 5, 5-dimethyl-1-pyrroline-N-oxide were measured by using an electron spin resonance (ESR, brookEMX nano type) and the result was shown in FIG. 1.
As can be seen from FIG. 1, this signal is consistent with the ESR signal of a typical superoxide anion radical and 5, 5-dimethyl-1-pyrroline-N-oxide adduct, indicating the generation of superoxide anion radicals. FeSO 4 When reacted with sodium bromate for 10min, the super-oxyanion radical had an ESR signal intensity of 0.57a.u..
In this example, when FeSO 4 When reacting with sodium bromate, fe 2+ The reaction principle of the method is shown in a reaction formula (1) that bromate ions are reduced by one electron to generate superoxide anion free radicals and hypobromite ions:
Fe 2+ +BrO 3 - →BrO - +Fe 3+ +O 2 ·- (1)
example 2
In this example, by changing FeSO 4 The initial concentration of the catalyst was studied for its effect on the production of superoxide anion radicals. Specific experimental procedure As in example 1, feSO alone was adjusted 4 Initial concentration in the reaction solution. FeSO 4 The initial concentrations of the catalyst were 0.018mmol/L, 0.18mmol/L, 1.8mmol/L, 3.5mmol/L and 5mmol, respectivelyL; the initial concentration of sodium bromate is 0.5mmol/L; the initial pH of the reaction was 4.
The signal of superoxide anion radical at 10min of reaction was detected by the method of example 1. As can be seen from FIG. 2, when FeSO 4 When the initial concentration is 1.8mmol/L, the ESR signal of the superoxide anion radical is strongest, which indicates that the FeSO with proper concentration 4 Can efficiently decompose bromate to generate superoxide anion free radical.
Example 3
In this example, the initial concentration change of sodium bromate versus FeSO was studied 4 Catalytic activation of bromates produces the effect of superoxide anion radicals. Specific experimental procedure as in example 1, the initial concentration of sodium bromate in the reaction liquid was adjusted only. The initial concentration of 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; feSO 4 Initial concentrations were 1.8mmol/L; the initial pH of the reaction was 4.
The signal of superoxide anion radical at 10min of reaction was detected by the method of 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 studied. Specific experimental procedure as in example 1, the initial pH of the reaction solution was adjusted to different values and the catalyst was replaced with ferrous chloride. FeCl 2 And initial concentrations of sodium bromate of 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 detected by the method of example 1. As can be seen from FIG. 4, the ESR signal intensity of the superoxide anion radical is obviously reduced with the increase of the initial pH value, which proves that the acidic pH condition is favorable for FeCl 2 Catalytic activation of bromates generates superoxide anion radicals.
Example 5
In the present embodiment of the present invention, in the present embodiment,selecting commercial products of chemical purity FeSO 4 As a catalyst, catalytically activating bromates generates superoxide anion radicals. By adopting the method for generating superoxide anion free radical by catalytically activating bromate, 0.5mL FeSO with the concentration of 5mmol/L is added into 49.5mL sodium bromate methanol solution 4 Methanol solution, 0.1mol/L HClO was used 4 The pH value of the aqueous solution and 0.1mol/L NaOH aqueous solution is regulated to 4, so that a reaction solution is obtained, and the reaction is stirred for 30min. Sodium hydrobromic acid and FeSO 4 The initial concentrations in the reaction solution were 5mmol/L and 0.05mmol/L, respectively.
The signal of superoxide anion radical was detected by the method of example 1. As shown in FIG. 5, the ESR signal intensity of the superoxide anion radical was 0.17a.u. at 30min of reaction.
In the present embodiment, when Fe 2+ Upon reaction with sodium hydrobromic acid, fe 2+ The reaction principle of the method is shown in a reaction formula (2) that the reduction of hydrobromic acid ions by one electron leads to the generation of superoxide anion free radicals and bromide ions:
Fe 2+ +BrO 2 - →Br - +Fe 3+ +O 2 ·- (2)
example 6
In this example, commercial nano Fe is selected 3 O 4 As a catalyst, catalytically activating bromates generates superoxide anion radicals. By adopting the method for generating superoxide anion free radical by catalytically activating bromate, 4.6mg of nano Fe is added into 50mL of aqueous solution with concentration of 2.5mmol/L potassium bromate 3 O 4 0.1mol/L HClO is adopted 4 The pH value of the aqueous solution and 0.1mol/L NaOH aqueous solution is regulated to 5, so that a reaction solution is obtained, and the reaction is stirred for 20min. Potassium bromate and nano Fe 3 O 4 The initial concentrations in the reaction solution were 2.5mmol/L and 0.4mmol/L, respectively.
The signal of superoxide anion radical was detected by the method of example 1. As shown in FIG. 5, the ESR signal intensity of the superoxide anion radical was 0.13a.u. at 20min of reaction.
In the present embodiment, when nano Fe 3 O 4 And potassium bromate, nanometerFe 3 O 4 Surface ferrous iron (≡Fe) 2+ "≡" means the surface of a solid catalyst, and is not described in detail below), the reaction principle of the catalyst is shown in the reaction formula (3) that the reduction of bromate ions by one electron causes the generation of superoxide anion free radicals and hypobromite ions:
≡Fe 2+ +BrO 3 - →BrO - +≡Fe 3+ +O 2 ·- (3)
example 7
In this embodiment, a commercial FeS is selected 2 As a catalyst, catalytically activating bromates generates superoxide anion radicals. By adopting the method for generating superoxide anion free radical by catalytically activating bromate, 6mg FeS is added into 50mL of aqueous solution with concentration of 0.1mmol/L potassium bromate 2 Solid particles, 0.1mol/LHClO 4 The pH value of the aqueous solution and 0.1mol/L NaOH aqueous solution is regulated to 7, so that a reaction solution is obtained, and the reaction is stirred for 10min. Potassium bromate and FeS 2 The initial concentrations in the reaction solution were 0.1mmol/L and 1mmol/L, respectively.
The signal of superoxide anion radical was detected by 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 reaction.
In the present embodiment, when FeS 2 FeS during reaction with potassium bromate 2 Surface ferrous iron (≡Fe) 2+ ) The reaction principle of the method is shown in a reaction formula (3) and the bromate ions are generated by reducing bromate ions through one electron.
Example 8
In this embodiment, a commercial FeS is selected 2 As a catalyst, catalytically activating bromates generates superoxide anion radicals. By adopting the method for generating superoxide anion free radical by catalytically activating bromate, 6mg FeS is added into 50mL of aqueous solution with concentration of 0.1mmol/L sodium hypobromite 2 Solid particles, 0.1mol/LHClO 4 The pH value of the aqueous solution and 0.1mol/L NaOH aqueous solution is regulated to 7, so that a reaction solution is obtained, and the reaction is stirred for 30min. Sodium hydrobromic acid and FeS 2 Initial concentration in the reaction solution0.1mmol/L and 1mmol/L, respectively.
The signal of superoxide anion radical was detected by the method of example 1. As shown in FIG. 5, the ESR signal intensity of the superoxide anion radical was 0.12a.u. at 30min of reaction.
In the present embodiment, when FeS 2 FeS during reaction with sodium hydrobromic acid 2 Surface ferrous iron (≡Fe) 2+ ) The reaction principle of the method is shown in a reaction formula (4) that the reduction of hydrobromic acid ions by one electron leads to the generation of superoxide anion free radicals and bromide ions:
≡Fe 2+ +BrO 2 - →Br - +≡Fe 3+ +O 2 ·- (4)
example 9
In this example, commercial FeSO is selected 4 And Ni (NO) 3 ) 2 As a catalyst, catalytically activating bromates generates superoxide anion radicals. By adopting the method for generating superoxide anion free radical by catalytically activating bromate, 0.5mL FeSO with the concentration of 10mmol/L is added into 49mL sodium bromate aqueous solution 4 Aqueous solution and 0.5mL of Ni (NO) with concentration of 100mmol/L 3 ) 2 Aqueous solution, using 0.1mol/L HClO 4 The pH value of the aqueous solution and the aqueous solution of 0.1mol/LNaOH is regulated to 2.5, so that a reaction solution is obtained, and the reaction is stirred for 60 minutes. Sodium bromate, feSO 4 And Ni (NO) 3 ) 2 The initial concentrations in the reaction solution were 0.1mmol/L,0.1mmol/L and 1mmol/L, respectively.
The signal of superoxide anion radical was detected by the method of example 1. As shown in FIG. 5, the ESR signal intensity of the superoxide anion radical was 0.21a.u. at 60min of reaction.
Example 10
In this example, commercial zero-valent molybdenum (i.e., metallic molybdenum) was chosen as the catalyst to catalyze the activation of bromates to generate superoxide anion radicals. The method for producing superoxide anion free radical by catalytically activating bromate of the invention is characterized in that 4.8mg of zero-valent molybdenum solid particles and 0.1mol/L HClO are added into 50mL of aqueous solution with concentration of 0.05mmol/L sodium bromate 4 Aqueous solution and 0.1mol/L NaOH aqueous solutionThe pH value is 5, and the reaction is stirred for 90min. The initial concentrations of sodium bromate and zero-valent molybdenum in the reaction liquid were 0.05mmol/L and 1mmol/L, respectively.
The production of superoxide anion radical was detected by 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, when zero-valent molybdenum is reacted with sodium bromate, zero-valent molybdenum (≡Mo) 0 ) Releasing electrons to reduce bromate ions to generate superoxide anion free radicals and hypobromite ions, and the reaction principle is shown in a reaction formula (5):
≡Mo 0 +4BrO 3 - →≡Mo 4+ +4BrO - +4O 2 ·- (5)
example 11
In this example, commercial CuCl was chosen as the catalyst for the catalytic activation of bromates to generate superoxide anion radicals. The method for producing superoxide anion free radical by catalytically activating bromate of the invention is characterized in 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 adopted 4 The pH value of the aqueous solution and 0.1mol/L NaOH aqueous solution is regulated to 7, so that a reaction solution is obtained, and the reaction is stirred for 10min. The initial concentrations of potassium bromate and CuCl in the reaction solution were 0.1mmol/L and 10mmol/L, respectively.
