CN107008326A - A kind of carbon quantum dot loads the preparation method of the efficient out-phase class fenton catalyst of iron-based material - Google Patents

A kind of carbon quantum dot loads the preparation method of the efficient out-phase class fenton catalyst of iron-based material Download PDF

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CN107008326A
CN107008326A CN201710350155.1A CN201710350155A CN107008326A CN 107008326 A CN107008326 A CN 107008326A CN 201710350155 A CN201710350155 A CN 201710350155A CN 107008326 A CN107008326 A CN 107008326A
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iron
quantum dot
carbon quantum
class fenton
fenton catalyst
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CN107008326B (en
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姚忠平
夏琦兴
王建康
李东琦
刘冠杰
孟艳秋
张凌儒
戴鹏程
姜兆华
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Harbin Institute of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74Iron group metals
    • B01J23/745Iron
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • CCHEMISTRY; METALLURGY
    • C25ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25CPROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C5/00Electrolytic production, recovery or refining of metal powders or porous metal masses
    • C25C5/02Electrolytic production, recovery or refining of metal powders or porous metal masses from solutions
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • C02F2101/345Phenols
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/02Specific form of oxidant
    • C02F2305/026Fenton's reagent

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Abstract

A kind of carbon quantum dot loads the preparation method of the efficient out-phase class fenton catalyst of iron-based material, and 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 to solve existing different-phase catalyst to prepare complexity, poor activity, Fe Ion releases and produce iron cement etc. and easily cause secondary pollution, and the problem of multiple cycle performance degradation.Method:First, quantum dot precursor solution is prepared;2nd, suspension is prepared;3rd, hydro-thermal reaction;4th, filter, clean, vacuum drying obtains the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material.Carbon quantum dot prepared by the present invention load efficient out-phase class fenton catalyst of iron-based material can be degraded in 10min more than 99% phenol.The present invention can obtain a kind of carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material.

Description

A kind of carbon quantum dot loads the preparation of the efficient out-phase class fenton catalyst of iron-based material Method
Technical field
The invention belongs to water treatment field, and in particular to a kind of preparation method of efficient out-phase fenton catalyst.
Background technology
Chemical industry, as the pillars of the national economy, is that rapid economic development is made that great contribution, but consequently also bring Increasing pollution problem, 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) to react at normal temperatures and pressures, easy to operate, oxidability is strong, in soil remediation and treatment of Organic Wastewater application Have a extensive future.And in current Fenton oxidation technology, be commonly present Fe Ion releases and produce iron cement etc. and easily cause secondary pollution, and Multiple cycle performance degradation.Therefore in the exploitation of efficient different-phase catalyst, prepare cheap and easy to get, specific surface area big, active The class fenton catalyst material that high and pH has a wide range of application has important application value in water treatment field.
The content of the invention
The purpose of invention is to solve existing different-phase catalyst to prepare complexity, poor activity, Fe Ion releases and produce 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 carbon quantum dot loads the preparation method of the efficient out-phase class fenton catalyst of iron-based material, specifically following steps Complete:
First, quantum dot precursor solution is prepared:
Carbon source is dissolved into deionized water, organic molecule solvent is added, is well mixed, obtains quantum dot presoma Solution;
Carbon source described in step one is glucose, sucrose, fructose, soluble starch, ascorbic acid, citric acid and second two One kind or wherein several mixtures in amine;
The quality of carbon source described in step one and the volume ratio of deionized water are (0g~0.5g):1mL;
The volume ratio of deionized water and organic molecule solvent described in step one is 1:(9~99);
2nd, iron or dendritic iron-copper powder are added in quantum dot precursor solution, then ultrasonic disperse 0.5min~ 2min, obtains suspension;
The quality and the volume ratio of quantum dot precursor solution of iron or dendritic iron-copper powder described in step 2 be (1g~30g):1L;
What the dendritic iron-copper powder described in step 2 was specifically realized by the following steps:
1., electrolyte is placed in electrolytic cell, using fine copper electrode as negative electrode, using ring-shaped graphite electrode as anode, made The negative pole of dc source is connected with negative electrode with wire, wire is reused and the positive pole of power supply is connected with anode, is set just Beginning current density is 1.4A/dm2~1.6A/dm2, dc source 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 negative electrode;
Step 2 1. described in electrolyte mixed by ferrous sulfate, copper sulphate, absolute ethyl alcohol and distilled water or by Ferrous sulfate, absolute ethyl alcohol and distilled water are mixed;
2., dendritic copper alloy powder is cleaned 3 times~5 times first by deionized water, washes of absolute alcohol is reused 3 times ~5 times, then dried in the case where temperature is 60 DEG C, obtain dendritic iron-copper powder;
3rd, suspension is transferred in polytetrafluoroethyllining lining, then polytetrafluoroethyllining lining is put into stainless steel cauldron In, 24h~28h is reacted in stainless steel cauldron to be put into the baking oven that temperature is 140 DEG C~220 DEG C, is obtained containing reaction production The solution of thing;
4th, the solution containing reaction product is filtered, collects powder, the powder of collection is cleaned using deionized water 3 times~5 times, reuse absolute ethyl alcohol and the powder of collection is cleaned 3 times~5 times, then vacuum is done in the case where temperature is 50 DEG C~70 DEG C Dry 4h~12h, obtains the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material.
Advantages of the present invention:
First, the inventive method preparation method is simple, and raw material is cheap and easy to get, with using graphene, carbon nanometer in the prior art The method that pipe even load prepares catalyst is compared, and the present invention directly uses glucose cheap and easy to get, and sucrose, 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;
2nd, present invention experiment is controllable, such as time, temperature, carbon source kind, quantity, can have by adjusting suitable parameter Machine small molecule solvent etc. obtains more excellent catalyst;
3rd, the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material that prepared by the present invention is difficult to reunite, catalysis Active high, relative to other nm-class catalysts, scantling prepared by the present invention is in micron order, and it disperses in actual use Property it is good, be difficult reunite;Further, since this material has multilevel hierarchy, its trunk is in micron order size, and its secondary structure is being received Rice structure, also with the more preferable quantum dot of size, thus impart its high catalytic activity the characteristics of;
4th, the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material that prepared by the present invention can be in 10min The phenol of degraded more than 99%, degradation property can improve 30%~200% compared with catalyst prepared by prior art;
5th, the efficient out-phase class fenton catalyst of carbon quantum dot load iron-based material that 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 For original 19%;
6th, carbon quantum dot prepared by the present invention loads the efficient out-phase class fenton catalyst of iron-based material in degradation of phenol After 30min, iron dissolution is less than 1.2mg/L, and compared with existing catalyst, iron stripping quantity reduces 20%~60%.
The present invention can obtain a kind of carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material.
Brief description of the drawings
Fig. 1 is the ultraviolet absorpting spectrum of the solution containing reaction product, and 1 is that step 3 is obtained 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, 3 be the ultraviolet absorption curve of the solution containing reaction product that step 3 is obtained 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 Collection of illustrative plates;
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 figures of agent;
Fig. 7 is the efficient out-phase class fenton catalyst of carbon quantum dot load iron/copper/ferroferric oxide prepared by embodiment three SEM schemes;
Fig. 8 is the curve map of degradation of phenol, in Fig. 81 be iron powder degradation of phenol curve, 2 be carbon prepared by embodiment one The curve of the efficient out-phase class fenton catalyst degradation of phenol of quantum dot load iron/ferroso-ferric oxide, 3 be carbon prepared by embodiment two Quantum dot loads the curve of the dendritic efficient out-phase class fenton catalyst degradation of phenol of iron powder/ferroso-ferric oxide, and 4 be that embodiment three is made 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 map of degradation of phenol, in Fig. 91 be iron powder degradation of phenol curve, 2 for second of circulation iron powder The curve of degradation of phenol, 3 be that the efficient out-phase class Fenton of carbon quantum dot load iron/copper/ferroferric oxide prepared by embodiment three is 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;
1 is iron powder degradation of phenol in iron dissolution situation map when Figure 10 is different catalysts degradation of phenol 30min, Figure 10 Iron dissolution block diagram during 30min, 2 be that the efficient out-phase class of carbon quantum dot load iron/ferroso-ferric oxide prepared by embodiment one is fragrant Iron dissolution block diagram during catalyst degradation phenol 30min, 3 be carbon quantum dot prepared by embodiment two load dendritic iron powders/ Iron dissolution block diagram during the efficient out-phase class fenton catalyst degradation of phenol 30min of ferroso-ferric oxide, 4 be prepared by embodiment three Iron dissolution column during the efficient out-phase class fenton catalyst degradation of phenol 30min of carbon quantum dot load iron/copper/ferroferric oxide Figure;
Figure 11 is 1 dendritic iron powder/tetra- of carbon quantum dot load prepared for embodiment two in the curve map of degradation of phenol, Figure 11 The curve of the efficient out-phase class fenton catalyst degradation of phenol of Fe 3 O, the 2 carbon quantum dot load irons prepared for embodiment three/ The curve of the efficient out-phase class fenton catalyst degradation of phenol of copper/ferroferric oxide, 3 be carbon quantum dot load prepared by example IV The curve of the dendritic efficient out-phase class fenton catalyst degradation of phenol of iron powder/ferroso-ferric oxide, 4 be carbon quantum prepared by embodiment five The curve of the point efficient out-phase class fenton catalyst degradation of phenol of load iron/copper/ferroferric oxide.
Embodiment
Embodiment one: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:
First, quantum dot precursor solution is prepared:
Carbon source is dissolved into deionized water, organic molecule solvent is added, is well mixed, obtains quantum dot presoma Solution;
Carbon source described in step one is glucose, sucrose, fructose, soluble starch, ascorbic acid, citric acid and second two One kind or wherein several mixtures in amine;
The quality of carbon source described in step one and the volume ratio of deionized water are (0g~0.5g):1mL;
The volume ratio of deionized water and organic molecule solvent described in step one is 1:(9~99);
2nd, iron or dendritic iron-copper powder are added in quantum dot precursor solution, then ultrasonic disperse 0.5min~ 2min, obtains suspension;
The quality and the volume ratio of quantum dot precursor solution of iron or dendritic iron-copper powder described in step 2 be (1g~30g):1L;
What the dendritic iron-copper powder described in step 2 was specifically realized by the following steps:
1., electrolyte is placed in electrolytic cell, using fine copper electrode as negative electrode, using ring-shaped graphite electrode as anode, made The negative pole of dc source is connected with negative electrode with wire, wire is reused and the positive pole of power supply is connected with anode, is set just Beginning current density is 1.4A/dm2~1.6A/dm2, dc source 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 negative electrode;
Step 2 1. described in electrolyte mixed by ferrous sulfate, copper sulphate, absolute ethyl alcohol and distilled water or by Ferrous sulfate, absolute ethyl alcohol and distilled water are mixed;
2., dendritic copper alloy powder is cleaned 3 times~5 times first by deionized water, washes of absolute alcohol is reused 3 times ~5 times, then dried in the case where temperature is 60 DEG C, obtain dendritic iron-copper powder;
3rd, suspension is transferred in polytetrafluoroethyllining lining, then polytetrafluoroethyllining lining is put into stainless steel cauldron In, 24h~28h is reacted in stainless steel cauldron to be put into the baking oven that temperature is 140 DEG C~220 DEG C, is obtained containing reaction production The solution of thing;
4th, the solution containing reaction product is filtered, collects powder, the powder of collection is cleaned using deionized water 3 times~5 times, reuse absolute ethyl alcohol and the powder of collection is cleaned 3 times~5 times, then vacuum is done in the case where temperature is 50 DEG C~70 DEG C Dry 4h~12h, obtains the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material.
The advantage of present embodiment:
First, present embodiment method preparation method is simple, and raw material is cheap and easy to get, with using graphene, carbon in the prior art The method that nanotube even load prepares catalyst is compared, and present embodiment directly uses glucose cheap and easy to get, and sucrose is anti-bad Hematic acid etc. greatly reduces cost as carbon source;Solvent-thermal method is used in present embodiment preparation method, selected solvent is also Small molecule solvent, it is cheap and easy to get;
2nd, present embodiment experiment is controllable, can be by adjusting suitable parameter, such as time, temperature, carbon source kind, number Amount, organic molecule solvent etc. obtain more excellent catalyst;
3rd, the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material that prepared by present embodiment is difficult to reunite, Catalytic activity is high, and relative to other nm-class catalysts, scantling prepared by present embodiment is in micron order, and it actually makes Middle good dispersion is used, is difficult to reunite;Further, since this material has multilevel hierarchy, its trunk is in micron order size, and it is secondary Structure is in nanostructured, also with the more preferable quantum dot of size, thus impart its high catalytic activity the characteristics of;
4th, the carbon quantum dot load iron-based material efficient out-phase class fenton catalyst that prepared by present embodiment can be The phenol of degraded more than 99% in 10min, degradation property compared with catalyst prepared by prior art, can improve 30%~ 200%;
5th, the efficient out-phase class fenton catalyst of carbon quantum dot load iron-based material that prepared by present embodiment recycles 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%;
6th, carbon quantum dot prepared by present embodiment loads the efficient out-phase class fenton catalyst of iron-based material in degradation of phenol After 30min, iron dissolution is less than 1.2mg/L, and compared with existing catalyst, iron stripping quantity reduces 20%~60%.
Present embodiment can obtain a kind of carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material.
Embodiment two:Present embodiment is with the difference of embodiment one:It is organic described in step one Small molecule solvent is one kind or wherein several mixed liquors in absolute ethyl alcohol, ethylene glycol, propyl alcohol and propane diols.Other steps with Embodiment one is identical.
Embodiment three:One of present embodiment and embodiment one or two difference is:Step 2 1. in Fe in described 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 identical with embodiment one or two.
Embodiment four:One of present embodiment and embodiment one to three difference is:Step 2 1. in The concentration of absolute ethyl alcohol is 20mL/L~40mL/L in described electrolyte.Other steps and embodiment one to three-phase Together.
Embodiment five:One of present embodiment and embodiment one to four difference is:Institute in step 2 The power for the ultrasonic disperse stated is 10W~20W.Other steps are identical with embodiment one to four.
Embodiment six:One of present embodiment and embodiment one to five difference is:Institute in step one The quality for the carbon source stated and the volume ratio of deionized water are (0.1g~0.5g):1mL.Other steps and embodiment one to Five is identical.
Embodiment seven:One of present embodiment and embodiment one to six difference is:Institute in step one The deionized water and the volume ratio of organic molecule solvent stated are 1:(11~29).Other steps and embodiment one to six It is identical.
Embodiment eight:One of present embodiment and embodiment one to seven difference is:Institute in step one The deionized water and the volume ratio of organic molecule solvent stated are 1:(29~59).Other steps and embodiment one to seven It is identical.
Embodiment nine:One of present embodiment and embodiment one to eight difference is:Institute in step 2 The volume ratio of the iron or the quality of dendritic iron-copper powder stated and quantum dot precursor solution is (1g~10g):1L.Other steps Suddenly it is identical with embodiment one to eight.
Embodiment ten:One of present embodiment and embodiment one to nine difference is:Will in step 3 Suspension is transferred in polytetrafluoroethyllining lining, then polytetrafluoroethyllining lining is put into stainless steel cauldron, by stainless steel Reactor, which is put into the baking oven that temperature is 140 DEG C~160 DEG C, reacts 24h~28h, obtains the solution containing reaction product.Other Step is identical with embodiment one to nine.
Embodiment 11:One of present embodiment and embodiment one to ten difference is: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 with embodiment one to ten.
Embodiment 12:Present embodiment is with the difference of embodiment one to one of 11:Step 2 1. Fe in the electrolyte described in2+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 with embodiment one to 11.
Embodiment 13:Present embodiment is with the difference of embodiment one to one of 12:Step 2 1. Fe in the electrolyte described in2+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 with embodiment one to 12.
Beneficial effects of the present invention are verified using following examples:
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:
First, quantum dot precursor solution is prepared:
0.5g carbon sources are dissolved into 5mL deionized waters, 55mL organic molecule solvents are added, is well mixed, obtains Quantum dot precursor solution;
Carbon source described in step one is soluble starch;
Organic molecule solvent described in step one is propyl alcohol;
2nd, 0.5g iron powders are added in the quantum dot precursor solution obtained in step one, then ultrasonic disperse 2min, obtain To suspension;
The power of ultrasonic disperse described in step 2 is 15W;
3rd, the suspension obtained in step 2 is transferred in polytetrafluoroethyllining lining, then polytetrafluoroethyllining lining is put Enter in stainless steel cauldron, react 48h in stainless steel cauldron to be put into the baking oven that temperature is 160 DEG C, obtain containing reaction The solution of product;
4th, the solution containing reaction product is filtered, collects powder, the powder of collection is cleaned using deionized water 3 times, reuse absolute ethyl alcohol and the powder of collection is cleaned 3 times, then 6h is dried in vacuo in the case where temperature is 60 DEG C, obtain carbon quantum dot The efficient out-phase class fenton catalyst of load iron/ferroso-ferric oxide.
Iron powder described in the step 2 of embodiment one is common commercially available iron powder.
Embodiment two:A kind of carbon quantum dot loads the system of the dendritic efficient out-phase class fenton catalyst of iron powder/ferroso-ferric oxide Preparation Method, is specifically realized by the following steps:
First, quantum dot precursor solution is prepared:
0.2g carbon sources are dissolved into 2mL deionized waters, 58mL organic molecule solvents are added, is well mixed, obtains Quantum dot precursor solution;
Carbon source described in step 2 is ascorbic acid;
Organic molecule solvent described in step 2 is ethylene glycol;
2nd, the tree-like nano-iron of 0.6g multilevel hierarchies is added in the quantum dot precursor solution obtained in step 2, Ultrasonic disperse 2min, obtains suspension again;
The power of ultrasonic disperse described in step 2 is 10W;
3rd, the suspension obtained in step 2 is transferred in polytetrafluoroethyllining lining, then polytetrafluoroethyllining lining is put Enter in stainless steel cauldron, react 24h in stainless steel cauldron to be put into the baking oven that temperature is 200 DEG C, obtain containing reaction The solution of product;
4th, the solution containing reaction product is filtered, collects powder, the powder of collection is cleaned using deionized water 3 times, reuse absolute ethyl alcohol and the powder of collection is cleaned 3 times, then 6h is dried in vacuo in the case where temperature is 60 DEG C, 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 hierarchy described in the step 2 of embodiment two is according to Application No. 201210344112.X, it is entitled《A kind of method of the quick tree-like nano-iron for preparing multilevel hierarchy》In embodiment one Prepare.
Embodiment three:A kind of 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:
First, quantum dot precursor solution is prepared:
0.5g carbon sources are dissolved into 1mL deionized waters, 59mL organic molecule solvents are added, is well mixed, obtains Quantum dot precursor solution;
Carbon source described in step one is glucose;
Organic molecule solvent described in step one is absolute ethyl alcohol;
2nd, 0.6g iron or dendritic iron-copper powder are added in the quantum dot precursor solution obtained in step one, Ultrasonic disperse 2min, obtains suspension again;
The power of ultrasonic disperse described in step 2 is 15W;
What the dendritic iron-copper powder described in step 2 was specifically realized by the following steps:
1., electrolyte is placed in electrolytic cell, using fine copper electrode as negative electrode, using ring-shaped graphite electrode as anode, made The negative pole of dc source is connected with negative electrode with wire, wire is reused and the positive pole of power supply is connected with anode, is set just Beginning current density is 1.6A/dm2, dc source 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 negative electrode;
Step 2 1. described in electrolyte mixed by ferrous sulfate, copper sulphate, absolute ethyl 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 absolute ethyl alcohol concentration be 40mL/L;
2., dendritic copper alloy powder is cleaned 3 times first by deionized water, washes of absolute alcohol is reused 3 times, then Temperature is dry at 60 DEG C, obtains dendritic iron-copper powder;
3rd, suspension is transferred in polytetrafluoroethyllining lining, then polytetrafluoroethyllining lining is put into stainless steel cauldron In, 24h is reacted in stainless steel cauldron to be put into the baking oven that temperature is 180 DEG C, the solution containing reaction product is obtained;
4th, the solution containing reaction product is filtered, collects powder, the powder of collection is cleaned using deionized water 3 times~5 times, reuse absolute ethyl alcohol and the powder of collection is cleaned 3 times, then 8h is dried in vacuo in the case where temperature is 60 DEG C, obtain carbon Quantum dot loads the efficient out-phase class fenton catalyst of iron-based material.
Example IV:The present embodiment and the difference of embodiment two are:Organic molecule solvent described in step 2 is Absolute ethyl alcohol.Other steps and parameter are identical with embodiment two.
Embodiment five:The present embodiment and the difference of embodiment three are:Suspension is transferred to polytetrafluoroethyl-ne in step 3 In alkene liner, then polytetrafluoroethyllining lining is put into stainless steel cauldron, stainless steel cauldron is being put into temperature for 140 DEG C Baking oven in react 24h, obtain the solution containing reaction product.Other steps and parameter are identical with 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 that 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 To be made up 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 is that step 3 is obtained 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, 3 be the ultraviolet absorption curve of the solution containing reaction product that step 3 is obtained in embodiment three;
From fig. 1, it can be seen that the solution containing reaction product that step 3 is obtained in embodiment one has absworption peak at 218nm, And the solution containing reaction product and the step 3 of embodiment three that the step 3 of embodiment two is obtained are obtained containing reaction product Solution has obvious absworption peak at 267nm, and the two absworption peaks all correspond to the absworption peak of carbon quantum dot, show embodiment First, the reaction product obtained in embodiment two and embodiment three generates quantum dot, and simply 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 Collection of illustrative plates;
As can be seen from Figure 2, the efficient out-phase class fenton catalyst of carbon quantum dot load iron/ferroso-ferric oxide that prepared by embodiment one Mainly by Fe and Fe3O4Composition.Because 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 main 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.Because 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 main by Fe, Cu and Fe3O4Composition, it is efficiently different relative to carbon quantum dot load iron/ferroso-ferric oxide prepared by embodiment one 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, because carbon quantum dot size is smaller, its diffraction maximum is not occurred.
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 that prepared by embodiment one To be blocky-shaped particle composition.Wherein particle size is about 6 μm.There are some amorphous irregular materials between particle and particle, This is probably 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 figures of agent;
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, and 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 schemes;
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, and this shows under conditions of heat treatment, and the level Four dendritic morphology of iron-copper is obtained To being effectively maintained.Sample size is at 8 μm~12 μm.
The Degrading experiment one of phenol:The oxidation of the carbon quantum dot load iron for respectively preparing 5mg iron powders, 5mg embodiments one/tetra- It is efficient that carbon quantum dot prepared by the efficient out-phase class fenton catalyst of three-iron, 5mg embodiments 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 embodiments three Catalyst is added to during four parts of 50mL concentration are the phenol solution that 35mg/L, pH value are 4, then in the case where power is 15W by four parts of benzene Phenol solution carries out ultrasonic 10s respectively, then it is 30wt.%'s to be separately added into 34 μ L concentration into four parts of phenol solutions under agitation 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;Described phenol solution PH value be to be adjusted using 0.1mol/L sulfuric acid solution.
Cycle performance is tested: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 point efficient out-phase class fenton catalyst of load iron/copper/ferroferric oxide and phenol Iron powder afterwards takes out, and is cleaned 5 times using distilled water respectively, then is dried in vacuo 10h at 60 DEG C, obtains the implementation of second of circulation The efficient out-phase class fenton catalyst of carbon quantum dot load iron/copper/ferroferric oxide and the iron powder of 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 powders, 5mg embodiments three, The efficient out-phase class fenton catalyst of carbon quantum dot load iron/copper/ferroferric oxide prepared by the embodiment three of second of circulation of 5mg It is added separately to the iron powders circulated of 5mg second during four parts of 50mL concentration are the phenol solution that 35mg/L, pH value are 4, then Power is that four parts of phenol solutions are carried out into ultrasonic 10s respectively under 15W, then into four parts of phenol solutions is separately added into 34 under agitation μ L concentration is 30wt.% H2O2Solution, then four parts of phenol solutions are separately heated to 30 DEG C, effect such as Fig. 9 of degradation of phenol It is shown;The pH value of described phenol solution is adjusted using 0.1mol/L sulfuric acid solution.
Fig. 8 is the curve map of degradation of phenol, in Fig. 81 be iron powder degradation of phenol curve, 2 be carbon prepared by embodiment one The curve of the efficient out-phase class fenton catalyst degradation of phenol of quantum dot load iron/ferroso-ferric oxide, 3 be carbon prepared by embodiment two Quantum dot loads the curve of the dendritic efficient out-phase class fenton catalyst degradation of phenol of iron powder/ferroso-ferric oxide, and 4 be that embodiment three is made 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, the degradation rate for 40min phenol of degrading is up to 80%, and degradation capability is weaker than iron powder;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, degraded 12min phenol Degradation rate is up to 90%, and degradation capability is slightly better than iron powder;Carbon quantum dot load iron/copper/ferroferric oxide prepared by embodiment three The best results of the degradation of phenol of efficient out-phase class fenton catalyst, can degrade more than 99% phenol in 10min, far better than Iron powder.
Fig. 9 is the curve map of degradation of phenol, in Fig. 91 be iron powder degradation of phenol curve, 2 for second of circulation iron powder The curve of degradation of phenol, 3 be that the efficient out-phase class Fenton of carbon quantum dot load iron/copper/ferroferric oxide prepared by embodiment three is 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, as degraded 15min, carbon quantum dot load iron/copper that for the second time prepared by the embodiment three of circulation/ The efficient out-phase class fenton catalyst degradation of phenol of ferroso-ferric oxide remains to the phenol of degraded 97%, and iron powder is in the first Degrading experiment In, the phenol of removal 90% during 15min, and the iron powder circulated 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.
1 is iron powder degradation of phenol in iron dissolution situation map when Figure 10 is different catalysts degradation of phenol 30min, Figure 10 Iron dissolution block diagram during 30min, 2 be that the efficient out-phase class of carbon quantum dot load iron/ferroso-ferric oxide prepared by embodiment one is fragrant Iron dissolution block diagram during catalyst degradation phenol 30min, 3 be carbon quantum dot prepared by embodiment two load dendritic iron powders/ Iron dissolution block diagram during the efficient out-phase class fenton catalyst degradation of phenol 30min of ferroso-ferric oxide, 4 be prepared by embodiment three Iron dissolution column during the efficient out-phase class fenton catalyst degradation of phenol 30min of carbon quantum dot load iron/copper/ferroferric oxide 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 dendritic efficient out-phase class fenton catalyst of iron powder/ferroso-ferric oxide and embodiment The three efficient out-phase class fenton catalysts of carbon quantum dot load iron/copper/ferroferric oxide prepared are 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 stripping quantity is minimum, and carbon quantum dot prepared by embodiment two loads dendritic iron powder/tetra- and aoxidizes 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 respectively prepared by 5mg embodiments two loads dendritic iron powder/tetra- and aoxidizes 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 embodiments three Carbon quantum dot prepared by class fenton catalyst, 5mg example IVs loads the dendritic efficient out-phase class Fenton of iron powder/ferroso-ferric oxide and urged The efficient out-phase class fenton catalyst of carbon quantum dot load iron/copper/ferroferric oxide prepared by agent, 5mg embodiments five is added to During four parts of 50mL concentration are the phenol solution that 35mg/L, pH value are 4, then in the case where power is 15W four parts of phenol solutions are entered respectively Row ultrasound 10s, then H of the 34 μ L concentration for 30wt.% is separately added into four parts of phenol solutions under agitation2O2Solution, 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 described phenol solution is to use 0.1mol/L sulfuric acid solution regulation.
Figure 11 is 1 dendritic iron powder/tetra- of carbon quantum dot load prepared for embodiment two in the curve map of degradation of phenol, Figure 11 The curve of the efficient out-phase class fenton catalyst degradation of phenol of Fe 3 O, the 2 carbon quantum dot load irons prepared for embodiment three/ The curve of the efficient out-phase class fenton catalyst degradation of phenol of copper/ferroferric oxide, 3 be carbon quantum dot load prepared by example IV The curve of the dendritic efficient out-phase class fenton catalyst degradation of phenol of iron powder/ferroso-ferric oxide, 4 be carbon quantum prepared by 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, when small molecule solvent is different, and catalyst performance also can be by Influence, small molecule solvent is that the catalyst performance of the preparation of ethylene glycol is better than the catalyst performance that small molecule solvent is ethanol; 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 influences larger to catalyst, and small molecule solvent influences smaller to catalyst performance.However, it is noted that for Different solvent hot systems, can be caused obtaining by adjusting experiment parameter such as time, temperature, carbon source kind and quantity etc. Catalyst performance is optimal.Between each experiment parameter, with certain synergy.
In summary, 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 is greatly promoted, and the dissolution of iron also decreases.

Claims (10)

1. a kind of carbon quantum dot loads the preparation method of the efficient out-phase class fenton catalyst of iron-based material, it is characterised in that this method Specifically following steps are completed:
First, quantum dot precursor solution is prepared:
Carbon source is dissolved into deionized water, organic molecule solvent is added, is well mixed, obtains quantum dot presoma molten Liquid;
Carbon source described in step one is in glucose, sucrose, fructose, soluble starch, ascorbic acid, citric acid and ethylenediamine One kind or wherein several mixtures;
The quality of carbon source described in step one and the volume ratio of deionized water are (0g~0.5g):1mL;
The volume ratio of deionized water and organic molecule solvent described in step one is 1:(9~99);
2nd, iron or dendritic iron-copper powder are added in quantum dot precursor solution, then ultrasonic disperse 0.5min~2min, Obtain suspension;
The quality of iron or dendritic iron-copper powder described in step 2 and the volume ratio of quantum dot precursor solution for (1g~ 30g):1L;
What the dendritic iron-copper powder described in step 2 was specifically realized by the following steps:
1., electrolyte is placed in electrolytic cell, using fine copper electrode as negative electrode, using ring-shaped graphite electrode as anode, using leading The negative pole of dc source is connected by line with negative electrode, reuses wire and the positive pole of power supply is connected with anode, sets initial electricity Current density is 1.4A/dm2~1.6A/dm2, dc source 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 10s is reacted under 2 times of initial current density ~15s, stops reaction, dendritic copper alloy powder is obtained on negative electrode;
Step 2 1. described in electrolyte mixed by ferrous sulfate, copper sulphate, absolute ethyl alcohol and distilled water or by sulfuric acid Ferrous, absolute ethyl alcohol and distilled water are mixed;
2., dendritic copper alloy powder is cleaned 3 times~5 times first by deionized water, washes of absolute alcohol 3 times~5 is reused It is secondary, then dried in the case where temperature is 60 DEG C, obtain dendritic iron-copper powder;
3rd, suspension is transferred in polytetrafluoroethyllining lining, then polytetrafluoroethyllining lining is put into stainless steel cauldron, Stainless steel cauldron is put into the baking oven that temperature is 140 DEG C~220 DEG C and reacts 24h~28h, is obtained containing the molten of reaction product Liquid;
4th, the solution containing reaction product is filtered, collects powder, the powder of collection is cleaned 3 times using deionized water ~5 times, reuse absolute ethyl alcohol and the powder of collection is cleaned 3 times~5 times, then 4h is dried in vacuo in the case where temperature is 50 DEG C~70 DEG C ~12h, obtains the carbon quantum dot load efficient out-phase class fenton catalyst of iron-based material.
2. a kind of carbon quantum dot according to claim 1 loads the preparation side of the efficient out-phase class fenton catalyst of iron-based material Method, it is characterised in that the organic molecule solvent described in step one is one in absolute ethyl alcohol, ethylene glycol, propyl alcohol and propane diols Plant or wherein several mixed liquors.
3. a kind of carbon quantum dot according to claim 1 loads the preparation side of the efficient out-phase class fenton catalyst of iron-based material 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 0%~10% of total ion.
4. a kind of carbon quantum dot according to claim 1 loads the preparation side of the efficient out-phase class fenton catalyst of iron-based material Method, it is characterised in that step 2 1. described in electrolyte in absolute ethyl alcohol concentration be 20mL/L~40mL/L.
5. a kind of carbon quantum dot according to claim 1 loads the preparation side of the efficient out-phase class fenton catalyst of iron-based material Method, it is characterised in that the power of the ultrasonic disperse described in step 2 is 10W~20W.
6. a kind of carbon quantum dot according to claim 1 loads the preparation side of the efficient out-phase class fenton catalyst of iron-based material Method, it is characterised in that the quality of the carbon source described in step one and the volume ratio of deionized water are (0.1g~0.5g):1mL.
7. a kind of carbon quantum dot according to claim 1 loads the preparation side of the efficient out-phase class fenton catalyst of iron-based material Method, it is characterised in that the volume ratio of deionized water and organic molecule solvent described in step one is 1:(11~29).
8. a kind of carbon quantum dot according to claim 1 loads the preparation side of the efficient out-phase class fenton catalyst of iron-based material Method, it is characterised in that the volume ratio of deionized water and organic molecule solvent described in step one is 1:(29~59).
9. a kind of carbon quantum dot according to claim 1 loads the preparation side of the efficient out-phase class fenton catalyst of iron-based material Method, it is characterised in that the quality of iron or dendritic iron-copper powder described in step 2 and the volume of quantum dot precursor solution Than for (1g~10g):1L.
10. a kind of carbon quantum dot according to claim 1 loads the preparation of the efficient out-phase class fenton catalyst of iron-based material Method, it is characterised in that suspension is transferred in polytetrafluoroethyllining lining in step 3, then polytetrafluoroethyllining lining is put into In stainless steel cauldron, 24h~28h is reacted in stainless steel cauldron to be put into the baking oven that temperature is 140 DEG C~160 DEG C, is obtained To the solution containing reaction product.
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