CN108940342A - A kind of in-situ doping type cobalt system's fenton catalyst and its synthetic method and application - Google Patents
A kind of in-situ doping type cobalt system's fenton catalyst and its synthetic method and application Download PDFInfo
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- CN108940342A CN108940342A CN201810801489.0A CN201810801489A CN108940342A CN 108940342 A CN108940342 A CN 108940342A CN 201810801489 A CN201810801489 A CN 201810801489A CN 108940342 A CN108940342 A CN 108940342A
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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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/24—Nitrogen compounds
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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
- 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
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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
- 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
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Abstract
The invention discloses a kind of in-situ doping type cobalt system's fenton catalyst and its synthetic method and applications, the synthetic method of in-situ doping type cobalt system fenton catalyst, which is included in presoma, is added cobalt source, then synthesizes in-situ doping type cobalt system fenton catalyst by the roasting process adulterated in situ；The presoma is melamine, cyanamide, dicyanodiamine or urea.In-situ doping type cobalt system fenton catalyst (in-situ-Co-g-C of the invention3N4) showing that typical carbonitride is laminar structured, the formation of C-O-Co key promotes the formation of double reaction centers, H in structure2O2With pollutant respectively the problem of electron rich center and short of electricity subcenter respectively obtain reduction and decomposition, avoid metal ion disproportionation and lead to loss of active component.in-situ-Co-g-C3N4There is good removal effect to novel organic pollutant difficult to degrade in neutral conditions, and during degradation of contaminant, there is strong activation H2O2Ability, also there is good stability, cobalt ions dissolution rate therein is low.
Description
Technical field
The present invention relates to sewage treatment field more particularly to a kind of in-situ doping type cobalts of energy catalytic degradation organic pollutant
It is fenton catalyst and its synthetic method and application.
Background technique
Water be on the earth all life depend on for existence, one of human lives and the indispensable base substance of production.In recent years
Come, the life of the mankind and the activity of production etc. result in the generation of various novel organic pollutants, such as pesticide, phenols, doctor
Medicine, dyestuff, insecticide and incretion interferent etc. cause great pollution to natural water environment.These novel organic contaminations
Object enters after environment, it is difficult to be degraded, retention time is long, can convey by various modes and influence region and global ring
Border, and the health of the mankind can be finally seriously affected by the enrichment of food chain.Since these novel organic pollutants have
Complicated component, refractory organics, persistence and toxicity are difficult to be effectively removed using traditional sewage disposal technology.For a long time with
Come, people have been devoted to find more economical, more efficient and more stable sewage disposal technology, it would be desirable to breach is found, with
Achieve the purpose that solve the problems, such as the bottleneck that current conventional water treatment technology is not thorough novel organic pollutant degradation.
The hydroxyl free that Fenton catalytic oxidation technologies are generated as a kind of representative high-level oxidation technology, reaction process
Base has non-selectivity to the attack of pollutant, and obvious action has been played in sewage treatment.And in classical Fenton's reaction base
The feature of the multiphase Fenton catalyst maximum to grow up on plinth is by metal ion immobilization, although it is to a certain extent more
The deficiency of classical Fenton's reaction is mended, but it does not have still metal species in the classical homogeneous Fenton's reaction of substantive disengaging that single position occurs
, still there is the problems such as stability is poor, hydrogen peroxide utilization rate is low and digestion of metallic ion is big in the redox of point.Therefore, such as
Active component can be incorporated into carrier by fruit by the method adulterated in situ, be allowed to be bonded, and reinforce the electron pole of catalyst surface
Change distribution, is then avoided that the active component and H of catalyst in the reaction2O2Directly redox reaction occurs for contact, can also be same
When solve the problems, such as catalyst activity and stability, moreover it is possible to improve H2O2Utilization rate.
