CN110280300A - A kind of preparation method and application loading Mn oxide ordered mesoporous carbon composite material - Google Patents
A kind of preparation method and application loading Mn oxide ordered mesoporous carbon composite material Download PDFInfo
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- CN110280300A CN110280300A CN201910510819.5A CN201910510819A CN110280300A CN 110280300 A CN110280300 A CN 110280300A CN 201910510819 A CN201910510819 A CN 201910510819A CN 110280300 A CN110280300 A CN 110280300A
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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
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/076—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
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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
- C02F2101/34—Organic compounds containing oxygen
- C02F2101/345—Phenols
Abstract
The present invention provides a kind of preparation methods for loading Mn oxide ordered mesoporous carbon composite material, comprising: S1) small molecule carbon source, acid are mixed in alcoholic solvent with mesoporous material, heating carries out polymerization reaction, obtains the first intermediate product；S2 the intermediate product is mixed in alcoholic solvent with manganese source), after solvent volatilization, is calcined in protective atmosphere, obtains the second intermediate product；S3 the mesoporous material in second intermediate product) is removed, load Mn oxide ordered mesoporous carbon composite material is obtained.Compared with prior art, on the one hand Mn oxide uniform load is in mesoporous carbon surface in the composite material obtained, improve the exposed area of Mn oxide, and then improve reaction site quantity, another aspect composite material had not only saved the mesopore orbit for being conducive to mass transfer using ordered mesopore carbon as substrate, but also can adsorb pollutant, improved surface concentration, it is finally reached the purpose for improving pollutant removal rate, there is preferable enrichment and catalytic degradation effect to pollutant.
Description
Technical field
The invention belongs to water-treatment technology field more particularly to a kind of load Mn oxide ordered mesoporous carbon composite materials
Preparation method and application.
Background technique
High-level oxidation technology is a kind of water treatment technology of efficiently removal Organic Pollutants In Water.Traditional advanced oxidation mistake
Journey is to utilize hydroxyl radical free radical (OH) Lai Shixian pollutant mineralising, potentiometric titrations (SO mostly4 -) as a kind of novel
Reactive oxygen species have higher redox potential and longer relaxation time compared to OH.Furthermore for raw material,
For persulfate compared to hydrogen peroxide cheaper, chemical property is more stable, is also easier to storage and transport, therefore be based on
SO4 -With more broad application prospect.
Transition metal ions is common to make persulfate activator, though it, which can preferably decompose persulfate, generates SO4 -Freely
Base, but there are metal ion secondary pollution, can not reuse the problems such as, therefore the heterogeneous class for practical application system
Catalyst is more applicable in.It is worth pointing out that heterogeneous class catalytic process is an interfacial reaction process, therefore how to improve
Interfacial reaction rate is the core of entire heterogeneous catalysis process.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that provide a kind of load Mn oxide ordered mesopore carbon compound
The load Mn oxide ordered mesoporous carbon composite material of the preparation method and application of material, this method preparation is urged as advanced oxidation
Agent catalytic capability with higher.
The present invention provides a kind of preparation methods for loading Mn oxide ordered mesoporous carbon composite material, comprising:
S1) small molecule carbon source, acid are mixed in alcoholic solvent with mesoporous material, heating carries out polymerization reaction, obtains first
Intermediate product；
S2 it after) mixing first intermediate product in alcoholic solvent with manganese source, is calcined in protective atmosphere, obtains second
Intermediate product；
S3 the mesoporous material in second intermediate product) is removed, load Mn oxide ordered mesopore carbon composite wood is obtained
Material.
Preferably, the small molecule carbon source is selected from one of furfuryl alcohol, sucrose and small molecule resin or a variety of；
The acid is selected from oxalic acid and/or sulfuric acid；
The mesoporous material is selected from one of SBA-15, SBA-1, SBA-16, MCM-48, FDU-5 and FDU-12 or more
Kind；
The manganese source is selected from one of manganese acetylacetonate, manganese nitrate, manganese sulfate and manganese chloride or a variety of.
Preferably, the mass ratio of the small molecule carbon source and mesoporous material is (1~2.5): 1；The quality of the manganese source is
The 3%~12.5% of small molecule carbon source quality.
Preferably, the step S1) specifically:
Small molecule carbon source, acid are mixed in alcoholic solvent with mesoporous material, are heated to 70 DEG C~90 DEG C progress polymerization reactions,
Then it is handled at 120 DEG C~160 DEG C, obtains the first intermediate product.
Preferably, the time of the polymerization reaction is 6~10h；The time of the processing is 2~4h.
Preferably, the step S2) in calcine temperature be 600 DEG C~1000 DEG C；The time of calcining is 1~3h；Calcining
Heating rate be 1~5 DEG C/min.
Preferably, the step S3) specifically:
Second intermediate product is heated into removing mesoporous material in strong alkali solution, it is orderly to obtain load Mn oxide
Mesoporous carbon composite material.
Preferably, the concentration of the strong alkali solution is 2~3mol/L；The temperature of heating is 60 DEG C~100 DEG C.
Preferably, the step S3) specifically:
Second intermediate product is impregnated to removing mesoporous material in a solution of hydrofluoric acid, it is orderly to obtain load Mn oxide
Mesoporous carbon composite material.
The present invention also provides above-mentioned prepared load Mn oxide ordered mesoporous carbon composite materials as advanced oxidation
The application of technology catalyst.
The present invention provides a kind of preparation methods for loading Mn oxide ordered mesoporous carbon composite material, comprising: S1) it will be small
Molecule carbon source, acid mix in alcoholic solvent with mesoporous material, and heating carries out polymerization reaction, obtain the first intermediate product；S2) by institute
It states intermediate product and is mixed in alcoholic solvent with manganese source, after solvent volatilization, calcined in protective atmosphere, obtain the second intermediate product；
S3 the mesoporous material in second intermediate product) is removed, load Mn oxide ordered mesoporous carbon composite material is obtained.With it is existing
Technology is compared, and the present invention is using mesoporous material as template, and small molecule carbon source is under the catalysis of acid centre in mesoporous material duct
It is in situ that polymerization reaction occurs, so that duct is partially filled, then manganese source is filled in duct, so that manganese source uniform load is in carbon
Source polymer surfaces, high temperature pyrolysis make its decomposition, finally remove mesoporous material, on the one hand exposure mesopore orbit structure makes to obtain
Composite material in Mn oxide uniform load improve the exposed area of Mn oxide in mesoporous carbon surface, and then improve
Reaction site quantity, another aspect composite material had both saved the mesopore orbit for being conducive to mass transfer using ordered mesopore carbon as substrate,
Pollutant can be adsorbed again in composite material surface, improves surface concentration, be finally reached the purpose for improving pollutant removal rate, it is right
Pollutant has preferable enrichment and catalytic degradation effect, and preparation method of the present invention is simple, obtains composite structure rule
Then, aperture is uniform, compositely proportional easy-regulating.
Detailed description of the invention
Fig. 1 be the embodiment of the present invention preparation load Mn oxide ordered mesoporous carbon composite material as catalyst at
Manage phenol solution different time phenol residual concentration curve graph；
Fig. 2 be the embodiment of the present invention preparation load Mn oxide ordered mesoporous carbon composite material as catalyst at
Manage the curve graph of TOC content in phenol solution different time solution；
Fig. 3 be the embodiment of the present invention preparation load Mn oxide ordered mesoporous carbon composite material as catalyst at
Manage phenol solution different time solution phenol residual concentration curve graph.
Specific embodiment
Below in conjunction with the embodiment of the present invention, technical scheme in the embodiment of the invention is clearly and completely described,
Obviously, described embodiments are only a part of the embodiments of the present invention, instead of all the embodiments.Based in the present invention
Embodiment, every other embodiment obtained by those of ordinary skill in the art without making creative efforts, all
Belong to the scope of protection of the invention.
The present invention provides a kind of preparation methods for loading Mn oxide ordered mesoporous carbon composite material, comprising: S1)
Small molecule carbon source, acid are mixed in alcoholic solvent with mesoporous material, heating carries out polymerization reaction, obtains the first intermediate product；S2)
The intermediate product is mixed in alcoholic solvent with manganese source, after solvent volatilization, is calcined in protective atmosphere, obtains producing among second
Object；S3 the mesoporous material in second intermediate product) is removed, load Mn oxide ordered mesoporous carbon composite material is obtained.
The present invention is not particularly limited the source of all raw materials, is commercially available.
Wherein, the small molecule carbon source is preferably one of furfuryl alcohol, sucrose and small molecule resin or a variety of；The acid is excellent
It is selected as oxalic acid and/or sulfuric acid；The mesoporous material is preferably silicon-based mesoporous material, more preferably SBA-15, SBA-1, SBA-16,
One of MCM-48, FDU-5 and FDU-12 or a variety of；The alcoholic solvent is preferably methanol and/or ethyl alcohol, more preferably second
Alcohol；The manganese source is preferably manganese acetylacetonate (MnC15H21O6), manganese nitrate, one of manganese sulfate and manganese chloride or a variety of.
Small molecule carbon source, acid are mixed in alcoholic solvent with mesoporous material, preferably by small molecule carbon source and acid in the present invention
After being mixed in alcoholic solvent, then mix with mesoporous material；The mass ratio of the small molecule carbon source and mesoporous material be preferably (1~
2.5): 1, more preferably (1.5~2): 1, it is further preferably (1.7~2): 1；The quality of the acid is preferably small molecule carbon source quality
5%~15%, more preferably 8%~13%, be further preferably 9%~12%, most preferably 10%；The volume of the alcoholic solvent
Preferably 3~10 times of small molecule carbon source volume, more preferably 4~7 times are further preferably 4~6 times, most preferably 5 times；It is described
After small molecule carbon source, acid are mixed with alcoholic solvent, preferably it is added dropwise in mesoporous material；The rate of the dropwise addition is preferably 0.5~
1ml/min, more preferably 0.6~0.9ml/min are further preferably 0.7~0.8ml/min；To be better mixed uniformly, preferred side
Side stirring is added dropwise until mesoporous material is infiltrated.
After mixing, heating carries out polymerization reaction, 70 DEG C~90 DEG C progress polymerization reactions is preferably first heated to, then 120
DEG C~160 DEG C at handled, obtain the first intermediate product, be more preferably first heated to 75 DEG C~85 DEG C progress polymerization reactions, so
It is handled at 130 DEG C~150 DEG C afterwards, obtains the first intermediate product, be further preferably first heated to 80 DEG C of progress polymerization reactions, so
It is handled at 140 DEG C afterwards, obtains the first intermediate product；The time of the polymerization reaction is preferably 6~10h, and more preferably 7
~9h is further preferably 8h；The time of the processing is preferably 2~4h, more preferably 2.5~3.5h, is further preferably 3h；Small molecule
In mesoporous material duct polymerization reaction occurs in situ for carbon source, so that duct is partially filled, heating treatment makes unpolymerized
Small molecule carbon source is volatilized, and space further discharges in duct.
First intermediate product is mixed in alcoholic solvent with manganese source；The quality of the manganese source is preferably small molecule carbon source
The 3%~12.5% of quality, more preferably 6.2%~12.5%；The alcoholic solvent is preferably methanol and/or ethyl alcohol, more preferably
Ethyl alcohol；In the present invention, it is preferred to after first mixing manganese source with alcoholic solvent, then mix with the first intermediate product；The manganese source and alcohol
After solvent mixing, preferably it is added dropwise in the first intermediate product；The rate of the dropwise addition is preferably 0.5~1ml/min, more preferably
0.6~0.9ml/min is further preferably 0.6~0.7ml/min；To be better mixed uniformly, preferably stir when being added dropwise up to the
One intermediate product is infiltrated.
After mixing, preferably heated；The temperature of the heat treatment is preferably 70 DEG C~90 DEG C, more preferably 75
DEG C~85 DEG C, it is further preferably 80 DEG C；The time of the heat treatment is preferably 2~6h, more preferably 3~5h, is further preferably 4h.
It after heat treatment, is calcined in protective atmosphere, obtains the second intermediate product；The protective atmosphere is preferably nitrogen
And/or argon gas；The temperature of the calcining is preferably 600 DEG C~1000 DEG C, and more preferably 700 DEG C~1000 DEG C, be further preferably 800
DEG C~1000 DEG C, most preferably 900 DEG C；The time of the calcining is preferably 1~3h, more preferably 1.5~2.5h, further preferably for
2h；The heating rate of the calcining is preferably 1~5 DEG C/min, more preferably 2~4 DEG C/min, is further preferably 3 DEG C/min.
Remove the mesoporous material in second intermediate product；Preferably second intermediate product is existed in the present invention
Heating removing mesoporous material in strong alkali solution；The strong alkali solution is preferably alkali hydroxide soln, more preferably
Sodium hydroxide solution and/or potassium hydroxide solution；The concentration of the strong alkali solution is preferably 2~3mol/L；The heating
Temperature is preferably 60 DEG C~100 DEG C, more preferably 70 DEG C~80 DEG C；Preferably to remove mesoporous material, it is preferred to use repeatedly de-
It removes, more preferably removes 2~3 times；The time removed every time is preferably 1~3h, more preferably 1.5~2.5h, is further preferably 2h；Also
Removing mesoporous material is preferably impregnated by second intermediate product in a solution of hydrofluoric acid.
It after removing mesoporous material, preferably washes, filter, it is dry, obtain load Mn oxide ordered mesoporous carbon composite material；
The quality of manganese element is preferably 2.7%~10.1% in the load Mn oxide ordered mesoporous carbon composite material.
For the present invention using mesoporous material as template, small molecule carbon source is former in mesoporous material duct under the catalysis of acid centre
Polymerization reaction occurs for position, so that duct is partially filled, then manganese source is filled in duct, so that manganese source uniform load is in carbon source
Polymer surfaces, high temperature pyrolysis make its decomposition, finally remove mesoporous material, on the one hand exposure mesopore orbit structure makes
Mn oxide uniform load improves the exposed area of Mn oxide in mesoporous carbon surface in composite material, and then improves anti-
Bit number of points are answered, another aspect composite material had not only saved the mesopore orbit for being conducive to mass transfer using ordered mesopore carbon as substrate, but also
Pollutant can be adsorbed in composite material surface, improve surface concentration, be finally reached the purpose for improving pollutant removal rate, and
Preparation method of the present invention is simple, obtains composite structure rule, aperture is uniform, compositely proportional easy-regulating.
The present invention also provides the load Mn oxide ordered mesoporous carbon composite materials of above-mentioned preparation as advanced oxidation skill
The application of art catalyst.
Mn oxide ordered mesoporous carbon composite material is loaded as high-level oxidation technology catalyst and is used for water process, is preferably existed
Water process is carried out in the presence of persulfate；The persulfate is preferably sodium peroxydisulfate；The water process be preferably industrial wastewater,
The processing of the water depths such as micro- pollutant effluents and municipal sewage；The load Mn oxide ordered mesoporous carbon composite material is at water
Dosage when reason is preferably 50~200mg/L, more preferably 80~150mg/L, is further preferably 90~120mg/L, most preferably
100mg/L；The pH value of its aqueous solution to be processed when being used for water process is preferably 7~9, and more preferably 7.5~8.5, further preferably
It is 8.
Load Mn oxide ordered mesoporous carbon composite material prepared by the present invention has orderly uniform aperture structure, manganese oxidation
Object is supported in mesoporous carbon substrate with sheet property.Oxygen in Mn oxide lattice has good mobility, can guarantee
Different valence state manganese freely changes in oxidation-reduction process, is a kind of efficient high grade oxidation catalytic agent；Ordered mesopore carbon is one
The mesoporous material of class cellular structure uniform and ordered has both bigger serface and excellent mass-transfer performance because of the meso-hole structure of its rule；
Meanwhile mesoporous carbon surface functional group rich in, therefore there is good absorption property to pollutant.
