CN102600831B - Graphene-modified bismuth molybdate powder with high photocatalytic activity and preparation method thereof - Google Patents
Graphene-modified bismuth molybdate powder with high photocatalytic activity and preparation method thereof Download PDFInfo
- Publication number
- CN102600831B CN102600831B CN 201010203046 CN201010203046A CN102600831B CN 102600831 B CN102600831 B CN 102600831B CN 201010203046 CN201010203046 CN 201010203046 CN 201010203046 A CN201010203046 A CN 201010203046A CN 102600831 B CN102600831 B CN 102600831B
- Authority
- CN
- China
- Prior art keywords
- graphite oxide
- bismuth molybdate
- graphene
- preparation
- water
- 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
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention relates to a graphene-modified bismuth molybdate powder with high photocatalytic activity and a preparation method thereof. The preparation method comprises the following steps of: dispensing graphite oxide into water and carrying out ultrasonic treatment to obtain uniformly dispensed dispersing solution; adding Bi2MoO6 into the dispersing solution, stirring, carrying out ultrasonic treatment and centrifugally drying to obtain bismuth molybdate powder solid products carried on the graphite oxide; adding solid products into deionized water, adding a hydrazine hydrate solution and stronger ammonia water to carry out water bath reaction, cooling, washing and centrifugally drying to obtain a required graphene-modified bismuth molybdate composite material, wherein the graphite oxide is prepared by adopting a Hummer's chemical method. An apparent reaction rate constant k of methylene blue degradation of a product required to be protected is 1-3 times of that of bismuth molybdate matrix powder under a visible light condition. The preparation method of the graphene-modified bismuth molybdate powder with the high photocatalytic activity, disclosed by the invention, is a method capable of obtaining a photocatalyst with high photocatalytic activity through a simpler preparation process.
Description
Technical field
The present invention relates to a kind of Graphene and modify bismuth molybdate nano composite photocatalytic material and preparation method thereof, belong to the photocatalyst material preparing technical field.
Background technology
From TiO in 1972
2Since monocrystalline electrode light decomposition water is in the news, the multiphase photocatalysis material was once once worldwide starting research boom, obtained bigger progress aspect the difficult degradation pollutant of conductor photocatalysis in removing various surrounding mediums in recent years, shown strong oxidizing property, pollutant mineralising fully, can directly utilize advantage such as sunshine.Therefore how to utilize natural daylight to carry out light-catalyzed reaction efficiently, exploitation can be caused people's interest just day by day by the photochemical catalyst of excited by visible light.Expanding light abstraction width and the development of new photochemical catalyst of photochemical catalyst, all is the important content of present photocatalysis research.Bismuth molybdate is a kind of important functional material, and tempting application prospect is arranged aspect photocatalytic degradation, is the preparation method who uses more bismuth molybdate photochemical catalyst at present based on the bismuth molybdate powder preparation method of hydrothermal synthesis method.At publication number CN101254463A, name is called " a kind of visible light catalyst Bi
2MoO
6Synthetic method " patent application in, a kind of bismuth molybdate photochemical catalyst and preparation method thereof is disclosed, this method is with Bi (NO
3)
35H
2O and (NH
4)
6Mo
7O
244H
2O is primary raw material, has prepared flaxen bismuth molybdate photochemical catalyst by hydrothermal synthesis method under 160 ℃ of conditions.But the bismuth molybdate material that utilizes such preparation method to make also exists shortcomings such as photocatalysis efficiency under the visible light condition is lower, and this has brought and must limit to practical application, need utilize other means to improve its photocatalytic activity.
Summary of the invention
The purpose of this invention is to provide a kind of Graphene that under visible light, has highlight catalytic active and modify bismuth molybdate nano composite material and preparation method thereof.Be matrix with the bismuth molybdate, utilize Graphene to modify on the bismuth molybdate surface, thereby constitute a kind of advanced composite material (ACM) that under visible light, has highlight catalytic active.
Technical conceive of the present invention is such:
Graphene is a kind of carbonaceous new material by the tightly packed one-tenth bi-dimensional cellular of monolayer carbon atom shape lattice structure, and its structure is similar to the CNT that does not curl.Having particular structure feature and unusual electric property, is the very promising basic structural unit that constitutes new material.Characteristics according to grapheme material, Graphene has more excellent electronic transmission performance with respect to other conjugated molecular carbon material (as C60 molecule, CNT, graphite), effect by graphene molecules and bismuth molybdate surface chemistry key, the light induced electron that the bismuth molybdate photochemical catalyst produces under radiation of visible light can be transferred to rapidly on the graphene molecules, promote separating of light induced electron and hole, increase the photohole amount, thereby increased substantially its photocatalytic activity.
Technical scheme of the present invention is: graphite oxide is distributed in the water, ultrasonic it is peeled off into the graphite oxide sheet, obtain homodisperse dispersion liquid; Afterwards with Bi
2MoO
6Join in the dispersion liquid bismuth molybdate powder solid product that stir, ultrasonic, centrifugal oven dry obtains the graphite oxide load; Then solid product is added in the deionized water, add in hydrazine hydrate solution and the concentrated ammonia liquor, water-bath, reaction finishes the back cooling, after washing, centrifugal oven dry, gets required Graphene and modifies the bismuth molybdate composite; Described graphite oxide is to adopt the oxidation of Hummer ' s chemical method to make by native graphite.
Described preparation method's concrete steps are as follows:
(1) graphite oxide (GO) is distributed in the water, then with ultrasonic 30～60 minutes of solution, graphite oxide is peeled off into the graphite oxide sheet under the effect of electrostatic repulsion, obtain homodisperse graphite oxide dispersion liquid, wherein graphite oxide is to adopt the oxidation of Hummer ' s chemical method to make by native graphite;
(2) with Bi
2MoO
6Join in the GO dispersion liquid of homogeneous dispersion stirring, the ultrasonic Bi that makes
2MoO
6Be uniformly dispersed, centrifugal after ultrasonic 0.5～1 hour, 80 ℃ of oven dry;
(3) will join in the deionized water by the bismuth molybdate powder of step (2) gained graphite oxide load, the hydrazine hydrate solution and the concentrated ammonia liquor (analyzing pure) that add 35% (percentage by volume) again mix in beaker, both volume ratios are 1: 7, the mass ratio of hydrazine hydrate and GO is 7: 10 in the system, after the vigorous stirring 3～5 minutes, be placed in 90～95 ℃ of water-baths and react, the graphite oxide that loads on the bismuth molybdate surface is carried out in-situ reducing 1～2h; Time and the temperature of strict control reaction system are the keys that graphite oxide is converted into Graphene.
(4) after reaction finishes, treat product cooling deionized water rinsing, centrifugal, 80 ℃ of oven dry namely obtain required Graphene and modify the bismuth molybdate composite.
The doping of graphite oxide/bismuth molybdate is 0.5%～5% mass percent.
The simultaneously claimed Graphene with highlight catalytic active of the present invention is modified the bismuth molybdate powder, and its apparent reaction rate constant k that under the visible light condition methylene blue is degraded than the high 1-3 of bismuth molybdate matrix powder doubly.
The invention has the beneficial effects as follows that adopting local reduction way to prepare Graphene modifies the bismuth molybdate composite, obtains characteristic higher to the organic pollution decomposition efficiency under radiation of visible light; A kind of method that can pass through to obtain than easy manufacture technology the photochemical catalyst of highlight catalytic active is provided.
Description of drawings
The present invention has accompanying drawing 1 width of cloth;
Fig. 1 is the X-ray diffraction spectrogram that bismuth molybdate and Graphene are modified the bismuth molybdate composite.
The specific embodiment
(1) graphite oxide (GO) that takes by weighing 5mg joins in the 10ml deionized water, the graphite oxide ratio is easier to be distributed in the water, then ultrasonic 30 minutes of solution is peeled off into the graphite oxide sheet with graphite oxide, obtain homodisperse graphite oxide dispersion liquid;
(2) the 1g bismuth molybdate is joined in the graphite oxide dispersion liquid that is made by step (1), stirring, the ultrasonic GO that makes are at Bi
2MoO
6The surface is uniformly dispersed, and is centrifugal after ultrasonic 0.5 hour, 80 ℃ of oven dry.GO/Bi in this experiment
2MoO
6Mass ratio be 0.5%.
(3) will by step (2) make graphite oxide-bismuth molybdate powder add 50ml deionized water, the hydrazine hydrate solution of 10 μ l 35%, 70 μ l concentrated ammonia liquors and in beaker, mix, after the vigorous stirring 3 minutes, be placed in 95 ℃ of water-baths under the condition and reacted 1 hour.
(4) after reaction finishes, treat product cooling deionized water rinsing, centrifugal, 80 ℃ of oven dry namely obtain required Graphene and modify the bismuth molybdate composite.
(1) graphite oxide (GO) that takes by weighing 10mg joins in the 20ml deionized water, the graphite oxide ratio is easier to be distributed in the water, then ultrasonic 30 minutes of solution is peeled off into the graphite oxide sheet with graphite oxide, obtain homodisperse graphite oxide dispersion liquid;
(2) the 1g bismuth molybdate is joined in the graphite oxide dispersion liquid that is made by step (1), stirring, the ultrasonic GO that makes are at Bi
2MoO
6The surface is uniformly dispersed, and is centrifugal after ultrasonic 0.5 hour, 80 ℃ of oven dry.GO/Bi in this experiment
2MoO
6Mass ratio be 1%.
(3) will by step (2) make graphite oxide-bismuth molybdate powder add 50ml deionized water, the hydrazine hydrate solution of 20 μ l 35%, 140 μ l concentrated ammonia liquors and in beaker, mix, after the vigorous stirring 3 minutes, be placed in 95 ℃ of water-baths under the condition and reacted 1 hour.
(4) after reaction finishes, treat product cooling deionized water rinsing, centrifugal, 80 ℃ of oven dry namely obtain required Graphene and modify the bismuth molybdate composite.
(1) graphite oxide (GO) that takes by weighing 15mg joins in the 30ml deionized water, the graphite oxide ratio is easier to be distributed in the water, then ultrasonic 30 minutes of solution is peeled off into the graphite oxide sheet with graphite oxide, obtain homodisperse graphite oxide dispersion liquid;
(2) the 1g bismuth molybdate is joined in the graphite oxide dispersion liquid that is made by step (1), stirring, the ultrasonic GO that makes are at Bi
2MoO
6The surface is uniformly dispersed, and is centrifugal after ultrasonic 1 hour, 80 ℃ of oven dry.GO/Bi in this experiment
2MoO
6Mass ratio be 1.5%.
(3) will by step (2) make graphite oxide-bismuth molybdate powder add 50ml deionized water, the hydrazine hydrate solution of 30 μ l 35%, 210 μ l concentrated ammonia liquors and in beaker, mix, after the vigorous stirring 4 minutes, be placed in 90 ℃ of water-baths under the condition and reacted 1.5 hours.
(4) after reaction finishes, treat product cooling deionized water rinsing, centrifugal, 80 ℃ of oven dry namely obtain required Graphene and modify the bismuth molybdate composite.
(1) graphite oxide (GO) that takes by weighing 20mg joins in the 40ml deionized water, the graphite oxide ratio is easier to be distributed in the water, then ultrasonic 1 hour of solution is peeled off into the graphite oxide sheet with graphite oxide, obtain homodisperse graphite oxide dispersion liquid;
(2) the 1g bismuth molybdate is joined in the graphite oxide dispersion liquid that is made by step (1), stirring, the ultrasonic GO that makes are at Bi
2MoO
6The surface is uniformly dispersed, and is centrifugal after ultrasonic 1 hour, 80 ℃ of oven dry.GO/Bi in this experiment
2MoO
6Mass ratio be 2%.
(3) will by step (2) make graphite oxide-bismuth molybdate powder add 50ml deionized water, the hydrazine hydrate solution of 40 μ l 35%, 280 μ l concentrated ammonia liquors and in beaker, mix, after the vigorous stirring 5 minutes, be placed in 95 ℃ of water-baths under the condition and reacted 1.5 hours.
(4) after reaction finishes, treat product cooling deionized water rinsing, centrifugal, 80 ℃ of oven dry namely obtain required Graphene and modify the bismuth molybdate composite.
The sample that embodiment 1,2,3,4 is obtained is numbered 1# respectively, 2#, and 3#, 4# is numbered 0# with original bismuth molybdate powder, and sample is carried out X-ray diffraction analysis, shows that by XRD result the main crystalline phase of 0#-4# sample still all is γ-Bi
2MoO
6
In order to check prepared Graphene to modify the photocatalytic degradation performance of bismuth molybdate composite, the present invention selects for use methylene blue as the photocatalytic degradation object.Five kinds of samples of 0#-4# are carried out the photocatalytic degradation performance test respectively, estimate with the new preparation catalyst methylene blue in the degradation water (MB) molecule under the visible light condition.Light source is the xenon lamp of 500W, and (λ＞420nm) filters the following ultraviolet light of 420nm with optical filter.With 100mL 10
-5MolL
-1MB solution put into the beaker of 250mL, add the 0.05g photochemical catalyst, ultrasonic dispersions of lucifuge 10min, stirring 20min makes MB reach adsorption equilibrium at catalyst surface.The photocatalytic degradation reaction is carried out in the irradiation of turning on light, the 3mL that takes a sample respectively after 3 hours, and (4000rpm, 10min) the centrifugation catalyst granules is got supernatant, uses the absorbance of UV-vis spectrophotometer monitoring MB, and then the change in concentration of following the tracks of MB in the solution with centrifuge.According to first order reaction kinetic to ln (C/C
0)-kt curve carry out linear fit can calculate apparent reaction rate constant k, can judge the height of the photocatalytic activity of photochemical catalyst by the size of k value.The result shows (seeing Table 1), and the bismuth molybdate that Graphene is modified has shown higher photocatalytic activity under the visible light condition.
The degradation rate table of comparisons of table 1. pair methylene blue
Claims (2)
1. having the preparation method that the Graphene of highlight catalytic active is modified the bismuth molybdate powder, is that graphite oxide is distributed in the water, ultrasonic it is peeled off into the graphite oxide sheet, obtains homodisperse dispersion liquid; Afterwards with Bi
2MoO
6Join in the dispersion liquid bismuth molybdate powder solid product that stir, ultrasonic, centrifugal oven dry obtains the graphite oxide load; Then solid product is added in the deionized water, add in hydrazine hydrate solution and the concentrated ammonia liquor, water-bath, reaction finishes the back cooling, after washing, centrifugal oven dry, gets required Graphene and modifies the bismuth molybdate powder;
Described graphite oxide is to adopt the oxidation of Hummer ' s chemical method to make by native graphite.
2. the Graphene with highlight catalytic active as claimed in claim 1 preparation method that modifies the bismuth molybdate powder is characterized in that described preparation method's step is as follows:
(1) graphite oxide is distributed in the water, then ultrasonic 30～60 minutes of solution is peeled off into the graphite oxide sheet with graphite oxide, obtain homodisperse graphite oxide dispersion liquid, described graphite oxide is to adopt the oxidation of Hummer ' s chemical method to make by native graphite;
(2) with Bi
2MoO
6Join in the graphite oxide dispersion liquid of homogeneous dispersion stirring, the ultrasonic Bi that makes
2MoO
6Be uniformly dispersed, centrifugal after ultrasonic 0.5～1 hour, 80 ℃ of oven dry;
(3) will join in the deionized water by the bismuth molybdate powder of step (2) gained graphite oxide load, the hydrazine hydrate solution and the analytically pure ammoniacal liquor that add 35% percentage by volume again mix in beaker, hydrazine hydrate solution and ammoniacal liquor volume ratio are 1 ︰ 7, the mass ratio of hydrazine hydrate and graphite oxide is 7:10 in the system, after vigorous stirring 3-5 minute, be placed in the 90-95 ℃ of water-bath and react, the graphite oxide that loads on the bismuth molybdate surface is carried out in-situ reducing 1-2h;
(4) after reaction finishes, treat product cooling deionized water rinsing, centrifugal, 80 ℃ of oven dry namely obtain required Graphene and modify the bismuth molybdate powder;
The doping of graphite oxide/bismuth molybdate is the 0.5%-5% mass percent.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010203046 CN102600831B (en) | 2010-06-10 | 2010-06-10 | Graphene-modified bismuth molybdate powder with high photocatalytic activity and preparation method thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010203046 CN102600831B (en) | 2010-06-10 | 2010-06-10 | Graphene-modified bismuth molybdate powder with high photocatalytic activity and preparation method thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102600831A CN102600831A (en) | 2012-07-25 |
| CN102600831B true CN102600831B (en) | 2013-07-10 |
Family
ID=46518819
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN 201010203046 Expired - Fee Related CN102600831B (en) | 2010-06-10 | 2010-06-10 | Graphene-modified bismuth molybdate powder with high photocatalytic activity and preparation method thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102600831B (en) |
Families Citing this family (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103623809B (en) * | 2013-08-27 | 2015-08-19 | 南昌航空大学 | A kind of ternary heterojunction 1% Graphene-Bi 2moO 6/ Bi 3.64mo 0.36o 6.55catalysts and its preparation method |
| CN103657634B (en) * | 2013-12-31 | 2015-05-06 | 长沙理工大学 | Preparation method of graphene/bismuth molybdate nanobelt visible light catalytic material |
| CN103779105B (en) * | 2014-02-12 | 2017-01-04 | 东华大学 | A kind of nickel molybdate and the preparation method of graphene nanocomposite material |
| CN104001498B (en) * | 2014-06-06 | 2016-06-08 | 河南师范大学 | The preparation method of a kind of zinc molybdate/Graphene composite visible light catalyst |
| CN104478656B (en) * | 2014-11-26 | 2016-02-10 | 广西大学 | A kind of method of carbon dioxide reduction |
| CN105879855B (en) * | 2016-04-27 | 2019-05-03 | 武汉工程大学 | A kind of graphene-γ-bismuth molybdate nanocomposite and its preparation method and application |
| CN109195431B (en) * | 2018-10-22 | 2020-02-18 | 中原工学院 | Multilayer, micrometer flower-like NiCo2O4/GN/Fe3O4Preparation method of novel wave absorbing agent |
| CN112221486B (en) * | 2020-11-06 | 2023-06-30 | 生态环境部南京环境科学研究所 | Nanosheet RGO-flower-shaped multilayer structure Bi 2 M O O 6 Heterojunction visible light catalyst and preparation method and application thereof |
| CN113351221B (en) * | 2021-06-08 | 2023-09-29 | 常州大学 | Preparation method and application of graphene-based bismuth-based heterostructure catalyst |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254463A (en) * | 2008-04-11 | 2008-09-03 | 南京大学 | Synthetic method of visible light catalyst Bi2MoO6 |
| CN101658786A (en) * | 2009-09-25 | 2010-03-03 | 上海大学 | Method for preparing graphene-based titanium dioxide composite photocatalyst by radiation of electron beams |
-
2010
- 2010-06-10 CN CN 201010203046 patent/CN102600831B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101254463A (en) * | 2008-04-11 | 2008-09-03 | 南京大学 | Synthetic method of visible light catalyst Bi2MoO6 |
| CN101658786A (en) * | 2009-09-25 | 2010-03-03 | 上海大学 | Method for preparing graphene-based titanium dioxide composite photocatalyst by radiation of electron beams |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102600831A (en) | 2012-07-25 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102600831B (en) | Graphene-modified bismuth molybdate powder with high photocatalytic activity and preparation method thereof | |
| Chen et al. | Tuning excited state electronic structure and charge transport in covalent organic frameworks for enhanced photocatalytic performance | |
| Xiao et al. | Molecule self-assembly synthesis of porous few-layer carbon nitride for highly efficient photoredox catalysis | |
| Cui et al. | Constructing highly uniform onion-ring-like graphitic carbon nitride for efficient visible-light-driven photocatalytic hydrogen evolution | |
| Wang et al. | 0D/2D heterojunctions of Ti3C2 MXene QDs/SiC as an efficient and robust photocatalyst for boosting the visible photocatalytic NO pollutant removal ability | |
| Wu et al. | Remedying defects in carbon nitride to improve both photooxidation and H2 generation efficiencies | |
| Fattahimoghaddam et al. | Enhancement in photocatalytic H2O2 production over g-C3N4 nanostructures: a collaborative approach of nitrogen deficiency and supramolecular precursors | |
| Wang et al. | Mn-doped g-C3N4 nanoribbon for efficient visible-light photocatalytic water splitting coupling with methylene blue degradation | |
| Jiang et al. | Phosphorus-and sulfur-codoped g-C3N4: facile preparation, mechanism insight, and application as efficient photocatalyst for tetracycline and methyl orange degradation under visible light irradiation | |
| Tudu et al. | Electronic integration and thin film aspects of Au–Pd/rGO/TiO2 for improved solar hydrogen generation | |
| Wu et al. | Control strategy on two-/four-electron pathway of water splitting by multidoped carbon based catalysts | |
| Zhao et al. | Noble-metal-free iron phosphide cocatalyst loaded graphitic carbon nitride as an efficient and robust photocatalyst for hydrogen evolution under visible light irradiation | |
| Yan et al. | Photodegradation of rhodamine B and methyl orange over boron-doped g-C3N4 under visible light irradiation | |
| Hu et al. | Construction of g-C3N4/Zn0. 11Sn0. 12Cd0. 88S1. 12 hybrid heterojunction catalyst with outstanding nitrogen photofixation performance induced by sulfur vacancies | |
| Li et al. | Shear stress triggers ultrathin-nanosheet carbon nitride assembly for photocatalytic H2O2 production coupled with selective alcohol oxidation | |
| Liu et al. | Graphene supported Co-g-C3N4 as a novel metal–macrocyclic electrocatalyst for the oxygen reduction reaction in fuel cells | |
| Qian et al. | Low-temperature nitrogen doping in ammonia solution for production of N-doped TiO2-hybridized graphene as a highly efficient photocatalyst for water treatment | |
| Fang et al. | Synthesis and photocatalysis of ZnIn2S4 nano/micropeony | |
| Zhang et al. | Construction of hybrid MoS2 phase coupled with SiC heterojunctions with promoted photocatalytic activity for 4-nitrophenol degradation | |
| Zheng et al. | Selective CH4 partial photooxidation by positively charged metal clusters anchored on carbon aerogel under mild conditions | |
| Jiang et al. | In situ turning defects of exfoliated Ti3C2 MXene into Fenton-like catalytic active sites | |
| Xiao et al. | An S-scheme NH2-UiO-66/SiC photocatalyst via microwave synthesis with improved CO2 reduction activity | |
| Deng et al. | The pivotal role of defects in fabrication of polymeric carbon nitride homojunctions with enhanced photocatalytic hydrogen evolution | |
| Dou et al. | Graphitic carbon nitride with S and Fe (III) codoping for improved photodegradation performance | |
| Zhang et al. | Tremella-like porous carbon nitride co-doped with oxygen and carbon towards efficient visible-light-driven purification of wastewater |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20130710 Termination date: 20170610 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |