CN112340829A - Application of phosphate in promoting green rust to activate molecular oxygen - Google Patents

Application of phosphate in promoting green rust to activate molecular oxygen Download PDF

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CN112340829A
CN112340829A CN202011158796.5A CN202011158796A CN112340829A CN 112340829 A CN112340829 A CN 112340829A CN 202011158796 A CN202011158796 A CN 202011158796A CN 112340829 A CN112340829 A CN 112340829A
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patina
phosphate
complex
molar ratio
contaminant
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方利平
李芳柏
刘凯
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Institute of Eco Environmental and Soil Sciences of Guangdong Academy of Sciens
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Institute of Eco Environmental and Soil Sciences of Guangdong Academy of Sciens
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    • 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
    • C02F2101/00—Nature of the contaminant
    • C02F2101/10—Inorganic compounds
    • C02F2101/103—Arsenic 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
    • C02F2101/34—Organic compounds containing oxygen
    • C02F2101/345—Phenols
    • 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
    • C02F2101/36—Organic compounds containing halogen
    • 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 environmental protection, and discloses application of phosphate in promoting green rust to activate molecular oxygen. The phosphate is soluble phosphate; the patina is at least one of chloride ion intercalation patina, sulfate ion intercalation patina and carbonate ion intercalation patina; the molar ratio of phosphorus element of the phosphate to iron element of the patina is (0.2-80): 1; the pH of the mixture of phosphate and patina is 6-8. Compared with single patina, the invention can obviously promote the patina to activate molecular oxygen by adding phosphate, and realize the oxidation and detoxification of various pollutants.

Description

Application of phosphate in promoting green rust to activate molecular oxygen
Technical Field
The invention belongs to the technical field of environmental protection, and particularly relates to application of phosphate in promoting green rust to activate molecular oxygen.
Background
The method utilizes iron-containing minerals to activate substances such as hydrogen peroxide and the like, is a classic Fenton-like reaction process, can generate active oxygen species (such as superoxide radicals, hydroxyl radicals and the like) with strong oxidizing property, and is an important advanced oxidation technology for treating organic matters and heavy metals in media such as water, soil and the like to detoxify.
In recent years, researchers have found that by utilizing ferrous clay minerals (such as reduced montmorillonite and nontronite), deposits can be directly reacted with oxygen to generate hydroxyl radicalsThe active hydrogen radical (. OH) can generate oxidation reaction with pollutants in the environment, thereby realizing the purpose of oxidation and detoxification. The reaction is different from the traditional Fenton-like reaction, chemical substances with higher price and cost and poorer stability, such as hydrogen peroxide, and the like, do not need to be added, and the method is regarded as a technical means for oxidizing pollutants in an economic, green and environment-friendly manner. The technical principle of the process is that the structural state ferrous iron in the clay mineral has lower potential, which is beneficial to the generation of the electron transfer process with oxygen and the generation of active oxygen species. Although the reaction process is theoretically feasible, in the actual application process, the yield of active oxygen species generated by activating oxygen with the traditional reduced clay mineral is often low, and the efficient oxidation of pollutants cannot be really realized, so that the popularization and the application of the active oxygen species in the actual process are hindered. The main reason is that the iron content of these reduced iron-containing clay minerals is often low, about 1-5% or less, resulting in low available electron quantities (geochemical report of mineral rocks, 2019, 38, 1007 and 2802). Therefore, the use of a mineral with a high ferrous content, such as patina (ferrous content up to 30% or more), is an effective solution to the above problem. Green Rust (GR) is a lamellar structure composed of octahedral iron with Cl embedded between layers-,SO4 2-Or CO3 2-The anion achieves charge balance. Although patina is rich in electrons, unfortunately, our earlier studies found that patina reacts directly with oxygen in solution, with very low yields of reactive oxygen species and insignificant oxidation of contaminants. The main reasons for this problem are: 1. the transfer or transfer of oxygen from the e-clock patina to produce reactive oxygen species is inefficient; 2. the generated reactive oxygen species are quickly consumed by the ferrous iron of the patina itself, resulting in insufficient final cumulative concentration of the reactive oxygen species, i.e. low effective electron utilization. Therefore, increasing the efficiency of the patina activating molecular oxygen to generate the cumulative concentration of active oxygen species is an important technical challenge. The inventor of the present invention discloses in patent document CN111153492A that patina has a good adsorption effect on phosphate, and the work of increasing the molecular oxygen activated by patina to generate active oxygen species and further applying the active oxygen species to pollutant degradation has been carried outIt is not reported.
Disclosure of Invention
In order to overcome the disadvantage of extremely low yields of patina activating molecular oxygen generating reactive oxygen species, it is an object of the first aspect of the invention to provide the use of a phosphate salt to promote patina activating molecular oxygen.
It is an object of a second aspect of the invention to provide a composite comprising phosphate and patina.
The third aspect of the present invention is to provide a method for producing the above-described composite.
A fourth aspect of the invention is directed to the use of the above-described complex for degrading contaminants.
It is an object of a fifth aspect of the invention to provide a method of degrading a contaminant.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
in a first aspect of the invention, there is provided the use of a phosphate salt to promote the activation of molecular oxygen by patina.
The phosphate is preferably a soluble phosphate; more preferably a soluble orthophosphate; most preferably sodium hydrogen phosphate.
The patina is preferably at least one of chloride ion intercalation patina, sulfate ion intercalation patina and carbonate ion intercalation patina; more preferably sulfate intercalated patina.
The molar ratio of ferrous iron to ferric iron in the green rust is preferably (2-4): 1; more preferably (1.5-3.0): 1; most preferably 2.5: 1.
the preparation method of the patina is preferably as follows: stirring Fe (OH)2Suspending to oxidize part of ferrous iron to obtain Fe (OH)2And Fe (OH)3The suspension of (4); then continuously stirring in an oxygen-free environment to remove O in the suspension2And obtaining the patina.
The Fe (OH)2The suspension is preferably obtained by mixing an alkali solution with a ferrous salt.
The alkali is preferably at least one of sodium hydroxide and potassium hydroxide.
The ferrous salt is preferably at least one of ferrous sulfate and ferrous chloride.
The preferable molar ratio of the ferrous salt to the alkali is (0.5-1.5): 1; more preferably (0.7-1): 1; most preferably 0.7: 1.
the molar ratio of the phosphorus element of the phosphate to the iron element of the patina is preferably (0.2-80): 1; more preferably (0.2 to 8): 1; most preferably (0.2-0.4): 1.
the pH of the mixture of the phosphate and the patina is preferably 6-8; more preferably 6.5 to 7.5; most preferably 7 to 7.5.
In a second aspect of the invention, a composite is provided comprising a phosphate and patina.
The phosphate is preferably a soluble phosphate; more preferably a soluble orthophosphate; most preferably sodium hydrogen phosphate.
The patina is preferably at least one of chloride ion intercalation patina, sulfate ion intercalation patina and carbonate ion intercalation patina; more preferably sulfate intercalated patina.
The molar ratio of ferrous iron to ferric iron in the green rust is preferably (2-4): 1; more preferably (1.5-3.0): 1; most preferably 2.5: 1.
the preparation method of the patina is preferably as follows: stirring Fe (OH)2Suspending to oxidize part of ferrous iron to obtain Fe (OH)2And Fe (OH)3The suspension of (4); then continuously stirring in an oxygen-free environment to remove O in the suspension2And obtaining the patina.
The Fe (OH)2The suspension is preferably obtained by mixing an alkali solution with a ferrous salt.
The alkali is preferably at least one of sodium hydroxide and potassium hydroxide.
The ferrous salt is preferably at least one of ferrous sulfate and ferrous chloride.
The preferable molar ratio of the ferrous salt to the alkali is (0.5-1.5): 1; more preferably (0.7-1): 1; most preferably 0.7: 1.
the molar ratio of the phosphorus element of the phosphate to the iron element of the patina is preferably (0.2-80): 1; more preferably (0.2 to 8): 1; most preferably (0.2-0.4): 1.
the pH value of the complex is preferably 6-8; more preferably 6.5 to 7.5; most preferably 7 to 7.5.
According to a third aspect of the present invention, there is provided a method for producing the above complex, comprising mixing patina and a phosphate, and adjusting the pH to 6 to 8.
The phosphate is preferably a soluble phosphate; more preferably a soluble orthophosphate; most preferably sodium hydrogen phosphate.
The patina is preferably at least one of chloride ion intercalation patina, sulfate ion intercalation patina and carbonate ion intercalation patina; more preferably sulfate intercalated patina.
