CN111420708B - Graphene covalent grafted aminobenzene terpyridine-iron complex Fenton catalyst and preparation method thereof - Google Patents
Graphene covalent grafted aminobenzene terpyridine-iron complex Fenton catalyst and preparation method thereof Download PDFInfo
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- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
- B01J31/181—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine
- B01J31/1815—Cyclic ligands, including e.g. non-condensed polycyclic ligands, comprising at least one complexing nitrogen atom as ring member, e.g. pyridine with more than one complexing nitrogen atom, e.g. bipyridyl, 2-aminopyridine
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- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/1616—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts
- B01J31/1625—Coordination complexes, e.g. organometallic complexes, immobilised on an inorganic support, e.g. ship-in-a-bottle type catalysts immobilised by covalent linkages, i.e. pendant complexes with optional linking groups
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- C01B32/15—Nano-sized carbon materials
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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
- C02F1/722—Oxidation by peroxides
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- C—CHEMISTRY; METALLURGY
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- 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
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/02—Compositional aspects of complexes used, e.g. polynuclearity
- B01J2531/0213—Complexes without C-metal linkages
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/84—Metals of the iron group
- B01J2531/842—Iron
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- 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
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/02—Specific form of oxidant
- C02F2305/026—Fenton's reagent
Abstract
The invention relates to a graphene covalent grafted aminobenzene terpyridine-iron complex Fenton catalyst and a preparation method thereof, belonging to the technical field of advanced oxidation water treatment. According to the invention, the iron complex is used as a Fenton reagent, the graphene is used as a carrier of the Fenton reagent, and the graphene and the iron complex are connected through an amido bond, so that iron ions can be firmly and firmly loaded on the surface of the graphene, and the problems of iron ion current and secondary pollution are effectively solved. Meanwhile, the graphene has high electron transfer efficiency and large specific surface area, and can cooperate with a Fenton reagent to exert high degradation capability on organic pollutants. The Fenton catalyst has the degradation rate of 100mg/L rhodamine B close to 100% in 60min under the condition that the pH value is 4, and the degradation rate is not reduced after 5 times of circulation, so that the Fenton catalyst shows higher degradation efficiency and good stability, and has better application prospect.
Description
Technical Field
The invention relates to a graphene covalent grafted aminobenzene terpyridine-iron complex Fenton catalyst and a preparation method thereof, belonging to the technical field of advanced oxidation water treatment.
Background
Among the technologies for deeply oxidizing and treating organic wastewater, the Fenton oxidation method is the wastewater treatment technology with the greatest industrial application prospect. On one hand, compared with other deep oxidation technologies, the method has the characteristics of wide application range, strong anti-interference capability and the like, and can quickly degrade and mineralize organic pollutants; on the other hand, the system utilizes the environment-friendly oxidant-hydrogen peroxide, and the final decomposition product is O2And H2And O, accords with the concept of 'green oxidation'.
The essence of the Fenton reaction is Fe2+Under strongly acidic conditions and H2O2The reaction generates hydroxyl radicals (. OH) with high reactivity, which, despite their many advantages, still have a number of disadvantages. The most important point is that iron salt used as a catalyst in the reaction forms iron mud after the reaction is finished, a separation step needs to be added, and no good disposal method exists for the iron mud at present, so that secondary pollution is easily caused. In order to overcome the above disadvantages of the Fenton oxidation technology, the heterogeneous Fenton oxidation technology in which a catalyst is supported on a solid carrier has become the current technologyThe research focus.
Graphene is a new type of carbon nanomaterial which has emerged in recent years, is a nanomaterial which has the thinnest thickness, the largest strength and the best electric and heat conducting properties in the current carbon material, and has a larger specific surface area, good electron transfer capacity and stronger adsorption capacity. The Fenton active component is loaded on the surface of the graphene with high conductivity and high strength, so that more active sites can be provided for the graphene, and the catalytic performance of the graphene is improved.
In the organometallic complex, a metal atom and an organic ligand are bonded to each other by a coordinate bond, and the complex can exist in an aqueous solution relatively stably. These complexes generally have excellent properties in the fields of light, electricity, magnetism, and the like, and are widely used in the field of catalysis. The polypyridine ligand and the derivative thereof are common organic ligands, and can effectively anchor iron ions after being coordinated with the iron ions.