Summary of the invention
A kind of energy organic dirt of catalytic degradation is provided it is an object of the invention to overcome the shortcomings of the prior art place
The in-situ doping type cobalt system's fenton catalyst and its synthetic method of dye object and application.In-situ doping type cobalt system Fenton of the invention is urged
Agent is sheet, and nitrogen carbon substrate, Co is equably entrained in the skeleton of carbonitride, with traditional fenton catalyst and often
The multiphase Fenton catalyst of rule is compared, and catalyst of the invention acts on strongerly and significant the catalytic degradation of organic pollutant
Improve H2O2Utilization rate.
To achieve the above object, the technical scheme adopted by the invention is as follows:
The synthetic method of a kind of in-situ doping type cobalt system fenton catalyst comprising cobalt source is added in presoma, then
In-situ doping type cobalt system fenton catalyst is synthesized by the roasting process adulterated in situ；The presoma be melamine,
Cyanamide, dicyanodiamine or urea.The presoma that the present invention is enumerated is only preferred embodiment, and the present inventor gos deep by series
The study found that C, N can calcine out g-C with triazine ring3N4Substance can be used as presoma.
Preferably, the synthetic method of the in-situ doping type cobalt system fenton catalyst, includes the following steps:
(1) presoma and cobalt source are dissolved in ethyl alcohol, obtain solution A；
(2) solution A is evaporated, obtains solid product A；
(3) solid product A is dried, and ground uniform；
(4) solid product A uniform to grinding is roasted, and in-situ doping type cobalt system Fenton is obtained after natural cooling
Catalyst；
(5) in-situ doping type cobalt system after cooling fenton catalyst is washed with water, is then dried.
Hereinafter, in order to express easily, in-situ doping type cobalt system's fenton catalyst is known as " in- by inventor
situ-Co-g-C3N4”。
Cobalt source is added in the present invention in presoma, and then the roasting process by adulterating in situ synthesizes in-situ-Co-g-
C3N4.In-situ-Co-g-C made from this synthetic method3N4For the solid powder of taupe；Its microstructure is typical nitridation
Carbon it is laminar structured.This synthetic method brings the doping of Co and the generation of C-O-Co key, in-situ-Co-g-C3N4In work
Property component (cobalt) is equably entrained in the skeleton of carbonitride, shows typical porous structure.in-situ-Co-g-C3N4In
Cobalt enter nitridation carbon skeleton in formed C-O-Co key, result in in-situ-Co-g-C3N4The electronic polarization on surface is distributed,
So that H2O2It will not be with in-situ-Co-g-C with pollutant3N4In active component (cobalt) directly contact react, and
It is to respectively obtain reduction and decomposition at electron rich center and short of electricity subcenter respectively.It is more with traditional fenton catalyst and routine
Phase fenton catalyst is compared, in-situ-Co-g-C3N4The catalytic activity and degradation efficiency of organic pollutant are significantly improved.
Preferably, in step (1), the molar ratio of cobalt ions is 5:1~20:1 in the presoma and cobalt source；Most preferably
The molar ratio of cobalt ions is 10:1 in ground, the presoma and cobalt source.When the molar ratio of presoma and cobalt ions is lower than 5:1, cobalt
Doping it is excessively high, will lead to synthesized final catalyst (in-situ-Co-g-C3N4) in cobalt doped it is uneven, be easy shape
Cause cobalt dissolution more at more cobalt/cobalt oxide, and then during Fenton's reaction occurs.The molar ratio of presoma and cobalt ions
When higher than 20:1, the doping of cobalt is too low, will lead to synthesized final catalyst (in-situ-Co-g-C3N4) Fenton activity
It is poor.The molar ratio of precursor and cobalt ions be 5:1~20:1 when, Co can Uniform Doped into the skeleton of carbonitride, and with
It is bonded, synthesized final catalyst (in-situ-Co-g-C3N4) preferable catalytic degradation work is shown to pollutant
Property and adaptability.When the molar ratio of precursor and cobalt ions is 10:1, the target that the doping situation of Co is best and synthesized is urged
Agent is best to the catalytic degradation activity and adaptability of pollutant.
