CN107008326B - A kind of preparation method of the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material - Google Patents
A kind of preparation method of the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material Download PDFInfo
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- CN107008326B CN107008326B CN201710350155.1A CN201710350155A CN107008326B CN 107008326 B CN107008326 B CN 107008326B CN 201710350155 A CN201710350155 A CN 201710350155A CN 107008326 B CN107008326 B CN 107008326B
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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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/745—Iron
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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
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
- C25C5/00—Electrolytic production, recovery or refining of metal powders or porous metal masses
- C25C5/02—Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
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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
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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
A kind of preparation method of the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material, it belongs to water treatment field, and in particular to a kind of preparation method of efficient out-phase fenton catalyst.The purpose of invention is complicated, the poor activity that solve the preparation of existing different-phase catalyst, Fe Ion release and generate iron cement etc. and easily cause secondary pollution, and repeatedly cycle performance degradation the problem of.Method: one, quantum dot precursor solution is prepared；Two, suspension is prepared；Three, hydro-thermal reaction；Four, it filters, cleans, vacuum drying obtains the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material.The carbon quantum dot prepared by the present invention load efficient out-phase class fenton catalyst of iron-based material can degrade in 10min 99% or more phenol.The present invention can get a kind of carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material.
Description
Technical field
The invention belongs to water treatment fields, and in particular to a kind of preparation method of efficient out-phase fenton catalyst.
Background technique
Chemical industry is made that great contribution as the pillars of the national economy, for rapid economic development, but consequently also brings
More and more pollution problems, such as water pollution, soil pollution and atmosphere pollution.In soil pollution and water pollution, with benzene
Phenol is the arene pollutant of representative, seriously endangers human body and ecological environment.Advanced catalytic oxidation (Fenton oxidation and class
Fenton oxidation) it reacts at normal temperatures and pressures, it is easy to operate, oxidability is strong, in soil remediation and treatment of Organic Wastewater application
It has a extensive future.And in current Fenton oxidation technology, it is commonly present Fe Ion release and generates iron cement etc. and easily cause secondary pollution, and
Multiple cycle performance degradation.Therefore in the exploitation of efficient different-phase catalyst, cheap and easy to get, large specific surface area, activity are prepared
The class fenton catalyst material that high and pH has a wide range of application has important application value in water treatment field.
Summary of the invention
The purpose of invention is complicated, the poor activity that solve the preparation of existing different-phase catalyst, Fe Ion release and generate iron cement
Etc. easily causing secondary pollution, and repeatedly cycle performance degradation the problem of, and provide a kind of carbon quantum dot load iron-based material
The preparation method of efficient out-phase class fenton catalyst.
A kind of preparation method of the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material, specifically following steps
It completes:
One, quantum dot precursor solution is prepared:
Carbon source is dissolved into deionized water, small organic molecule solvent is added, is uniformly mixed, obtains quantum dot presoma
Solution；
Carbon source described in step 1 is glucose, sucrose, fructose, soluble starch, ascorbic acid, citric acid and second two
One of amine or in which several mixtures；
The quality of carbon source described in step 1 and the volume ratio of deionized water are (0g~0.5g): 1mL；
Deionized water described in step 1 and the volume ratio of small organic molecule solvent are 1:(9~99)；
Two, iron or dendritic iron-copper powder are added in quantum dot precursor solution, re-ultrasonic dispersion 0.5min~
2min obtains suspension；
The volume ratio of the quality and quantum dot precursor solution of iron described in step 2 or dendritic iron-copper powder is
(1g~30g): 1L；
Dendritic iron-copper powder described in step 2 is specifically realized by the following steps:
1., electrolyte is placed in electrolytic cell, using fine copper electrode as cathode, using ring-shaped graphite electrode as anode, make
The cathode of DC power supply is connected with cathode with conducting wire, conducting wire is reused and the anode of power supply is connected with anode, setting is just
Beginning current density is 1.4A/dm2~1.6A/dm2, DC power supply is connected, is 1.4A/dm in initial current density2~1.6A/dm2
Lower reaction 10s~15s, then current density is increased to 2 times of initial current density, then under 2 times of initial current density instead
10s~15s is answered, stops reaction, dendritic copper alloy powder is obtained on cathode；
Step 2 1. described in electrolyte mixed by ferrous sulfate, copper sulphate, dehydrated alcohol and distilled water or by
Ferrous sulfate, dehydrated alcohol and distilled water mix；
2., first using deionized water to dendritic copper alloy powder clean 3 times~5 times, reuse washes of absolute alcohol 3 times
~5 times, then dried at being 60 DEG C in temperature, obtain dendritic iron-copper powder；
Three, suspension is transferred in polytetrafluoroethyllining lining, then polytetrafluoroethyllining lining is put into stainless steel cauldron
In, then stainless steel cauldron is put into the baking oven that temperature is 140 DEG C~220 DEG C and reacts for 24 hours~28h, it obtains producing containing reaction
The solution of object；
Four, the solution containing reaction product is filtered, collects powder, cleaned using powder of the deionized water to collection
It 3 times~5 times, reuses dehydrated alcohol and the powder of collection is cleaned 3 times~5 times, then vacuum is dry at being 50 DEG C~70 DEG C in temperature
Dry 4h~12h obtains the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material.