The production of superoxide anion radical was detected by 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 reaction.
In this example, cu in CuCl was found to be Cu when reacting with potassium bromate + The reaction principle of the method is shown in a reaction formula (6) that the reduction of bromate ions by one electron leads to the generation of superoxide anion free radicals and hypobromite ions:
Cu + +BrO 3 - →BrO - +Cu 2+ +O 2 ·- (6)
example 12
In this embodiment, the commodity Mn is selected 2 O 3 Catalytic activation of bromate production as a catalystGenerating superoxide anion radical. By adopting the method for generating superoxide anion radical by catalytically activating bromate, 79mg Mn is added into 50mL of aqueous solution with concentration of 0.1mol/L sodium bromate 2 O 3 Solid, 0.1mol/LHClO 4 The pH value of the aqueous solution and 0.1mol/L NaOH aqueous solution is regulated to 10, so that a reaction solution is obtained, and the reaction is stirred for 10min. Sodium bromate and Mn 2 O 3 The initial concentrations in the reaction solution were 0.1mol/L and 10mmol/L, respectively.
The production of superoxide anion radical was detected by the method of example 1. As shown in FIG. 6, the ESR signal intensity of the superoxide anion radical was 0.25a.u. at 10min of reaction.
In the present embodiment, when Mn 2 O 3 When reacting with sodium bromate, mn 2 O 3 Trivalent manganese (Mn) 3+ ) The reaction principle of the method is shown in a reaction formula (7) that the reduction of bromate ions by one electron leads to the generation of superoxide anion free radicals and hypobromite ions:
≡Mn 3+ +BrO 3 - →BrO - +≡Mn 4+ +O 2 ·- (7)
example 13
In this example, commercially available chemically pure FeSO was selected 4 As a catalyst, the catalytic activation of bromate to generate superoxide anion free radical realizes the oxidative conversion of the coexisting organic pollutant phenol. Firstly preparing 49.72mL of mixed solution of sodium bromate and phenol, generating superoxide anion free radical to degrade phenol by adopting the method for generating superoxide anion free radical by the catalytic activation of bromate, and adding 0.28mL of FeSO with the concentration of 0.18mol/L into the prepared 49.72mL of mixed solution 4 0.1mol/L HClO is adopted 4 The pH value of the aqueous solution and the aqueous solution of 0.1mol/LNaOH is regulated to 4, so that a reaction liquid is obtained, and the reaction is started by stirring. Sodium bromate, phenol and FeSO 4 Initial concentrations of (C) were 0.1mmol/L, 0.05mmol/L and 1mmol/L, respectively. Sampling from the reaction liquid at different reaction times, and analyzing the concentrations of phenol, bromate and bromide ions in the reaction liquid; as shown in figure 7, after 120min of treatment, the removal efficiency of phenol is 100%, and sodium bromate is removedThe removal efficiency was 94% and the selectivity of sodium bromate to bromide was 99.5%. In contrast, feSO was not added 4 When the catalyst is used, the phenol removal efficiency is 0% and the sodium bromate removal efficiency is 0% after 120min of treatment. It follows that the FeSO of the present example 4 The catalyst can catalyze and activate bromate to generate superoxide anion free radical, and the obtained superoxide anion free radical can effectively remove phenol as an organic pollutant.

Claims (6)

1. A method for generating superoxide anion free radicals by catalytically activating bromate, which is characterized in that the superoxide anion free radicals are generated by catalyzing bromate reaction by adopting transition metal or transition metal compound as a catalyst, and the superoxide anion free radicals are generated by bromate ion decomposition;
adding the catalyst into a bromate-containing solution, and adjusting the pH value to 2.5-10, wherein the obtained reaction solution reacts to generate superoxide anion free radicals; the bromate is any one or more of sodium bromate, potassium bromate, sodium hypobromite and potassium hypobromite;
the transition metal is iron, copper, manganese, molybdenum, silver and/or nickel metal simple substance; the transition metal compound is any one or more of oxide, hydroxide, sulfide, phosphate, chloride, carbonate, sulfate and nitrate of the transition metal;
when the transition metal is iron, the molar concentration of the catalyst in the reaction liquid is 0.01-10 times of the molar concentration of bromate; when the transition metal is not iron, the molar concentration of the catalyst in the reaction liquid is 0.1-100 times of the molar concentration of bromate.
2. The method for producing superoxide anion radical by catalytically activating bromate according to claim 1, wherein the concentration of bromate in the reaction solution is 0.05 mmol/L-0.1 mol/L.
3. A method of catalytically activating bromate to generate superoxide anion radicals as claimed in claim 1, wherein the bromate containing solution is an aqueous bromate solution or an alcoholic bromate solution.
4. Use of superoxide anion radicals produced by a method for the catalytic activation of bromates to generate superoxide anion radicals based on any of claims 1-3 in sewage treatment.
5. The use according to claim 4, characterized in that: the sewage is sewage containing organic pollutants.
6. The use according to claim 4, characterized in that: the sewage is sewage containing organic pollutants and bromate.
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