Preferably, the cobalt source is at least one of cobalt chloride hexahydrate, cobalt nitrate, cobaltous sulfate.
Preferably, in step (2), the solution A is placed under water bath condition and is stirred to being evaporated；Preferably, the water-bath
Temperature be 60~90 DEG C；The time of water bath method is 2~3h；Most preferably, the temperature of the water-bath is 70 DEG C.Preferably,
The solution A carries out water bath method in heat collecting type constant temperature blender with magnetic force.
Preferably, in step (3), the solid product A is placed in baking oven and is dried, oven temperature is 50~80 DEG C；It dries
The dry time is 3~7h；Preferably, the oven temperature is 70 DEG C.
Preferably, in step (4), the solid product A is placed in Muffle kiln roasting, maturing temperature is 500~550
DEG C, calcining time is 2~3h；Preferably, maturing temperature is 550 DEG C, calcining time 2h；Preferably, the heating of the roasting
Rate is less than 10 DEG C/min；It is highly preferred that the heating rate of the roasting is less than 5 DEG C/min.The heating rate of roasting can shadow
Ring in-situ-Co-g-C3N4Surface nature；It heats up too fast, in-situ-Co-g-C3N4In metal Co species can be very big
Aoxidize to degree, so that the doping of cobalt is uneven, in-situ-Co-g-C3N4Finished product is in dark-brown, and there are black cobalt oxides on surface
Compound little particle；And slowly heat up, conducive to in-situ-Co-g-C is gradually removed3N4Micro absorption water in solid product, makes it
The metal Co species on surface are dispersed denaturation, and are equably doped in carrier framework, make in-situ-Co-g-C3N4Finished product
In taupe.
Preferably, in step (5), by the in-situ doping type cobalt system fenton catalyst deionized water after natural cooling
Washing 3~4 times, is subsequently placed in baking oven and dries, and oven temperature is 50~100 DEG C；Preferably, the oven temperature is 70 DEG C.
In addition, the object of the invention is also to provide a kind of in-situ doping type cobalt system fenton catalyst (in-situ-Co-g-
C3N4), it is made by the above-mentioned synthetic method of the present invention.
In addition, the object of the invention is also to provide in-situ-Co-g-C3N4Purposes.Preferably, the in-situ-
Co-g-C3N4For catalytic degradation organic pollutant.Preferably, the organic pollutant includes rhodamine B, bisphenol-A, cyclopropyl sand
At least one of star, 2- chlorophenol, phenytoinum naticum, 2,4 dichloro benzene monoxone.Preferably, the in-situ-Co-g-C3N4With
In sewage treatment field.Preferably, the in-situ-Co-g-C3N4For handling the organic pollutant in sewage.Preferably,
The in-situ-Co-g-C3N4With H2O2Combination, for handling the organic pollutant in water.in-situ-Co-g-C3N4With H2O2
When being combined in water, hydroxyl radical free radical and superoxide radical can be generated.In addition, in-situ-Co-g-C3N4It is also applicable in water ring
Other field other than the reparation of border.
In addition, containing the in-situ-Co-g- the object of the invention is also to provide a kind of sewage-treating agent
C3N4。
Compared with prior art, the beneficial effects of the present invention are:
1. classical fenton catalyst is constrained by the pH reaction condition for being 2~3, sound of the existing multiphase Fenton catalyst to pH
Answer range also smaller, and in-situ-Co-g-C of the invention3N4It is larger to the response range of pH not by the constraint of pH condition, and
There is good catalytic degradation activity to pollutant in neutral conditions.
2. in-situ-Co-g-C of the invention3N4It is laminar structured to show typical carbonitride, C-O-Co key in structure
Formation promote the formation of double reaction centers, H2O2It is respectively obtained respectively at electron rich center and short of electricity subcenter with pollutant
Reduction and decomposition, the problem of avoiding metal ion disproportionation and lead to loss of active component.