Based on the technical cognition, the graphene covalent grafting aminobenzene terpyridine-iron complex Fenton catalyst is developed, and graphene is connected with an iron complex through an amido bond, so that iron ions can be firmly supported on the surface of the graphene, and the problems of iron ion current and secondary pollution are effectively solved. The heterogeneous Fenton catalyst prepared by the invention can efficiently catalyze and degrade organic pollutants, and has potential application prospects.
Disclosure of Invention
The invention aims to provide a graphene covalent grafted aminobenzene terpyridine-iron complex Fenton catalyst, wherein graphene is used as a carrier, the aminobenzene terpyridine-iron complex is used as a Fenton reagent, the graphene and the complex are connected through a covalent bond, and the metal iron accounts for 5-10wt% of the catalyst.
Further, the graphene and the complex are connected through an amide bond.
The invention also aims to provide a preparation method of the graphene covalent grafted aminobenzene terpyridine-iron complex Fenton catalyst, which comprises the following preparation steps:
(1) dispersing Graphene Oxide (GO) in dichloromethane, ultrasonically dispersing for 0.5-1h, dropwise adding thionyl chloride with the mass 5-10 times that of GO under the ultrasonic-assisted condition, introducing Ar gas for protection, heating and refluxing, reacting at the temperature of 40-60 ℃ for 12-20h, and performing rotary evaporation to remove redundant reactants and solvent to obtain acylchlorinated graphene oxide;
(2) dissolving ferrous sulfate in 50-200ml of water, stirring for dissolving, adding an aminophenylterpyridine ligand, wherein the molar ratio of the ferrous sulfate to the ligand is 1:1, magnetically stirring for 1-3h to obtain a homogeneous mixture, transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 120-140 ℃, reacting for 24-48h, naturally cooling to room temperature after the reaction is finished, filtering, and washing to obtain an aminophenylterpyridine-iron complex;
(3) dissolving the aminobenzene terpyridine-iron complex prepared in the step (2) in dichloromethane, adding the acylchlorinated graphene oxide prepared in the step (1), wherein the mass ratio of the aminobenzene terpyridine-iron complex to GO is 1:0.3-3, dropwise adding a small amount of DMF (dimethyl formamide) as a catalyst, reacting at 80-120 ℃ for 20-48h, and performing centrifugal separation to obtain the aminobenzene terpyridine-iron complex Fenton catalyst grafted by the graphene in a covalent mode.
Further, the reaction temperature in the step (1) is preferably 50-60 ℃, and the reaction time is preferably 18-20 h; the reaction temperature in the step (3) is preferably 100-120 ℃, and the reaction time is preferably 40-48 h.
The core of the Fenton reaction is Fe2+ + H2O2→Fe3+ +·OH + OH－Wherein, OH has high reaction activity, and can efficiently oxidize organic pollutants to realize wastewater treatment. However, Fe in the reaction system3+Reduction to Fe2+The steps are quite slow, and after the Fenton reagent is compounded with the graphene, the Fe can be promoted due to the high electron transfer efficiency of the graphene3+Faster electron acquisition and conversion to Fe2+And the reaction circulation is accelerated. Meanwhile, the graphene has a relatively high adsorption capacity to pollutants due to a relatively large specific surface area, and is more beneficial to contact between organic pollutant molecules and Fenton active components.
The invention adoptsThe method is characterized in that aminophenylterpyridine is used as a ligand of metal iron, metal atoms are anchored through a coordination bond, and meanwhile, graphene oxide and a metal complex are bonded through an amido bond by a covalent grafting method, so that a Fenton reagent is firmly loaded on the surface of graphene. Meanwhile, when organic pollutants are treated by Fenton reaction, the Fenton catalyst can controllably release Fe2+And participate in the cyclic reaction, effectively overcoming the problems of iron ion current and secondary pollution.
The Fenton catalyst has the degradation rate of 100mg/L rhodamine B close to 100% in 60min under the condition that the pH value is 4, and the degradation rate is not reduced after 5 times of circulation, so that the Fenton catalyst shows higher degradation efficiency and good stability, and has better application prospect.