Load Mn oxide ordered mesoporous carbon composite material prepared by the present invention is made by high-temperature calcination, preparation process letter
It is single.In the presence of persulfate, even if being directed to the micro quantity organic pollutant catalysis material, to can be realized pollutant adsorbing-oxidising
Collaboration removal has many advantages, such as that removal efficiency is high, mineralization rate is good, harmless, applied widely.The material is widely portable to make
Paper, pharmacy, textile printing and dyeing, daily-use chemical industry, the fields such as advanced treatment of wastewater, have efficient water treatment efficiency, be it is a kind of green,
Efficient high-level oxidation technology catalyst.
In order to further illustrate the present invention, orderly to a kind of load Mn oxide provided by the invention with reference to embodiments
The preparation method and application of mesoporous carbon composite material is described in detail.
Reagent used in following embodiment is commercially available.
Embodiment
0.135g oxalic acid is dissolved in 6mL ethyl alcohol, 1.2mL furfuryl alcohol is added and is uniformly mixed；Above-mentioned mixed solution is added dropwise
Enter in 0.8g SBA-15 silicon template, time for adding about 10min, and be sufficiently mixed and stir to get pasty solid, then respectively 80
It polymerize at 8h and 140 DEG C at DEG C and handles 3h；It repeats the above steps, prepares four parts of samples altogether.0,42.5,85 are weighed respectively,
170mg MnC15H21O6It is dissolved in 6ml ethyl alcohol, and corresponds to and above-mentioned obtained solid powder is added dropwise, time for adding about 10min is mixed
Close stirring, 80 DEG C of processing 4h；The mixture is calcined into 2h under 900 DEG C of nitrogen atmospheres；Gained powder is in 200mLNaOH solution
80 DEG C of desiliconization 2h, altogether twice.Last gained load Mn oxide ordered mesoporous carbon composite material is according to MnC15H21O6Additional amount
It is ascending to be successively labeled as OMC, MnOx(2.7%)@OMC,MnOx(5.2%)@OMC,MnOx(10.1%)(inferior horn is designated as manganese element to@OMC
Account for the percentage of products therefrom).
The boric acid for weighing certain mass is configured to 20mM boric acid solution, adjusts pH to 8 with NaOH.With above-mentioned solution allocation four
Part concentration is 1mM sodium peroxydisulfate, 20mg/L phenol mixed solution 30mL；300rmp revolving speed is separately added into 3.0mg after mixing
The load Mn oxide ordered mesoporous carbon composite material of the different manganese load capacity of above embodiments preparation is as catalyst；Reaction is special
Film is crossed after fixing time separates catalyst with solution, and remaining phenol is measured by HPLC in solution, and it is surplus to obtain different time phenol
Remaining concentration curve is as shown in Figure 1.
As seen from Figure 1, with Mn oxide load capacity by 0% improve to 5.2%, 15min phenol removal efficiency gradually from
45% improves to 90%, finally reaches 100%.And when Mn oxide load capacity continues to improve to 10.1%, phenol removal effect
Rate decline.This illustrates catalysis material (MnOx when manganese load factor is 5.2%(5.2%)@OMC) performance is best.
The boric acid for weighing certain mass is configured to 20mM boric acid solution, adjusts pH to 8 with NaOH.With above-mentioned solution allocation six
Part concentration is 1mM sodium peroxydisulfate, 20mg/L phenol mixed solution 30mL；300rmp revolving speed is separately added into 3.0mg after mixing
MnOx(5.2%)@OMC catalysis material；3,8,11,15 are reacted respectively, and crossing film after twenty minutes separates catalyst with solution, measures molten
Liquid TOC obtains the curve graph of TOC content in different time solution, as shown in Figure 2.
As shown in Figure 2, as the reaction time extends, TOC removal rate is gradually risen, and 20min TOC removal rate almost
Reach 100%.This shows that the load Mn oxide ordered mesoporous carbon composite material can realize organic matter removal very well, and final
Realize that mineralising is nontoxic.
The boric acid for weighing certain mass is configured to 20mM boric acid solution, adjusts pH to 8 with NaOH.With above-mentioned solution allocation four
Part concentration is 20mg/L phenol mixed solution 30mL；The difference of 3.0mg above embodiments preparation is separately added under 300rmp revolving speed
The load Mn oxide ordered mesoporous carbon composite material of manganese load capacity measures in 2,5,8 minutes solution of absorption as catalyst
Phenol concentration.1mL 30mM sodium peroxydisulfate solution is added after 8 minutes to be adsorbed, respectively measurement reaction 0.5,1,1.5,3,5,7.5,
It is as shown in Figure 3 to obtain different time solution phenol residual concentration curve graph for 10 minutes solution residue phenol concentrations.
From the above results, it can be seen that the four classes load Mn oxide ordered mesoporous carbon composite material of preparation of the embodiment of the present invention is equal
Pyrogentisinic Acid has good adsorption effect.Though slightly declining as Mn oxide load capacity increase adsorption efficiency has, it is still
So maintain 25%~30%.After persulfate is added, load Mn oxide ordered mesoporous carbon composite material group phenol removal
Rate is obviously accelerated, and can realize that phenol 100% removes in 7.5min after persulfate addition.Meanwhile manganese load capacity is
Performance is best when 5.2%, phenol can be reached within 3min and completely removed.This shows that prepared load Mn oxide is orderly situated between
Hole carbon composite has good absorption-catalytic oxidation performance, so that phenol be promoted to remove.
Claims (10)
1. a kind of preparation method for loading Mn oxide ordered mesoporous carbon composite material characterized by comprising
S1) small molecule carbon source, acid are mixed in alcoholic solvent with mesoporous material, heating carries out polymerization reaction, obtains among first
Product；
S2 it after) mixing first intermediate product in alcoholic solvent with manganese source, calcines, is obtained among second in protective atmosphere
Product；
S3 the mesoporous material in second intermediate product) is removed, load Mn oxide ordered mesoporous carbon composite material is obtained.
2. preparation method according to claim 1, which is characterized in that the small molecule carbon source be selected from furfuryl alcohol, sucrose with it is small
One of molecule resin is a variety of；
The acid is selected from oxalic acid and/or sulfuric acid；
The mesoporous material is selected from one of SBA-15, SBA-1, SBA-16, MCM-48, FDU-5 and FDU-12 or a variety of；
The manganese source is selected from one of manganese acetylacetonate, manganese nitrate, manganese sulfate and manganese chloride or a variety of.
3. preparation method according to claim 1, which is characterized in that the mass ratio of the small molecule carbon source and mesoporous material
For (1~2.5): 1；The quality of the manganese source is the 3%~12.5% of small molecule carbon source quality.
4. preparation method according to claim 1, which is characterized in that the step S1) specifically:
Small molecule carbon source, acid are mixed in alcoholic solvent with mesoporous material, are heated to 70 DEG C~90 DEG C progress polymerization reactions, then
It is handled at 120 DEG C~160 DEG C, obtains the first intermediate product.
5. the preparation method according to claim 4, which is characterized in that the time of the polymerization reaction is 6~10h；It is described
The time of processing is 2~4h.
6. preparation method according to claim 1, which is characterized in that the step S2) in calcine temperature be 600 DEG C~
1000℃；The time of calcining is 1~3h；The heating rate of calcining is 1~5 DEG C/min.
7. preparation method according to claim 1, which is characterized in that the step S3) specifically:
Second intermediate product is heated into removing mesoporous material in strong alkali solution, it is order mesoporous to obtain load Mn oxide
Carbon composite.
8. preparation method according to claim 7, which is characterized in that the concentration of the strong alkali solution is 2~3mol/L；
The temperature of heating is 60 DEG C~100 DEG C.
9. preparation method according to claim 1, which is characterized in that the step S3) specifically:
Second intermediate product is impregnated to removing mesoporous material in a solution of hydrofluoric acid, it is order mesoporous to obtain load Mn oxide
Carbon composite.
10. load Mn oxide ordered mesoporous carbon composite material conduct prepared by claim 1~claim 9 any one
The application of high-level oxidation technology catalyst.
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| CN113044949A (en) * | 2021-03-10 | 2021-06-29 | 浙江工商大学 | Sodium persulfate slow release agent suitable for catalytic oxidation degradation of antibiotics and preparation and application thereof |
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