CN108083416A - A kind of method that carbon material activation persulfate orientation is carbonylated and generates singlet oxygen - Google Patents
A kind of method that carbon material activation persulfate orientation is carbonylated and generates singlet oxygen Download PDFInfo
- Publication number
- CN108083416A CN108083416A CN201711399032.3A CN201711399032A CN108083416A CN 108083416 A CN108083416 A CN 108083416A CN 201711399032 A CN201711399032 A CN 201711399032A CN 108083416 A CN108083416 A CN 108083416A
- Authority
- CN
- China
- Prior art keywords
- carbon material
- singlet oxygen
- persulfate
- carbonylated
- orientation
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B13/00—Oxygen; Ozone; Oxides or hydroxides in general
- C01B13/02—Preparation of oxygen
- C01B13/0203—Preparation of oxygen from inorganic compounds
- C01B13/0211—Peroxy compounds
-
- 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
-
- 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
- C02F2305/08—Nanoparticles or nanotubes
Abstract
A kind of method that carbon material activation persulfate orientation is carbonylated and generates singlet oxygen, it is related to a kind of method for orienting and generating singlet oxygen.The present invention be in order to solve at present generate singlet oxygen method used in photosensitizer for poisonous and harmful substance, be unfavorable for later separation and the generation with other active oxygen species the technical issues of.The present invention：Carbonylation carbon material is added in pending sewage and is stirred, the aqueous solution of persulfate is then added in, obtains mixed liquor, be persistently stirred liquid, you can generates singlet oxygen and sewage is handled；The present invention provides a kind of new method for efficient, orientation generation singlet oxygen, while this method is safe, economical, environmentally friendly, can be in the application of the fields such as biomedical and water process, wide market.The present invention is applied to water treatment field.
Description
Technical field
The present invention relates to a kind of methods for orienting and generating singlet oxygen.
Background technology
Singlet oxygen is a kind of important active oxygen species, and there is molecular orbit the electronics different from ground state oxygen molecule to arrange
Cloth is a kind of existence form of excited state molecule of oxygen.Since its activity is very high, in physics, chemistry, environment and biomedicine
The fields of grade play an important role, and receive the extensive concern of researcher.
At present, it is photosensitizer method to generate the most common method of singlet oxygen, i.e. photosensitizer transits to sharp under illumination condition
State is sent out, then transfers energy to ground state oxygen molecule and then forms singlet oxygen.However, this method is also asked at present there are following
Topic：1st, commonly used photosensitizer is poisonous and harmful substance (such as highly toxic Porphyrin-Based Sensitizer), therefore this method exists
The application in the biomedical fields such as with water process is restricted；2nd, photosensitizer used in this method is generally water-soluble object
Matter is unfavorable for later separation；3rd, this method is frequently accompanied by the generation (example of other active oxygen species when generating singlet oxygen
Such as superoxide radical, hydroxyl radical free radical), it is impossible to efficiently, orient generation singlet oxygen.Therefore, research and develop safe and environment-friendly, economical
New method with realize singlet oxygen it is efficient, orientation generate, it is significant.
The content of the invention
The present invention is in order to which photosensitizer used in solving to generate the method for singlet oxygen at present is poisonous and harmful substance, no
Beneficial to later separation and with other active oxygen species generation the technical issues of, and provide it is a kind of carbonylation carbon material activation
The method that persulfate orientation generates singlet oxygen.
The present invention carbonylation carbon material activation persulfate orientation generation singlet oxygen method be according to the following steps into
Capable：
Carbonylation carbon material is added to stirring 5min~10min in pending sewage, then adds in persulfate
Aqueous solution obtains mixed liquor, is persistently stirred liquid, you can generates singlet oxygen and sewage is handled；
Carbon material in the carbonylation carbon material is amorphous carbon material, sp2The carbon material and sp of hydridization3Hydridization
The carbon material of one or both of carbon material hybrid form mixing composition；
The carbonylation carbon material is to orient the oxygen-containing functional group of carbon material surface using physics and chemical method, is fixed
Amount is changed into the carbon material of carbonyl；
The concentration that carbon material is carbonylated in the mixed liquor is 0.01g/L~5g/L；
The concentration of persulfate is 0.1mmol/L~10mmol/L in the mixed liquor.
The present invention orientation generation singlet oxygen principle be：Contain in the carbonyl of carbon material surface there are one unsaturated double-bond,
With electrophilic characteristic；And contain peroxide bridge in persulfate, there are properties.Therefore, electronics is easily from the persulfuric acid of nucleophilicity
Salt is transferred on the carbonyl of electrophilicity, and then generates five free radical (SO of sulphur5 ·-)；Due to SO5 ·-The self-reacting rate of free radical is very
Height (2 × 108M-1·S-1), and the very low (7.4 ± 2.4kcalmol of activation energy-1), autoreaction easily occurs, and then generates single
Line state oxygen.At the same time, other active oxygen species such as hydroxyl radical free radical and potentiometric titrations will not be generated.
