CN103816901A - Magnetic nano composite photocatalytic material based on graphene and preparation method thereof - Google Patents

Magnetic nano composite photocatalytic material based on graphene and preparation method thereof Download PDF

Info

Publication number
CN103816901A
CN103816901A CN201410065594.4A CN201410065594A CN103816901A CN 103816901 A CN103816901 A CN 103816901A CN 201410065594 A CN201410065594 A CN 201410065594A CN 103816901 A CN103816901 A CN 103816901A
Authority
CN
China
Prior art keywords
graphene
tio
preparation
nano composite
magnetic
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201410065594.4A
Other languages
Chinese (zh)
Inventor
姜炜
马培昌
沈萍
谢覃
李凤生
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Nanjing University of Science and Technology
Original Assignee
Nanjing University of Science and Technology
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nanjing University of Science and Technology filed Critical Nanjing University of Science and Technology
Priority to CN201410065594.4A priority Critical patent/CN103816901A/en
Publication of CN103816901A publication Critical patent/CN103816901A/en
Pending legal-status Critical Current

Links

Images

Landscapes

  • Catalysts (AREA)
  • Carbon And Carbon Compounds (AREA)

Abstract

The invention discloses a magnetic nano composite photocatalytic material based on graphene and a preparation method thereof. The material is a novel multifunctional composite material formed by loading TiO2 nanoparticles having a photocatalytic property and Fe3O4 nanoparticles having a magnetic recycling effect on a graphene sheet layer. The preparation method of the material comprises the steps: preparing the paramagnetic Fe3O4 particles by a solvent thermal method; preparing the anatase TiO2 particles directly by a gas thermal method; carrying out ultrasonic dispersion of graphite oxide in a water and ethanol solution to obtain a graphene oxide solution; directly dispersing the synthesized TiO2 particles and the synthesized Fe3O4 particles in the graphene oxide solution; transferring the reaction system to a hydrothermal kettle, and carrying out a reaction; and finally, carrying out magnet separation, washing, and drying to obtain the Fe3O4/TiO2/graphene nano composite photocatalytic material. The hydrothermal method not only allows graphite oxide to be reduced into graphene, but also allows the two kinds of nanoparticles to be loaded on the graphene sheet layer. The preparation process is simple, and moreover, the product is the environment-friendly type photocatalytic composite material which has high efficiency and low cost and can be magnetically recycled.

Description

A kind of magnetic Nano composite photocatalyst material based on Graphene and preparation method thereof
Technical field
The invention belongs to new material and preparing technical field thereof, be specifically related to a kind of magnetic Nano composite photocatalyst material based on Graphene and preparation method thereof.
Background technology
Since Fujishima in 1972 and Honda reported first TiO 2electrode occurs that under illumination water catalytic decomposition generates hydrogen and oxygen.TiO 2cause that from the organic pollution in factory and life people pay close attention to greatly as low toxicity, low cost, efficient photocatalyst for degrading.But, pure TiO 2mainly under ultraviolet light, have an effect, and the easy combination of light induced electron and hole, simultaneously TiO 2nano particle is difficult for reclaiming, and has seriously limited TiO 2extensive use.Therefore, adopt distinct methods to TiO 2carry out modification, suppress the combination in light induced electron and hole, thereby the photocatalysis efficiency of raising photochemical catalyst becomes the research emphasis of this area.
In 2004, the employing micromechanics stripping methods such as British scholar Novoselov have successfully been prepared the superthin layer grapheme material of two-dimensional structure, this material is the former molecular two-dimensional nanostructure of monolayer carbon, there is large specific area, higher electron mobility, the mechanical strength of excellence and good translucidus, started the research boom of a grapheme material.At present, Graphene is due to its unique electron transport property, it is combined with semiconductor light-catalyst and can serves as " wire " that electronics transmits, reduce the combination in light induced electron and hole, thereby improve photocatalysis efficiency [Ping Wang, Jin Wang, Xuefei Wang, Huogen Yu, Jiaguo Yu, Ming Lei, Yonggang Wang, One-step synthesis of easy-recycling TiO2-rGO nanocomposite photocatalysts with enhance photocatalytic activity, Applied Catalytic B:Environmental 132-133 (2013) 452-459].
In recent years, ecological deterioration problem becomes increasingly conspicuous, and photocatalysis is as a kind of low cost, and free of contamination green technology processing environment pollutes the extensive concern that has caused scientist.And photocatalyst for degrading organic polluting water is conventionally in solid-liquid system, for fear of the wasting of resources, secondary pollution, the separation of catalyst and recovery problem are absolutely necessary.Therefore, catalyst that can Magnetic Isolation can keep higher catalytic efficiency in suspension system, again can be under additional magnetic after reaction convenient separation, recycle [Kou Shengzhong, Hu Congli. nano-photocatalyst TiO 2/ Fe 3o 4preparation and characterization [J]. application chemical industry, 2008,37 (1): 67-70].
For TiO 2the study on the modification discovery of conductor photocatalysis material, there be limited evidence currently of researcher is by the TiO of photocatalysis performance 2, the Fe of magnetic recovery 3o 4with together with three kinds of combinations of materials of Graphene of excellent properties, be configured to a kind of megnetic nano composite photocatalyst based on Graphene.This trielement composite material can not only keep higher photocatalysis efficiency in photocatalytic process, and after reaction, can under magnetic fields power, be convenient to reclaim, and recycles.Therefore, from economizing on resources, the angle reducing costs is set out, and prepares a kind of magnetic Nano composite photocatalyst material based on Graphene and has vast potential for future development.
Summary of the invention
The object of the present invention is to provide a kind of magnetic Nano composite photocatalyst material based on Graphene and preparation method thereof, it is characterized in that by electrostatic interaction Fe 3o 4, TiO 2be combined with graphene oxide, under hydro-thermal reaction, graphene oxide is reduced into Graphene, simultaneously Fe 3o 4, TiO 2nano particle loads on respectively on graphene sheet layer, is a kind of Multifunction tri compound catalysis material.
Realizing technical scheme of the present invention is:
A magnetic Nano composite photocatalyst material based on Graphene, described catalysis material is by TiO 2nano particle and Fe 3o 4nano particle directly loads on graphene sheet layer and forms; Described Fe 3o 4, TiO 2mass ratio be 1:1-4.Its preparation method specifically comprises the steps:
The first step, adopts solvent-thermal method to prepare the Fe of superparamagnetism 3o 4nano particle;
Second step, adopts hydro-thermal method directly to prepare anatase TiO 2nano particle, changes crystal formation without high-temperature calcination;
The 3rd step, by graphite oxide with surfactant is ultrasonic in water and ethanolic solution is dispersed into graphene oxide solution, and adds surfactant;
The 4th step, by synthetic Fe 3o 4nanoparticle and TiO 2nano particle is dispersed in graphene oxide solution;
The 5th step, is transferred to the reaction system of the 4th step in water heating kettle and reacts;
The 6th step, separates the product of the 5th step by externally-applied magnetic field, and with deionized water washing, obtains Fe after vacuum drying 3o 4/ TiO 2/ graphene nano composite photocatalyst material.
Wherein, the water described in the 3rd step and the volume ratio 1:1-3 of ethanol.The surfactant of described interpolation is neopelex, and quality is 0-1 g.
The temperature of the hydro-thermal reaction described in the 5th step is 100-200 ℃, and the time is 3-12 h.
Compared with prior art, its remarkable advantage is in the present invention: (1) Graphene has larger specific area, sets it as backing material, can the magnetic Fe of load tool 3o 4particle and the TiO with photocatalysis property 2particle, forms a kind of multifunctional composite, and Graphene has excellent transmission electronic ability, TiO simultaneously 2under illumination, the light induced electron exciting is easily transferred to Graphene surface, has suppressed the combination in light induced electron and hole, thereby has improved photocatalysis efficiency, under the background that is difficult for reclaiming at catalysis material, by adding magnetic Fe 3o 4particle, makes composite be easy to reclaim, and recycling, has avoided the waste of resource, has good application prospect and economic benefits.The method adopts simple hydro-thermal method not only graphene oxide to be reduced into Graphene, simultaneously also by two kinds of nanometer particle loads on graphene sheet layer.The method is simple, and reagent is cheap, is conducive to large-scale preparation, simultaneously for the composite of more difference in functionalitys provides a kind of simple, and feasible new method.
 
Below in conjunction with accompanying drawing, the present invention is described in further detail.
Accompanying drawing explanation
Fig. 1 is raw material graphite oxide of the present invention (a), synthetic material Fe 3o 4(b), TiO 2and Fe (c) 3o 4/ TiO 2the XRD image of/graphene composite material (d).
Fig. 2 is the TEM image of the magnetic Nano composite photocatalyst material of Graphene of the present invention.
Fig. 3 is the magnetic schematic diagram of the magnetic Nano composite photocatalyst material of Graphene of the present invention.
The specific embodiment
The following examples can make the present invention of those skilled in the art comprehend.
Embodiment 1
(1) superparamagnetism Fe 3o 4the preparation of nano particle.Adopt traditional solvent-thermal method to prepare Fe 3o 4nano particle, the ferric sesquichloride of 1.35 g is dissolved in to 40 mL ethylene glycol, then add the polyglycol surfactants of 1 g and the ammonium acetate of 4 g, after ultrasonic several minutes, transfer in 100 mL reactors and under 200 oC, react 16 h, naturally cooling, water and ethanol is washing several alternately, natural drying, obtain having certain hollowness, Fig. 1 (b) is shown in by the XRD collection of illustrative plates of product.In Fig. 1 (b), diffraction maximum is mainly at 30.1 °, 35.5 °, 43.3 °, 57.0 ° and 62.6 °, respectively corresponding magnetic Fe 3o 4(220), (311), (400), (511) and (440) characteristic peak;
(2) anatase TiO 2the preparation of nano particle.In the small beaker of 20 mL, the butyl titanate (TBOT) of getting 1 mL is dispersed in the absolute ethyl alcohol of 10 mL, then small beaker is transferred in the reactor that deionized water is housed, under 150 oC, react 10 h, naturally cool to room temperature, centrifugation, under 50 oC, vacuum drying 8h, obtains anatase TiO 2nano particle, Fig. 1 (c) is shown in by the XRD collection of illustrative plates of product.In Fig. 1 (c), diffraction maximum, mainly at 25.4 °, 38.0 °, 48.0 °, 53.9 °, 54.7 ° and 62.7 °, is distinguished corresponding anatase TiO 2(101), (112), (200), (105), (211) and (204) characteristic peak;
(3) preparation of graphene oxide solution.The graphite oxide of 20 mg (GO) is dispersed in the deionized water mixed solution of 40 mL ethanol and 20 mL to ultrasonic time 30 min;
(4) in the graphene oxide solution forming in step (3), add respectively the Fe of 0.1 g SDBS surfactant, 50 mg 3o 4tiO with 50 mg 2, ultrasonic time 1 h;
(5) reaction system step (4) being formed is transferred in reactor, reacts 3 h under 120 oC, naturally cooling, and ethanol and water wash respectively for several times, and under 50 oC, vacuum drying 8 h, finally obtain Fe 3o 4/ TiO 2/ graphene nanocomposite material, Fig. 1 (d) is shown in by the XRD collection of illustrative plates of product.In Fig. 1 (d), diffraction maximum had both comprised magnetic Fe 3o 4characteristic peak also comprised anatase TiO 2characteristic peak, implied that this composite is by magnetic Fe 3o 4with anatase TiO 2composition.TEM figure is shown in Fig. 2, and Magnetic Isolation figure is shown in Fig. 3;
Embodiment 2
(1) with the step in embodiment 1 (1);
(2) with the step in embodiment 1 (2);
(3) preparation of graphene oxide solution.The graphite oxide of 20 mg (GO) is dispersed in the deionized water mixed solution of 40 mL ethanol and 20 mL to ultrasonic time 30 min;
(4) with the step in embodiment 1 (4);
(5) reaction system step (4) being formed is transferred in reactor, reacts 6 h under 120 oC, naturally cooling, and ethanol and water wash respectively for several times, and under 50 oC, vacuum drying 8 h, finally obtain Fe 3o 4/ TiO 2/ graphene nanocomposite material.
Embodiment 3
(1) with the step in embodiment 1 (1);
(2) with the step in embodiment 1 (2);
(3) preparation of graphene oxide solution.The graphite oxide of 20 mg (GO) is dispersed in the deionized water mixed solution of 40 mL ethanol and 20 mL to ultrasonic time 30 min;
(4) in the graphene oxide solution forming in step (3), add respectively the Fe of 0.5 g SDBS surfactant, 50 mg 3o 4tiO with 100 mg 2, ultrasonic time 1 h; ;
(5) reaction system step (4) being formed is transferred in reactor, reacts 3 h under 150 oC, naturally cooling, and ethanol and water wash respectively for several times, and under 50 oC, vacuum drying 8 h, finally obtain Fe 3o 4/ TiO 2/ graphene nanocomposite material.
Embodiment 4:
(1) with the step in embodiment 1 (1);
(2) with the step in embodiment 1 (2);
(3) preparation of graphene oxide solution.The graphite oxide of 20 mg (GO) is dispersed in the deionized water mixed solution of 60 mL ethanol and 20 mL to ultrasonic time 30 min;
(4) in the graphene oxide solution forming in step (3), add respectively the Fe of 0.5 g SDBS surfactant, 50 mg 3o 4tiO with 150 mg 2, ultrasonic time 1 h;
(5) reaction system step (4) being formed is transferred in reactor, reacts 6 h under 150 oC, naturally cooling, and ethanol and water wash respectively for several times, and under 50 oC, vacuum drying 8 h, finally obtain Fe 3o 4/ TiO 2/ graphene nanocomposite material.
Embodiment 5:
(1) with the step in embodiment 1 (1);
(2) with the step in embodiment 1 (2);
(3) preparation of graphene oxide solution.The graphite oxide of 20 mg (GO) is dispersed in the deionized water mixed solution of 60 mL ethanol and 20 mL to ultrasonic time 30 min;
(4) in the graphene oxide solution forming in step (3), add respectively the Fe of 0 g SDBS surfactant, 50 mg 3o 4tiO with 50 mg 2, ultrasonic time 1 h;
(5) reaction system step (4) being formed is transferred in reactor, reacts 3 h under 180 oC, naturally cooling, and ethanol and water wash respectively for several times, and under 50 oC, vacuum drying 8 h, finally obtain Fe 3o 4/ TiO 2/ graphene nanocomposite material.
Embodiment 6:
(1) with the step in embodiment 1 (1);
(2) with the step in embodiment 1 (2);
(3) preparation of graphene oxide solution.The graphite oxide of 20 mg (GO) is dispersed in the deionized water mixed solution of 60 mL ethanol and 20 mL to ultrasonic time 30 min;
(4) in the graphene oxide solution forming in step (3), add respectively the Fe of 0g SDBS surfactant, 50 mg 3o 4tiO with 50 mg 2, ultrasonic time 1 h;
(5) reaction system step (4) being formed is transferred in reactor, reacts 6 h under 180 oC, naturally cooling, and ethanol and water wash respectively for several times, and under 50 oC, vacuum drying 8 h, finally obtain Fe 3o 4/ TiO 2/ graphene nanocomposite material.

