CN104759282B - A kind of method that microwave radiation technology prepares zinc oxide/graphene/silver nanoparticle composite photo-catalyst - Google Patents
A kind of method that microwave radiation technology prepares zinc oxide/graphene/silver nanoparticle composite photo-catalyst Download PDFInfo
- Publication number
- CN104759282B CN104759282B CN201410719245.XA CN201410719245A CN104759282B CN 104759282 B CN104759282 B CN 104759282B CN 201410719245 A CN201410719245 A CN 201410719245A CN 104759282 B CN104759282 B CN 104759282B
- Authority
- CN
- China
- Prior art keywords
- graphene
- catalyst
- solution
- zinc oxide
- composite photo
- 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.)
- Expired - Fee Related
Links
Abstract
The invention discloses a kind of method that microwave radiation technology prepares zinc oxide/graphene/silver nanoparticle composite photo-catalyst, mainly comprise the following steps：1) by graphite oxide it is soluble in water and it is ultrasonic peel off；2) it is placed in after mixing obtained graphene oxide solution and each reactive component in microwave reaction instrument and carries out microwave radiation, prepares zinc oxide/graphene/silver nanoparticle composite photo-catalyst.Preparation process of the present invention is simple, reaction condition is gentle, raw material reaction is abundant, energy consumption is low, preparation time is substantially reduced particularly by Microwave-assisted Reduction, preparation efficiency is improved, prepared zinc oxide/graphene/silver nanoparticle composite photo-catalyst has good photocatalysis performance, be expected to the photocatalysis treatment applied to trade effluent.
Description
Technical field
The invention belongs to field of new material preparation, it is multiple that specially a kind of microwave radiation technology prepares zinc oxide/graphene/silver nanoparticle
The method of closing light catalyst.
Background technology
Along with rapid industrial development, largely the industrial wastewater containing toxic organic pollutant is flowed into environment, is given people
Class health care belt is seriously endangered, and this promotes people to strengthen the exploitation for contaminating sewage Treatment process.Conductor photocatalysis degraded has
Organic pollutants have low energy consumption, high efficiency, simple to operate, applicability wide and the contaminant degradation outstanding advantages such as thoroughly, are a kind of
The green environmental protection technique of great prospect.In numerous semiconductor light-catalysts, zinc oxide is because of safety non-toxic, and stability is high, light is urged
Change performance it is good, especially its it is cheap be considered as most one of photochemical catalyst of application scenario and enjoy pro-gaze.But, by
There is exhibiting high surface defect in zinc oxide and serve as charge recombination center, light induced electron, to easily compound, causes its photocatalysis with hole
Efficiency and service life reduction, limit its application.Then, improve the separative efficiency in zinc-oxide nano photochemical catalyst electronics and hole into
For new study hotspot.Result of study in recent years shows, noble-metal-supported, ion doping, complex carbon material and other partly leads
Body material can suppress the compound of photo-generated carrier.
The carbon atom of graphene is with sp2Hydridization is linked, and is constituted bi-dimensional cellular shape crystal structure, is made it have and greatly compare table
Area, and excellent electric conductivity is shown, it is combined with zinc-oxide nano photochemical catalyst, can not only same composite noble metal
Equally play a part of electron transmission passage, and have good adsorption capacity to pollutant.Carry out zinc oxide/graphene/silver
Tri compound can more effectively suppress light into the quick compound of electron-hole pair, so as to significantly improve the photocatalysis of zinc oxide
Efficiency and recycling performance, document report confirm this point [Dae-Hwang Y, Tran VC, Van HL, Nguyen TK,
Eui JK,Seung HH, Sung HH.Photocatalytic Performance of a Ag/ZnO/CCG
Multidimensional Heterostructure Prepared by a Solution-Based Method[J]
.J.Phys.Chem.C,2012,116:7180-7184.S.Sarkar,D. Basak.One-step nano-engineering
of dispersed Ag-ZnO nanoparticles’hybrid in reduced graphene oxide matrixand
its superior photocatalytic property[J].Cryst EngComm,2013,15:7606-7614].But text
The preparation method cost of material for offering reported zinc oxide/graphene/silver nanoparticle composite photo-catalyst is higher or not friendly enough, system
For complex steps, it is necessary to which high temperature or high pressure, especially reaction time are long, it is unfavorable for promoting.Therefore, simple, quick, environment friend is developed
The preparation method of good zinc oxide/graphene/silver nanoparticle composite photo-catalyst has important application value.
The content of the invention
It is low, environment-friendly, simple to operate it is an object of the invention to provide a kind of energy consumption, the high zinc oxide of preparation efficiency/
The preparation method of graphene/silver nanoparticle composite photo-catalyst.
The above-mentioned purpose of the present invention is achieved by following technical solution：
(1) it is 27 by the mass ratio of Zinc diacetate dihydrate, citric acid, silver nitrate, deionized water:20:1:1600~1700
Zinc diacetate dihydrate, citric acid and silver nitrate are dissolved in deionized water, solution A is obtained；
(2) it is 1 by the mass ratio of graphite oxide and water:600~720 are added to graphite oxide in deionized water, control
Ultrasonic power is ultrasonically treated 2h under the conditions of 300W~500W, obtains graphene oxide water solution B；
(3) it is 1 by the volume ratio of solution B and solution A:7.5~8 mix solution A and solution B, while stirring by hydrogen-oxygen
The mass ratio for changing sodium and Zinc diacetate dihydrate is 1:1 is added dropwise 1molL thereto-1Sodium hydroxide solution, then by absolute ethyl alcohol
Volume ratio with sodium hydroxide solution is 1:2 are added dropwise to absolute ethyl alcohol thereto, and continue to react 30min under agitation, obtain
Black suspension C；
(4) suspension C obtained by step (3) is placed in microwave reaction instrument, is 300W~500W, microwave work(in ultrasonic power
Rate density is 3kWm-2~10kWm-2Under conditions of carry out 30min~60min Microwave-assisted Reduction；
(5) step (4) gained reactant is centrifuged, and gained precipitation is washed with deionized three times, then will washing
Precipitation afterwards, which is placed in 70 DEG C of baking ovens, dries 24h, obtains zinc oxide/graphene/silver nanoparticle composite photo-catalyst.
The present invention prepares zinc oxide/graphene/silver nanoparticle composite photo-catalyst using Microwave-assisted Reduction, with condition temperature
With, reaction rate is fast, yield is big the advantages of, overcome that current reported other method preparation process is cumbersome, the reaction time
Length is, it is necessary to which the deficiency such as high temperature or high pressure, is adapted to a large amount of prepare.
Brief description of the drawings
Fig. 1 is the Raman of gained zinc oxide/graphene/silver nanoparticle composite photo-catalyst and graphene oxide in embodiment 1
Spectrum.
Fig. 2 is the XRD diffracting spectrums of gained zinc oxide/graphene/silver nanoparticle composite photo-catalyst in embodiment 1.
Fig. 3 is the SEM photograph of gained zinc oxide/graphene/silver nanoparticle composite photo-catalyst in embodiment 1.
Fig. 4 is the TEM photos of gained zinc oxide/graphene/silver nanoparticle composite photo-catalyst in embodiment 1.
Fig. 5 is that gained zinc oxide/graphene/silver is molten as catalyst degradation methyl orange using in embodiment 1 under ultraviolet light
Methyl orange degradation rate changes over time curve during liquid.