The molar ratio of ferrous iron to ferric iron in the green rust is preferably (2-4): 1; more preferably (1.5-3.0): 1; most preferably 2.5: 1.
the preparation method of the patina is preferably as follows: stirring Fe (OH)2Suspending to oxidize part of ferrous iron to obtain Fe (OH)2And Fe (OH)3The suspension of (4); then continuously stirring in an oxygen-free environment to remove O in the suspension2And obtaining the patina.
The Fe (OH)2The suspension is preferably obtained by mixing an alkali solution with a ferrous salt.
The alkali is preferably at least one of sodium hydroxide and potassium hydroxide.
The ferrous salt is preferably at least one of ferrous sulfate and ferrous chloride.
The preferable molar ratio of the ferrous salt to the alkali is (0.5-1.5): 1; more preferably (0.7-1): 1; most preferably 0.7: 1.
the molar ratio of the phosphorus element of the phosphate to the iron element of the patina is preferably (0.2-80): 1; more preferably (0.2 to 8): 1; most preferably (0.2-0.4): 1.
the pH is preferably 6.5-7.5; more preferably 7 to 7.5.
In a fourth aspect of the invention, there is provided the use of a complex as described above for degrading a contaminant.
The contaminant is preferably at least one of an organic contaminant and a metalloid contaminant; more preferably at least one of trivalent arsenic, carbamazepine and dichlorophenol.
According to a fifth aspect of the invention, a method for degrading pollutants is provided, wherein the complex is mixed with pollutants, the pH is adjusted to 6-8, and reaction is carried out.
The contaminant is preferably at least one of an organic contaminant and a metalloid contaminant; more preferably at least one of trivalent arsenic, carbamazepine and dichlorophenol.
The mass ratio of the green rust to the pollutant of the composite is preferably (30-200): 1; more preferably (40-60): 1; most preferably 50: 1.
the reaction is preferably carried out with open stirring.
The reaction time is preferably 30-180 min.
The invention has the beneficial effects that:
(1) compared with single patina, the phosphate can obviously promote the patina to activate molecular oxygen, and the oxidation detoxification effect on various pollutants is efficiently realized;
(2) the patina-phosphate complex provided by the invention is an environment-friendly and nontoxic material; meanwhile, the complex can directly activate molecular oxygen to generate hydroxyl radicals, chemical agents such as hydrogen peroxide and the like are not required to be added, and the cost is saved and the practical application is facilitated.
Drawings
FIG. 1 is an X-ray diffraction chart of a patina-phosphate complex obtained in example 3.
FIG. 2 is a graph of green rust and/or phosphate OH production under aerobic/anaerobic conditions.
FIG. 3 is a graph of the kinetics of the OH reaction of patina and/or phosphate systems in aerobic conditions.
FIG. 4 is a graph showing the effect of pH on the amount of OH generated by molecular oxygen activated by a patina-phosphate complex.
Figure 5 is a graph of the degradation effect of patina and/or phosphate systems on dichlorophenol under aerobic/anaerobic conditions.
Detailed Description
The present invention will be described in further detail with reference to the following specific embodiments and accompanying drawings.
The materials, reagents and the like used in the present examples are commercially available reagents and materials unless otherwise specified.
In this embodiment: the method for measuring the molar ratio of the ferrous iron to the ferric iron in the suspension refers to the method for measuring the iron content in the national standard GB/T8570.7;
methods for determining dichlorophenol concentration reference: new information in the biological interaction and synthetic mechanism of chemical activation by zero-value biological (Iron/Copper) for organic polar degradation, Journal of biological materials, 2021,403,123669;
reference to assay methods for carbamazepine: visable-light-drive N-TiO2@SiO2@Fe3O4magnetic nanophotocatalysts:Synthesis,characterization,and photocatalytic degradation of PPCPs,Journal of Hazardous Materials，2019,370，108-116；
Reference to assay methods for trivalent arsenic (as (iii)): simultaneous removal of Cd (II) and As (III) by graphene-like biochar-supported zero-value iron from incidence water units airborne conditions, synthetic effects and mechanisms, Journal of Hazardous Materials, 2020,395, 122623.
EXAMPLE 1 preparation of patina-phosphate Complex
(1) 2g of ferrous sulfate heptahydrate is directly added into 10mL of NaOH solution (1mol/L), and the mixture is stirred uniformly by a glass rod and then put into a 6cm magnetic rotor; then 90mL of deionized water was added to obtain 100mLFe (OH)2Magnetically stirring the suspension at a stirring speed of 400 rpm;
(2) stirring open to cause Fe (OH)2Partial oxidation, wherein the molar ratio of ferrous to ferric in the suspension is measured in the stirring process, and when the molar ratio of ferrous to ferric in the suspension is 2.5: 1, stopping reaction, and continuously stirring in an oxygen-free environment to remove suspensionO in (1)2The obtained sulfate radical intercalation state green embroidery is immediately transferred to a 250mL blue cap bottle and then transferred to an anaerobic glove box to prevent the green embroidery from being continuously oxidized, and then the green embroidery is stored under anaerobic conditions after being filtered, solid-liquid separated and dried;
(3) taking 50mg of the patina obtained in the step (2), adding 100mL of 0.05mmol/L sodium hydrogen phosphate aqueous solution, wherein the final concentration of the patina is 0.5g/L, and the molar ratio of iron elements in the patina to phosphorus elements in the sodium hydrogen phosphate is 80: 1, after thorough stirring, adjusting the pH to 7.5, obtaining a Fe/P molar ratio of 80: 1 of the above suspension of patina-phosphate complex.
EXAMPLE 2 preparation of patina-phosphate Complex
The preparation method of the complex in this example is identical to that of example 2, and differs only in step (3), specifically as follows:
(3) taking 50mg of the patina obtained in the step (2), adding 100mL of 0.5mmol/L sodium hydrogen phosphate aqueous solution, wherein the final concentration of the patina is 0.5g/L, and the molar ratio of iron elements in the patina to phosphorus elements in the sodium hydrogen phosphate is 8: 1, after thorough stirring, adjusting the pH to 7.5, obtaining a mixture with a Fe/P molar ratio of 8: 1 of the above suspension of patina-phosphate complex.
EXAMPLE 3 preparation of patina-phosphate Complex
The preparation method of the complex in this example is identical to that of example 2, and differs only in step (3), specifically as follows:
(3) taking 50mg of the patina obtained in the step (2), adding 100mL of 10mmol/L sodium hydrogen phosphate aqueous solution, wherein the final concentration of the patina is 0.5g/L, and the molar ratio of iron elements in the patina to phosphorus elements in the sodium hydrogen phosphate is 0.4: 1, after thorough stirring, a molar ratio Fe/P of 0.4: 1 of the above suspension of patina-phosphate complex.
EXAMPLE 4 preparation of patina-phosphate Complex
The preparation method of the complex in this example is identical to that of example 2, and differs only in step (3), specifically as follows:
(3) taking 50mg of the patina obtained in the step (2), adding 100mL of 20mmol/L sodium hydrogen phosphate aqueous solution, wherein the final concentration of the patina is 0.5g/L, and the molar ratio of iron elements in the patina to phosphorus elements in the sodium hydrogen phosphate is 0.2: 1, after thorough stirring, a molar ratio Fe/P of 0.2: 1 of the above suspension of patina-phosphate complex.
Comparative example 1 preparation of patina
(1) 2g of ferrous sulfate heptahydrate is directly added into 10mL of NaOH solution (1mol/L), and the mixture is stirred uniformly by a glass rod and then put into a 6cm magnetic rotor; then 90mL of deionized water was added to obtain 100mLFe (OH)2Magnetically stirring the suspension at a stirring speed of 400 rpm;
(2) stirring open to cause Fe (OH)2Partial oxidation, wherein the molar ratio of ferrous to ferric in the suspension is measured in the stirring process, and when the molar ratio of ferrous to ferric in the suspension is 2.5: 1, stopping the reaction to obtain sulfate radical intercalation state green embroidery, immediately transferring to a 250mL blue cap bottle, and then transferring to an anaerobic glove box to prevent the green embroidery from being continuously oxidized.
Effects of the embodiment
Effect example 1
The patina-phosphate complex obtained in example 3 was characterized by X-ray diffraction (XRD) and the results are shown in fig. 1: after the green rust is compounded with the phosphate, the crystal structure of the phosphate is still similar to that of the sulfate intercalated green rust, which shows that phosphate ions are not inserted into the interlayer structure of the green rust but are complexed on the outer surface of the interlayer structure, and the phenomenon is different from the phenomenon that other anion states can be intercalated into the green rust layers.
Effect example 2
Diluting the patina prepared in the comparative example 1 with deionized water to obtain the patina with the concentration of 0.5 g/L; respectively taking 40mL of the patina-phosphate complex (the final concentration of the patina in the complex is 0.5g/L) prepared in the example 2-5 and 40mL of the patina with the concentration of 0.5g/L, adding the patina-phosphate complex into a 50mL centrifuge tube, adjusting the pH value to 7.5, and directly exposing the patina-phosphate complex in the air condition to carry out aerobic reaction; meanwhile, filling argon into a 50mL centrifuge tube, adding 40mL of patina with the concentration of 0.5g/L into the 50mL centrifuge tube, adjusting the pH value to 7.5, and carrying out anaerobic reaction; when the charge was completed, the amount of hydroxyl radicals (. OH) produced was measured by sampling at 0, 15, 30, 60, 120 and 180min, and the method for measuring OH was as follows: the reaction mixture was passed through a 0.22 μm water film, and then added with a benzoic acid solution (used as a probe) to react and convert into parahydroxybenzoic acid assay OH (see the methods in the literature: quantitative identification of the Oxidizing Capacity of Nanoparticulate Zero-Valent Iron, environ, Sci, technol.2005,39,1263-1268), and the results of OH accumulation (accumulation kinetics) are shown in Table 1 and FIG. 2: the patina can not generate OH under anaerobic condition, while the OH accumulation amount generated by single patina under aerobic condition is only 1.3 mu M (reaction time: 3 hours); when phosphate is added to the green embroidery, OH generation is significantly increased, and as the molar ratio of iron element in the green embroidery to phosphorus element in sodium hydrogen phosphate is decreased, OH generation is significantly increased: when the Fe/P ratio reaches 0.2-0.4, the OH generation amount reaches 21.3-21.8 μ M; OH accumulation quasi-second order reaction kinetic constants are shown in fig. 3 and table 2: the OH accumulation amount generation kinetic reaction conforms to the quasi-second order kinetic equation, and the second order kinetic reaction constant increases as the molar ratio of the iron element in patina to the phosphorus element in sodium hydrogen phosphate decreases.
TABLE 1 Rust and/or phosphate OH Generation after 3h reaction under aerobic/anaerobic conditions
Figure BDA0002743668750000061
Figure BDA0002743668750000071
TABLE 2 Rust and/or phosphate System OH kinetics constants in aerobic conditions
Experimental group Reaction system Kinetic constant (μ M/min)
1 0.5g/L patina 0.010
2 0.5g/L Rust +0.05mM PO4 3- 0.065
3 0.5g/L Rust +0.5mM PO4 3- 0.105
4 0.5g/L Rust +10mM PO4 3- 0.125
5 0.5g/L Rust +20mM PO4 3- 0.130
Effect example 3
40mL of the patina-phosphate complex (final patina concentration in complex: 0.5g/L) prepared in example 5 was taken and put into a 50mL centrifuge tube, the pH of the complex was adjusted to 6.5, 7.5, and 8.5, respectively, and when the feeding was completed, the amount of hydroxyl radical (. OH) produced was measured by sampling at 180min (OH quantitative method same as in example 2), and the results are shown in FIG. 4: at pH 7.5, the amount of OH accumulated is the highest, so that the reaction system is optimized under neutral conditions; in contrast, both acidic and basic properties exert some inhibitory effect on. OH.
Effect example 4
Taking 40mL of the patina with the concentration of 0.5g/L prepared in the effect example 2 and the complex (the final concentration of the patina in the complex is 0.5g/L) obtained in the examples 3 and 5 respectively, adding 0.2mL of a dichlorophenol solution with the mother liquor concentration of 2000mg/L into a 50mL centrifuge tube to obtain a mixed solution, adjusting the pH to 7.5, and directly exposing the mixed solution to the air for aerobic reaction; meanwhile, nitrogen is filled into a 50mL centrifuge tube, 40mL of patina with the concentration of 0.5g/L prepared in the effect example 2 is taken to be placed into the 50mL centrifuge tube, 0.2mL of dichlorophenol solution with the mother liquor concentration of 2000mg/L is added to obtain mixed solution, the final concentration of the patina in the mixed solution is 0.5g/L, the concentration of the dichlorophenol is 10mg/L, the pH is adjusted to 7.5, and anaerobic reaction is carried out; when the timing is started after the feeding is finished, the dichlorophenol concentration is measured by sampling for 0min, 20 min, 30 min, 60 min, 120 min and 180min respectively, and the result is shown in figure 5 and table 3, wherein the degradation rate of the dichlorophenol by the green embroidery is very low: wherein, when the reaction is carried out for 3 hours, the removal rate is 1.2 percent under the aerobic condition and 4.0 percent under the anaerobic condition; the addition of phosphate (patina-phosphate complex) can significantly increase the removal rate of dichlorophenol and increases as the molar ratio of iron element in patina to phosphorus element in sodium hydrogen phosphate decreases: when the reaction time is 3h, when the Fe/P molar ratio is 8: at 1 hour, the removal rate of dichlorophenol is 10.1 percent; when the Fe/P molar ratio is 0.4: at 1, the removal rate of dichlorophenol was 30.5%.
TABLE 3 Degradability of Rust and/or phosphate systems on dichlorophenol under aerobic/anaerobic conditions (reaction time 3h)
Experimental group Reaction system Dichlorophenol removal rate (%)
1 0.5g/L Rust + oxygen 1.2％
2 0.5g/L patina + nitrogen 4.0％
3 0.5g/L Rust +0.5mM PO4 3-+ oxygen 10.1％
4 0.5g/L Rust +10mM PO4 3-+ oxygen 30.5％
Effect example 5
Respectively taking 40mL of the patina with the concentration of 0.5g/L prepared in the effect example 2 and the complex (the final concentration of the patina in the complex is 0.5g/L) obtained in the example 5 into a 50mL centrifuge tube, respectively adding 0.2mL of mother liquor with the concentration of 2000mg/L carbamazepine, As (III) and dichlorophenol solution to obtain a mixed solution, wherein the final concentration of the patina in the mixed solution is 0.5g/L, and the concentrations of the carbamazepine, As (III) and the dichlorophenol solution are all 10mg/L, and adjusting the pH to 7.5; when the feeding was completed, the reaction mixture was passed through a 0.22 μm water film, and the concentrations of carbamazepine, trivalent arsenic (as (iii)), pentavalent arsenic produced by oxidation [ as (v)), and dichlorophenol were measured to calculate the removal rate of contaminants, and the results are shown in table 4: the phosphate is added, so that the removal rate of the patina to different pollutants (carbamazepine, trivalent arsenic and dichlorophenol) can be obviously improved, and the effect of oxidative detoxification is achieved.
TABLE 4 Rust and/or phosphate removal rates for various contaminants under aerobic conditions
Figure BDA0002743668750000081
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such changes, modifications, substitutions, combinations, and simplifications are intended to be included in the scope of the present invention.

Claims (10)

1. A composite body, characterized by: including phosphates and patina.
2. The composite of claim 1, wherein: the molar ratio of the phosphorus element of the phosphate to the iron element of the patina is (0.2-80): 1.
3. the composite of claim 2, wherein:
the phosphate is soluble phosphate;
the patina is preferably at least one of a chloride ion-intercalated patina, a sulfate ion-intercalated patina, and a carbonate ion-intercalated patina.
4. The composite body according to any one of claims 1 to 3, wherein: the pH value of the complex is 6-8.
5. Use of a phosphate salt to promote the activation of molecular oxygen by patina.
6. Use according to claim 5, characterized in that:
the phosphate is soluble phosphate;
the patina is preferably at least one of chloride ion intercalation patina, sulfate ion intercalation patina and carbonate ion intercalation patina;
the molar ratio of the phosphorus element of the phosphate to the iron element of the patina is preferably (0.2-80): 1.
7. a method for producing the composite body according to any one of claims 1 to 4, characterized in that: and mixing the patina and the phosphate, and adjusting the pH value to 6-8 to obtain the rust inhibitor.
8. Use of the complex of any one of claims 1-4 for degrading a contaminant.
9. A method of degrading a contaminant, comprising: mixing the complex according to any one of claims 1 to 4 with a contaminant, adjusting the pH to 6 to 8, and reacting.
10. The method of claim 9, wherein:
the mass ratio of the green rust to the pollutant of the complex is (30-200): 1;
the contaminant is preferably at least one of an organic contaminant and a metalloid contaminant.
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