Advantages of the present invention：
1st, by the method for the present invention, efficient, the orientation generation of singlet oxygen are realized for the first time；
2nd, for the method for the present invention when generating singlet oxygen, without any poisonous and harmful substance is added, entire reaction process is green
Color, environmental protection, therefore can be promoted the use of in fields such as biomedicine, purification of water quality；
It is heterogeneous system that system, which occurs, for the singlet oxygen that the 3rd, the method for the present invention is provided, and activator is solid with oxidant
Body powder, is easy to transport in practical applications, store, use and regeneration, activator separate reuse, has higher warp
Ji property.
4th, carbonylation carbon material of the invention activation persulfate, which generates singlet oxygen, has high specificity, in the system
In the by-products such as hydroxyl radical free radical and potentiometric titrations are not detected.
Constructed singlet oxygen system is up to 87% to the removal rate of parachlorophenol based on patent of the present invention.
It can be seen that patent of the present invention generates singlet oxygen for efficient, orientation provides a kind of new method, while the party
Method safety, economic, environmental protection can apply, wide market biomedical with fields such as water process.
Carbonylation carbon material in the present invention is activating agent, and persulfate is oxidant.
Description of the drawings
Fig. 1 is the removal rate datagram of furancarbinol；
Fig. 2 is the removal rate datagram of Atrazine and terephthalic acid (TPA)；
Fig. 3 is spectral profile figure；
Fig. 4 is fluorescent spectrum curve figure；
Fig. 5 is spectral profile figure；
Fig. 6 is the removal rate datagram of parachlorophenol.
Specific embodiment
Specific embodiment one：Present embodiment activates persulfate orientation for a kind of carbonylation carbon material and generates singlet
The method of oxygen specifically carries out according to the following steps：
Carbonylation carbon material is added to stirring 5min~10min in pending sewage, then adds in persulfate
Aqueous solution obtains mixed liquor, is persistently stirred liquid, you can generates singlet oxygen and sewage is handled；
Carbon material in the carbonylation carbon material is amorphous carbon material, sp2The carbon material and sp of hydridization3Hydridization
The carbon material of one or both of carbon material hybrid form mixing composition；
The concentration that carbon material is carbonylated in the mixed liquor is 0.01g/L~5g/L；
The concentration of persulfate is 0.1mmol/L~10mmol/L in the mixed liquor.
Specific embodiment two：The present embodiment is different from the first embodiment in that：The amorphous carbon material
For activated carbon or mesoporous carbon.Other are same as the specific embodiment one.
Specific embodiment three：The present embodiment is different from the first and the second embodiment in that：The sp2Hydridization
Carbon material is carbon nanotubes, graphene or fullerene.Other are the same as one or two specific embodiments.
Specific embodiment four：Unlike one of present embodiment and specific embodiment one to three：The sp3It is miscellaneous
The carbon material of change is Nano diamond.Other are identical with one of specific embodiment one to three.
Specific embodiment five：Unlike one of present embodiment and specific embodiment one to four：Described two kinds
The carbon material of hybrid form mixing composition is onion carbon.Other are identical with one of specific embodiment one to four.
Specific embodiment six：Unlike one of present embodiment and specific embodiment one to four：The over cure
Hydrochlorate is peroxy-monosulfate, peroxydisulfate or persulfate complex salt.Other are identical with one of specific embodiment one to five.
Specific embodiment seven：Present embodiment is unlike specific embodiment six：The peroxy-monosulfate is
Potassium hydrogen peroxymonosulfate or hydrogen peroxymonosulfate sodium；The peroxydisulfate is potassium peroxydisulfate or sodium peroxydisulfate；The persulfuric acid
Salt complex salt is single potassium hydrogen persulfate composite salts.Other are identical with specific embodiment six.
Specific embodiment eight：Unlike one of present embodiment and specific embodiment one to seven：The carbonyl
It is sp to change the carbon material in carbon material3The carbon material Nano diamond of hydridization, and the preparation method that Nano diamond is carbonylated is：
First, Nano diamond powder is uniformly layered in quartz boat, and in quartz boat Nano diamond powder thickness it is small
In 1.5cm；It is subsequently placed in tube furnace, inert gas 30min is led to the flow velocity of 100mL/min；The nano-diamond powder
The content of surface oxygen at end is 2wt%~10wt%, and particle size distribution range is 3nm~10nm；
2nd, the flow velocity of inert gas is adjusted to 50mL/min~180mL/min, then with 3 DEG C/min~10 DEG C/min's
Heating rate makes the temperature of tube furnace rise to 450 DEG C~950 DEG C, and is 450 DEG C~950 DEG C and the guarantor of inert gas in temperature
The lower annealing 0.5h~4h of shield；
3rd, cooled to room temperature under inert gas shielding then obtains the Nano diamond of carbonylation；
Inert gas described in step 1 is the mixed gas of one or more of nitrogen, argon gas and helium；
Nano diamond powder described in step 1 is prepared using explosion method.Other with specific embodiment one to
One of seven is identical.
The present invention is verified with tests below：
It is generated for simple, intuitive research singlet oxygen, first using the probe molecule furancarbinol of singlet oxygen as target
Object, the different carbonylation degree Nano diamonds catalysis permonosulphuric acid complex salts (PMS) of preliminary assessment generate singlet oxygens degradation
The efficiency of furancarbinol.