Drawings
FIG. 1 shows the degradation rate of the graphene covalent grafted aminobenzene terpyridine-iron complex Fenton catalyst on rhodamine B along with time.
Detailed Description
The technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
(1) Dispersing Graphene Oxide (GO) in dichloromethane, ultrasonically dispersing for 0.5h, dropwise adding thionyl chloride with the mass 5 times that of GO under the ultrasonic-assisted condition, introducing Ar gas for protection, heating and refluxing at the reaction temperature of 60 ℃ for 20h, and performing rotary evaporation to remove redundant reactants and solvent to obtain acyl-chlorinated graphene oxide;
(2) dissolving ferrous sulfate in 200ml of water, stirring for dissolving, adding an aminophenylterpyridine ligand, wherein the molar ratio of the ferrous sulfate to the ligand is 1:1, magnetically stirring for 2 hours to obtain a homogeneous mixture, transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 130 ℃, reacting for 36 hours, naturally cooling to room temperature after the reaction is finished, filtering, and washing to obtain an aminophenylterpyridine-iron complex;
(3) dissolving the aminophenyl terpyridine-iron complex prepared in the step (2) in dichloromethane, adding the acylchlorinated graphene oxide prepared in the step (1), wherein the mass ratio of the aminophenyl terpyridine-iron complex to GO is 1: 3, dropwise adding a small amount of DMF (dimethyl formamide) as a catalyst, reacting at 120 ℃ for 36 hours, and performing centrifugal separation to obtain the aminophenyl terpyridine-iron complex fenton catalyst covalently grafted by graphene, which is recorded as S1; wherein the mass fraction of the metallic iron in the catalyst is 5 wt%.
Example 2
(1) Dispersing Graphene Oxide (GO) in dichloromethane, ultrasonically dispersing for 1h, dropwise adding thionyl chloride with the mass 7 times that of GO under the ultrasonic auxiliary condition, introducing Ar gas for protection, heating and refluxing at the reaction temperature of 60 ℃ for 20h, and performing rotary evaporation to remove redundant reactants and solvent to obtain acyl-chlorinated graphene oxide;
(2) dissolving ferrous sulfate in 200ml of water, stirring for dissolving, adding an aminophenylterpyridine ligand, wherein the molar ratio of the ferrous sulfate to the ligand is 1:1, magnetically stirring for 2 hours to obtain a homogeneous mixture, transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 130 ℃, reacting for 36 hours, naturally cooling to room temperature after the reaction is finished, filtering, and washing to obtain an aminophenylterpyridine-iron complex;
(3) dissolving the aminobenzene terpyridine-iron complex prepared in the step (2) in dichloromethane, adding the acylchlorinated graphene oxide prepared in the step (1), wherein the mass ratio of the aminobenzene terpyridine-iron complex to GO is 1:1, dropwise adding a small amount of DMF (dimethyl formamide) as a catalyst, reacting at 110 ℃ for 36 hours, and performing centrifugal separation to obtain the aminobenzene terpyridine-iron complex fenton catalyst covalently grafted by the graphene, which is recorded as S2; wherein the mass fraction of the metallic iron in the catalyst is 8 wt%.
Example 3
(1) Dispersing Graphene Oxide (GO) in dichloromethane, ultrasonically dispersing for 1h, dropwise adding thionyl chloride with the mass 10 times that of GO under the ultrasonic auxiliary condition, introducing Ar gas for protection, heating and refluxing at the reaction temperature of 60 ℃ for 20h, and performing rotary evaporation to remove redundant reactants and solvent to obtain acyl-chlorinated graphene oxide;
(2) dissolving ferrous sulfate in 200ml of water, stirring for dissolving, adding an aminophenylterpyridine ligand, wherein the molar ratio of the ferrous sulfate to the ligand is 1:1, magnetically stirring for 2 hours to obtain a homogeneous mixture, transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 130 ℃, reacting for 36 hours, naturally cooling to room temperature after the reaction is finished, filtering, and washing to obtain an aminophenylterpyridine-iron complex;
(3) dissolving the aminophenyl terpyridine-iron complex prepared in the step (2) in dichloromethane, adding the acylchlorinated graphene oxide prepared in the step (1), wherein the mass ratio of the aminophenyl terpyridine-iron complex to GO is 1:0.8, dropwise adding a small amount of DMF (dimethyl formamide) as a catalyst, reacting at 100 ℃ for 30 hours, and performing centrifugal separation to obtain the aminophenyl terpyridine-iron complex Fenton catalyst covalently grafted by graphene, which is recorded as S3; wherein the mass fraction of the metallic iron in the catalyst is 10 wt%.