Advantages of the present invention:
One, the method for the present invention preparation method is simple, and raw material is cheap and easy to get, in the prior art use graphene, carbon nanometer
The method that the loads such as pipe prepare catalyst is compared, and the present invention directlys adopt glucose cheap and easy to get, sucrose, and ascorbic acid etc. is made
For carbon source, cost is greatly reduced；Solvent-thermal method is used in preparation method of the present invention, selected solvent is also small molecule solvent,
It is cheap and easy to get；
Two, present invention experiment is controllable, such as the time, temperature, carbon source kind, quantity, can have by adjusting suitable parameter
The acquisitions such as machine small molecule solvent more preferably catalyst；
Three, the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material prepared by the present invention is not easy to reunite, catalysis
Active high, relative to other nm-class catalysts, scantling prepared by the present invention in the micron-scale, disperses in actual use
Property is good, not easy to reunite；In addition, since this material has multilevel structure, trunk size in the micron-scale, and its secondary structure is being received
Rice structure, also have the better quantum dot of size, therefore impart its high catalytic activity the characteristics of；
Four, the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material prepared by the present invention can be in 10min
The phenol of 99% or more degradation, degradation property can be improved 30%~200% compared with the catalyst of prior art preparation；
Five, the efficient out-phase class fenton catalyst of carbon quantum dot load iron-based material prepared by the present invention is recycled 2 times, drop
The ability for solving phenol is original 90%, and the catalyst prepared in the prior art, is recycled 2 times, the ability of degradation of phenol
It is original 19%；
Six, the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material prepared by the present invention is in degradation of phenol
After 30min, iron dissolution is less than 1.2mg/L, and compared with existing catalyst, iron the amount of dissolution reduces 20%~60%.
The present invention can get a kind of carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material.
Detailed description of the invention
Fig. 1 is the ultraviolet absorpting spectrum of the solution containing reaction product, and 1 obtains for step 3 in embodiment one in Fig. 1
The ultraviolet absorption curve of solution containing reaction product, 2 solution containing reaction product obtained for step 3 in embodiment two
Ultraviolet absorption curve, the ultraviolet absorption curve of 3 solution containing reaction product obtained for step 3 in embodiment three；
Fig. 2 is the XRD of the efficient out-phase class fenton catalyst of carbon quantum dot load iron/ferroso-ferric oxide prepared by embodiment one
Map；
Fig. 3 is that carbon quantum dot prepared by embodiment two loads the efficient out-phase class Fenton catalysis of dendritic iron powder/ferroso-ferric oxide
The XRD spectrum of agent；
Fig. 4 is the efficient out-phase class fenton catalyst of carbon quantum dot load iron/copper/ferroferric oxide prepared by embodiment three
XRD spectrum；
Fig. 5 is the SEM of the efficient out-phase class fenton catalyst of carbon quantum dot load iron/ferroso-ferric oxide prepared by embodiment one
Figure；
Fig. 6 is that carbon quantum dot prepared by embodiment two loads the efficient out-phase class Fenton catalysis of dendritic iron powder/ferroso-ferric oxide
The SEM of agent schemes；
Fig. 7 is the efficient out-phase class fenton catalyst of carbon quantum dot load iron/copper/ferroferric oxide prepared by embodiment three
SEM figure；
Fig. 8 is the curve graph of degradation of phenol, in Fig. 81 be iron powder degradation of phenol curve, 2 carbon prepared for embodiment one
The curve of the efficient out-phase class fenton catalyst degradation of phenol of quantum dot load iron/ferroso-ferric oxide, 3 carbon prepared for embodiment two
Quantum dot loads the curve of the efficient out-phase class fenton catalyst degradation of phenol of dendritic iron powder/ferroso-ferric oxide, and 4 make for embodiment three
The curve of the efficient out-phase class fenton catalyst degradation of phenol of standby carbon quantum dot load iron/copper/ferroferric oxide；
Fig. 9 is the curve graph of degradation of phenol, in Fig. 91 be iron powder degradation of phenol curve, 2 for second of circulation iron powders
The curve of degradation of phenol, the 3 efficient out-phase class Fentons of carbon quantum dot load iron/copper/ferroferric oxide prepared for embodiment three are urged
The curve of agent degradation of phenol, the 4 carbon quantum dot load iron/copper/ferroferric oxides prepared for the embodiment three of second of circulation
The curve of efficient out-phase class fenton catalyst degradation of phenol；
Iron when Figure 10 is different catalysts degradation of phenol 30min dissolves out situation map, and 1 is iron powder degradation of phenol in Figure 10
Iron when 30min dissolves out histogram, the 2 efficient out-phase class sweet smell of carbon quantum dot load iron/ferroso-ferric oxide prepared for embodiment one
Iron when catalyst degradation phenol 30min dissolves out histogram, 3 for carbon quantum dot prepared by embodiment two load dendritic iron powder/
Iron when the efficient out-phase class fenton catalyst degradation of phenol 30min of ferroso-ferric oxide dissolves out histogram, and 4 prepare for embodiment three
Iron when the efficient out-phase class fenton catalyst degradation of phenol 30min of carbon quantum dot load iron/copper/ferroferric oxide dissolves out column
Figure；
Figure 11 is the curve graph of degradation of phenol, 1 dendritic iron powder/tetra- of carbon quantum dot load prepared for embodiment two in Figure 11
The curve of the efficient out-phase class fenton catalyst degradation of phenol of Fe 3 O, 2 for embodiment three prepare carbon quantum dot load iron/
The curve of the efficient out-phase class fenton catalyst degradation of phenol of copper/ferroferric oxide, 3 load for the carbon quantum dot of example IV preparation
The curve of the dendritic efficient out-phase class fenton catalyst degradation of phenol of iron powder/ferroso-ferric oxide, 4 carbon quantums prepared for embodiment five
The curve of the point efficient out-phase class fenton catalyst degradation of phenol of load iron/copper/ferroferric oxide.
Specific embodiment
Specific embodiment 1: present embodiment is a kind of efficient out-phase class Fenton catalysis of carbon quantum dot load iron-based material
What the preparation method of agent, specifically following steps were completed:
One, quantum dot precursor solution is prepared:
Carbon source is dissolved into deionized water, small organic molecule solvent is added, is uniformly mixed, obtains quantum dot presoma
Solution；
Carbon source described in step 1 is glucose, sucrose, fructose, soluble starch, ascorbic acid, citric acid and second two
One of amine or in which several mixtures；
The quality of carbon source described in step 1 and the volume ratio of deionized water are (0g~0.5g): 1mL；
Deionized water described in step 1 and the volume ratio of small organic molecule solvent are 1:(9~99)；
Two, iron or dendritic iron-copper powder are added in quantum dot precursor solution, re-ultrasonic dispersion 0.5min~
2min obtains suspension；
The volume ratio of the quality and quantum dot precursor solution of iron described in step 2 or dendritic iron-copper powder is
(1g~30g): 1L；
Dendritic iron-copper powder described in step 2 is specifically realized by the following steps:
1., electrolyte is placed in electrolytic cell, using fine copper electrode as cathode, using ring-shaped graphite electrode as anode, make
The cathode of DC power supply is connected with cathode with conducting wire, conducting wire is reused and the anode of power supply is connected with anode, setting is just
Beginning current density is 1.4A/dm2~1.6A/dm2, DC power supply is connected, is 1.4A/dm in initial current density2~1.6A/dm2
Lower reaction 10s~15s, then current density is increased to 2 times of initial current density, then under 2 times of initial current density instead
10s~15s is answered, stops reaction, dendritic copper alloy powder is obtained on cathode；
Step 2 1. described in electrolyte mixed by ferrous sulfate, copper sulphate, dehydrated alcohol and distilled water or by
Ferrous sulfate, dehydrated alcohol and distilled water mix；
2., first using deionized water to dendritic copper alloy powder clean 3 times~5 times, reuse washes of absolute alcohol 3 times
~5 times, then dried at being 60 DEG C in temperature, obtain dendritic iron-copper powder；
Three, suspension is transferred in polytetrafluoroethyllining lining, then polytetrafluoroethyllining lining is put into stainless steel cauldron
In, then stainless steel cauldron is put into the baking oven that temperature is 140 DEG C~220 DEG C and reacts for 24 hours~28h, it obtains producing containing reaction
The solution of object；
Four, the solution containing reaction product is filtered, collects powder, cleaned using powder of the deionized water to collection
It 3 times~5 times, reuses dehydrated alcohol and the powder of collection is cleaned 3 times~5 times, then vacuum is dry at being 50 DEG C~70 DEG C in temperature
Dry 4h~12h obtains the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material.
The advantages of present embodiment:
One, present embodiment method preparation method is simple, and raw material is cheap and easy to get, in the prior art use graphene, carbon
The method that the loads such as nanotube prepare catalyst is compared, and present embodiment directlys adopt glucose cheap and easy to get, and sucrose is anti-bad
Hematic acid etc. is used as carbon source, greatly reduces cost；Solvent-thermal method is used in present embodiment preparation method, selected solvent is also
Small molecule solvent, it is cheap and easy to get；
Two, present embodiment experiment is controllable, can be by adjusting suitable parameter, such as time, temperature, carbon source kind, number
The acquisitions such as amount, small organic molecule solvent more preferably catalyst；
Three, the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material of present embodiment preparation is not easy to reunite,
Catalytic activity is high, and relative to other nm-class catalysts, the scantling of present embodiment preparation in the micron-scale, actually makes
It is not easy to reunite with middle good dispersion；In addition, since this material has multilevel structure, trunk size in the micron-scale, and it is secondary
Structure in nanostructure, also have the better quantum dot of size, therefore impart its high catalytic activity the characteristics of；
Four, the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material of present embodiment preparation can be
The phenol of 99% or more degradation in 10min, degradation property compared with the catalyst of prior art preparation, can be improved 30%~
200%；
Five, the efficient out-phase class fenton catalyst of carbon quantum dot load iron-based material of present embodiment preparation is recycled 2
Secondary, the ability of degradation of phenol is original 90%, and the catalyst prepared in the prior art, is recycled 2 times, degradation of phenol
Ability is original 19%；
Six, the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material of present embodiment preparation is in degradation of phenol
After 30min, iron dissolution is less than 1.2mg/L, and compared with existing catalyst, iron the amount of dissolution reduces 20%~60%.
Present embodiment can get a kind of carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material.
Specific embodiment 2: the differences between this implementation mode and the specific implementation mode are that: it is described in step 1 organic
Small molecule solvent is one of dehydrated alcohol, ethylene glycol, propyl alcohol and propylene glycol or in which several mixed liquors.Other steps with
Specific embodiment one is identical.
Specific embodiment 3: one of present embodiment and specific embodiment one or two difference are: step 2 1. in
Fe in the electrolyte2+With Cu2+Total ion concentration be 0.5mol/L~1.0mol/L, and Cu2+Account for Fe2+With Cu2+Always from
The 0%~10% of son.Other steps are the same as one or two specific embodiments.
Specific embodiment 4: one of present embodiment and specific embodiment one to three difference are: step 2 1. in
The concentration of dehydrated alcohol is 20mL/L~40mL/L in the electrolyte.Other steps and specific embodiment one to three-phase
Together.
Specific embodiment 5: one of present embodiment and specific embodiment one to four difference are: institute in step 2
The power for the ultrasonic disperse stated is 10W~20W.Other steps are identical as specific embodiment one to four.
Specific embodiment 6: one of present embodiment and specific embodiment one to five difference are: institute in step 1
The quality for the carbon source stated and the volume ratio of deionized water are (0.1g~0.5g): 1mL.Other steps and specific embodiment one to
Five is identical.
Specific embodiment 7: one of present embodiment and specific embodiment one to six difference are: institute in step 1
The volume ratio of the deionized water and small organic molecule solvent stated is 1:(11~29).Other steps and specific embodiment one to six
It is identical.
Specific embodiment 8: one of present embodiment and specific embodiment one to seven difference are: institute in step 1
The volume ratio of the deionized water and small organic molecule solvent stated is 1:(29~59).Other steps and specific embodiment one to seven
It is identical.
Specific embodiment 9: one of present embodiment and specific embodiment one to eight difference are: institute in step 2
The quality of the iron or dendritic iron-copper powder stated and the volume ratio of quantum dot precursor solution are (1g~10g): 1L.Other steps
Suddenly identical as specific embodiment one to eight.
Specific embodiment 10: one of present embodiment and specific embodiment one to nine difference are: will in step 3
Suspension is transferred in polytetrafluoroethyllining lining, then polytetrafluoroethyllining lining is put into stainless steel cauldron, then by stainless steel
Reaction kettle, which is put into the baking oven that temperature is 140 DEG C~160 DEG C, reacts for 24 hours~28h, obtains the solution containing reaction product.Other
Step is identical as specific embodiment one to nine.
Specific embodiment 11: one of present embodiment and specific embodiment one to ten difference are: step 2 is 1.
Described in electrolyte in Fe2+With Cu2+Total ion concentration be 0.5mol/L~1.0mol/L, and Cu2+Account for Fe2+With Cu2+Always
The 2%~4% of ion.Other steps are identical as specific embodiment one to ten.
Specific embodiment 12: present embodiment is with one to one of 11 difference of specific embodiment: step 2
Fe in electrolyte described in 1.2+With Cu2+Total ion concentration be 0.5mol/L~1.0mol/L, and Cu2+Account for Fe2+With Cu2+
The 4%~6% of total ion.Other steps are identical as specific embodiment one to 11.
Specific embodiment 13: present embodiment is with one to one of 12 difference of specific embodiment: step 2
Fe in electrolyte described in 1.2+With Cu2+Total ion concentration be 0.5mol/L~1.0mol/L, and Cu2+Account for Fe2+With Cu2+
The 6%~8% of total ion.Other steps are identical as specific embodiment one to 12.
Beneficial effects of the present invention are verified using following embodiment:
Embodiment one: a kind of preparation method of the efficient out-phase class fenton catalyst of carbon quantum dot load iron/ferroso-ferric oxide,
It is specifically realized by the following steps:
One, quantum dot precursor solution is prepared:
0.5g carbon source is dissolved into 5mL deionized water, 55mL small organic molecule solvent is added, is uniformly mixed, obtains
Quantum dot precursor solution；
Carbon source described in step 1 is soluble starch；
Small organic molecule solvent described in step 1 is propyl alcohol；
Two, 0.5g iron powder is added in quantum dot precursor solution obtained in step 1, re-ultrasonic dispersion 2min is obtained
To suspension；
The power of ultrasonic disperse described in step 2 is 15W；
Three, suspension obtained in step 2 is transferred in polytetrafluoroethyllining lining, then polytetrafluoroethyllining lining is put
Enter in stainless steel cauldron, then stainless steel cauldron is put into the baking oven that temperature is 160 DEG C and reacts 48h, obtains containing reaction
The solution of product；
Four, the solution containing reaction product is filtered, collects powder, cleaned using powder of the deionized water to collection
It 3 times, reuses dehydrated alcohol and the powder of collection is cleaned 3 times, then be dried in vacuo 6h at being 60 DEG C in temperature, obtain carbon quantum dot
The efficient out-phase class fenton catalyst of load iron/ferroso-ferric oxide.
Iron powder described in one step 2 of embodiment is common commercially available iron powder.
Embodiment two: a kind of carbon quantum dot loads the system of the efficient out-phase class fenton catalyst of dendritic iron powder/ferroso-ferric oxide
Preparation Method is specifically realized by the following steps:
One, quantum dot precursor solution is prepared:
0.2g carbon source is dissolved into 2mL deionized water, 58mL small organic molecule solvent is added, is uniformly mixed, obtains
Quantum dot precursor solution；
Carbon source described in step 2 is ascorbic acid；
Small organic molecule solvent described in step 2 is ethylene glycol；
Two, the tree-like nano-iron of 0.6g multilevel structure is added in quantum dot precursor solution obtained in step 2,
Re-ultrasonic dispersion 2min, obtains suspension；
The power of ultrasonic disperse described in step 2 is 10W；
Three, suspension obtained in step 2 is transferred in polytetrafluoroethyllining lining, then polytetrafluoroethyllining lining is put
Enter in stainless steel cauldron, then stainless steel cauldron is put into the baking oven that temperature is 200 DEG C and is reacted for 24 hours, obtains containing reaction
The solution of product；
Four, the solution containing reaction product is filtered, collects powder, cleaned using powder of the deionized water to collection
It 3 times, reuses dehydrated alcohol and the powder of collection is cleaned 3 times, then be dried in vacuo 6h at being 60 DEG C in temperature, obtain carbon quantum dot
Load the efficient out-phase class fenton catalyst of dendritic iron powder/ferroso-ferric oxide.
The tree-like nano-iron of multilevel structure described in two step 2 of embodiment be according to application No. is
201210344112.X, the embodiment one in entitled " a method of quickly prepare the tree-like nano-iron of multilevel structure "
Preparation.
A kind of embodiment three: preparation side of the efficient out-phase class fenton catalyst of carbon quantum dot load iron/copper/ferroferric oxide
Method is specifically realized by the following steps:
One, quantum dot precursor solution is prepared:
0.5g carbon source is dissolved into 1mL deionized water, 59mL small organic molecule solvent is added, is uniformly mixed, obtains
Quantum dot precursor solution；
Carbon source described in step 1 is glucose；
Small organic molecule solvent described in step 1 is dehydrated alcohol；
Two, 0.6g iron or dendritic iron-copper powder are added in quantum dot precursor solution obtained in step 1,
Re-ultrasonic dispersion 2min, obtains suspension；
The power of ultrasonic disperse described in step 2 is 15W；
Dendritic iron-copper powder described in step 2 is specifically realized by the following steps:
1., electrolyte is placed in electrolytic cell, using fine copper electrode as cathode, using ring-shaped graphite electrode as anode, make
The cathode of DC power supply is connected with cathode with conducting wire, conducting wire is reused and the anode of power supply is connected with anode, setting is just
Beginning current density is 1.6A/dm2, DC power supply is connected, is 1.6A/dm in initial current density2Lower reaction 10s, then electric current is close
Degree increases to 3.2A/dm2, then in 3.2A/dm2Lower reaction 10s stops reaction, dendritic copper alloy powder is obtained on cathode；
Step 2 1. described in electrolyte mixed by ferrous sulfate, copper sulphate, dehydrated alcohol and distilled water；
Step 2 1. described in electrolyte in Fe2+With Cu2+Total ion concentration be 0.5mol/L, and Cu2+Account for Fe2+With
Cu2+The 10% of total ion；
Step 2 1. described in electrolyte in dehydrated alcohol concentration be 40mL/L；
2., first using deionized water to dendritic copper alloy powder clean 3 times, reuse washes of absolute alcohol 3 times, then
Temperature is drying at 60 DEG C, obtains dendritic iron-copper powder；
Three, suspension is transferred in polytetrafluoroethyllining lining, then polytetrafluoroethyllining lining is put into stainless steel cauldron
In, then stainless steel cauldron is put into react in the baking oven that temperature is 180 DEG C and obtains the solution containing reaction product for 24 hours；
Four, the solution containing reaction product is filtered, collects powder, cleaned using powder of the deionized water to collection
It 3 times~5 times, reuses dehydrated alcohol and the powder of collection is cleaned 3 times, then be dried in vacuo 8h at being 60 DEG C in temperature, obtain carbon
Quantum dot loads the efficient out-phase class fenton catalyst of iron-based material.
Example IV: the difference of the present embodiment and embodiment two are as follows: small organic molecule solvent described in step 2 is
Dehydrated alcohol.Other steps and parameter are identical as embodiment two.
Embodiment five: the difference of the present embodiment and embodiment three are as follows: suspension is transferred to polytetrafluoroethyl-ne in step 3
In alkene liner, then polytetrafluoroethyllining lining is put into stainless steel cauldron, then it is 140 DEG C that stainless steel cauldron, which is put into temperature,
Baking oven in react and obtain the solution containing reaction product for 24 hours.Other steps and parameter are identical as embodiment three.
Table 1 is power spectrum result.
Table 1
As known from Table 1, the efficient out-phase class fenton catalyst of carbon quantum dot load iron/ferroso-ferric oxide prepared by embodiment one
The dendritic efficient out-phase class fenton catalyst of iron powder/ferroso-ferric oxide is loaded by C, O and Fe with carbon quantum dot prepared by embodiment two
Three kinds of element compositions, the efficient out-phase class fenton catalyst master of carbon quantum dot load iron/copper/ferroferric oxide prepared by embodiment three
It to be made of C, O, Fe and Cu.This shows that three kinds of material surfaces have successfully coated carbon, and these carbon its principal modes is carbon quantum
Point.
Fig. 1 is the ultraviolet absorpting spectrum of the solution containing reaction product, and 1 obtains for step 3 in embodiment one in Fig. 1
The ultraviolet absorption curve of solution containing reaction product, 2 solution containing reaction product obtained for step 3 in embodiment two
Ultraviolet absorption curve, the ultraviolet absorption curve of 3 solution containing reaction product obtained for step 3 in embodiment three；
From fig. 1, it can be seen that the solution containing reaction product that step 3 obtains in embodiment one has absorption peak at 218nm,
And the solution containing reaction product and three step 3 of embodiment that two step 3 of embodiment obtains obtain containing reaction product
Solution has apparent absorption peak at 267nm, the two absorption peaks all correspond to the absorption peak of carbon quantum dot, shows embodiment
One, reaction product obtained in embodiment two and embodiment three produces quantum dot, and only quantum dot is slightly poor in nature
It is different.
Fig. 2 is the XRD of the efficient out-phase class fenton catalyst of carbon quantum dot load iron/ferroso-ferric oxide prepared by embodiment one
Map；
As can be seen from Figure 2, the efficient out-phase class fenton catalyst of carbon quantum dot load iron/ferroso-ferric oxide prepared by embodiment one
Mainly by Fe and Fe3O4Composition.Since carbon quantum dot size is smaller, its diffraction maximum is not occurred.
Fig. 3 is that carbon quantum dot prepared by embodiment two loads the efficient out-phase class Fenton catalysis of dendritic iron powder/ferroso-ferric oxide
The XRD spectrum of agent；
As can be seen from Figure 3, carbon quantum dot prepared by the embodiment two that prepared by embodiment two loads dendritic iron powder/ferroso-ferric oxide
Efficient out-phase class fenton catalyst is mainly by Fe and Fe3O4Composition, carbon quantum dot load iron/tetra- prepared relative to embodiment one
The efficient out-phase class fenton catalyst of Fe 3 O, it is high that carbon quantum dot prepared by embodiment two loads dendritic iron powder/ferroso-ferric oxide
Imitate Fe in out-phase class fenton catalyst3O4Content it is less.Since carbon quantum dot size is smaller, its diffraction maximum is not occurred.
Fig. 4 is the efficient out-phase class fenton catalyst of carbon quantum dot load iron/copper/ferroferric oxide prepared by embodiment three
XRD spectrum；
As can be seen from Figure 4, the efficient out-phase class Fenton of carbon quantum dot load iron/copper/ferroferric oxide that prepared by embodiment three is urged
Agent is mainly by Fe, Cu and Fe3O4Composition, the carbon quantum dot load iron/ferroso-ferric oxide prepared relative to embodiment one are efficiently different
Similar fenton catalyst, the efficient out-phase class fenton catalyst of carbon quantum dot load iron/copper/ferroferric oxide prepared by embodiment three
Middle Fe3O4Content it is less, since carbon quantum dot size is smaller, do not occur its diffraction maximum.
Fig. 5 is the SEM of the efficient out-phase class fenton catalyst of carbon quantum dot load iron/ferroso-ferric oxide prepared by embodiment one
Figure；
As can be seen from Figure 5, the efficient out-phase class fenton catalyst of carbon quantum dot load iron/ferroso-ferric oxide prepared by embodiment one
It to be formed for blocky-shaped particle.Wherein particle size is about 6 μm.There are also some amorphous irregular substances between particle and particle,
This may be that starch carbonizing not exclusively leaves.
Fig. 6 is that carbon quantum dot prepared by embodiment two loads the efficient out-phase class Fenton catalysis of dendritic iron powder/ferroso-ferric oxide
The SEM of agent schemes；
As can be seen from Figure 6, the carbon quantum dot that prepared by embodiment two loads the dendritic efficient out-phase class Fenton of iron powder/ferroso-ferric oxide
Catalyst is mainly three-level dendritic morphology composition, this shows that the dendritic morphology of iron is effectively maintained.Wherein dendritic size is at 3 μm
~6 μm.
Fig. 7 is the efficient out-phase class fenton catalyst of carbon quantum dot load iron/copper/ferroferric oxide prepared by embodiment three
SEM figure；
As can be seen from Figure 7, the efficient out-phase class Fenton of carbon quantum dot load iron/copper/ferroferric oxide that prepared by embodiment three is urged
Agent is mainly the dendritic morphology of quaternary structure, this shows under conditions of heat treatment, and the level Four dendritic morphology of iron-copper obtains
To being effectively maintained.Sample size is at 8 μm~12 μm.
The Degrading experiment one of phenol: the carbon quantum dot load iron for respectively preparing 5mg iron powder, 5mg embodiment one/tetra- oxidations
It is efficient that carbon quantum dot prepared by the efficient out-phase class fenton catalyst of three-iron, 5mg embodiment two loads dendritic iron powder/ferroso-ferric oxide
The efficient out-phase class Fenton of carbon quantum dot load iron/copper/ferroferric oxide prepared by out-phase class fenton catalyst and 5mg embodiment three
It is 35mg/L, in the phenol solution that pH value is 4 that catalyst, which is added to four parts of 50mL concentration, then in the case where power is 15W by four parts of benzene
Phenol solution carries out ultrasound 10s respectively, then being separately added into the concentration of 34 μ L into four parts of phenol solutions under stiring is 30wt.%'s
H2O2Solution, then four parts of phenol solutions are separately heated to 30 DEG C, the effect of degradation of phenol is as shown in Figure 8；The phenol solution
PH value be to be adjusted using the sulfuric acid solution of 0.1mol/L.
Cycle performance test: carbon amounts prepared by the embodiment three after degradation of phenol 40min in the Degrading experiment one of phenol
Degradation of phenol 40min in the Degrading experiment one of the son efficient out-phase class fenton catalyst of point load iron/copper/ferroferric oxide and phenol
Iron powder afterwards takes out, and makes 5 times wash with distilled water, then be dried in vacuo 10h at 60 DEG C respectively, obtains the implementation of second of circulation
The iron powder of the efficient out-phase class fenton catalyst of carbon quantum dot load iron/copper/ferroferric oxide and second of circulation prepared by example three；
The efficient out-phase class fenton catalyst of carbon quantum dot load iron/copper/ferroferric oxide prepared by 5mg iron powder, 5mg embodiment three,
The efficient out-phase class fenton catalyst of carbon quantum dot load iron/copper/ferroferric oxide prepared by second of the 5mg embodiment three recycled
Being added separately to four parts of 50mL concentration with second of iron powder recycled of 5mg is 35mg/L, in the phenol solution that pH value is 4, then
Power is four parts of phenol solutions to be carried out to ultrasound 10s respectively under 15W, then be separately added into 34 into four parts of phenol solutions under stiring
The concentration of μ L is the H of 30wt.%2O2Solution, then four parts of phenol solutions are separately heated to 30 DEG C, the effect of degradation of phenol such as Fig. 9
It is shown；The pH value of the phenol solution is adjusted using the sulfuric acid solution of 0.1mol/L.
Fig. 8 is the curve graph of degradation of phenol, in Fig. 81 be iron powder degradation of phenol curve, 2 carbon prepared for embodiment one
The curve of the efficient out-phase class fenton catalyst degradation of phenol of quantum dot load iron/ferroso-ferric oxide, 3 carbon prepared for embodiment two
Quantum dot loads the curve of the efficient out-phase class fenton catalyst degradation of phenol of dendritic iron powder/ferroso-ferric oxide, and 4 make for embodiment three
The curve of the efficient out-phase class fenton catalyst degradation of phenol of standby carbon quantum dot load iron/copper/ferroferric oxide；
As it can be observed in the picture that the efficient out-phase class Fenton of carbon quantum dot load iron/ferroso-ferric oxide prepared using embodiment one is urged
Agent degradation of phenol, for the degradation rate for 40min phenol of degrading up to 80%, degradation capability is weaker than iron powder；It is prepared using embodiment two
Carbon quantum dot load the dendritic efficient out-phase class fenton catalyst degradation of phenol of iron powder/ferroso-ferric oxide, degradation 12min phenol
For degradation rate up to 90%, degradation capability is slightly better than iron powder；Carbon quantum dot load iron/copper/ferroferric oxide prepared by embodiment three
The effect of the degradation of phenol of efficient out-phase class fenton catalyst is best, can degrade 99% or more phenol in 10min, far better than
Iron powder.
Fig. 9 is the curve graph of degradation of phenol, in Fig. 91 be iron powder degradation of phenol curve, 2 for second of circulation iron powders
The curve of degradation of phenol, the 3 efficient out-phase class Fentons of carbon quantum dot load iron/copper/ferroferric oxide prepared for embodiment three are urged
The curve of agent degradation of phenol, the 4 carbon quantum dot load iron/copper/ferroferric oxides prepared for the embodiment three of second of circulation
The curve of efficient out-phase class fenton catalyst degradation of phenol；
As can be seen from Figure 9, when degrade 15min when, carbon quantum dot load iron/copper prepared by the embodiment three of second circulation/
The efficient out-phase class fenton catalyst degradation of phenol of ferroso-ferric oxide remains to the phenol of degradation 97%, and iron powder is in the first Degrading experiment
In, the phenol of removal 90% when 15min, and the iron powder recycled for the second time, 17% phenol could be removed in 15min, it is known that,
The cycle performance of the efficient out-phase class fenton catalyst of carbon quantum dot load iron/copper/ferroferric oxide prepared by embodiment three is significantly
Increase.
Iron when Figure 10 is different catalysts degradation of phenol 30min dissolves out situation map, and 1 is iron powder degradation of phenol in Figure 10
Iron when 30min dissolves out histogram, the 2 efficient out-phase class sweet smell of carbon quantum dot load iron/ferroso-ferric oxide prepared for embodiment one
Iron when catalyst degradation phenol 30min dissolves out histogram, 3 for carbon quantum dot prepared by embodiment two load dendritic iron powder/
Iron when the efficient out-phase class fenton catalyst degradation of phenol 30min of ferroso-ferric oxide dissolves out histogram, and 4 prepare for embodiment three
Iron when the efficient out-phase class fenton catalyst degradation of phenol 30min of carbon quantum dot load iron/copper/ferroferric oxide dissolves out column
Figure；
As can be seen from Figure 10, the efficient out-phase class Fenton catalysis of carbon quantum dot load iron/ferroso-ferric oxide that prepared by embodiment one
Carbon quantum dot prepared by agent, embodiment two loads the efficient out-phase class fenton catalyst of dendritic iron powder/ferroso-ferric oxide and embodiment
The efficient out-phase class fenton catalyst of carbon quantum dot load iron/copper/ferroferric oxide of three preparations is respectively less than the dissolution of original iron powder
Situation alleviates release of the metal ion in system, carbon quantum dot load iron/ferroso-ferric oxide that wherein prepared by embodiment one
Efficient out-phase class fenton catalyst iron the amount of dissolution is minimum, and carbon quantum dot prepared by embodiment two loads dendritic iron powder/tetra- oxidations three
The efficient out-phase class fenton catalyst of iron is taken second place, carbon quantum dot load iron/efficient out-phase of copper/ferroferric oxide prepared by embodiment three
Class fenton catalyst dissolved iron is maximum.
The Degrading experiment two of phenol: the carbon quantum dot for respectively preparing 5mg embodiment two loads dendritic iron powder/tetra- oxidations three
Carbon quantum dot load iron/efficient out-phase of copper/ferroferric oxide prepared by the efficient out-phase class fenton catalyst of iron, 5mg embodiment three
Class fenton catalyst, the carbon quantum dot of 5mg example IV preparation load the dendritic efficient out-phase class Fenton of iron powder/ferroso-ferric oxide and urge
The efficient out-phase class fenton catalyst of carbon quantum dot load iron/copper/ferroferric oxide prepared by agent, 5mg embodiment five is added to
Four parts of 50mL concentration are 35mg/L, in the phenol solution that pH value is 4, then power be 15W under by four parts of phenol solutions respectively into
Row ultrasound 10s, then being separately added into the concentration of 34 μ L into four parts of phenol solutions under stiring is the H of 30wt.%2O2Solution, then will
Four parts of phenol solutions are separately heated to 30 DEG C, and the effect of degradation of phenol is as shown in Figure 9；The pH value of the phenol solution be using
What the sulfuric acid solution of 0.1mol/L was adjusted.
Figure 11 is the curve graph of degradation of phenol, 1 dendritic iron powder/tetra- of carbon quantum dot load prepared for embodiment two in Figure 11
The curve of the efficient out-phase class fenton catalyst degradation of phenol of Fe 3 O, 2 for embodiment three prepare carbon quantum dot load iron/
The curve of the efficient out-phase class fenton catalyst degradation of phenol of copper/ferroferric oxide, 3 load for the carbon quantum dot of example IV preparation
The curve of the dendritic efficient out-phase class fenton catalyst degradation of phenol of iron powder/ferroso-ferric oxide, 4 carbon quantums prepared for embodiment five
The curve of the point efficient out-phase class fenton catalyst degradation of phenol of load iron/copper/ferroferric oxide；
As can be seen from Figure 11, embodiment two is compared with example IV, and when small molecule solvent difference, catalyst performance also can be by
It influences, small molecule solvent is the catalyst performance that the catalyst performance of the preparation of ethylene glycol is better than that small molecule solvent is ethyl alcohol；
Embodiment three is compared with five, it is known that, the catalyst performance of 180 DEG C of acquisitions is better than the catalyst performance of 140 DEG C of acquisitions.Two kinds because
Element is compared, and temperature is affected to catalyst, and small molecule solvent influences catalyst performance smaller.However, it is noted that for
Different solvent hot systems, can be by adjusting experiment parameter such as time, temperature, carbon source kind and quantity etc. come so that obtaining
Catalyst performance is optimal.Between each experiment parameter, there is certain synergistic effect.
In conclusion embodiment three is prepared for the efficient class fenton catalyst of out-phase, by area load carbon quantum dot, iron
The degradation capability of base catalyst greatly promotes, and the dissolution of iron also decreases.
Claims (9)
1. a kind of preparation method of the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material, it is characterised in that this method
Specifically following steps are completed:
One, quantum dot precursor solution is prepared:
Carbon source is dissolved into deionized water, small organic molecule solvent is added, is uniformly mixed, it is molten to obtain quantum dot presoma
Liquid；
Carbon source described in step 1 is in glucose, sucrose, fructose, soluble starch, ascorbic acid, citric acid and ethylenediamine
One kind or in which several mixtures；
The quality of carbon source described in step 1 and the volume ratio of deionized water are (0.1g~0.5g): 1mL；
Deionized water described in step 1 and the volume ratio of small organic molecule solvent are 1:(9~99)；
Two, dendritic iron-copper powder is added in quantum dot precursor solution, re-ultrasonic dispersion 0.5min~2min is obtained
Suspension；
The volume ratio of the quality of dendritic iron-copper powder described in step 2 and quantum dot precursor solution be (1g~
30g):1L；
Dendritic iron-copper powder described in step 2 is specifically realized by the following steps:
1., electrolyte is placed in electrolytic cell, using fine copper electrode as cathode, using ring-shaped graphite electrode as anode, using leading
The cathode of DC power supply is connected by line with cathode, reuses conducting wire and the anode of power supply is connected with anode, initial electricity is arranged
Current density is 1.4A/dm2~1.6A/dm2, DC power supply is connected, is 1.4A/dm in initial current density2~1.6A/dm2It is lower anti-
10s~15s is answered, then current density is increased to 2 times of initial current density, then react 10s under 2 times of initial current density
~15s stops reaction, dendritic copper alloy powder is obtained on cathode；
Step 2 1. described in electrolyte mixed by ferrous sulfate, copper sulphate, dehydrated alcohol and distilled water；
2., first using deionized water to dendritic copper alloy powder clean 3 times~5 times, reuse washes of absolute alcohol 3 times~5
It is secondary, then dried at being 60 DEG C in temperature, obtain dendritic iron-copper powder；
Three, suspension is transferred in polytetrafluoroethyllining lining, then polytetrafluoroethyllining lining is put into stainless steel cauldron, then
Stainless steel cauldron is put into the baking oven that temperature is 140 DEG C~220 DEG C and reacts for 24 hours~28h, is obtained containing the molten of reaction product
Liquid；
Four, the solution containing reaction product is filtered, collects powder, cleaned 3 times using powder of the deionized water to collection
It~5 times, reuses dehydrated alcohol and the powder of collection is cleaned 3 times~5 times, then be dried in vacuo 4h at being 50 DEG C~70 DEG C in temperature
~12h obtains the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material.
2. a kind of preparation side of carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material according to claim 1
Method, it is characterised in that small organic molecule solvent described in step 1 is one in dehydrated alcohol, ethylene glycol, propyl alcohol and propylene glycol
Kind or in which several mixed liquors.
3. a kind of preparation side of carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material according to claim 1
Method, it is characterised in that step 2 1. described in electrolyte in Fe2+With Cu2+Total ion concentration be 0.5mol/L~1.0mol/
L, and Cu2+Account for Fe2+With Cu2+The 2%~10% of total ion.
4. a kind of preparation side of carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material according to claim 1
Method, it is characterised in that step 2 1. described in electrolyte in dehydrated alcohol concentration be 20mL/L~40mL/L.
5. a kind of preparation side of carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material according to claim 1
Method, it is characterised in that the power of ultrasonic disperse described in step 2 is 10W~20W.
6. a kind of preparation side of carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material according to claim 1
Method, it is characterised in that the volume ratio of deionized water described in step 1 and small organic molecule solvent is 1:(11~29).
7. a kind of preparation side of carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material according to claim 1
Method, it is characterised in that the volume ratio of deionized water described in step 1 and small organic molecule solvent is 1:(29~59).
8. a kind of preparation side of carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material according to claim 1
Method, it is characterised in that the quality of dendritic iron-copper powder described in step 2 and the volume ratio of quantum dot precursor solution are
(1g~10g): 1L.
9. a kind of preparation side of carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material according to claim 1
Method, it is characterised in that suspension is transferred in polytetrafluoroethyllining lining in step 3, then polytetrafluoroethyllining lining is put into not
In rust steel reaction kettle, then stainless steel cauldron is put into the baking oven that temperature is 140 DEG C~160 DEG C and reacts for 24 hours~28h, obtained
Solution containing reaction product.
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