Claims (5)

1. the magnetic Nano composite photocatalyst material based on Graphene, is characterized in that described catalysis material is by TiO 2nano particle and Fe 3o 4nano particle directly loads on graphene sheet layer and forms; Described Fe 3o 4, TiO 2mass ratio be 1:1-4.
2. the preparation method of the magnetic Nano composite photocatalyst material of Graphene according to claim 1, is characterized in that specifically comprising the steps:
The first step, adopts solvent-thermal method to prepare the Fe of superparamagnetism 3o 4nano particle;
Second step, adopts hydro-thermal method directly to prepare anatase TiO 2nano particle, changes crystal formation without high-temperature calcination;
The 3rd step, by graphite oxide with surfactant is ultrasonic in water and ethanolic solution is dispersed into graphene oxide solution, and adds surfactant;
The 4th step, by synthetic Fe 3o 4nanoparticle and TiO 2nano particle is dispersed in graphene oxide solution;
The 5th step, is transferred to the reaction system of the 4th step in water heating kettle and reacts;
The 6th step, separates the product of the 5th step by externally-applied magnetic field, and with deionized water washing, obtains Fe after vacuum drying 3o 4/ TiO 2/ graphene nano composite photocatalyst material.
3. the preparation method for material of the magnetic Nano composite photocatalyst material of Graphene described in claim 1, is characterized in that: the water described in the 3rd step and the volume ratio 1:1-3 of ethanol.
4. the material preparation method of the magnetic Nano composite photocatalyst material of Graphene described in claim 1, is characterized in that: in the 3rd step, the surfactant of described interpolation is neopelex, and quality is 0-1 g.
5. the preparation method of the magnetic Nano composite photocatalyst material of Graphene described in claim 1, is characterized in that: the temperature of the hydro-thermal reaction described in the 5th step is 100-200 ℃, the time is 3-12 h.
CN201410065594.4A 2014-02-26 2014-02-26 Magnetic nano composite photocatalytic material based on graphene and preparation method thereof Pending CN103816901A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201410065594.4A CN103816901A (en) 2014-02-26 2014-02-26 Magnetic nano composite photocatalytic material based on graphene and preparation method thereof

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201410065594.4A CN103816901A (en) 2014-02-26 2014-02-26 Magnetic nano composite photocatalytic material based on graphene and preparation method thereof

Publications (1)

Publication Number Publication Date
CN103816901A true CN103816901A (en) 2014-05-28

Family

ID=50752359

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201410065594.4A Pending CN103816901A (en) 2014-02-26 2014-02-26 Magnetic nano composite photocatalytic material based on graphene and preparation method thereof

Country Status (1)

Country Link
CN (1) CN103816901A (en)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104874398A (en) * 2015-05-26 2015-09-02 上海大学 Preparation method for recyclable titanium dioxide (P25)/graphene/iron oxide ternary photocatalytic material
CN104907070A (en) * 2015-04-09 2015-09-16 宁波西博恩新材料科技有限公司 Alpha-Fe2O3 / graphene nanocomposite surface enhanced Raman scattering substrate and photocatalyst and preparation method thereof
CN104962232A (en) * 2015-06-24 2015-10-07 南京理工大学 Fe3O4@BaTiO3/RGO ternary composite wave-absorbing material and preparation method thereof
CN110152668A (en) * 2019-06-19 2019-08-23 张斌翔 A kind of preparation method of composite titania material photocatalyst catalyst
CN110152600A (en) * 2018-03-01 2019-08-23 济南开发区星火科学技术研究院 The preparation method of the graphite oxide aerogel with high reusing for water process
CN114146708A (en) * 2021-11-26 2022-03-08 哈尔滨工业大学（深圳） Magnetic TiO2Matrix modified photocatalyst and preparation and application thereof

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110260270A1 (en) * 2010-04-26 2011-10-27 Headway Technologies Inc. MR enhancing layer (MREL) for spintronic devices
CN103007944A (en) * 2012-12-13 2013-04-03 同济大学 Preparation method of graphene-based magnetic composite visible light catalysis material Fe3O4-G-TiO2

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20110260270A1 (en) * 2010-04-26 2011-10-27 Headway Technologies Inc. MR enhancing layer (MREL) for spintronic devices
CN103007944A (en) * 2012-12-13 2013-04-03 同济大学 Preparation method of graphene-based magnetic composite visible light catalysis material Fe3O4-G-TiO2

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
YUE LIN等: ""Ternary Graphene-TiO2-Fe3O4 Nanocomposite as a Recollectable Photocatalyst with Enhanced Durability"", 《EUR. J. INORG. CHEM.》, 23 August 2012 (2012-08-23), pages 4439 - 4444 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104907070A (en) * 2015-04-09 2015-09-16 宁波西博恩新材料科技有限公司 Alpha-Fe2O3 / graphene nanocomposite surface enhanced Raman scattering substrate and photocatalyst and preparation method thereof
CN104874398A (en) * 2015-05-26 2015-09-02 上海大学 Preparation method for recyclable titanium dioxide (P25)/graphene/iron oxide ternary photocatalytic material
CN104962232A (en) * 2015-06-24 2015-10-07 南京理工大学 Fe3O4@BaTiO3/RGO ternary composite wave-absorbing material and preparation method thereof
CN110152600A (en) * 2018-03-01 2019-08-23 济南开发区星火科学技术研究院 The preparation method of the graphite oxide aerogel with high reusing for water process
CN110152668A (en) * 2019-06-19 2019-08-23 张斌翔 A kind of preparation method of composite titania material photocatalyst catalyst
CN114146708A (en) * 2021-11-26 2022-03-08 哈尔滨工业大学（深圳） Magnetic TiO2Matrix modified photocatalyst and preparation and application thereof

Similar Documents

Publication Publication Date Title
CN103816901A (en) Magnetic nano composite photocatalytic material based on graphene and preparation method thereof
Yang et al. Constructing electrostatic self-assembled 2D/2D ultra-thin ZnIn2S4/protonated g-C3N4 heterojunctions for excellent photocatalytic performance under visible light
Li et al. Recent developments in visible-light photocatalytic degradation of antibiotics
CN102489284B (en) Graphene composite titanium dioxide photocatalyst capable of magnetic separation and recovery, and preparation method thereof
US10472243B2 (en) Industrial method for preparing large-sized graphene
Bai et al. Uniformly distributed anatase TiO2 nanoparticles on graphene: Synthesis, characterization, and photocatalytic application
CN101264449B (en) Preparation of TiO2/ZnFe2O4 magnetic composite photocatalyst
CN102583336B (en) Preparation method of magnetic-functionalized graphene composite material
CN102861586B (en) Preparation method of visible light composite photocatalyst capable of being magnetically controlled and recycled
CN104401948A (en) Preparation method for single-layer graphite-type carbon nitride nanosheet solution
CN104402052A (en) TiO2-quantum-dot-and-MoS2-nanometer-flower-combined heterojunction semiconductor material and preparation method thereof
CN105600828B (en) A kind of porous nano CuFe2O4Preparation method
CN102631913A (en) Preparation method of graphene supported cerium oxide nano cubit compound
CN103447549B (en) Preparation method of cobalt nanosphere
CN102527387A (en) Copper ferrite-graphene nano complex and preparation method thereof
CN105688943A (en) Method for preparing layered MoS2-TiO2 nano composite material
CN108479752A (en) A kind of BiVO of two dimension carbon-coating load4/TiO2The preparation method of heterogeneous visible light catalyst
CN105688944A (en) Method for preparing layered MoS2-SnO2 nano composite material
Yang et al. Graphene oxide/carbon nanotubes–Fe 3 O 4 supported Pd nanoparticles for hydrogenation of nitroarenes and C–H activation
CN105923625A (en) Method for preparing single-oxide uniformly-loaded graphene quantum dots
CN104874398A (en) Preparation method for recyclable titanium dioxide (P25)/graphene/iron oxide ternary photocatalytic material
CN107890861A (en) One kind has the preparation method of the titanium dioxide lamella/graphene composite film of { 001 } crystal face
CN111659369A (en) Preparation method of porous titanium dioxide/silicon dioxide/carbon nano composite material
CN105664975A (en) Preparation method of layered MoS2-Bi2MoO6 nanocomposite
CN113751049A (en) Preparation method, product and application of titanium carbide/carbon nitride composite photocatalyst

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
C02 Deemed withdrawal of patent application after publication (patent law 2001)
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20140528