Example 4
A Fenton oxidative degradation test is carried out by taking rhodamine B as a test organic pollutant. The Fenton catalyst prepared in examples 1-3 was added to 100mg/L rhodamine B solution in an amount of 1mg to 10ml, the pH of the system was adjusted to 4, and 2ml of H was added2O2The degradation rate of organic contaminants with time was determined by shaking the reaction in a shaker at 35 ℃ and the results are shown in FIG. 1.
As can be seen from fig. 1, the degradation rate of the graphene covalently grafted aminobenzene terpyridine-iron complex fenton catalyst prepared in embodiments 1 to 3 of the present invention to rhodamine B is over 75% in 60min, wherein the degradation rate of the catalyst prepared in embodiment 2 to rhodamine is almost 100%. Therefore, the Fenton catalyst obtained by the invention has higher degradation efficiency on organic pollutants.
A5-cycle degradation test is carried out on the Fenton catalyst obtained in example 2, and the degradation rate of the catalyst on rhodamine B in 60min is still close to 100% after 5 cycles, so that good stability is shown.
Furthermore, it should be understood that although the present description refers to embodiments, not every embodiment may contain only a single embodiment, and such description is for clarity only, and those skilled in the art should integrate the description, and the embodiments may be combined as appropriate to form other embodiments understood by those skilled in the art.
Claims (2)
1. A preparation method of a graphene covalent grafted aminobenzene terpyridine-iron complex Fenton catalyst is characterized in that graphene is used as a carrier, the aminobenzene terpyridine-iron complex is used as a Fenton reagent, the graphene and the complex are connected through a covalent bond, and metal iron accounts for 5-10wt% of the catalyst; the graphene and the complex are connected through an amido bond;
the preparation method comprises the following preparation steps:
(1) dispersing Graphene Oxide (GO) in dichloromethane, ultrasonically dispersing for 0.5-1h, dropwise adding thionyl chloride with the mass 5-10 times that of GO under the ultrasonic-assisted condition, introducing Ar gas for protection, heating and refluxing, reacting at the temperature of 40-60 ℃ for 12-20h, and performing rotary evaporation to remove redundant reactants and solvent to obtain acylchlorinated graphene oxide;
(2) dissolving ferrous sulfate in 50-200ml of water, stirring for dissolving, adding an aminophenylterpyridine ligand, wherein the molar ratio of the ferrous sulfate to the ligand is 1:1, magnetically stirring for 1-3h to obtain a homogeneous mixture, transferring the mixture into a stainless steel reaction kettle with a polytetrafluoroethylene lining, heating to 120-140 ℃, reacting for 24-48h, naturally cooling to room temperature after the reaction is finished, filtering, and washing to obtain an aminophenylterpyridine-iron complex;
(3) dissolving the aminobenzene terpyridine-iron complex prepared in the step (2) in dichloromethane, adding the acylchlorinated graphene oxide prepared in the step (1), wherein the mass ratio of the aminobenzene terpyridine-iron complex to GO is 1:0.3-3, dropwise adding a small amount of DMF (dimethyl formamide) as a catalyst, reacting at 80-120 ℃ for 20-48h, and performing centrifugal separation to obtain the aminobenzene terpyridine-iron complex Fenton catalyst grafted by the graphene in a covalent mode.
2. The method according to claim 1, wherein the reaction temperature in the step (1) is 50 to 60 ℃; the reaction time is 18-20 h; the reaction temperature in the step (3) is 100-120 ℃, and the reaction time is 40-48 h.
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