CN104001498A - Preparation method of zinc molybdate/graphene composite visible light catalyst - Google Patents

Preparation method of zinc molybdate/graphene composite visible light catalyst Download PDF

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CN104001498A
CN104001498A CN201410247440.7A CN201410247440A CN104001498A CN 104001498 A CN104001498 A CN 104001498A CN 201410247440 A CN201410247440 A CN 201410247440A CN 104001498 A CN104001498 A CN 104001498A
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solution
water
visible light
zinc molybdate
graphene composite
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CN104001498B (en
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孙剑辉
董淑英
孙靖宇
冯精兰
皮运清
崔延瑞
苏现伐
闫旭
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Henan Normal University
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Henan Normal University
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    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W10/00—Technologies for wastewater treatment
    • Y02W10/30—Wastewater or sewage treatment systems using renewable energies
    • Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy

Abstract

The invention discloses a preparation method of a zinc molybdate/graphene composite visible light catalyst. The preparation method comprises the following steps of (1) adding 2 mmol of Na2M0O4 into a graphene oxide solution, and performing ultrasonic dissolution for 30 min, so as to prepare a solution X; (2) mixing and dissolving 2mmol of Zn(CH3COO)2.2H20 into 40 ml of water, so as to obtain a transparent clear solution Y; (3) dropwise adding the solution Y into the solution X under the ultrasonic action, performing ultrasonic operation for 120 min, then adding hydrazine hydrate, uniformly mixing, and then reducing in a water bath at 80 DEG C to polymerize and precipitate, so that the solution is clear; (4) naturally cooling the solution to room temperature after reaction, filtering, washing with water and ethanol respectively for three times, and then drying in a constant-temperature drying box at 80 DEG C for 5 hours, so as to prepare the zinc molybdate/graphene composite visible light catalyst. By using the zinc molybdate/graphene composite visible light catalyst prepared with the preparation method, the light absorption can be improved. The zinc molybdate/graphene composite visible light catalyst has the advantages of wide absorption spectrum range, stable performance, no toxicity, high efficiency and cheapness, can be applied to degrading organic pollutants which are difficult to biodegrade and has a strong market application prospect.

Description

A kind of preparation method of zinc molybdate/Graphene composite visible light catalyst
Technical field
The invention belongs to visible light catalytic material technical field, be specifically related to a kind of preparation method of zinc molybdate/Graphene composite visible light catalyst that can efficient degradation rhdamine B waste water.
Background technology
Waste water from dyestuff is one of typical difficult for biological degradation organic wastewater, a large amount of dyestuffs that basicity is high, color and luster is dark, stink is large entered environment in producing and using, what wherein have also contains the carcinogens such as phenyl ring, amido, azo group, serious environment pollution, adopts conventional biological treatment removal effect not ideal enough.Nanosecond science and technology are forward position, the intercrossing new branch of science that progressively grow up in late 1980s, and it has tremendous potential at the new production technology of creation, the new aspect such as material and new product.Nano semiconductor photocatalysis oxidation technique receives publicity increasingly, especially, showing good application prospect aspect the removal of difficult for biological degradation pollutant, has become study hotspot both domestic and external.The single-phase semiconductor nano photocatalyst powder suspension system being widely studied at present, exist that nanoparticle is easily condensed, easily low, the difficult separation and recycling of inactivation, utilization ratio and the defect such as absorption spectrum ranges is narrow, seriously limited the industrial applications of nano photo catalyzed oxidation.Therefore support type, highly active composite Nano photochemical catalyst become study hotspot now.For above-mentioned defect, improved novel nano photochemical catalyst need meet the condition of three aspects: (1) can effectively stop the compound of light induced electron and hole; (2) catalyst has good adsorption capacity to pollutant; (3) catalyst cupport on suitable carrier with avoid particulate reunite.
Because Graphene has excellent electric conductivity, make it easily catch light induced electron and serve as the medium that electronics shifts, greatly strengthen the Transport Rate of electric charge, thereby can effectively stop the compound of carrier; Secondly Graphene specific area is larger, is about 2600m 2g -1, its inner aromatic structure can form π-πconjugation with pollutant, thereby shows the suction-operated strong to pollutant; Moreover Graphene has higher mechanical strength, for the deposition of catalyst provides a two-dimensional surface structure; Graphene is that a kind of energy gap is zero semimetal simultaneously, adjust its energy gap by modification, not only can realize broadband light absorption, and can also make electric charge more mate with catalyst in transfer process, improve its photocatalysis performance, so Graphene becomes the desirable material of load.
Summary of the invention
The technical problem that the present invention solves has been to provide the effectively preparation method of zinc molybdate/Graphene composite visible light catalyst of rhodamine B degradation (RhB) waste water from dyestuff of one.
Technical scheme of the present invention is: a kind of preparation method of zinc molybdate/Graphene composite visible light catalyst, it is characterized in that comprising the following steps: (1) joins the graphene oxide of 4.8-43.2mg in 40mL water, ultrasonic dispersion 60min forms graphite oxide aqueous solution, then by 2mmol Na 2moO 4join in graphite oxide aqueous solution, continue ultrasonic dissolution 30min and make solution X; (2) by 2mmol Zn (CH 3cOO) 22H 2o stirring and dissolving, in 40mL water, obtains transparent settled solution Y; (3) under ultrasonication, solution Y is dropwise joined in solution X, continue ultrasonic 120min, add hydrazine hydrate, after stirring, be reduced to polymerization precipitation in 80 DEG C of water-baths, solution becomes clarification, and wherein often adding the quality of the corresponding graphene oxide of 1mL hydrazine hydrate is 48mg; (4) after reaction finishes, solution naturally cools to room temperature, filters, and water and ethanol are respectively washed three times, then in thermostatic drying chamber, make zinc molybdate/Graphene composite visible light catalyst in 80 DEG C of dry 5h.
Zinc molybdate/Graphene composite visible light catalyst that the present invention makes has good crystal formation and absorbing properties, and there is visible light-responded photocatalysis performance, under sunshine, there is the performance of efficient degradation rhdamine B waste water, there is absorption spectrum ranges wide, stable performance, nontoxic, efficiently cheap, can be applied to the degraded of difficult for biological degradation organic pollution, there is stronger market application foreground.
Detailed description of the invention
By the following examples foregoing of the present invention is described in further details, but this should be interpreted as to the scope of the above-mentioned theme of the present invention only limits to following embodiment, all technology realizing based on foregoing of the present invention all belong to scope of the present invention.
Embodiment 1
By 2mmol Na 2moO 4join in 40 mL water, ultrasonic dissolution 30min obtains settled solution, is designated as solution X.Meanwhile, by 2mmol Zn (CH 3cOO) 22H 2o stirring and dissolving, in 40mL water, obtains transparent settled solution, is designated as solution Y.Then ultrasonic lower by solution Y dropwise (about 2mL/min) join in solution X, continue ultrasonic 120min.After reaction finishes, filter, water and ethanol are respectively washed three times, and then 80 DEG C of dry 5h in thermostatic drying chamber, make pure zinc molybdate photochemical catalyst.The RhB clearance of rhdamine B waste water 10h of degrading under natural sunshine is 28.4%.
Embodiment 2
0.0048g graphene oxide (GO) is joined in 40mL water to ultrasonic dispersion 60min.Then by 2mmol Na 2moO 4join in graphite oxide aqueous solution, continue ultrasonic dissolution 30min, be designated as solution X.Meanwhile, by 2mmol Zn (CH 3cOO) 22H 2o stirring and dissolving, in 40mL water, obtains transparent settled solution, is designated as solution Y.Then ultrasonic lower by solution Y dropwise (about 2mL/min) join in solution X, continue ultrasonic 120min.Then add 0.1mL hydrazine hydrate, after stirring, proceed in thermostat water bath, 80 DEG C of water-bath reduction reaction to polymerizations precipitate, and solution becomes clarification.After reaction finishes, solution naturally cools to room temperature, filters, and water and ethanol are respectively washed three times, and then 80 DEG C of dry 5h in thermostatic drying chamber, make the zinc molybdate/Graphene composite visible light catalyst that contains 1wt% Graphene.The RhB clearance of rhdamine B waste water 10h of degrading under natural sunshine is 77.2%.
Embodiment 3
0.0144g graphene oxide is joined in 40mL water to ultrasonic dispersion 60min.Then by 2mmol Na 2moO 4join in graphite oxide aqueous solution, continue ultrasonic dissolution 30min, be designated as solution X.Meanwhile, by 2mmol Zn (CH 3cOO) 22H 2o stirring and dissolving, in 40mL water, obtains transparent settled solution, is designated as solution Y.Then ultrasonic lower by solution Y dropwise (about 2mL/min) join in solution X, continue ultrasonic 120min.Then add 0.3mL hydrazine hydrate, after stirring, proceed in thermostat water bath, 80 DEG C of water-bath reduction reaction to polymerizations precipitate, and solution becomes clarification.After reaction finishes, solution naturally cools to room temperature, filters, and water and ethanol are respectively washed three times, and then 80 DEG C of dry 5h in thermostatic drying chamber, make the zinc molybdate/Graphene composite visible light catalyst that contains 3wt% Graphene.The RhB clearance of rhdamine B waste water 10h of degrading under natural sunshine is 96.5%.
Embodiment 4
0.024g graphene oxide is joined in 40mL water to ultrasonic dispersion 60min.Then by 2mmol Na 2moO 4join in graphite oxide aqueous solution, continue ultrasonic dissolution 30min, be designated as solution X.Meanwhile, by 2mmol Zn (CH 3cOO) 22H 2o stirring and dissolving, in 40mL water, obtains transparent settled solution, is designated as solution Y.Then ultrasonic lower by solution Y dropwise (about 2mL/min) join in solution X, continue ultrasonic 120min.Then add 0.5mL hydrazine hydrate, after stirring, proceed in thermostat water bath, 80 DEG C of water-bath reduction reaction to polymerizations precipitate, and solution becomes clarification.After reaction finishes, solution naturally cools to room temperature, filters, and water and ethanol are respectively washed three times, and then 80 DEG C of dry 5h in thermostatic drying chamber, make the zinc molybdate/Graphene composite visible light catalyst that contains 5wt% Graphene.The RhB clearance of rhdamine B waste water 10h of degrading under natural sunshine is 84.3%.
Embodiment 5
0.0336g graphene oxide is joined in 40mL water to ultrasonic dispersion 60min.Then by 2mmol Na 2moO 4join in graphite oxide aqueous solution, continue ultrasonic dissolution 30min, be designated as solution X.Meanwhile, by 2mmol Zn (CH 3cOO) 22H 2o stirring and dissolving, in 40mL water, obtains transparent settled solution, is designated as solution Y.Then ultrasonic lower by solution Y dropwise (about 2mL/min) join in solution X, continue ultrasonic 120min.Then add 0.7mL hydrazine hydrate, after stirring, proceed in thermostat water bath, 80 DEG C of water-bath reduction reaction to polymerizations precipitate, and solution becomes clarification.After reaction finishes, solution naturally cools to room temperature, filters, and water and ethanol are respectively washed three times, and then 80 DEG C of dry 5h in thermostatic drying chamber, make the zinc molybdate/Graphene composite visible light catalyst that contains 7wt% Graphene.The RhB clearance of rhdamine B waste water 10h of degrading under natural sunshine is 80.3%.
Embodiment 6
0.0432g graphene oxide is joined in 40mL water to ultrasonic dispersion 60min.Then by 2mmol Na 2moO 4join in graphite oxide aqueous solution, continue ultrasonic dissolution 30min, be designated as solution X.Meanwhile, by 2mmol Zn (CH 3cOO) 22H 2o stirring and dissolving, in 40mL water, obtains transparent settled solution, is designated as solution Y.Then ultrasonic lower by solution Y dropwise (about 2mL/min) join in solution X, continue ultrasonic 120min.Then add 0.9mL hydrazine hydrate, after stirring, proceed in thermostat water bath, 80 DEG C of water-bath reduction reaction to polymerizations precipitate, and solution becomes clarification.After reaction finishes, solution naturally cools to room temperature, filters, and water and ethanol are respectively washed three times, and then 80 DEG C of dry 5h in thermostatic drying chamber, make the zinc molybdate/Graphene composite visible light catalyst that contains 9wt% Graphene.The RhB clearance of rhdamine B waste water 10h of degrading under natural sunshine is 65%.
Above embodiment has described general principle of the present invention, principal character and advantage; the technical staff of the industry should understand; the present invention is not restricted to the described embodiments; that in above-described embodiment and description, describes just illustrates principle of the present invention; do not departing under the scope of the principle of the invention; the present invention also has various changes and modifications, and these changes and improvements all fall in the scope of protection of the invention.

Claims (1)

1. the preparation method of zinc molybdate/Graphene composite visible light catalyst, it is characterized in that comprising the following steps: (1) joins the graphene oxide of 4.8-43.2mg in 40mL water, ultrasonic dispersion 60min forms graphite oxide aqueous solution, then by 2mmol Na 2moO 4join in graphite oxide aqueous solution, continue ultrasonic dissolution 30min and make solution X; (2) by 2mmol Zn (CH 3cOO) 22H 2o stirring and dissolving, in 40mL water, obtains transparent settled solution Y; (3) under ultrasonication, solution Y is dropwise joined in solution X, continue ultrasonic 120min, add hydrazine hydrate, after stirring, be reduced to polymerization precipitation in 80 DEG C of water-baths, solution becomes clarification, and wherein often adding the quality of the corresponding graphene oxide of 1mL hydrazine hydrate is 48mg; (4) after reaction finishes, solution naturally cools to room temperature, filters, and water and ethanol are respectively washed three times, then in thermostatic drying chamber, make zinc molybdate/Graphene composite visible light catalyst in 80 DEG C of dry 5h.
CN201410247440.7A 2014-06-06 2014-06-06 The preparation method of a kind of zinc molybdate/Graphene composite visible light catalyst Expired - Fee Related CN104001498B (en)

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CN112844368A (en) * 2021-02-18 2021-05-28 辽宁大学 ZnMOO with adjustable oxygen vacancy concentration4Photocatalyst and preparation method and application thereof

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