Embodiment
Embodiment 1：
(1) 0.8g Zinc diacetate dihydrates, 0.6g citric acids and 0.03g silver nitrates are dissolved in 50mL deionized waters, obtained
To solution A；
(2) 0.15g graphite oxides are taken to be added in 100mL deionized waters, it is 500W to control ultrasonic power, ultrasonically treated
2h, obtains graphene oxide water solution B；
(3) 6.6mL solution Bs and 50mL solution As are mixed, 20mL concentration is added dropwise thereto while stirring is
1mol·L-1Sodium hydroxide solution, be then added dropwise 10mL absolute ethyl alcohols again, and continue to react 30min under agitation, obtain
To black suspension C；
(4) suspension C obtained by step (3) is placed in microwave reaction instrument, it is 500W to control ultrasonic power, microwave power is
6.3kW·m-2, radiate 30min, Microwave-assisted Reduction；
(5) step (4) gained reactant is centrifuged, and gained precipitation is washed with deionized three times, then will washing
Precipitation afterwards, which is placed in 70 DEG C of baking ovens, dries 24h, obtains zinc oxide/graphene/silver nanoparticle composite photo-catalyst.
Graphene oxide is shown in accompanying drawing 1 with the Raman spectrum for preparing product.From accompanying drawing 1 as can be seen that graphene oxide has two
Individual main Raman peaks：D peaks and G peaks, respectively positioned at 1350cm-1And 1594cm-1.D peaks are drawn by the defect in graphite-structure
Rise, G peaks are attributed to the SP of carbon atom2The vibrations of key in the plane.Compared with graphene oxide, the Raman spectrum of product is prepared
The increase of D peak intensities, D/G (ID/IG) value becomes big, shows that graphene oxide is reduced during microwave reaction.
The XRD spectrum for preparing product is shown in accompanying drawing 2.ZnO (100), ZnO (002), ZnO (101), the ZnO marked in accompanying drawing 2
(102), ZnO (110), ZnO (103), ZnO (200), ZnO (112), ZnO (201) each crystal face, correspond to lattice constant a=respectively
0.3249nm, c=0.5206nm hexagonal wurtzite structure ZnO corresponding Miller index, its peak position peak intensity and hexagonal wurtzite
The standard diagram JCPDS (36-1451) of structure ZnO matches, and showing to prepare in product has hexagonal wurtzite structure ZnO.Accompanying drawing 2
In Ag (111), Ag (200), Ag (220) each crystal face for marking, lattice constant a=4.086, α=β=γ=90 ° are corresponded to respectively
Cube Ag Miller index, its peak position peak intensity and cubic metal Ag standard spectrogram (JCPDS Card.No.04-0783) one
Cause, showing to prepare in product has cubic structure Ag.In addition, there is not any impurity diffraction maximum.By the diffraction maximum ratio in accompanying drawing 2
Relatively sharp, halfwidth is narrow to may determine that prepared product has relatively higher crystallinity.
The SEM photograph for preparing product different amplification is shown in accompanying drawing 3.Height in product is prepared it can be seen from accompanying drawing 3a to contain
It is flower type structure, 1 μm or so of diameter to measure component ZnO.And Fig. 3 b further show that flower pattern ZnO is made up of ZnO nano piece, and table
There are many little particles in face, it may be possible to be attached to the Ag on ZnO surfaces.
The TEM photos for preparing product are shown in accompanying drawing 4.The material of sheet structure is ZnO, the thing of piece layer film structure in accompanying drawing 4
Matter is graphene, and the little particle of high contrast is Ag.It can be seen that Ag particles are attached to graphene and ZnO surfaces.
Above-mentioned characterization result confirmation prepares product for zinc oxide/graphene/argentum nano composite material.
Using prepared zinc oxide/graphene/argentum nano composite material as photochemical catalyst, (luminous intensity is 100W mercury lamps
It is 63000lux) light source, Photocatalytic Degradation On Methyl Orange Solution, methyl orange degradation rate changes over time curve and sees accompanying drawing 5.By attached
Fig. 5 is visible, and degrade 20min, and the degradation rate of methyl orange reaches 92.7%.
Claims (1)
1. a kind of method that microwave radiation technology prepares zinc oxide/graphene/silver nanoparticle composite photo-catalyst, it is characterised in that this method
Concretely comprise the following steps：
(1) it is 27 by the mass ratio of Zinc diacetate dihydrate, citric acid, silver nitrate, deionized water:20:1:1600~1700 by two
Hydration zinc acetate, citric acid and silver nitrate are dissolved in deionized water, obtain solution A；
(2) it is 1 by the mass ratio of graphite oxide and water:600~720 are added to graphite oxide in deionized water, in ultrasonic work(
Rate is ultrasonically treated 2h under conditions of 300W~500W, obtains solution B, is 1 by the volume ratio of solution B and solution A:7.5~8 will
Solution A is mixed with solution B；
(3) mass ratio for pressing sodium hydroxide and Zinc diacetate dihydrate while stirring is 1:1 is added dropwise concentration into mixed liquor is
1mol·L-1Sodium hydroxide solution, then by absolute ethyl alcohol and sodium hydroxide solution volume ratio be 1:2 be added dropwise thereto it is anhydrous
Ethanol, and continue to react 30min under agitation, obtain black suspension C；
(4) suspension C obtained by step (3) is placed in microwave reaction instrument, it is 300W~500W, microwave power to control ultrasonic power
Density is 3kWm-2~10kWm-2, radiated time is 30min~60min, carries out Microwave-assisted Reduction；
(5) step (4) gained reactant is centrifuged, and gained precipitation is washed with deionized three times, then by after washing
Precipitation, which is placed in 70 DEG C of baking ovens, dries 24h, obtains zinc oxide/graphene/silver nanoparticle composite photo-catalyst.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410719245.XA CN104759282B (en) | 2014-12-01 | 2014-12-01 | A kind of method that microwave radiation technology prepares zinc oxide/graphene/silver nanoparticle composite photo-catalyst |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410719245.XA CN104759282B (en) | 2014-12-01 | 2014-12-01 | A kind of method that microwave radiation technology prepares zinc oxide/graphene/silver nanoparticle composite photo-catalyst |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN104759282A CN104759282A (en) | 2015-07-08 |
| CN104759282B true CN104759282B (en) | 2017-10-20 |
Family
ID=53641568
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410719245.XA Expired - Fee Related CN104759282B (en) | 2014-12-01 | 2014-12-01 | A kind of method that microwave radiation technology prepares zinc oxide/graphene/silver nanoparticle composite photo-catalyst |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104759282B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105498689B (en) * | 2015-12-09 | 2018-03-06 | 唐山冀东石墨烯科技发展有限公司 | Graphene-supported nano-ZnO/Ag composites and preparation method thereof |
| CN105561965B (en) * | 2015-12-31 | 2018-04-03 | 宿州学院 | A kind of preparation method of flower-shaped ZnO/ graphenes complex microsphere |
| CN105833853A (en) * | 2016-06-10 | 2016-08-10 | 苏州巨联环保科研有限公司 | Preparation method of calcium alginate fiber-based adsorbing material |
| CN106191985B (en) * | 2016-06-30 | 2019-03-19 | 武汉科技大学 | A kind of preparation method of stainless steel surface nanometic zinc oxide rod array |
| CN111205513B (en) * | 2020-03-16 | 2021-08-31 | 厦门捌斗新材料科技有限公司 | Graphene-based heat-conducting composite filler and preparation method and application thereof |
| CN115282960A (en) * | 2022-07-22 | 2022-11-04 | 皖西学院 | Method for synthesizing silver-doped nano ZnO with lasting high-efficiency photocatalytic performance by microwave method |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9422165B2 (en) * | 2012-04-27 | 2016-08-23 | Empire Technology Development Llc | Graphene compositions and methods of making the same |
| CN102698747B (en) * | 2012-06-14 | 2013-10-16 | 聊城大学 | Silver/graphene compound material and application |
| US20140213427A1 (en) * | 2013-01-31 | 2014-07-31 | Sunpower Technologies Llc | Photocatalyst for the Reduction of Carbon Dioxide |
| CN103252228A (en) * | 2013-06-08 | 2013-08-21 | 江苏悦达墨特瑞新材料科技有限公司 | Preparation method of composite nanomaterial of nano ZnO and graphene nanosheet |
| CN103480398B (en) * | 2013-09-22 | 2015-07-08 | 江苏大学 | Micronano-structured and graphene based composite visible light catalytic material and preparing method thereof |
-
2014
- 2014-12-01 CN CN201410719245.XA patent/CN104759282B/en not_active Expired - Fee Related
Also Published As
| Publication number | Publication date |
|---|---|
| CN104759282A (en) | 2015-07-08 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104759282B (en) | A kind of method that microwave radiation technology prepares zinc oxide/graphene/silver nanoparticle composite photo-catalyst | |
| Li et al. | Insight into photocatalytic activity, universality and mechanism of copper/chlorine surface dual-doped graphitic carbon nitride for degrading various organic pollutants in water | |
| Zhang et al. | Highly efficient photocatalysis toward tetracycline of nitrogen doped carbon quantum dots sensitized bismuth tungstate based on interfacial charge transfer | |
| Jin et al. | Bismuth-rich bismuth oxyhalides for environmental and energy photocatalysis | |
| Jiang et al. | Novel ternary BiOI/g-C3N4/CeO2 catalysts for enhanced photocatalytic degradation of tetracycline under visible-light radiation via double charge transfer process | |
| Cai et al. | 3D graphene/ZnO composite with enhanced photocatalytic activity | |
| Wu et al. | Facile synthesis of a novel full-spectrum-responsive Co2. 67S4 nanoparticles for UV-, vis-and NIR-driven photocatalysis | |
| Li et al. | Microwave hydrothermal synthesis of Sr2+ doped ZnO crystallites with enhanced photocatalytic properties | |
| Dash et al. | Microwave synthesis, photoluminescence, and photocatalytic activity of PVA-functionalized Eu3+-doped BiOX (X= Cl, Br, I) nanoflakes | |
| CN101913600B (en) | Method for preparing graphene/semiconductor quantum dot composite material | |
| Yu et al. | Novel rugby-ball-like Zn3 (PO4) 2@ C3N4 photocatalyst with highly enhanced visible-light photocatalytic performance | |
| Jing et al. | Bi/BiVO4 chainlike hollow microstructures: synthesis, characterization, and application as visible-light-active photocatalysts | |
| Xu et al. | Synthesis and behaviors of g-C3N4 coupled with LaxCo3-xO4 nanocomposite for improved photocatalytic activeity and stability under visible light | |
| CN103480398B (en) | Micronano-structured and graphene based composite visible light catalytic material and preparing method thereof | |
| Wang et al. | Emerging carbon-based quantum dots for sustainable photocatalysis | |
| Huang et al. | Morphology evolution and CL property of Ni-doped zinc oxide nanostructures with room-temperature ferromagnetism | |
| Wang et al. | Enhanced visible light-driven photocatalytic activities and photoluminescence characteristics of BiOF nanoparticles determined via doping engineering | |
| Khataee et al. | Kinetics and mechanism of enhanced photocatalytic activity under visible light using synthesized Pr x Cd1–x Se nanoparticles | |
| CN108311164B (en) | Iron modified photocatalytic material and preparation method and application thereof | |
| CN108745397A (en) | A kind of transient metal doped carbonitride/WO3Composite photo-catalyst and its preparation method and application | |
| Bi et al. | Direct Z-scheme CoS/g-C3N4 heterojunction with NiS co-catalyst for efficient photocatalytic hydrogen generation | |
| Vu et al. | Photocatalytic degradation of methylene blue (MB) over α-Fe2O3 nanospindles prepared by a hydrothermal route | |
| Liu et al. | Two-dimensional SnS 2 nanosheets exfoliated from an inorganic–organic hybrid with enhanced photocatalytic activity towards Cr (VI) reduction | |
| CN103560228A (en) | Method for compositing iron oxide and graphene by virtue of hydrothermal process | |
| Yang et al. | Investigation of photocatalytic properties based on Fe and Ce Co-doped ZnO via hydrothermal method and first principles |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| EXSB | Decision made by sipo to initiate substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20171020 Termination date: 20181201 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |