CN108970634A - Synthetic method, the porous fenton catalyst of carried with doped type cobalt system and its application of the porous fenton catalyst of carried with doped type cobalt system - Google Patents
Synthetic method, the porous fenton catalyst of carried with doped type cobalt system and its application of the porous fenton catalyst of carried with doped type cobalt system Download PDFInfo
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- CN108970634A CN108970634A CN201810938417.0A CN201810938417A CN108970634A CN 108970634 A CN108970634 A CN 108970634A CN 201810938417 A CN201810938417 A CN 201810938417A CN 108970634 A CN108970634 A CN 108970634A
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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
Abstract
The invention discloses a kind of synthetic methods of the porous fenton catalyst of carried with doped type cobalt system, including roasting: roasting 1~3h under the conditions of presoma is placed in 500~600 DEG C, carbonitride is made after Temperature fall, roast heating rate less than 10 DEG C/min；Mixing: soluble cobalt compound is soluble in water with carbonitride, solution ph is adjusted to 8~11 with alkaline solution, is uniformly mixed；Hydro-thermal reaction: reacting 4~7h under the conditions of mixed solution is placed in 100~150 DEG C, the porous fenton catalyst of carried with doped type cobalt system is made in natural cooling after having reacted.The invention also discloses the porous fenton catalyst of carried with doped type cobalt system and its applications.The advantages that porous fenton catalyst of carried with doped type cobalt system of the present invention has degradation condition common, and degrading activity is high, is convenient for recycling.
Description
Technical field
The present invention relates to a kind of conjunctions of the porous fenton catalyst of water-treatment technology field more particularly to carried with doped type cobalt system
At method, the porous Fenton of carried with doped type cobalt system prepared by the synthetic method of the porous fenton catalyst of carried with doped type cobalt system
The application of catalyst and the porous fenton catalyst of carried with doped type cobalt system in water treatment field.
Background technique
With population sustainable growth, rapid economic development is constantly progressive with science and technology, and people's water demand increasingly increases
Greatly, while unreasonable exploitation also results in the generations of various water pollution problems, and China is faced with resource-type and contamination type water money
The problem of source shortage, dyeing waste water is since its coloration is deep, water big (China be averaged daily discharge amount be 300~4,000,000 tons), has
The features such as machine toxic content is high receives the extensive concern of people.Rhodamine B is used as one of representative azo dyes,
A large amount of dissolved oxygens can not only be consumed by being discharged into natural water, jeopardize the existence of aqueous bio, can also play carcinogenic work into human body
With, it is therefore, extremely urgent to the processing of dyeing waste water, but due to the stability and refractory organics of azo dyes chemical structure, it is difficult
To be completely removed by biological method and conventional chemistry, therefore, constantly seeking more efficient sewage disposal technology is solution
The inevitable requirement of certainly current water pollution problems.
Fenton's reaction is as a kind of representative advanced oxidation processes, since the hydroxyl radical free radical of its generation is to pollutant
Attack has non-selectivity and degradation completeness, gradually receives the favor of people, but exists in classical Fenton's reaction system big
The free metal ion of amount, and it is not suitable for current practical application, therefore, if could be by active component immobilization, and would make it
With pollutant and H2O2It comes into full contact with, then can solve current traditional wastewater processing technique for the technical bottleneck for the treatment of of dyeing wastewater
Problem, preferably will be in fenton catalyst technical application to China's wastewater treatment.
Summary of the invention
For overcome the deficiencies in the prior art, one of the objects of the present invention is to provide a kind of carried with doped type cobalt system is porous
The synthetic method of fenton catalyst, the porous fenton catalyst of carried with doped type cobalt system prepared by the synthetic method, to solve
Catalyst activity component can not immobilised problem.
The second object of the present invention is to provide a kind of carried with doped type cobalt system porous fenton catalyst, classical fragrant to solve
Exist in reaction system largely free metal ion, catalytic component can not immobilization, catalytic efficiency is low, time-consuming for degradation
The problems such as.
The third object of the present invention is to provide a kind of application of the porous fenton catalyst of carried with doped type cobalt system, to solve
Rhodamine B be discharged into natural water consume a large amount of dissolved oxygens, the existence for jeopardizing aqueous bio, can be played into human body it is carcinogenic and even
The problems such as refractory organics of nitrogen dyestuff.
An object of the present invention adopts the following technical scheme that realization:
A kind of synthetic method of the porous fenton catalyst of carried with doped type cobalt system, comprising the following steps:
Roasting: roasting 1~3h under the conditions of presoma is placed in 500~600 DEG C, carbonitride is made after Temperature fall, described
Heating rate is roasted less than 10 DEG C/min；
Mixing: soluble cobalt compound is soluble in water with carbonitride, with alkaline solution adjusting solution ph to 8~11,
It is uniformly mixed, wherein the ratio between amount of substance of carbonitride and cobalt element is 5~20:1 in mixed solution；
Hydro-thermal reaction: reacting 4~7h under the conditions of mixed solution is placed in 100~150 DEG C, natural cooling after having reacted, system
Obtain the porous fenton catalyst of carried with doped type cobalt system；
The presoma is one of cyanamide, dicyanodiamine and urea or several mixing, the alkaline solution
For the mixed solution or ammonium hydroxide of ammonium hydroxide, sodium hydroxide solution, ammonium hydroxide and sodium hydroxide and the mixed solution of ammonium chloride.
Further, in calcination steps, maturing temperature is 550 DEG C, calcining time 2h, and the roasting heating rate is
5℃/min。
Further, in mixing step, the soluble cobalt compound is cobalt chloride, cobaltous sulfate, cobalt nitrate, acetic acid
Cobalt, divalent cobalt oxalates, trivalent cobalt oxalates, cobalt naphthenate, EDETATE SODIUM cobalt, cobalt acid lithium, Mecobalamin, cobalt potassium nitrite, Asia
One of sodium cobaltinitrate and thunder Buddhist nun's cobalt or several mixing.
Further, in mixing step, the soluble cobalt compound is one in cobalt chloride, cobaltous sulfate and cobalt nitrate
Kind or several mixing.
Further, in mixing step, solution ph is adjusted to 9 with alkaline solution, stirs 1~5h, in mixed solution
The ratio between amount of substance of carbonitride and cobalt element is 10:1.
Further, in hydro-thermal reaction step, mixed solution reacts 5h under the conditions of being placed in 120 DEG C.
Further, in hydro-thermal reaction step, the porous fenton catalyst of the carried with doped type cobalt system is filtered by film,
It is soluble in water that solid slag is not filtered, and repeated centrifugation is dried after resuspension procedure 2~4 times, and the carried with doped type cobalt system that purifying is made is porous
Fenton catalyst.
Further, drying temperature is 50~80 DEG C, and drying time is 5~12h；
The film is filtered into the film that aperture is 0.45 μm and filters, and the revolving speed of the centrifugation is 8000~10000r/min.
The second object of the present invention adopts the following technical scheme that realization:
A kind of porous fenton catalyst of carried with doped type cobalt system, the porous fenton catalyst of carried with doped type cobalt system use
It is prepared by the synthetic method of the porous fenton catalyst of carried with doped type cobalt system described in any of the above embodiments.
The third object of the present invention adopts the following technical scheme that realization:
A kind of porous fenton catalyst of carried with doped type cobalt system answering on catalysis azo dyes rhodamine B catalytic degradation
With.
Compared with prior art, the beneficial effects of the present invention are:
(1) it the synthetic method of the porous fenton catalyst of carried with doped type cobalt system of the present invention and is prepared by this method
The porous fenton catalyst of carried with doped type cobalt system has the advantages that catalytic reaction process no longer needs harsh pH reaction condition
(2-3) has wider pH response range, shows good degradation effect for rhodamine B in neutral conditions；It urges
Agent catalyst amount under optimum reaction condition is less, and cost is relatively low, is adapted to practical popularization and application；Catalyst was reacting
The solid foreign materials such as iron cement will not be generated in journey, do not need foreign body eliminating apparatus；Catalyst has during degradation of contaminant
Strong activation H2O2Ability；Catalyst belongs to solid catalyst, convenient for being separated from water, convenient for recycling
(2) the porous fenton catalyst of carried with doped type cobalt system of the present invention is on catalysis azo dyes rhodamine B catalytic degradation
Application have the advantages that degradation condition is common, under neutrallty condition i.e. to rhodamine B show well degrade effect
Fruit, degrading activity is high, will not generate the solid foreign materials such as iron cement, convenient for recycling.
Detailed description of the invention
Fig. 1 is transmission electron microscope (SEM) figure of the porous fenton catalyst of carried with doped type cobalt system prepared by embodiment 4；
Fig. 2 is scanning electron microscope (TEM) figure of the porous fenton catalyst of carried with doped type cobalt system prepared by embodiment 4；
Fig. 3 is the Co 2p x-ray photoelectron spectroscopy of the porous fenton catalyst of carried with doped type cobalt system prepared by embodiment 4
(XPS)；
Fig. 4 is the OH and HO in the porous fenton catalyst suspension of carried with doped type cobalt system prepared by embodiment 42 ·/
O2 ·-Epr signal figure, wherein left figure be capture system in OH, right figure be capture system in HO2 ·/O2 ·-；
Fig. 5 is condition of the porous fenton catalyst of carried with doped type cobalt system in different catalysts dosage of the preparation of embodiment 4
Under for rhodamine B (RhB) degradation curve.
Specific embodiment
In the following, being described further in conjunction with attached drawing and specific embodiment to the present invention, it should be noted that not
Under the premise of conflicting, new implementation can be formed between various embodiments described below or between each technical characteristic in any combination
Example.
Hereinafter, elaborating a kind of conjunction of the porous fenton catalyst of carried with doped type cobalt system of the invention by embodiment 1-6
At method and the porous fenton catalyst (sup-Co-g-C of carried with doped type cobalt system prepared by this method3N4)。
Embodiment 1
Calcination steps: urea is placed in Muffle furnace, and it is 10 DEG C/min that Muffle furnace, which is heated to 500 DEG C and heating rate,
Stop continuing to heat (heating) after roasting 3h, carbonitride (g-C is made after Temperature fall3N4)。
Mixing step: Cobalt monosulfate heptahydrate and the carbonitride of above-mentioned preparation are dissolved in deionized water, mixing is stirred and evenly mixed
Solution.Mixed solution pH value is adjusted to 11 with the sodium hydroxide solution that pH value is 11.2, is stirred 3.5h, is nitrogenized in mixed solution
The ratio between amount of substance of carbon and cobalt ions is 5:1.
Hydro-thermal reaction step: mixed solution being placed under the conditions of 100 DEG C and reacts 7h, natural cooling after having reacted, and is made negative
Carry the porous fenton catalyst of doping type cobalt system.
Embodiment 2
Calcination steps: cyanamide is placed in Muffle furnace, by Muffle furnace be heated to 520 DEG C and heating rate be 8 DEG C/
Min stops continuing to heat (heating), carbonitride is made after Temperature fall after roasting 3h.
Mixing step: seven nitric hydrate cobalts and the carbonitride of above-mentioned preparation are dissolved in deionized water, mixing is stirred and evenly mixed
Solution.The mixed solution of the ammonium hydroxide and sodium hydroxide that are 11.2 with pH value adjusts mixed solution pH value to 10, wherein ammonium hydroxide and hydrogen
The ratio between substance withdrawl syndrome of sodium oxide molybdena is 3:1, stirs 4h, and the ratio between carbonitride and the amount of substance of cobalt ions are in mixed solution
6.5:1。
Hydro-thermal reaction step: mixed solution being placed under the conditions of 100 DEG C and reacts 7h, natural cooling after having reacted, and is made negative
Carry the porous fenton catalyst of doping type cobalt system.
Purification step: it is 0.45 μm that the porous fenton catalyst of carried with doped type cobalt system of above-mentioned preparation, which is passed through aperture,
Filtering with microporous membrane scrapes the filter residue on filter membrane and is transferred in centrifuge tube, deionized water suspension filter residue, 8000r/min is added
3min is rotated, repeats above-mentioned suspension, centrifugal process twice, the porous fenton catalyst of carried with doped type cobalt system of purifying is made.
Embodiment 3
Calcination steps: dicyanodiamine is placed in Muffle furnace, by Muffle furnace be heated to 540 DEG C and heating rate be 6 DEG C/
Min stops continuing to heat (heating), carbonitride is made after Temperature fall after roasting 2.5h.
Mixing step: EDETATE SODIUM cobalt and the carbonitride of above-mentioned preparation are dissolved in deionized water, and it is molten to stir and evenly mix mixing
Liquid.The ammonium hydroxide for being 10.7 with pH value adjusts mixed solution pH value to 10.5, stirs 5h, carbonitride and cobalt ions in mixed solution
The ratio between amount of substance is 15:1.
Hydro-thermal reaction step: mixed solution being placed under the conditions of 110 DEG C and reacts 6.5h, and natural cooling after having reacted is made
The porous fenton catalyst of carried with doped type cobalt system.
Purification step: it is 0.45 μm that the porous fenton catalyst of carried with doped type cobalt system of above-mentioned preparation, which is passed through aperture,
Filtering with microporous membrane scrapes the filter residue on filter membrane and is transferred in centrifuge tube, deionized water suspension filter residue, 9000r/min is added
4min is rotated, repeats above-mentioned suspension, centrifugal process twice, the porous fenton catalyst of carried with doped type cobalt system of purifying is made.
Embodiment 4
Calcination steps: urea is placed in Muffle furnace, and it is 5 DEG C/min that Muffle furnace, which is heated to 550 DEG C and heating rate,
Stop continuing to heat (heating) after roasting 2h, carbonitride is made after Temperature fall.
Mixing step: cobalt chloride hexahydrate and the carbonitride of above-mentioned preparation are dissolved in deionized water, mixing is stirred and evenly mixed
Solution.The ammonium hydroxide for being 11.0 with pH value adjusts mixed solution pH value to 9, stirs 2h, carbonitride and cobalt ions in mixed solution
The ratio between amount of substance is 10:1.
Hydro-thermal reaction step: mixed solution being placed under the conditions of 120 DEG C and reacts 5h, natural cooling after having reacted, and is made negative
Carry the porous fenton catalyst of doping type cobalt system.
Purification step: it is 0.45 μm that the porous fenton catalyst of carried with doped type cobalt system of above-mentioned preparation, which is passed through aperture,
Filtering with microporous membrane scrapes the filter residue on filter membrane and is transferred in centrifuge tube, deionized water suspension filter residue, 8000r/min is added
5min is rotated, repeats above-mentioned suspension, centrifugal process twice, the porous fenton catalyst of carried with doped type cobalt system of purifying is made.
Embodiment 5
Calcination steps: the mixture that cyanamide, dicyanodiamine and urea are 1:1:1 in mass ratio is placed in Muffle furnace,
It is 3 DEG C/min that Muffle furnace, which is heated to 570 DEG C and heating rate, stops continuing to heat (heating) after roasting 2h, after Temperature fall
Carbonitride is made.
Mixing step: cobalt naphthenate, cobalt acid lithium, divalent cobalt oxalates are mixed by the ratio between amount of substance for 3:1:1
Mixing soluble cobalt compound and the carbonitride of above-mentioned preparation be dissolved in deionized water, stir and evenly mix mixed solution.Use pH value
Mixed solution pH value is adjusted to 8.5 for 11.0 ammonium hydroxide and the mixed solution of ammonium chloride, wherein the substance of ammonium hydroxide and sodium hydroxide
The ratio between amount concentration be 1:1, stir 1.5h, the ratio between amount of substance of carbonitride and cobalt ions is 20:1 in mixed solution.
Hydro-thermal reaction step: mixed solution being placed under the conditions of 140 DEG C and reacts 4.5h, and natural cooling after having reacted is made
The porous fenton catalyst of carried with doped type cobalt system.
Purification step: it is 0.45 μm that the porous fenton catalyst of carried with doped type cobalt system of above-mentioned preparation, which is passed through aperture,
Filtering with microporous membrane scrapes the filter residue on filter membrane and is transferred in centrifuge tube, deionized water suspension filter residue, 10000r/min is added
4min is rotated, repeats above-mentioned suspension, centrifugal process twice, the porous fenton catalyst of carried with doped type cobalt system of purifying is made.
Embodiment 6
Calcination steps: the mixture that cyanamide and urea are 1:3 in mass ratio is placed in Muffle furnace, by Muffle stove heating
To 600 DEG C and heating rate is 1 DEG C/min, stops continuing to heat (heating) after roasting 1h, carbonitride is made after Temperature fall.
Mixing step: the mixing solubility cobalt that cobalt naphthenate, cobalt acid lithium are mixed by the ratio between amount of substance for 1:1
The carbonitride for closing object and above-mentioned preparation is dissolved in deionized water, stirs and evenly mixs mixed solution.The sodium hydroxide for being 11.0 with pH value
Solution adjusts mixed solution pH value to 8.0, stirs 1h, the ratio between amount of substance of carbonitride and cobalt ions is 8:1 in mixed solution.
Hydro-thermal reaction step: mixed solution being placed under the conditions of 150 DEG C and reacts 4h, natural cooling after having reacted, and is made negative
Carry the porous fenton catalyst of doping type cobalt system.
Purification step: it is 0.45 μm that the porous fenton catalyst of carried with doped type cobalt system of above-mentioned preparation, which is passed through aperture,
Filtering with microporous membrane scrapes the filter residue on filter membrane and is transferred in centrifuge tube, deionized water suspension filter residue, 9000r/min is added
4min is rotated, repeats above-mentioned suspension, centrifugal process twice, the porous fenton catalyst of carried with doped type cobalt system of purifying is made.
Structural characterization, knot are carried out to the porous fenton catalyst of purified carried with doped type cobalt system prepared by embodiment 4
Fruit is as follows:
Fig. 1 and Fig. 2 is the porous fenton catalyst (sup-Co-g- of carried with doped type cobalt system being prepared in embodiment 4
C3N4) SEM figure and TEM figure.From the figure we can see that sup-Co-g-C3N4With typical g-C3N4It is laminar structured,
Its surface forms a large amount of cluster objects, illustrates that metallic cobalt largely loads and has been collected at g-C3N4Surface.It is measured by BET, sup-
Co-g-C3N4With bigger specific surface area, about 54.6m2/g.Pass through XPS analysis, sup-Co-g-C3N4Co content be
10.6wt% shows that the surface of catalyst there are a large amount of active site, is conducive to catalyst and H2O2It contacts and occurs with pollutant
Redox reaction.
Fig. 3 is sup-Co-g-C3N4Co 2p XPS spectrum figure.As can be seen from the figure do not showed in catalyst with
Co3+And Co3O4Relevant signal peak, Co are with Co in the catalyst2+(monovalent state cobalt) existing for form.
The DMPO that Fig. 4 is captures sup-Co-g-C3N4OH and HO in suspension2 ·/O2 ·-EPR spectrogram.It can from figure
To find out that catalyst produces a large amount of OH and HO during catalyzing and degrading pollutant2 ·/O2 ·-, illustrate sup-Co-g-
C3N4With stronger activation H2O2Ability.In addition, the addition of rhodamine B consumes a large amount of OH, and HO2 ·/O2 ·-'s
Signal is then remarkably reinforced, and illustrates that rhodamine B is effectively degraded during the reaction, sup-Co-g-C3N4Pollutant is urged
Change degradation and still follows classical Fenton's reaction mechanism.This two width figure of Fig. 4 reacted the free radical to work, explanation for determination
For catalyst to the degradation of pollutant mainly by Fenton's reaction process come what is carried out, EPR detection means is current authentication Fenton
The difference of one main means of reaction mechanism, two width figures is the difference of its each self-sensing method.The preparation method of suspension:
(1) DMPO of 50mg is dissolved in 200 microlitres of ultrapure waters, freezen protective.(2) 0.01g sup-Co-g-C is weighed3N4(embodiment
The porous fenton catalyst of purified carried with doped type cobalt system of 4 preparations), 1ml ultrapure water and 100 microlitres of H are added2O2After shake
It swings 5~10 seconds.(3) after the reaction system in step (2) reacts, it is molten in 10 microlitres of DMPO that 100 microlitres of mixed liquors are drawn
Sup-Co-g-C can be obtained in liquid3N4Suspension.And the detection in the case of existing to pollutant then will be ultrapure in reaction system
Water changes pollutant into.Above-mentioned prepared sup-Co-g-C3N4For the OH in capture system, i.e., pair suspension is
Left figure is answered, and to right figure HO2 ·/O2 ·-Capture then change the ultrapure water in above-mentioned system into methanol.
Degrading experiment is carried out to the porous fenton catalyst of purified carried with doped type cobalt system prepared by embodiment 4:
Test method: the catalyst of the above-mentioned synthesis of 0.02g is put into the rhodamine B solution of 10mg/L, in neutrallty condition
Under, 35 DEG C of constant temperature, 15mM H is added2O2Start Fenton's reaction, puts the concentration of sample detection pollutant in different times.
Experimental result: Fig. 5 is differential responses system in the degradation curve of rhodamine B (RhB).It can be seen from the figure that 120
In minute, Fe3O4/H2O2、g-C3N4/H2O2、sup-Co-g-C3N4Degradation rate of these three reaction systems to 10ppm rhodamine B
Respectively 40%, 33% and 30%, and in sup-Co-g-C3N4/H2O2100% is then up in system, this illustrates sup-Co-
g-C3N4To degradation mainly dependence and the H of pollutant2O2Fenton's reaction process is reacted to carry out, pure sup-Co-g-
C3N4Absorption property the degradation of pollutant is influenced less, with traditional fenton catalyst Fe3O4It compares, pollutant is urged
Change degrading activity to significantly increase.
The above embodiment is only the preferred embodiment of the present invention, and the scope of protection of the present invention is not limited thereto,
The variation and replacement for any unsubstantiality that those skilled in the art is done on the basis of the present invention belong to institute of the present invention
Claimed range.
Claims (10)
1. a kind of synthetic method of the porous fenton catalyst of carried with doped type cobalt system, which comprises the following steps:
Roasting: 1~3h is roasted under the conditions of presoma is placed in 500~600 DEG C, carbonitride, the roasting is made after Temperature fall
Heating rate is less than 10 DEG C/min；
Mixing: soluble cobalt compound is soluble in water with carbonitride, solution ph is adjusted to 8~11 with alkaline solution, is stirred
It is uniformly mixed, wherein the ratio between amount of substance of carbonitride and cobalt element is 5~20:1 in mixed solution；
Hydro-thermal reaction: reacting 4~7h under the conditions of mixed solution is placed in 100~150 DEG C, natural cooling after having reacted, and is made negative
Carry the porous fenton catalyst of doping type cobalt system；
The presoma is one of cyanamide, dicyanodiamine and urea or several mixing, and the alkaline solution is ammonia
Water, sodium hydroxide solution, the mixed solution or ammonium hydroxide of ammonium hydroxide and sodium hydroxide and ammonium chloride mixed solution.
2. the synthetic method of the porous fenton catalyst of carried with doped type cobalt system as described in claim 1, which is characterized in that roasting
It burns in step, maturing temperature is 550 DEG C, calcining time 2h, and the roasting heating rate is 5 DEG C/min.
3. the synthetic method of the porous fenton catalyst of carried with doped type cobalt system as described in claim 1, which is characterized in that mixed
It closes in step, the soluble cobalt compound is cobalt chloride, cobaltous sulfate, cobalt nitrate, cobalt acetate, divalent cobalt oxalates, trivalent cobalt
In oxalates, cobalt naphthenate, EDETATE SODIUM cobalt, cobalt acid lithium, Mecobalamin, cobalt potassium nitrite, natrium cobaltinitrosum and thunder Buddhist nun's cobalt
One or several kinds of mixing.
4. the synthetic method of the porous fenton catalyst of carried with doped type cobalt system as described in claim 1, which is characterized in that mixed
It closes in step, the soluble cobalt compound is one of cobalt chloride, cobaltous sulfate and cobalt nitrate or several mixing.
5. the synthetic method of the porous fenton catalyst of carried with doped type cobalt system as described in claim 1, which is characterized in that mixed
Close in step, adjust solution ph to 9 with ammonium hydroxide, stir 1~5h, in mixed solution the amount of the substance of carbonitride and cobalt element it
Than for 10:1.
6. the synthetic method of the porous fenton catalyst of carried with doped type cobalt system as described in claim 1, which is characterized in that in water
In thermal response step, mixed solution reacts 5h under the conditions of being placed in 120 DEG C.
7. the synthetic method of the porous fenton catalyst of carried with doped type cobalt system as described in claim 1, which is characterized in that in water
In thermal response step, the porous fenton catalyst of the carried with doped type cobalt system is filtered by film, and it is soluble in water not filter solid slag, weight
It is multiple to be centrifuged, dried after resuspension procedure 2~4 times, the porous fenton catalyst of carried with doped type cobalt system of purifying is made.
8. the synthetic method of the porous fenton catalyst of carried with doped type cobalt system as claimed in claim 7, which is characterized in that drying
Temperature is 50~80 DEG C, and drying time is 5~12h；
The film is filtered into the film that aperture is 0.45 μm and filters, and the revolving speed of the centrifugation is 8000~10000r/min.
9. a kind of porous fenton catalyst of carried with doped type cobalt system, which is characterized in that the porous Fenton of the carried with doped type cobalt system
Catalyst is prepared using the synthetic method of the described in any item porous fenton catalysts of carried with doped type cobalt system of claim 1-9.
10. a kind of application of the porous fenton catalyst of carried with doped type cobalt system on catalysis azo dyes rhodamine B catalytic degradation.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN110026224A (en) * | 2019-05-08 | 2019-07-19 | 苏州十一方生物科技有限公司 | A kind of cobaltosic oxide modifies the preparation method of mesoporous azotized carbon nano composite material |
| CN114192178A (en) * | 2021-12-30 | 2022-03-18 | 常州大学 | Preparation method and application of cobalt-containing carbon nitride catalyst |
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Application publication date: 20181211 |