Experiment one：A kind of method that this experiment activates persulfate orientation generation singlet oxygen for carbon material, is specifically pressed
What following steps carried out：
Carbon material is added in furancarbinol aqueous solution and stirs 5min, the aqueous solution of PMS is then added in, is mixed
Liquid is persistently stirred liquid 1h；
The concentration of furancarbinol is 0.04mmol/L in the furancarbinol aqueous solution；
The concentration of carbon material is 0.1g/L in the mixed liquor；
The concentration of persulfate is 0.25mmol/L in the mixed liquor；
The carbon material is sp3The Nano diamond of hydridization；
The Nano diamond powder is prepared using explosion method；
The particle size distribution range of the Nano diamond powder is 3nm~10nm.
Experiment two：This experiment orients the method for generating singlet oxygen, tool for a kind of carbon material activation persulfate that is carbonylated
Body carries out according to the following steps：
Carbonylation carbon material is added in furancarbinol aqueous solution and stirs 5min, the aqueous solution of PMS is then added in, obtains
Mixed liquor is persistently stirred liquid 1h；
The concentration of furancarbinol is 0.04mmol/L in the furancarbinol aqueous solution；
The concentration that carbon material is carbonylated in the mixed liquor is 0.1g/L；
The concentration of persulfate is 0.25mmol/L in the mixed liquor；
Carbon material in the carbonylation carbon material is sp3The carbon material Nano diamond of hydridization, and nanometer is carbonylated
The preparation method of diamond is：
First, Nano diamond powder is uniformly layered in quartz boat, and in quartz boat Nano diamond powder thickness it is small
In 1.5cm；It is subsequently placed in tube furnace, inert gas 30min is led to the flow velocity of 100mL/min；The nano-diamond powder
The content of surface oxygen at end is 6.63 ± 0.04%, and particle size distribution range is 3nm~10nm；
2nd, the flow velocity of inert gas is adjusted to 160mL/min, and the temperature of tube furnace is then made with the heating rate of 10 DEG C/min
Degree rises to 500 DEG C, and the 3h that anneals in the case where temperature is 500 DEG C of protection with inert gas；
3rd, cooled to room temperature under inert gas shielding then obtains the Nano diamond of carbonylation；
Inert gas described in step 1 is argon gas；
Nano diamond powder described in step 1 is prepared using explosion method.
Experiment three：This experiment orients the method for generating singlet oxygen, tool for a kind of carbon material activation persulfate that is carbonylated
Body carries out according to the following steps：
Carbonylation carbon material is added in furancarbinol aqueous solution and stirs 5min, the aqueous solution of PMS is then added in, obtains
Mixed liquor is persistently stirred liquid 1h；
The concentration of furancarbinol is 0.04mmol/L in the furancarbinol aqueous solution；
The concentration that carbon material is carbonylated in the mixed liquor is 0.1g/L；
The concentration of persulfate is 0.25mmol/L in the mixed liquor；
Carbon material in the carbonylation carbon material is sp3The carbon material Nano diamond of hydridization, and nanometer is carbonylated
The preparation method of diamond is：
First, Nano diamond powder is uniformly layered in quartz boat, and in quartz boat Nano diamond powder thickness it is small
In 1.5cm；It is subsequently placed in tube furnace, inert gas 30min is led to the flow velocity of 100mL/min；The nano-diamond powder
The content of surface oxygen at end is 6.63 ± 0.04%, and particle size distribution range is 3nm~10nm；
2nd, the flow velocity of inert gas is adjusted to 120mL/min, and the temperature of tube furnace is then made with the heating rate of 3 DEG C/min
Degree rises to 700 DEG C, and the 2h that anneals in the case where temperature is 700 DEG C of protection with inert gas；
3rd, cooled to room temperature under inert gas shielding then obtains the Nano diamond of carbonylation；
Inert gas described in step 1 is argon gas；
Nano diamond powder described in step 1 is prepared using explosion method.
Experiment four：This experiment orients the method for generating singlet oxygen, tool for a kind of carbon material activation persulfate that is carbonylated
Body carries out according to the following steps：
Carbonylation carbon material is added in furancarbinol aqueous solution and stirs 5min, the aqueous solution of PMS is then added in, obtains
Mixed liquor is persistently stirred liquid 1h；
The concentration of furancarbinol is 0.04mmol/L in the furancarbinol aqueous solution；
The concentration that carbon material is carbonylated in the mixed liquor is 0.1g/L；
The concentration of persulfate is 0.25mmol/L in the mixed liquor；
Carbon material in the carbonylation carbon material is sp3The carbon material Nano diamond of hydridization, and nanometer is carbonylated
The preparation method of diamond is：
First, Nano diamond powder is uniformly layered in quartz boat, and in quartz boat Nano diamond powder thickness it is small
In 1.5cm；It is subsequently placed in tube furnace, inert gas 30min is led to the flow velocity of 100mL/min；The nano-diamond powder
The content of surface oxygen at end is 6.63 ± 0.04%, and particle size distribution range is 3nm~10nm；
2nd, the flow velocity of inert gas is adjusted to 80mL/min, and the temperature of tube furnace is then made with the heating rate of 5 DEG C/min
800 DEG C are risen to, and the 4h that anneals in the case where temperature is 700 DEG C of protection with inert gas；
3rd, cooled to room temperature under inert gas shielding then obtains the Nano diamond of carbonylation；
Inert gas described in step 1 is argon gas；
Nano diamond powder described in step 1 is prepared using explosion method.
