CN104525201A - Non-homogeneous-phase Fenton catalyst with magnetism and preparing method and application thereof - Google Patents

Non-homogeneous-phase Fenton catalyst with magnetism and preparing method and application thereof Download PDF

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CN104525201A
CN104525201A CN201510005587.XA CN201510005587A CN104525201A CN 104525201 A CN104525201 A CN 104525201A CN 201510005587 A CN201510005587 A CN 201510005587A CN 104525201 A CN104525201 A CN 104525201A
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catalyst
microballoon
tio
rgo
ultra
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CN104525201B (en
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杨晓玲
张建鹏
陈玮
朱以华
李成佳
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Shanghai Wending Water Treatment Engineering Co Ltd
SHANGHAI WINNER ENVIRONMENTAL TECHNOLOGIES Co Ltd
East China University of Science and Technology
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Shanghai Wending Water Treatment Engineering Co Ltd
SHANGHAI WINNER ENVIRONMENTAL TECHNOLOGIES Co Ltd
East China University of Science and Technology
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Abstract

The invention relates to a non-homogeneous-phase Fenton catalyst with magnetism. The non-homogeneous-phase Fenton catalyst is a nuclear shell type microsphere Fe3O4@rGO@TiO2 of a three-layer structure. The submicron-level Fe3O4 microsphere serves as the inner core, the outmost layer is TiO2 small nanometer particles, and the Fe3O4 microsphere and the TiO2 small nanometer particles are bonded together through an rGO layer with the thickness ranging from 2 nm to 5 nm. The Fe3O4 microsphere is formed by stacking Fe3O4 small nanometer particles with the grain size ranging from 15 nm to 30 nm, and the microsphere grain size ranges from 300 nm to 400 nm. The grain size of the TiO2 small nanometer particles ranges from 5 nm to 15 nm. The non-homogeneous-phase Fenton catalyst is prepared in a neutral environment or Fenton reaction is conducted, the dissolution and losses of ferric salt are greatly reduced, efficient recycling of the catalyst is achieved, and meanwhile multi-time repeated use of the catalyst is guaranteed; the catalyst has good superparamagnetism, the magnetic response performance is excellent, and the catalyst is easy to recycle and can be separated completely within about 30 s under the action of an external magnetic field; the utilization rate of visible light is increased; furthermore, the material surface energy is lowered, the catalyst is not prone to agglomeration, dispersity is maintained, and thus the utilization rate of the catalyst is increased.

Description

Magnetic heterogeneous type Fenton catalyst of a kind of tool and its preparation method and application
Technical field
The present invention relates to nanometer material science and environmental science, particularly a kind of for the treatment of the Fe needed for poisonous in waste water from dyestuff, hardly degraded organic substance 3o 4@rGO@TiO 2heterogeneous type Fenton catalyst and preparation method thereof.
Background technology
The materials such as methylene blue (MB), rhodamine B, methyl red are the main components of waste water from dyestuff, and toxicity is degraded greatly and not easily, can bring very large injury to human body.Conventional physical absorption, flocculating setting, counter-infiltration, chemical oxidation etc. process waste water from dyestuff at present.Compared to other processing method, chemical oxidization method can make organic pollution mineralising that is stable, difficult degradation, forms CO 2, H 2the small-molecule substance that O and inorganic matter etc. are little to environmental injury, the problem that fundamentally can solve environmental pollution is thus more concerned.And in chemical oxidization method, Fenton technology can by means of only utilizing Fe 2+and H 2o 2between reaction formed high oxidation potential HO and the organic substance of difficult degradation is degraded, rapidly and efficiently, simple, with low cost, the good biocompatibility of operating process, and just can react under the condition of normal temperature and pressure, so instead of other chemical oxidation techniques gradually, be widely used in the process engineering of the waste water such as paper pulp papermaking, food, dyestuff.
A lot of deficiencies is there is in traditional Fenton technology in the application of reality, as: 1) its oxidative degradation must carry out under acid condition (pH=2 ~ 3), only has in acid condition, Fe 2+could more efficient catalysis H 2o 2be decomposed to form HO, and when pH value is too high, the molysite in system can be made to form hydroxide, flocculating setting occurs; Under these conditions, when the waste water that emission treatment is crossed, need the readjustment carrying out pH value, make that the pH value of solution reaches neutral, the flocculating setting thing of molysite dissolves and reaches discharge standard, this brings great inconvenience to experimental implementation, also more serious to the corrosion of equipment while increasing running cost; 2) as the Fe of catalyst 2+subsequent recovery difficult treatment; 3) Fe in Fenton system 2+with H 2o 2oxidized formation Fe after reaction 3+, and Fe 3+be reduced to Fe 2+speed much smaller than Fe 2+oxidized speed, so the Fe in Fenton system 2+concentration can significantly decline, cause Fe 2+with H 2o 2the speed that reaction generates HO slows down, thus makes most of H remaining in system 2o 2with the HO reaction generated, cause H 2o 2utilization rate low, consumption is large; Above Problems existing all can make that the efficiency of water treatment reduces, cost increases.In order to address this problem, a lot of scholars attempts the ferrous salt replacing homogeneous phase with the solid catalyst such as heterogeneous iron system, copper system, this heterogeneous solid catalyst also can with H 2o 2reaction generates HO, causes Fenton reaction.
Chinese invention patent (publication number CN101549294A) discloses one " magnetic Nano material for organic pollution process ", proposes magnetic Nano material and has catalysis H 2o 2produce the ability of great amount of hydroxy group free radical, wherein said magnetic Nano material comprises Fe 2o 3and Fe 3o 4magnetic nanoparticle, can carry out recovery by the method for Magneto separate to catalyst material and use, the number of times of recycling can reach 5 times.
Directly using free magnetic nanoparticle as Fenton catalyst, because the circulation conversion efficiency between iron ion is low, cause catalytic degradation effect not high, and magnetic nanoparticle is easily assembled in the solution, the specific area of catalyst is reduced, and degradation efficiency is lower; One of effective solution is by nano particle load on a support material to improve the dispersiveness of material, and and then optimizes catalytic degradation performance.Chinese invention patent (publication number CN103537323A) discloses one " preparation method of mesoporous magnetic iron ore base type Fenton catalyst ", proposes to utilize the degradation effect degradation effect as catalyst more independent than magnetic iron ore of the poly phenol/magnetic iron ore type Fenton catalyst rhodamine B degradation prepared good." poly phenol/magnetic iron ore type Fenton catalyst effectively can realize the fast transfer of electronics, impels Fe 3+to Fe 2+rapid conversion, accelerated decomposition persulfate produce free radical, thus the efficiency of the organic pollution in catalytic degradation waste water is increased ".Visible, to Fe 3o 4carry out effective finishing, the switching rate between iron ion can be accelerated, indirectly increase the decomposition rate of oxidation material, thus the catalytic degradation efficiency of organic pollution is improved.
Be used alone Fenton system, catalytic effect not by Fenton system with other external worlds system as, luminous energy, electric energy, ultrasonic etc., combine and will get well.Chinese invention patent (publication number CN102941091A) discloses one " photo-assisted Fenton nanocatalyst and preparation method thereof ", proposes α-Fe 2o 3some substitute is all the time for the ferrous salt catalyst of photo-assisted Fenton reaction, effectively can improve the utilization ratio of catalyst to ultraviolet light, increase the catalytic effect of catalyst system and catalyzing, result shows, under the condition of pH acidity, ultraviolet lighting, material can reach 99.0% to the degradation efficiency of phenol wastewater.Fenton catalyst is combined with luminous energy, the treatment effeciency of waste water can be improved significantly.But the many of at present research application is the catalytic degradation effect combining Fenton catalyst to improve with ultraviolet light Fenton system, but in natural environment, ultraviolet light only accounts for 3 ~ 5% of sunshine, causes material very low to the utilization rate of sunshine.
In sum, be used as the magnetic Nano material of Fenton System Catalyst at present, there are the following problems: 1) nano particle is easily reunited in the solution, reduces the effective ratio area contacted with organic substance, and reaction efficiency is reduced; 2) magnetic heterogeneous catalysis is used alone under the condition of pH neutrality, Fe 3+be reduced to Fe 2+speed low, can not effective catalyzing and decomposing H 2o 2form HO, the remote-effects degradation efficiency of organic pollution; 3) by luminous energy, electric energy or the extraneous condition such as ultrasonic, the catalytic efficiency of Fenton system can be improved.Therefore, find a kind of suitable material it is combined with magnetic Nano material, prepare compound heterogeneous catalysis agent material, under the condition of pH value neutrality, have good catalytic activity and recycle performance, giving full play to the effectiveness of Fenton reagent, is the problem needing now to solve.
Summary of the invention
In view of above problem, the object of the invention is a kind of efficient heterogeneous Fenton-like composite of preparation, Fe can be realized under the condition that pH value is neutral 3+with Fe 2+rapid translating, increase Fe 2+catalysis H 2o 2generate the speed of HO, and still have higher catalytic activity after repeatedly recycling.Specific as follows:
The magnetic heterogeneous type Fenton catalyst of a kind of tool, described heterogeneous type Fenton catalyst is the core-shell microsphere Fe with three-decker 3o 4@rGO@TiO 2, wherein, with the Fe of submicron order 3o 4microballoon is kernel, and outermost layer is TiO 2nanometer granule, described Fe 3o 4microballoon and described TiO 2the rGO layer (" reduced graphene " layer) being 2 ~ 5nm by thickness between nanometer granule combines;
Described Fe 3o 4microballoon is by the Fe of 15 ~ 30nm 3o 4nanometer granule is piled up, and microspherulite diameter is 300 ~ 400nm;
Described TiO 2the short grained particle diameter of nanometer is about 5 ~ 15nm.
The preparation method of the magnetic heterogeneous type Fenton catalyst of above-mentioned tool, first adopts hydro-thermal method to prepare Fe 3o 4microballoon, then by the method for finishing, electrostatic self-assembled, GO layer (" Graphene " layer) is coated to Fe 3o 4the surface of microballoon, and then on GO layer, grow TiO by hydro-thermal 2nano particle, realizes the partial reduction of GO simultaneously.Concrete steps are as follows:
(1) hydro-thermal method prepares Fe 3o 4microballoon
By FeCl 3: trisodium citrate: sodium acetate is that 1:0.1 ~ 0.4:1 ~ 3 (mass ratio) join in ethylene glycol successively, and after stirring, transfer in water heating kettle, hydro-thermal reaction 8 ~ 12h, is cooled to room temperature at 200 ~ 250 DEG C, centrifugation, product Fe 3o 4after microballoon absolute ethyl alcohol and ultra-pure water wash 3 times respectively, drying for standby;
(2) Fe 3o 4the preparation of@GO microballoon
By the 0.3 ~ 0.7g Fe obtained in step 1 3o 4microballoon ultrasonic disperse in the isopropyl alcohol of 35 ~ 65mL, then adds the silane coupler (APTMS) of 0.5 ~ 1.5mL, and reflux 18 ~ 24h at 50 ~ 80 DEG C, is cooled to room temperature, centrifugation, the Fe that the product silane coupling agent obtained is modified 3o 4after microballoon ethanol and ultra-pure water wash 3 times respectively, drying for standby;
By the Fe that above-mentioned 0.3 ~ 0.7g silane coupler is modified 3o 4microballoon ultrasonic disperse is in the ultra-pure water of 100 ~ 150mL, and add the aqueous solution of GO of 100 ~ 150mL, 0.5 ~ 1.5mg/L, stir, centrifugation, obtains product Fe 3o 4after@GO microballoon ethanol and ultra-pure water wash 3 times respectively, drying for standby;
(3) Fe 3o 4@rGO@TiO 2the preparation of nano particle
Get the Fe of preparation in 20 ~ 60mg step 2 3o 4@GO microballoon, ultrasonic disperse is in the aqueous isopropanol of 25 ~ 50mL, to add after the TBOT of 100 ~ 200 μ L ultrasonic 30 ~ 50min under room temperature, dropwise add the ultra-pure water of 1.0 ~ 1.5mL, mixing 30 ~ 50min, proceeds to mixed solution in water heating kettle, 8 ~ 10h is reacted at 180 ~ 200 DEG C, be cooled to room temperature, centrifugation, obtain described Fe 3o 4@rGO@TiO 2after microballoon ethanol and ultra-pure water wash 3 times respectively, drying for standby.
Preferably, described FeCl 3: trisodium citrate: the mass ratio of sodium acetate is 1:0.2:2.
The application of the magnetic heterogeneous type Fenton catalyst of above-mentioned tool, at the magnetic heterogeneous type Fenton catalyst of described tool and H 2o 2in simultaneous situation, react with waste water from dyestuff, the organic substance MB (adding above) of the difficult degradation in degrading waste water; Wherein, with MB as simulated wastewater.
After wastewater treatment completes, utilize Fe 3o 4-rGO-TiO 2the magnetic of nano particle, carries out separation and recovery with magnet by catalyst, reuses.
Advantage applies of the present invention exists: the core of (1) catalyst is by Fe 3o 4the Fe of the submicron order that nanometer granule is piled up 3o 4microballoon forms, and has good superparamagnetism, magnetic response function admirable, is easy to reclaim, and under the effect of external magnetic field, can reach thorough separation at about 30s; (2) relative to other materials, Fe under the condition of pH acidity is needed 2+generating rate could than very fast, the catalyst material prepared is owing to there being semiconductor TiO 2existence, by conductive layer rGO, light induced electron can be passed to Fe fast under the condition of illumination 3+, accelerate Fe 3+be reduced to Fe 2+speed, make Fe 3o 4-rGO-TiO 2under pH neutrallty condition, have good catalytic performance, the neutrallty condition of guarantee system can reduce dissolving and the loss of molysite greatly, realizes the high efficiente callback of catalyst, ensures repeatedly using of catalyst simultaneously; (3) according to document (Advanced Material 2012,24,1084 – 1088) report, the existence of GO can increase TiO 2nano particle, to the utilization rate of visible ray, makes the TiO that originally can only absorb ultraviolet light 2also the transition of electronics can be there is in nano particle under the condition of visible ray; (4) the coated and TiO of graphene layer 2the existence of nano particle makes the Fe as kernel 3o 4microsphere surface can reduce, and not easily reunites, maintains Fe 3o 4-rGO-TiO 2dispersiveness, thus improve the utilization rate of catalyst.
Accompanying drawing explanation
Fig. 1 is the Fe that embodiment 1 prepares 3o 4the SEM photo of microballoon;
Fig. 2 is the Fe that embodiment 1 prepares 3o 4@rGO@TiO 2the photo of the TEM of microballoon;
Fig. 3 is with the Fe prepared in embodiment 2 3o 4@rGO@TiO 2as the cycle down solution curve figure that catalyst degradation MB obtains.
Detailed description of the invention
By the following examples to of the present invention a kind of be easy to the heterogeneous Fenton catalyst of Magneto separate preparation method and its application be specifically described, but embodiment is only for the present invention is further described, does not limit the scope of the invention.
Embodiment 1
(1) Fe 3o 4the preparation of microballoon: by 1.3gFeCl 3, 0.5g trisodium citrate, 2.0g sodium acetate joins in the ethylene glycol of 40mL successively, after stirring, is transferred to by mixed solution in the water heating kettle of 100mL, at 200 DEG C after hydro-thermal reaction 10h, is cooled to room temperature, centrifugal, the Fe obtained 3o 4microballoon absolute ethyl alcohol and ultra-pure water wash 3 times respectively, drying for standby;
(2) GO-Fe 3o 4preparation: get the above-mentioned Fe prepared of 0.4g 3o 4microballoon, ultrasonic disperse is in the isopropyl alcohol of 50mL, and add the silane coupler (APTMS) of 1mL in mixed solution after, reflux 24h at 65 DEG C, is cooled to room temperature, centrifugal, by the Fe modified with APTMS prepared 3o 4microballoon ethanol and ultra-pure water wash 3 times respectively, drying for standby.By the Fe that the above-mentioned 0.4g APTMS prepared modifies 3o 4microballoon mixes with the GO of 150mL ultra-pure water, 100mL 0.5mg/mL, after stirring 2h, centrifugal, the GO-Fe obtained 3o 43 times are washed respectively, drying for standby with ethanol and ultra-pure water.
(3) Fe 3o 4-rGO-TiO 2the preparation of Nano microsphere: get that 30mg is above-mentioned prepares GO-Fe 3o 4ultrasonic disperse, in 25mL isopropyl alcohol, to add after 100uLTBOT ultrasonic 30min under room temperature, then in mixed solution, dropwise adds 1mL ultra-pure water in mixed solution, stir 30min, mixed solution is proceeded in 50mL water heating kettle, at 180 DEG C, react 8h, be cooled to room temperature, centrifugal, the Fe obtained 3o 4-rGO-TiO 2microballoon ethanol and ultra-pure water wash 3 times respectively, drying for standby.
(4) light is adopted to help-the dye wastewater of heterogeneous Fenton-like method process MB, with the round-bottomed flask of 50mL for reactor, adopt Xe lamp as light source, with optical filter, the light below 400nm wavelength is filtered, the initial concentration of MB dye wastewater is 10mg/L, adds the Fe of 1.5g/L in waste water 3o 4-rGO-TiO 2catalyst microspheres, after stirring 0.5h, adds the H of 0.176mol/L in system 2o 2, carry out in process in reaction, take out a certain amount of reactant liquor in different preset times in section, centrifugal or with magnet, catalyst is separated completely, supernatant liquor is carried out UV detect to determine the change in concentration of MB.
Result shows, with Fe 3o 4-rGO-TiO 2nano microsphere is fine as the effect of the heterogeneous Fenton method process MB dye wastewater of catalyst, and after reaction 2h, the clearance of MB reaches more than 99%.
(5) by the catalyst Fe in step 4 3o 4-rGO-TiO 2be separated completely by attraction or centrifugal method, with second alcohol and water by Fe 3o 4-rGO-TiO 2catalyst microspheres washing is for several times, dry, then repeats the experimental implementation in step 4.
Result shows, the Fe that secondary uses 3o 4-rGO-TiO 2catalyst microspheres still keeps good catalytic effect, and after reaction 2h, the clearance of MB reaches more than 93%.
(6) experimental implementation in repetition step 58 times.
Comparative example 1
Repeat embodiment 1 step 4, by " the Fe in embodiment 1 step 4 3o 4@rGO@TiO 2catalyst microspheres " be adjusted to " Fe in step 1 in embodiment 1 3o 4microballoon ", other conditions are all identical.
After reaction 2h, the clearance of MB only has 47.2%.
Comparative example 2
According to document (Journal of Colloid and Interface Science 2005,289,125-131), prepare SiO by sol-gel process 2microballoon, radius is 300-400nm, with " the Fe prepared in embodiment 1 step 1 3o 4microballoon " particle diameter similar, use SiO 2microballoon, as stratum nucleare, repeats step 2,3 in embodiment 1, obtains SiO 2@rGO@TiO 2microballoon.By " the Fe in embodiment 1 step 4 3o 4@rGO@TiO 2catalyst microspheres " be adjusted to " SiO prepared 2@rGO@TiO 2microballoon ", other conditions are identical, repeat embodiment 1 step 4.
After reaction 2h, the clearance of MB only has 48.3%.

Claims (4)

1. the magnetic heterogeneous type Fenton catalyst of tool, is characterized in that, described heterogeneous type Fenton catalyst is the core-shell microsphere Fe with three-decker 3o 4@rGO@TiO 2, wherein, with the Fe of submicron order 3o 4microballoon is kernel, and outermost layer is TiO 2nanometer granule, described Fe 3o 4microballoon and described TiO 2the rGO layer being 2 ~ 5nm by thickness between nanometer granule combines;
Described Fe 3o 4microballoon is by the Fe of 15 ~ 30nm 3o 4nanometer granule is piled up, and microspherulite diameter is 300 ~ 400nm;
Described TiO 2the short grained particle diameter of nanometer is about 5 ~ 15nm.
2. the preparation method of the magnetic heterogeneous type Fenton catalyst of tool according to claim 1, is characterized in that, comprise the steps:
(1) hydro-thermal method prepares Fe 3o 4microballoon
By FeCl by quality ratio 3: trisodium citrate: sodium acetate is that 1:0.1 ~ 0.4:1 ~ 3 join in ethylene glycol successively, and after stirring, transfer in water heating kettle, hydro-thermal reaction 8 ~ 12h, is cooled to room temperature at 200 ~ 250 DEG C, centrifugation, product Fe 3o 4after microballoon absolute ethyl alcohol and ultra-pure water wash 3 times respectively, drying for standby;
(2) Fe 3o 4the preparation of@GO microballoon
By the 0.3 ~ 0.7g Fe obtained in step 1 3o 4microballoon ultrasonic disperse in the isopropyl alcohol of 35 ~ 65mL, then adds the silane coupler of 0.5 ~ 1.5mL, and reflux 18 ~ 24h at 50 ~ 80 DEG C, is cooled to room temperature, centrifugation, the Fe that the product silane coupling agent obtained is modified 3o 4after microballoon ethanol and ultra-pure water wash 3 times respectively, drying for standby;
By the Fe that above-mentioned 0.3 ~ 0.7g silane coupler is modified 3o 4microballoon ultrasonic disperse is in the ultra-pure water of 100 ~ 150mL, and add the aqueous solution of GO of 100 ~ 150mL, 0.5 ~ 1.5mg/L, stir, centrifugation, obtains product Fe 3o 4after@GO microballoon ethanol and ultra-pure water wash 3 times respectively, drying for standby;
(3) Fe 3o 4@rGO@TiO 2the preparation of nano particle
Get the Fe of preparation in 20 ~ 60mg step 2 3o 4@GO microballoon, ultrasonic disperse is in the aqueous isopropanol of 25 ~ 50mL, to add after the TBOT of 100 ~ 200 μ L ultrasonic 30 ~ 50min under room temperature, dropwise add the ultra-pure water of 1.0 ~ 1.5mL, mixing 30 ~ 50min, proceeds to mixed solution in water heating kettle, 8 ~ 10h is reacted at 180 ~ 200 DEG C, be cooled to room temperature, centrifugation, obtain described Fe 3o 4@rGO@TiO 2after microballoon ethanol and ultra-pure water wash 3 times respectively, drying for standby.
3. preparation method according to claim 2, is characterized in that, described FeCl 3: trisodium citrate: the mass ratio of sodium acetate is 1:0.2:2.
4. the application of the magnetic heterogeneous type Fenton catalyst of the tool of claim 1, is characterized in that, at the magnetic heterogeneous type Fenton catalyst of described tool and H 2o 2in simultaneous situation, react with waste water from dyestuff, the organic substance MB of the difficult degradation in degrading waste water; Wherein, with MB as simulated wastewater.
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CN106238053A (en) * 2016-07-06 2016-12-21 华南理工大学 A kind of light fenton catalyst Fe3o4/ rGO/TiO2and its preparation method and application
CN106006857A (en) * 2016-07-12 2016-10-12 中国石油化工股份有限公司 Method for degrading organic dye wastewater through graphene electrode and photoelectric Feton cooperatively
CN106076337A (en) * 2016-07-14 2016-11-09 中国科学院生态环境研究中心 A kind of composite photocatalyst material and preparation method thereof
CN106732232B (en) * 2016-12-30 2018-10-02 哈尔滨工业大学 A kind of preparation method of the yolk type Fenton microreactor of inner surface supported precious metal nano-particle
CN106732232A (en) * 2016-12-30 2017-05-31 哈尔滨工业大学 A kind of preparation method of the yolk type Fenton microreactor of inner surface supported precious metal nano-particle
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CN107381863A (en) * 2017-07-24 2017-11-24 河北师范大学 A kind of degraded highly salt containing organic waste water and the method for synchronously preparing iron oxide
CN108114720A (en) * 2017-12-28 2018-06-05 中国矿业大学(北京) A kind of preparation method of heterogeneous smooth Fenton catalysis material
CN108686655A (en) * 2018-04-25 2018-10-23 陕西科技大学 A kind of preparation method of dynamic Fenton-titanium dioxide coupling photochemical catalyst for environment remediation
CN108686655B (en) * 2018-04-25 2021-01-12 陕西科技大学 Preparation method of dynamic Fenton-titanium dioxide coupling photocatalyst for environmental remediation
CN109821532A (en) * 2019-02-27 2019-05-31 知合环境（北京）有限责任公司 A kind of modified ozone oxidation catalyst of magnetic oxygenated graphene and preparation method thereof
CN109879482A (en) * 2019-04-10 2019-06-14 华东交通大学 A kind of method of high magnetic graphene catalytic treatment coking wastewater
CN110104757A (en) * 2019-06-10 2019-08-09 青岛大学 Organic Pollutants in Wastewater minimizing technology based on type nanocomposite of ringing a bell
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CN112979008A (en) * 2021-05-11 2021-06-18 生态环境部华南环境科学研究所 Treatment method of thallium-containing wastewater
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