3. in-situ-Co-g-C of the invention3N4The solid foreign materials such as iron cement will not be generated during the reaction, be without the use of
Foreign matter removes equipment, and in-situ-Co-g-C of the invention3N4It is convenient for recycling for solid catalyst convenient for being separated from water
It recycles.
4. in-situ-Co-g-C of the invention3N4During degradation of contaminant, there is strong activation H2O2Energy
Power, also has good stability, and digestion of metallic ion rate therein is low.
Detailed description of the invention
Fig. 1 is in-situ-Co-g-C made from embodiment 13N4SEM figure；
Fig. 2 is in-situ-Co-g-C made from embodiment 13N4TEM figure；
Fig. 3 is in-situ-Co-g-C made from embodiment 13N4Co 2p and C 1s XPS spectrum figure；
Fig. 4 is in-situ-Co-g-C made from embodiment 13N4Suspension in OH and HO2 ·/O2 ·-Epr signal
Figure；
Fig. 5 is in-situ-Co-g-C made from embodiment 13N4It is bent for the degradation of BPA, 2-CP, CIP, 2,4-D and PHT
Line chart；
Fig. 6 is in-situ-Co-g-C made from embodiment 13N4Repetition assay activity evaluate figure.
Specific embodiment
To better illustrate the object, technical solutions and advantages of the present invention, below in conjunction with specific embodiment to the present invention
It is described further.
Embodiment 1
A kind of in-situ-Co-g-C3N4Synthetic method comprising following steps:
(1) 0.04mol melamine and 0.004mol cobalt chloride hexahydrate are dissolved in 20ml dehydrated alcohol, obtain solution
A；
(2) solution A is placed in heat collecting type constant temperature blender with magnetic force and is stirred evenly, the water bath method at 70 DEG C, consolidate
Body product A；
(3) step (2) is evaporated resulting solid product A to be transferred in baking oven, is dried completely at 70 DEG C, and ground equal
It is even；
(4) solid product A uniform to grinding, which is placed in Muffle furnace, roasts, and the heating rate of roasting is 5 DEG C/minute
Clock is warming up to 550 DEG C of holding 2h, obtains the in-situ-Co-g-C after Temperature fall3N4；
(5) to the in-situ-Co-g-C3N4After natural cooling, with deionized water centrifuge washing 3~4 times, then 70
DEG C baking oven in dry.
Embodiment 2
A kind of in-situ-Co-g-C3N4Synthetic method comprising following steps:
(1) 0.02mol melamine and 0.004mol cobalt chloride hexahydrate are dissolved in 15ml dehydrated alcohol, obtain solution
A；
(2) solution A is placed in heat collecting type constant temperature blender with magnetic force and is stirred evenly, the water bath method at 60 DEG C, consolidate
Body product A；
(3) step (2) is evaporated resulting solid product A to be transferred in baking oven, is dried completely at 50 DEG C, and ground equal
It is even；
(4) solid product A uniform to grinding, which is placed in Muffle furnace, roasts, and the heating rate of roasting is 5 DEG C/minute
Clock is warming up to 500 DEG C of holding 3h, obtains the in-situ-Co-g-C after Temperature fall3N4；
(5) to the in-situ-Co-g-C3N4After natural cooling, with deionized water centrifuge washing 3~4 times, then 50
DEG C baking oven in dry.
Embodiment 3
A kind of in-situ-Co-g-C3N4Synthetic method comprising following steps:
(1) 0.08mol melamine and 0.004mol cobalt chloride hexahydrate are dissolved in 30ml dehydrated alcohol, obtain solution
A；
(2) solution A is placed in heat collecting type constant temperature blender with magnetic force and is stirred evenly, the water bath method at 90 DEG C, consolidate
Body product A；
(3) step (2) is evaporated resulting solid product A to be transferred in baking oven, is dried completely at 80 DEG C, and ground equal
It is even；
(4) solid product A uniform to grinding, which is placed in Muffle furnace, roasts, and the heating rate of roasting is 10 DEG C/minute
Clock is warming up to 530 DEG C of holding 2.5h, obtains the in-situ-Co-g-C after Temperature fall3N4；
(5) to the in-situ-Co-g-C3N4After natural cooling, with deionized water centrifuge washing 3~4 times, then exist
It is dried in 100 DEG C of baking oven.
Above embodiments 1~3 are only the section Example enumerated of the present invention, can with cyanamide, dicyanodiamine or
Urea is as presoma, using cobalt nitrate or cobaltous sulfate as cobalt source, and in- is made referring to the synthetic method of Examples 1 to 3
situ-Co-g-C3N4.Since its composition principle and synthetic product are identical, therefore the present invention no longer enumerates.
In-situ-Co-g-C made from Examples 1 to 33N4Structural characterization:
To in-situ-Co-g-C made from Examples 1 to 33N4It is placed in scanning electron microscope (SEM) and transmitted electron is aobvious
It is observed under micro mirror (TEM), finds in-situ-Co-g-C made from Examples 1 to 33N4All have typical g-C3N4Sheet
Structure, and surfacing, the layer upon layer as silk do not find the nano particle of cobalt, illustrate that the doping of Co is visibly homogeneous.Together
When, in in-situ-Co-g-C3N4Surface can obviously observe the presence of cavernous structure, pore size is different, illustrates to implement
In-situ-Co-g-C made from example 1~33N4It is a porous material.Fig. 1 is in-situ-Co-g- made from embodiment 1
C3N4SEM figure, Fig. 2 be embodiment 1 made from in-situ-Co-g-C3N4TEM figure；The in- of embodiment 2 and embodiment 3
situ-Co-g-C3N4SEM figure and TEM scheme, no longer one by one attached drawing similar to embodiment 1.
It is measured as BET it is found that in-situ-Co-g-C made from Examples 1 to 33N4Certain specific surface area is all had,
Wherein, in-situ-Co-g-C made from embodiment 13N4Specific surface area be 5.3404m2/g。
By XPS analysis, in-situ-Co-g-C made from embodiment 13N4Co content be 3.8wt%, show a large amount of
The site Co is exposed to in-situ-Co-g-C3N4Surface.
Fig. 3 is in-situ-Co-g-C made from embodiment 13N4Co 2p and C 1s x-ray photoelectron spectroscopy (XPS)
Figure.Violent satellite-signal peak can be seen that cobalt in in-situ-Co-g-C from figure3N4In be with Co2+Existing for form, and
And in conjunction with that can be that observed the obvious characteristic peak for representing C-O functional group at 286.1eV, illustrate that Co has been doped to carbonitride
Skeleton among, form C-O-Co key.The in-situ-Co-g-C of embodiment 2 and embodiment 33N4Co 2p and C 1s XPS
Also occurs the obvious characteristic peak of C-O functional group in spectrogram, and cobalt is also with Co in the catalyst2+Form exist, due to a piece
Width is limited, no longer attached drawing one by one.
Fig. 4 is the in-situ-Co-g-C that DMPO captures embodiment 13N4OH and HO in suspension2 ·/O2 ·-EPR letter
Number figure.The test result of embodiment 2 and embodiment 3 is similar to Example 1, since length is limited, no longer attached drawing one by one.From figure
As can be seen that showing obvious OH and HO in the Fenton's reaction system2 ·/O2 ·-Epr signal, illustrate in-situ-Co-g-
C3N4With stronger activation H2O2Ability, OH and HO can be translated into2 ·/O2 ·-.Also, with the addition of pollutant,
OH and HO in reaction system2 ·/O2 ·-Signal have apparent enhancing and weakening respectively, illustrate pollutant during the reaction
Act as the effect of electron donor, in-situ-Co-g-C3N4The formation of itself promotes double reaction centers, i.e. electron deficient and richness
The formation of electronic center, reaction mechanism breach classical Fenton's reaction using metal as the basic theories of reactive component, this makes
Electron transport rate and H in reaction system2O2Rate of reduction and utilization rate be obviously improved, catalyst degradation is dirty
The activity of dye object significantly increases.
in-situ-Co-g-C3N4The preparation method of suspension:
(1) DMPO of 50mg is dissolved in 200 microlitres of ultrapure waters, freezen protective；
(2) 0.01g in-situ-Co-g-C is weighed3N4, 1ml ultrapure water and 100 microlitres of H are added2O25~10 are shaken afterwards
Second；
(3) after the reaction system in step (2) reacts, 100 microlitres of mixed liquors are drawn in 10 microlitres of DMPO solution
In in-situ-Co-g-C can be obtained3N4Suspension.
And the detection in the case of existing to pollutant then changes the ultrapure water in reaction system into pollutant, it is above-mentioned
Prepared in-situ-Co-g-C3N4Suspension is for the OH in capture system, and to HO2 ·/O2 ·-Capture then will be upper
The ultrapure water stated in system changes methanol into.
Application experiment:
Respectively with in-situ-Co-g-C made from Examples 1 to 33N4As sample, its drop to organic pollutant is tested
Solve performance.
0.05g sample is put into 50mL 10mg L-1Pollutant solution in, in the case where keeping neutral reaction condition, constant temperature
35 DEG C, 15 minutes are continuously stirred after reaching adsorption equilibrium between pollutant and sample, and 10mM H is added2O2Start Fenton's reaction,
Point samples and detects the concentration of wherein pollutant in different times.
Fig. 5 and Fig. 6 is respectively the in-situ-Co-g-C of embodiment 13N4In neutral conditions to the degradation of different pollutants
Curve graph and repetition assay activity evaluation figure.It can be seen that from 5 figures, in 120 minutes, 2- chlorophenol (2-CP), Ciprofloxacin
(CIP), phenytoinum naticum (PHT) and 2,4- dichlorphenoxyacetic acid (2,4-D) can be completely removed, and the degradation rate of bisphenol-A (BPA)
Also it is up to 89%, it is notable that various pollutants are largely degraded in 5 minutes, illustrate in-situ-
Co-g-C3N4With preferable catalytic activity and to the high-adaptability of pollutant.In addition, using rhodamine B as typical pollutant
Evaluate in-situ-Co-g-C3N4Repetition activity.It can be seen that from 6 figures, after continuous operation 6 times, in-situ-Co-g-C3N4It is right
The average degradation efficiency of rhodamine B is still up to 99.5%, also, in entire reaction process, in-situ-Co-g-C3N4Middle cobalt
Burst size it is seldom, be lower than 0.1mg/L, these results have all absolutely proved in-situ-Co-g-C3N4Stablize with preferable
Property.The test result of embodiment 2 and embodiment 3 is similar to Example 1, since length is limited, no longer Detailed description of the invention one by one.
In conclusion in-situ-Co-g-C of the invention3N4It is laminar structured to show typical carbonitride, in structure
The formation of C-O-Co key promotes the formation of double reaction centers, H2O2With pollutant respectively at electron rich center and short of electricity subcenter
The problem of respectively obtaining reduction and decomposition, avoiding metal ion disproportionation and lead to loss of active component.The present invention
In-situ-Co-g-C3N4When catalytic degradation organic pollutant, harsh pH reaction condition is not needed, is shown wider
PH response range, in neutral conditions to the novel organic pollutant of difficult for biological degradation with good removal effect, and
During degradation of contaminant, there is strong activation H2O2Ability, also there is good stability, cobalt ions dissolution rate is low.
Finally, it should be noted that the above embodiments are merely illustrative of the technical solutions of the present invention rather than protects to the present invention
The limitation of range is protected, although the invention is described in detail with reference to the preferred embodiments, those skilled in the art should
Understand, it can be with modification or equivalent replacement of the technical solution of the present invention are made, without departing from the essence of technical solution of the present invention
And range.
Claims (10)
1. a kind of synthetic method of in-situ doping type cobalt system fenton catalyst, which is characterized in that cobalt source is added in presoma, so
In-situ doping type cobalt system fenton catalyst is synthesized by the roasting process adulterated in situ afterwards；The presoma is melamine
Amine, cyanamide, dicyanodiamine or urea.
2. the synthetic method of in-situ doping type cobalt system as described in claim 1 fenton catalyst, which is characterized in that including as follows
Step:
(1) presoma and cobalt source are dissolved in ethyl alcohol, obtain solution A；
(2) solution A is evaporated, obtains solid product A；
(3) solid product A is dried, and ground uniform；
(4) solid product A uniform to grinding is roasted, and the catalysis of in-situ doping type cobalt system's Fenton is obtained after natural cooling
Agent；
(5) in-situ doping type cobalt system after cooling fenton catalyst is washed with water, is then dried.
3. the synthetic method of in-situ doping type cobalt as claimed in claim 2 system fenton catalyst, which is characterized in that step (1)
In, the molar ratio of cobalt ions is 5:1~20:1 in the presoma and cobalt source；Preferably, in the presoma and cobalt source cobalt from
The molar ratio of son is 10:1；Preferably, the cobalt source is at least one of cobalt chloride hexahydrate, cobalt nitrate, cobaltous sulfate.
4. the synthetic method of in-situ doping type cobalt as claimed in claim 2 system fenton catalyst, which is characterized in that step (2)
In, the solution A is placed under water bath condition and is stirred to being evaporated；Preferably, the temperature of the water-bath is 60~90 DEG C；Most preferably
Ground, the temperature of the water-bath are 70 DEG C.
5. the synthetic method of in-situ doping type cobalt system as claimed in claim 2 fenton catalyst, which is characterized in that step (3)
In, the solid product A is placed in baking oven and is dried, oven temperature is 50~80 DEG C；Preferably, the oven temperature is 70
℃。
6. the synthetic method of in-situ doping type cobalt as claimed in claim 2 system fenton catalyst, which is characterized in that step (4)
In, the solid product A is placed in Muffle kiln roasting, maturing temperature is 500~550 DEG C, and calcining time is 2~3h；It is preferred that
Ground, maturing temperature are 550 DEG C, calcining time 2h；Preferably, the heating rate of the roasting is less than 10 DEG C/min；More preferably
Ground, the heating rate of the roasting is less than 5 DEG C/min.
7. the synthetic method of in-situ doping type cobalt as claimed in claim 2 system fenton catalyst, which is characterized in that step (5)
In, the in-situ doping type cobalt system fenton catalyst after natural cooling is washed with deionized 3~4 times, baking is subsequently placed in
It is dried in case, oven temperature is 50~100 DEG C；Preferably, the oven temperature is 70 DEG C.
8. a kind of in-situ doping type cobalt system fenton catalyst, which is characterized in that synthesized by claim 1~7 is described in any item
Method is made.
9. a kind of sewage-treating agent, which is characterized in that be catalyzed including in-situ doping type cobalt as claimed in claim 8 system's Fenton
Agent.
10. a kind of application of in-situ doping type cobalt as claimed in claim 8 system fenton catalyst, which is characterized in that the original
Position doping type cobalt system's fenton catalyst is used for sewage treatment field；Preferably, in-situ doping type cobalt system's fenton catalyst is used
In catalytic degradation organic pollutant；Preferably, in-situ doping type cobalt system's fenton catalyst is organic in sewage for handling
Pollutant；Preferably, the organic pollutant includes rhodamine B, bisphenol-A, Ciprofloxacin, 2- chlorophenol, phenytoinum naticum, 2,4- bis-
At least one of chlorobenzene monoxone.
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