Nano diamond powder described in ND- initial representations experiment one, ND-1 represent the carbonylation described in experiment two
Nano diamond, ND-2 represent experiment three described in carbonylation Nano diamond, ND-3 represent experiment four described in
The Nano diamond of carbonylation.Four Nano diamonds are characterized, data are shown in Table 1, it can be seen that its surface carbonyl content
Increase successively, i.e. ND<ND-1<ND-2<ND-3.
Table 1
aCarbonyl relative amount derives from O1s x-ray photoelectron spectroscopy fitting results；
bCarbonyl absolute content computational methods：The carbonyl quantity on Nano diamond surface is measured using fluorescent marker method first,
On this basis again divided by its specific surface area.
Fig. 1 be furancarbinol removal rate datagram, curve- -for experiment one data, curve-zero-for experiment
Two data, curve-△-for experiment three data, curve-▽-for experiment four data, there it can be seen that four kinds
The different Nano diamond of carbonylation degree can effective activation PMS generation singlet oxygen degradation furancarbinols；In addition, carbonyl contains
The higher Nano diamond of amount is better to the degradation effect of furancarbinol.Accordingly it can be extrapolated that carbonylation Nano diamond can have
Effect activation PMS generates singlet oxygen；Meanwhile the yield of singlet oxygen and the carbonyl content on Nano diamond surface have it is stronger
Positive correlation.
In order to whether there is hydroxyl radical free radical and potentiometric titrations in confirmatory reaction system, hydroxyl is further studied certainly
By the degradation situation of the probe molecule Atrazine of base and the probe molecule terephthalic acid (TPA) of potentiometric titrations in system, tool
Body step is as follows：
Experiment five：This experiment orients the method for generating singlet oxygen, tool for a kind of carbon material activation persulfate that is carbonylated
Body carries out according to the following steps：
Carbonylation carbon material is added in Atrazine aqueous solution and stirs 5min, the aqueous solution of PMS is then added in, obtains
Mixed liquor is persistently stirred liquid 1h；
The concentration of Atrazine is 0.046mmol/L in the Atrazine aqueous solution；
The concentration that carbon material is carbonylated in the mixed liquor is 0.1g/L；
The concentration of persulfate is 0.25mmol/L in the mixed liquor；
Carbon material in the carbonylation carbon material is sp3The carbon material Nano diamond of hydridization, and nanometer is carbonylated
The preparation method of diamond is：
First, Nano diamond powder is uniformly layered in quartz boat, and in quartz boat Nano diamond powder thickness it is small
In 1.5cm；It is subsequently placed in tube furnace, inert gas 30min is led to the flow velocity of 100mL/min；The nano-diamond powder
The content of surface oxygen at end is 6.63 ± 0.04%, and particle size distribution range is 3nm~10nm；
2nd, the flow velocity of inert gas is adjusted to 80mL/min, and the temperature of tube furnace is then made with the heating rate of 5 DEG C/min
800 DEG C are risen to, and the 4h that anneals in the case where temperature is 700 DEG C of protection with inert gas；
3rd, cooled to room temperature under inert gas shielding then obtains the Nano diamond of carbonylation；
Inert gas described in step 1 is argon gas；
Nano diamond powder described in step 1 is prepared using explosion method.
Experiment six：This experiment orients the method for generating singlet oxygen, tool for a kind of carbon material activation persulfate that is carbonylated
Body carries out according to the following steps：
Carbonylation carbon material is added in aqueous terephthalic acid solution and stirs 5min, the aqueous solution of PMS is then added in, obtains
To mixed liquor, liquid 1h is persistently stirred；
The concentration of terephthalic acid (TPA) is 0.12mmol/L in the aqueous terephthalic acid solution；
The concentration that carbon material is carbonylated in the mixed liquor is 0.1g/L；
The concentration of persulfate is 0.25mmol/L in the mixed liquor；
Carbon material in the carbonylation carbon material is sp3The carbon material Nano diamond of hydridization, and nanometer is carbonylated
The preparation method of diamond is：
First, Nano diamond powder is uniformly layered in quartz boat, and in quartz boat Nano diamond powder thickness it is small
In 1.5cm；It is subsequently placed in tube furnace, inert gas 30min is led to the flow velocity of 100mL/min；The nano-diamond powder
The content of surface oxygen at end is 6.63 ± 0.04%, and particle size distribution range is 3nm~10nm；
2nd, the flow velocity of inert gas is adjusted to 80mL/min, and the temperature of tube furnace is then made with the heating rate of 5 DEG C/min
800 DEG C are risen to, and the 4h that anneals in the case where temperature is 700 DEG C of protection with inert gas；
3rd, cooled to room temperature under inert gas shielding then obtains the Nano diamond of carbonylation；
Inert gas described in step 1 is argon gas；
Nano diamond powder described in step 1 is prepared using explosion method.
Fig. 2 is the removal rate datagram of Atrazine and terephthalic acid (TPA), curve- -for terephthaldehyde in experiment six
The data of acid, curve-zero-to test the data of Atrazine in five, it is not difficult to see from it that, the probe molecule of the two can not
It is effectively removed in the system, there is no hydroxyl radical free radical and sulfate radical are free in this result side light reaction system
Base.Summary result understands, carbonylation Nano diamond can effectively catalytic activation PMS generation singlet oxygens, while in system
Hydroxyl radical free radical and potentiometric titrations may not contained.
Further to verify above-mentioned inference, active oxygen in reaction system is had studied using electron spin resonance spectrometer in situ
The Conduce Disciplinarian of species, concrete mode are as follows：
Experiment seven：This experiment orients the method for generating singlet oxygen, tool for a kind of carbon material activation persulfate that is carbonylated
Body carries out according to the following steps：
Carbonylation carbon material is added in DMPO aqueous solutions and stirs 5min, the aqueous solution of PMS is then added in, is mixed
Liquid is persistently stirred liquid；
The concentration of DMPO is 3.75mmol/L in the DMPO aqueous solutions；
The concentration that carbon material is carbonylated in the mixed liquor is 0.1g/L；
The concentration of persulfate is 0.25mmol/L in the mixed liquor；
Carbon material in the carbonylation carbon material is sp3The carbon material Nano diamond of hydridization, and nanometer is carbonylated
The preparation method of diamond is：
First, Nano diamond powder is uniformly layered in quartz boat, and in quartz boat Nano diamond powder thickness it is small
In 1.5cm；It is subsequently placed in tube furnace, inert gas 30min is led to the flow velocity of 100mL/min；The nano-diamond powder
The content of surface oxygen at end is 6.63 ± 0.04%, and particle size distribution range is 3nm~10nm；
2nd, the flow velocity of inert gas is adjusted to 80mL/min, and the temperature of tube furnace is then made with the heating rate of 5 DEG C/min
800 DEG C are risen to, and the 4h that anneals in the case where temperature is 700 DEG C of protection with inert gas；
3rd, cooled to room temperature under inert gas shielding then obtains the Nano diamond of carbonylation；
Inert gas described in step 1 is argon gas；
Nano diamond powder described in step 1 is prepared using explosion method.
Fig. 3 is spectral profile figure, and curve a is the sample that liquid 20min is persistently stirred in experiment seven, and curve b is experiment
The sample of liquid 14min is persistently stirred in seven, curve c is the sample that liquid 8min is persistently stirred in experiment seven, and curve d is
The sample of liquid 3min is persistently stirred in experiment seven, curve e is the sample that liquid 1min is persistently stirred in experiment seven, from figure
3 understand, when using DMPO as capturing agent, significant change does not occur in the wave spectrum collected, does not also find hydroxyl free
The characteristic peak of base and potentiometric titrations.The result shows the reaction system, really there is no above-mentioned free radicals.
In addition, having monitored the generation situation of hydroxyl radical free radical in reaction system on-line using fluorescence in situ spectrometer, utilize
Terephthalic acid (TPA) and hydroxyterephthalic acid of the hydroxyl radical reaction generation with fluorescent characteristic, specially test eight：By 5mg
Carbonylation carbon material, the sodium hydroxide of 0.2mmol, 0.5mmol terephthalic acid (TPA)s are added in the deionized water of 50mL, then
PMS is added in, the concentration of PMS is 0.25mmol/L in system, after reacting a period of time, 0.22 μm of membrane filtration of sample, general
Sample after filtering is 431nm in optical maser wavelength, and two-dimensional scan, it is 315nm to obtain in most strong spectral intensity.According to fluorescence spectrum
Variation of the instrument to fluorescence intensity, and then the yield of indirectly testing hydroxyl radical free radical.
Fig. 4 is fluorescent spectrum curve figure, and each curve reacts the sample of different time in 0~15min to test in eight, from
In understand, with the extension in reaction time, significantly enhancing does not occur in fluorescence signal, this illustrates not generate hydroxyl in system
Free radical.
Experiment nine：Carbonylation carbon material is added in TMP aqueous solutions and stirs 5min, the aqueous solution of PMS is then added in, obtains
To mixed liquor, liquid 5min is persistently stirred；
The concentration of TMP is 1mmol/L in the TMP aqueous solutions；
The concentration that carbon material is carbonylated in the mixed liquor is 0.1g/L；
The concentration of persulfate is 0.25mmol/L in the mixed liquor；
Carbon material in the carbonylation carbon material is sp3The carbon material Nano diamond of hydridization, and nanometer is carbonylated
The preparation method of diamond is：
First, Nano diamond powder is uniformly layered in quartz boat, and in quartz boat Nano diamond powder thickness it is small
In 1.5cm；It is subsequently placed in tube furnace, inert gas 30min is led to the flow velocity of 100mL/min；The nano-diamond powder
The content of surface oxygen at end is 6.63 ± 0.04%, and particle size distribution range is 3nm~10nm；
2nd, the flow velocity of inert gas is adjusted to 80mL/min, and the temperature of tube furnace is then made with the heating rate of 5 DEG C/min
800 DEG C are risen to, and the 4h that anneals in the case where temperature is 700 DEG C of protection with inert gas；
3rd, cooled to room temperature under inert gas shielding then obtains the Nano diamond of carbonylation；
Inert gas described in step 1 is argon gas；
Nano diamond powder described in step 1 is prepared using explosion method.
Experiment ten：The aqueous solution of PMS is added in TMP aqueous solutions and stirs 5min, is then added in, obtains mixed liquor, is held
It is continuous to be stirred liquid 5min；
The concentration of TMP is 1mmol/L in the TMP aqueous solutions；
The concentration of persulfate is 0.25mmol/L in the mixed liquor.
Test 11：Carbonylation carbon material is added in TMP aqueous solutions and stirs 5min, obtains mixed liquor；
The concentration of TMP is 1mmol/L in the TMP aqueous solutions；
The concentration that carbon material is carbonylated in the mixed liquor is 0.1g/L；
Carbon material in the carbonylation carbon material is sp3The carbon material Nano diamond of hydridization, and nanometer is carbonylated
The preparation method of diamond is：
First, Nano diamond powder is uniformly layered in quartz boat, and in quartz boat Nano diamond powder thickness it is small
In 1.5cm；It is subsequently placed in tube furnace, inert gas 30min is led to the flow velocity of 100mL/min；The nano-diamond powder
The content of surface oxygen at end is 6.63 ± 0.04%, and particle size distribution range is 3nm~10nm；
2nd, the flow velocity of inert gas is adjusted to 80mL/min, and the temperature of tube furnace is then made with the heating rate of 5 DEG C/min
800 DEG C are risen to, and the 4h that anneals in the case where temperature is 700 DEG C of protection with inert gas；
3rd, cooled to room temperature under inert gas shielding then obtains the Nano diamond of carbonylation；
Inert gas described in step 1 is argon gas；
Nano diamond powder described in step 1 is prepared using explosion method.
Using the wave spectrum of nine to 11 product of electron spin resonance spectrometer testing experiment in situ, Fig. 5 is spectral profile figure,
Curve a is the sample of experiment nine, and curve b is the sample of experiment ten, and curve c is the sample of experiment 11, it can be seen from the figure that
When using TMP as capturing agent, there is apparent triplet.The peak is singlet oxygen and the characteristic peak of TMP reactions.Accordingly
It understands, substantial amounts of singlet oxygen is generated in system.
Summary result understands that carbonylation Nano diamond can activate PMS orientations and generate singlet oxygen, and nothing in system
Method detects other active materials such as hydroxyl radical free radical.
Test 12：A kind of method that carbon material activation persulfate orientation is carbonylated and generates singlet oxygen, is specifically pressed
What following steps carried out：
Carbonylation carbon material is added in parachlorophenol sewage and stirs 5min, then adds in the aqueous solution of persulfate,
Mixed liquor is obtained, is persistently stirred liquid 1h, you can generates singlet oxygen and sewage is handled；
The concentration that carbon material is carbonylated in the mixed liquor is 0.1g/L；
The concentration of persulfate is 0.25mmol/L in the mixed liquor；
Carbon material in the carbonylation carbon material is sp3The carbon material Nano diamond of hydridization, and nanometer is carbonylated
The preparation method of diamond is：
First, Nano diamond powder is uniformly layered in quartz boat, and in quartz boat Nano diamond powder thickness it is small
In 1.5cm；It is subsequently placed in tube furnace, inert gas 30min is led to the flow velocity of 100mL/min；The nano-diamond powder
The content of surface oxygen at end is 6.63 ± 0.04%, and particle size distribution range is 3nm~10nm；
2nd, the flow velocity of inert gas is adjusted to 80mL/min, and the temperature of tube furnace is then made with the heating rate of 5 DEG C/min
800 DEG C are risen to, and the 4h that anneals in the case where temperature is 700 DEG C of protection with inert gas；
3rd, cooled to room temperature under inert gas shielding then obtains the Nano diamond of carbonylation.
Inert gas described in step 1 is argon gas；
Nano diamond powder described in step 1 is prepared using explosion method.
Test 13：By CoCl2It is added in parachlorophenol sewage and stirs 5min, then add in the water-soluble of persulfate
Liquid, obtains mixed liquor, is persistently stirred liquid 1h；
CoCl in the mixed liquor2Concentration be 8.33g/L；
The concentration of persulfate is 0.25mmol/L in the mixed liquor.
Test 14：By FeSO4It is added in parachlorophenol sewage and stirs 5min, then add in the water-soluble of persulfate
Liquid, obtains mixed liquor, is persistently stirred liquid 1h；
FeSO in the mixed liquor4Concentration be 0.1g/L；
The concentration of persulfate is 0.25mmol/L in the mixed liquor.
Fig. 6 be parachlorophenol removal rate datagram, curve- -for experiment 12 data, curve-zero-for examination
Test 14 data, curve-△-for the data of experiment 13, there it can be seen that constructed based on patent of the present invention
Singlet oxygen system be up to 87% to the removal rate of parachlorophenol, and based on cobalt ions or ferrous ion institute's construction it is equal
Phase oxidation system is only 10% and 4% to its removal rate, well below the oxidation system constructed by patent of the present invention.Thus it is not difficult
Find out, the more traditional oxidation system of patent of the present invention has apparent advantage, and market prospects can the phase.
Claims (7)
- A kind of 1. method that carbon material activation persulfate orientation is carbonylated and generates singlet oxygen, it is characterised in that carbonylation carbon materials The method that material activation persulfate orientation generates singlet oxygen carries out according to the following steps：Carbonylation carbon material is added to stirring 5min~10min in pending sewage, then adds in the water-soluble of persulfate Liquid obtains mixed liquor, is persistently stirred liquid, you can generates singlet oxygen and sewage is handled；Carbon material in the carbonylation carbon material is amorphous carbon material, sp2The carbon material and sp of hydridization3The carbon materials of hydridization The carbon material of one or both of material hybrid form mixing composition；The concentration that carbon material is carbonylated in the mixed liquor is 0.01g/L~5g/L；The concentration of persulfate is 0.1mmol/L~10mmol/L in the mixed liquor.
- 2. a kind of method that carbon material activation persulfate orientation is carbonylated and generates singlet oxygen according to claim 1, It is characterized in that the amorphous carbon material is activated carbon or mesoporous carbon.
- 3. a kind of method that carbon material activation persulfate orientation is carbonylated and generates singlet oxygen according to claim 1, It is characterized in that the sp2The carbon material of hydridization is carbon nanotubes, graphene or fullerene.
- 4. a kind of method that carbon material activation persulfate orientation is carbonylated and generates singlet oxygen according to claim 1, It is characterized in that the carbon material of two kinds of hybrid forms mixing composition is onion carbon.
- 5. a kind of method that carbon material activation persulfate orientation is carbonylated and generates singlet oxygen according to claim 1, It is characterized in that the persulfate is peroxy-monosulfate, peroxydisulfate or persulfate complex salt.
- 6. a kind of method that carbon material activation persulfate orientation is carbonylated and generates singlet oxygen according to claim 6, It is characterized in that the peroxy-monosulfate is potassium hydrogen peroxymonosulfate or hydrogen peroxymonosulfate sodium；The peroxydisulfate is over cure Sour potassium or sodium peroxydisulfate；The persulfate complex salt is single potassium hydrogen persulfate composite salts.
- 7. a kind of method that carbon material activation persulfate orientation is carbonylated and generates singlet oxygen according to claim 1, It is characterized in that the carbon material in the carbonylation carbon material is sp3The carbon material of hydridization, specially Nano diamond, and carbonyl The preparation method of base carbon material is：First, Nano diamond powder is uniformly layered in quartz boat, and the thickness of Nano diamond powder is less than in quartz boat 1.5cm；It is subsequently placed in tube furnace, inert gas 30min is led to the flow velocity of 100mL/min；The Nano diamond powder Content of surface oxygen for 2wt%~10wt%, particle size distribution range is 3nm~10nm；2nd, the flow velocity of inert gas is adjusted to 50mL/min~180mL/min, then with the heating of 3 DEG C/min~10 DEG C/min Rate makes the temperature of tube furnace rise to 450 DEG C~950 DEG C, and in the case where temperature is 450 DEG C~950 DEG C protection with inert gas Anneal 0.5h~4h；3rd, cooled to room temperature under inert gas shielding then obtains the Nano diamond of carbonylation；Inert gas described in step 1 is the mixed gas of one or more of nitrogen, argon gas and helium；In step 1 The Nano diamond powder is prepared using explosion method.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711399032.3A CN108083416B (en) | 2017-12-21 | 2017-12-21 | Method for directionally generating singlet oxygen by activating persulfate through carbon carbonylation material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711399032.3A CN108083416B (en) | 2017-12-21 | 2017-12-21 | Method for directionally generating singlet oxygen by activating persulfate through carbon carbonylation material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108083416A true CN108083416A (en) | 2018-05-29 |
| CN108083416B CN108083416B (en) | 2020-12-01 |
Family
ID=62178381
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711399032.3A Active CN108083416B (en) | 2017-12-21 | 2017-12-21 | Method for directionally generating singlet oxygen by activating persulfate through carbon carbonylation material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108083416B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109174074A (en) * | 2018-10-11 | 2019-01-11 | 南昌航空大学 | A kind of preparation method and applications with defect state carbon nanotube |
| CN110550688A (en) * | 2019-08-03 | 2019-12-10 | 浙江大学 | Method for removing phenols in water by activating persulfate through CO 2 activated charcoal |
| CN111847626A (en) * | 2020-07-27 | 2020-10-30 | 南昌航空大学 | Device for pretreating complex heavy metal in electroplating cleaning wastewater by catalytic oxidation method and using method thereof |
| CN114891060A (en) * | 2022-07-13 | 2022-08-12 | 深圳湾实验室 | Light activation dependent proximity labeling method for protein and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104743651A (en) * | 2013-12-27 | 2015-07-01 | 湖南大学 | Free radical-promoted catalysis wet-type oxydative degradation method for humic acid pollutant |
| CN105668758A (en) * | 2016-03-07 | 2016-06-15 | 中国科学院山西煤炭化学研究所 | Method for degrading organic wastewater by activating persulfates with in-situ sulfur-doped activated carbon |
| KR20170029746A (en) * | 2015-09-08 | 2017-03-16 | 주식회사 오이코스 | Treatment method and apparatus of water pollutants by surface modification nanodiamonds |
-
2017
- 2017-12-21 CN CN201711399032.3A patent/CN108083416B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104743651A (en) * | 2013-12-27 | 2015-07-01 | 湖南大学 | Free radical-promoted catalysis wet-type oxydative degradation method for humic acid pollutant |
| KR20170029746A (en) * | 2015-09-08 | 2017-03-16 | 주식회사 오이코스 | Treatment method and apparatus of water pollutants by surface modification nanodiamonds |
| CN105668758A (en) * | 2016-03-07 | 2016-06-15 | 中国科学院山西煤炭化学研究所 | Method for degrading organic wastewater by activating persulfates with in-situ sulfur-doped activated carbon |
Non-Patent Citations (1)
| Title |
|---|
| XIAOGUANG DUAN ETAL.: ""Surface-tailored nanodiamonds as excellent metal-free catalysts for organic oxidation"", 《CARBON》 * |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109174074A (en) * | 2018-10-11 | 2019-01-11 | 南昌航空大学 | A kind of preparation method and applications with defect state carbon nanotube |
| CN109174074B (en) * | 2018-10-11 | 2021-06-08 | 南昌航空大学 | Application of carbon nano tube with defect state |
| CN110550688A (en) * | 2019-08-03 | 2019-12-10 | 浙江大学 | Method for removing phenols in water by activating persulfate through CO 2 activated charcoal |
| CN111847626A (en) * | 2020-07-27 | 2020-10-30 | 南昌航空大学 | Device for pretreating complex heavy metal in electroplating cleaning wastewater by catalytic oxidation method and using method thereof |
| CN114891060A (en) * | 2022-07-13 | 2022-08-12 | 深圳湾实验室 | Light activation dependent proximity labeling method for protein and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108083416B (en) | 2020-12-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Jin et al. | Peroxymonosulfate activation by Fe3O4-MnO2/CNT nanohybrid electroactive filter towards ultrafast micropollutants decontamination: Performance and mechanism | |
| CN108083416A (en) | A kind of method that carbon material activation persulfate orientation is carbonylated and generates singlet oxygen | |
| Liu et al. | B-doped graphitic porous biochar with enhanced surface affinity and electron transfer for efficient peroxydisulfate activation | |
| Wang et al. | Electrocatalytic hydrogenation of N2 to NH3 by MnO: experimental and theoretical investigations | |
| Calabro et al. | Controlled nitrogen doping of graphene quantum dots through laser ablation in aqueous solutions for photoluminescence and electrocatalytic applications | |
| CN102755885B (en) | Hydrothermal preparation method of TiO2-rGO composite photochemical catalyst | |
| Khare et al. | Functionalization of carbon nanotubes via nitrogen glow discharge | |
| Powell et al. | Optical excitation of carbon nanotubes drives localized diazonium reactions | |
| Zaoralova et al. | Tunable synthesis of nitrogen doped graphene from fluorographene under mild conditions | |
| JP4944923B2 (en) | Method and apparatus for continuous surface treatment of carbon nanotubes | |
| Song et al. | Enhanced electrochemical N2 reduction to NH3 on reduced graphene oxide by tannic acid modification | |
| CN105948021B (en) | The method that nitrogen-doped graphene quantum dot is prepared using high-energy electron beam irradiation method | |
| CN106348281A (en) | Method for preparing bifluorescence graphene quantum dots hydrothermally | |
| Zhang et al. | Twin-brush ZnO mesocrystal for the piezo-activation of peroxymonosulfate to remove ibuprofen in water: performance and mechanism | |
| Barbour et al. | Sonochemistry and sonoluminescence in aqueous AuCl4-solutions in the presence of surface-active solutes | |
| CN106573222A (en) | Method for manufacturing reaction product in which phase interface reaction is employed, phase interface reactor, and method for manufacturing secondary reaction product | |
| CN110327980A (en) | A kind of application of metal-doped carbon quantum dot | |
| Dyachkova et al. | Functionalization of carbon nanotubes: methods, mechanisms and technological realization | |
| Liu et al. | Microwave (MW)-assisted design of cobalt anchored 2D graphene-like carbon nanosheets (Co@ GCNs) as peroxymonosulfate activator for tetracycline degradation and insight into the catalytic mechanism | |
| Ravishankar et al. | Rapid, solvent-free synthesis of amorphous, photoluminescent, carbon nanodots from imidazole and maleic anhydride solids | |
| Gao et al. | Doping phosphorus into Co3O4: A new promising pathway to boost the catalytic activity for peroxymonosulfate activation | |
| Xue et al. | Enhanced degradation of 4-Cholophenol by activation of peroxymonosulfate with Fe-MOF@ Mn2O3: Performance and mechanism | |
| Nadolska et al. | Synthesis of phosphonated carbon nanotubes: new insight into carbon nanotubes functionalization | |
| Yao et al. | Co nanoparticles encapsulated in nitrogen-doped nanocarbon derived from cobalt-modified covalent organic framework as peroxymonosulfate activator for sulfamerazine degradation | |
| Cen et al. | Oxidation-modulated CQDs derived from covalent organic frameworks as enhanced fluorescence sensors for the detection of chromium (VI) and ascorbic acid |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |