CN105879855A - Graphene-gamma-bismuth molybdate nano-composite material, method for preparing same and application of graphene-gamma-bismuth molybdate nano-composite material - Google Patents

Graphene-gamma-bismuth molybdate nano-composite material, method for preparing same and application of graphene-gamma-bismuth molybdate nano-composite material Download PDF

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CN105879855A
CN105879855A CN201610268468.8A CN201610268468A CN105879855A CN 105879855 A CN105879855 A CN 105879855A CN 201610268468 A CN201610268468 A CN 201610268468A CN 105879855 A CN105879855 A CN 105879855A
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graphene
bismuth
composite material
preparation
gamma
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CN105879855B (en
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郭雅妮
鲍世轩
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WUHAN STAR WATERPROOF MATERIALS CO.,LTD.
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Wuhan Institute of Technology
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/24Chromium, molybdenum or tungsten
    • B01J23/31Chromium, molybdenum or tungsten combined with bismuth
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/18Carbon
    • B01J35/39
    • B01J35/613
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/30Treatment of water, waste water, or sewage by irradiation
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2103/00Nature of the water, waste water, sewage or sludge to be treated
    • C02F2103/30Nature of the water, waste water, sewage or sludge to be treated from the textile industry
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2305/00Use of specific compounds during water treatment
    • C02F2305/10Photocatalysts

Abstract

The invention discloses a method for preparing a graphene-gamma-bismuth molybdate nano-composite material. The method includes steps of 1), carrying out solvent thermal reaction on graphene, bismuth nitrate and ethylene glycol to obtain reaction products and filtering, washing and drying the reaction products to obtain graphene-ethylene glycol bismuth compounds; 2), uniformly dispersing the compounds in sodium molybdate aqueous solution to obtain a solution system, regulating a pH (potential of hydrogen) value of the obtained solution system until the pH value is 0-3, then carrying out hydrothermal reaction on the solution system to obtain reaction products and filtering, washing and drying the reaction products to obtain the graphene-gamma-bismuth molybdate nano-composite material. The method has the advantages that the graphene-gamma-bismuth molybdate nano-composite material is mainly prepared from graphene, bismuth nitrate, sodium molybdate and ethylene glycol by the aid of solvent thermal processes and hydrothermal processes which are combined with one another; technologies and equipment for preparing the graphene-gamma-bismuth molybdate nano-composite material are simple, reaction conditions are mild, the method is low in energy consumption, the technologies are novel, and the graphene-gamma-bismuth molybdate nano-composite material prepared by the aid of the method has large specific surface area and is excellent in visible light photocatalytic performance.

Description

A kind of Graphene-γ-bismuth molybdate nano composite material and its preparation method and application
Technical field
The invention belongs to environmental friendly material field, be specifically related to a kind of Graphene-γ-bismuth molybdate nano composite material and preparation side thereof Method and application.
Background technology
The seriousness of environmental pollution, it has also become a direct threat human survival, needs the focal issue of solution badly.Photocatalysis technology As a branch of Green Chemistry, this technology can make the organic pollution generation oxidative decomposition in environment, is finally degraded to CO2, the small-molecule substance such as water and inorganic ions, non-secondary pollution, palliating degradation degree are high it is considered to be at the most promising pollution Reason method.But traditional TiO2Photocatalyst, band gap length, mainly absorb ultraviolet light, only with the ultraviolet light in sunlight, Low to the utilization rate of sunlight.Exploitation can utilize the nanometer new material of visible light photocatalysis as high catalytic activity, can make full use of The photocatalyst of sunlight, is one of method controlling environmental pollution most prospect.Therefore exploitation design new and effective, stable and Visible light-responded semiconductor light-catalyst is the focus of current photocatalysis research.
Nanometer γ-bismuth molybdate (Bi2MoO6) be rose in recent years, degree of receiving significant attention one visible ray semiconductor catalyst, It has good photocatalytic activity under visible light, can be used for degrading environmental organic pollutant, photocatalysis oxygen and photocatalysis also Former carbon dioxide etc..But its major defect is bismuth based semiconductor photocatalyst all exist photo-generate electron-hole easily in conjunction with, greatly Limit the large-scale application of bismuth series photocatalyst.Therefore, it is necessary to take certain measure to improve light induced electron transport efficiency, Effectively limit electron hole in conjunction with.Graphene is a kind of efficient electron acceptor material, itself and γ-bismuth molybdate (Bi2MoO6) Semiconductors coupling is conducive to improving the separation efficiency of electron-hole under illumination, reduce electron hole in conjunction with, thus improve composite wood The photocatalytic activity of material, therefore Graphene-γ-bismuth molybdate nano composite material has light more higher than simple nanometer γ-bismuth molybdate and urges Change efficiency.The preparation method developing a kind of technique simple Graphene-γ-bismuth molybdate nano composite material is significant.
Summary of the invention
It is an object of the invention to provide a kind of Graphene-γ-bismuth molybdate nano composite material and preparation method thereof, the method relates to Process equipment is simple, reaction condition is gentle, energy consumption is little, and the Graphene-γ of preparation-bismuth molybdate nano composite material specific surface area is big, Visible light photocatalysis excellent performance.
For achieving the above object, the technical solution used in the present invention is: the preparation of a kind of Graphene-γ-bismuth molybdate nano composite material Method, comprises the following steps: 1) by Graphene, bismuth nitrate is solvent thermal reaction together with ethylene glycol, then through filtering, washing, Dry to obtain Graphene-ethylene glycol bismuth complex;2) being dispersed in sodium molybdate aqueous solution by gained complex, regulation gained is molten The pH value of liquid system is 0-3, then carries out hydro-thermal reaction, then through filtering, wash, dry and to obtain Graphene-γ-bismuth molybdate nanometer Composite.
By such scheme, described Graphene is the 0.5-5% of bismuth nitrate quality.
By such scheme, described bismuth nitrate concentration in ethylene glycol is 10-100g/L.
By such scheme, described solvent thermal reaction condition is: be heated to 160-180 DEG C of insulation reaction 2-24 hour, then natural It is cooled to room temperature.
By such scheme, described sodium molybdate is (0.35-0.5) with the quality of Graphene-ethylene glycol bismuth complex: 1.
By such scheme, the concentration of described sodium molybdate aqueous solution is 20-100g/L.
By such scheme, described hydrothermal reaction condition is for being heated to 150-200 DEG C of insulation reaction 1-24 hour.
By such scheme, step 1) described drying temperature is 80-100 DEG C;Step 2) described drying temperature is 80-120 DEG C.
Graphene-γ-bismuth molybdate nano composite material that preparation method described above prepares, it is nanocrystalline lamellar, and wafer thickness is 10-40nm, specific surface area is 30-60m2/g。
Described Graphene-γ-bismuth molybdate nano composite material is as the application of catalysis material.
The mechanism of the present invention: owing to Graphene has a monolayer two-dimensional structure, high conductivity, excellent electron mobility and high The characteristics such as specific surface area so that it is quasiconductor-Graphene hetero-junctions can be constructed to strengthen visible light catalysis activity.The graphite of load Alkene is conducive to transfer and the storage of electronics, can effectively shift photo-generated carrier, suppression photoproduction electricity after γ-bismuth molybdate Material cladding Son-hole, to being combined, provides big specific surface area simultaneously, and the light of the Graphene-γ of improvement-bismuth molybdate nano-composite catalyst is urged Change activity, and the oxygen-containing functional group at graphene edge has strong adsorptivity to organic pollutant, also can strengthen composite Photocatalytic activity.
The invention have the benefit that the present invention, with Graphene, bismuth nitrate, ethylene glycol, sodium molybdate as primary raw material, uses molten Agent heat and hydro-thermal method prepare Graphene-γ-bismuth molybdate nano composite material, and the composite chemical composition obtained is homogeneous, Graphene High degree of dispersion, owing to Graphene has high electron acceptability, γ-bismuth molybdate composite when photocatalysis, electron-hole Separation rate is high, and photocatalysis effect significantly improves than compound phase ratio.This preparation technology equipment is simple simultaneously, reaction condition is gentle, energy Consume low.
Detailed description of the invention
In order to be more fully understood that the present invention, it is further elucidated with present disclosure below in conjunction with embodiment, but the present invention not only office It is limited to the following examples.
Following example as no specific instructions, the commercially available chemical reagent of reagent of employing or industrial products.
Embodiment 1
The preparation method of Graphene-γ-bismuth molybdate nano composite material, comprises the following steps:
1) 100g bismuth nitrate is dissolved in 1L ethylene glycol, is subsequently adding 0.5g Graphene powder and is uniformly mixed, stablized Suspension, transfers to this solution in the autoclave that volume is 2L, is heated to 160 DEG C and is incubated 24 hours;Question response still is cold But to room temperature, filter and by washing with alcohol 3 times, be then dried 12 hours at 80 DEG C, obtain Graphene-ethylene glycol bismuth meal body;
2) take 25g sodium molybdate to be dissolved in 250ml deionized water, then by 1) in prepare Graphene-ethylene glycol powder 50g and add In above-mentioned sodium molybdate aqueous solution, ultrasonic wave concussion stirring makes it be uniformly dispersed, and regulates solution ph extremely with concentrated nitric acid and concentrated hydrochloric acid Between 0-3, then gained mixed liquor is transferred in the autoclave that volume is 500mL, is warming up to 200 DEG C and is incubated 1 hour, Question response still is cooled to room temperature, by deionized water and washing with alcohol 5 times after filtration, then is dried 4 hours at 120 DEG C, obtains stone Ink alkene-bismuth molybdate sodium nano composite material.
The present embodiment products therefrom γ-bismuth molybdate nanometer wafer average thickness is 10nm, and specific surface area is 60m2/ g, in concentration During 1.0g/L, it is seen that light irradiate under can in 30min degradable 0.02g/L rhodamine.
Embodiment 2
The preparation method of Graphene-γ-bismuth molybdate nano composite material, comprises the following steps:
1) 50g bismuth nitrate is dissolved in 1L ethylene glycol, is subsequently adding 2.5g Graphene powder and is uniformly mixed, stablized Suspension, transfers to this solution in the autoclave that volume is 2L, is heated to 180 DEG C and is incubated 2 hours;Question response still cools down To room temperature, filter and by washing with alcohol 3 times, be then dried 6 hours at 80 DEG C, obtain Graphene-ethylene glycol bismuth meal body;
2) take 4g sodium molybdate to be dissolved in 200ml deionized water, then by 1) in prepare Graphene-ethylene glycol bismuth meal end 10g and add In above-mentioned sodium molybdate aqueous solution, ultrasonic wave concussion stirring makes it be uniformly dispersed, and regulates solution ph extremely with concentrated nitric acid and concentrated hydrochloric acid Between 0-3, then gained mixed liquor is transferred in the autoclave that volume is 500mL, is warming up to 150 DEG C and is incubated 24 hours, Question response still is cooled to room temperature, by deionized water and washing with alcohol 2 times after filtration, then is dried 12 hours at 80 DEG C, obtains stone Ink alkene-bismuth molybdate sodium nano composite material.
The present embodiment products therefrom γ-bismuth molybdate nanometer wafer average thickness is 12nm, and specific surface area is 55m2/ g, in concentration During 1.0g/L, it is seen that light irradiate under can in 30min degradable 0.02g/L rhodamine.
Embodiment 3
The preparation method of Graphene-γ-bismuth molybdate nano composite material, comprises the following steps:
1) 50g bismuth nitrate is dissolved in 1L ethylene glycol, is subsequently adding 2g Graphene powder and is uniformly mixed, stably hanged Turbid liquid, transfers to this solution in the autoclave that volume is 2L, is heated to 170 DEG C and is incubated 12 hours;Question response still cools down To room temperature, filter and by washing with alcohol 3 times, be then dried 4 hours at 100 DEG C, obtain Graphene-ethylene glycol bismuth meal body;
2) take 3.5g sodium molybdate to be dissolved in 100ml deionized water, then by 1) in prepare Graphene-ethylene glycol bismuth meal end 10g and add Entering in above-mentioned sodium molybdate aqueous solution, ultrasonic wave concussion stirring makes it be uniformly dispersed, and regulates solution ph with concentrated nitric acid and concentrated hydrochloric acid Between 0-3, then gained mixed liquor is transferred in the autoclave that volume is 200mL, is warming up to 180 DEG C of insulations 12 little Time, question response still is cooled to room temperature, by deionized water and washing with alcohol 3 times after filtration, then is dried 12 hours at 100 DEG C, Obtain Graphene-bismuth molybdate sodium nano composite material.
The present embodiment products therefrom γ-bismuth molybdate nanometer wafer average thickness is 20nm, and specific surface area is 40m2/ g, in concentration During 1.0g/L, it is seen that light irradiate under can in 30min degradable 0.02g/L rhodamine.
Embodiment 4
The preparation method of Graphene-γ-bismuth molybdate nano composite material, comprises the following steps:
1) 10g bismuth nitrate is dissolved in 1L ethylene glycol, is subsequently adding 0.5g Graphene powder and is uniformly mixed, stablized Suspension, transfers to this solution in the autoclave that volume is 2L, is heated to 160 DEG C and is incubated 24 hours;Question response still is cold But to room temperature, filter and by washing with alcohol 3 times, be then dried 4 hours at 100 DEG C, obtain Graphene-ethylene glycol bismuth meal body;
2) take 2.5g sodium molybdate to be dissolved in 100ml deionized water, then by 1) in prepare Graphene-ethylene glycol bismuth meal end 5g and add Entering in above-mentioned sodium molybdate aqueous solution, ultrasonic wave concussion stirring makes it be uniformly dispersed, and regulates solution ph with concentrated nitric acid and concentrated hydrochloric acid Between 0-3, then gained mixed liquor is transferred in the autoclave that volume is 200mL, is warming up to 200 DEG C of insulations 24 little Time, question response still is cooled to room temperature, by deionized water and washing with alcohol 3 times after filtration, then is dried 12 hours at 100 DEG C, Obtain Graphene-bismuth molybdate sodium nano composite material.
The present embodiment products therefrom γ-bismuth molybdate nanometer wafer average thickness is 40nm, and specific surface area is 30m2/ g, in concentration During 1.0g/L, it is seen that light irradiate under can in 60min degradable 0.02g/L rhodamine.
Each proportioning raw materials cited by the present invention can realize the present invention, and the bound value of each raw material, interval value can be real The existing present invention, the bound value of the technological parameter of the present invention and interval value can realize the present invention, reality numerous to list herein Execute example.

Claims (10)

1. a preparation method for Graphene-γ-bismuth molybdate nano composite material, comprises the following steps: 1) by Graphene, bismuth nitrate is solvent thermal reaction together with ethylene glycol, then through filtering, wash, dry and to obtain Graphene-ethylene glycol bismuth complex;2) being dispersed in sodium molybdate aqueous solution by gained complex, the pH value of regulation gained solution system is 0-3, then carries out hydro-thermal reaction, then through filtering, wash, dry and to obtain Graphene-γ-bismuth molybdate nano composite material.
Preparation method the most according to claim 1, it is characterised in that described Graphene is the 0.5-5% of bismuth nitrate quality.
Preparation method the most according to claim 1, it is characterised in that described bismuth nitrate concentration in ethylene glycol is 10-100g/L.
Preparation method the most according to claim 1, it is characterised in that described solvent thermal reaction condition is: is heated to 160-180 DEG C of insulation reaction 2-24 hour, then naturally cools to room temperature.
Preparation method the most according to claim 1, it is characterised in that described sodium molybdate is (0.35-0.5) with the quality of Graphene-ethylene glycol bismuth complex: 1.
Preparation method the most according to claim 1, it is characterised in that the concentration of described sodium molybdate aqueous solution is 20-100g/L.
Preparation method the most according to claim 1, it is characterised in that described hydrothermal reaction condition is for being heated to 150-200 DEG C of insulation reaction 1-24 hour.
Preparation method the most according to claim 1, it is characterised in that step 1) described drying temperature is 80-100 DEG C;Step 2) described drying temperature is 80-120 DEG C.
9. Graphene-γ-bismuth molybdate nano composite material that preparation method described in any one of claim 1~8 prepares, it is nanocrystalline lamellar, and wafer thickness is 10-40nm, and specific surface area is 30-60m2/g。
10. Graphene-the γ described in claim 9-bismuth molybdate nano composite material is as the application of catalysis material.
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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN108031467A (en) * 2017-12-08 2018-05-15 浙江工业大学 A kind of Bi2MoO6Coat halloysite nanotubes composite material and preparation method and application
CN111450822A (en) * 2020-04-09 2020-07-28 浙江工业大学 Preparation method of bismuth molybdate coated tourmaline composite photocatalyst
CN113789090A (en) * 2021-09-16 2021-12-14 广州特种承压设备检测研究院 Graphene modified photocatalytic water-based paint and preparation method and application thereof

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108031467A (en) * 2017-12-08 2018-05-15 浙江工业大学 A kind of Bi2MoO6Coat halloysite nanotubes composite material and preparation method and application
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CN111450822A (en) * 2020-04-09 2020-07-28 浙江工业大学 Preparation method of bismuth molybdate coated tourmaline composite photocatalyst
CN113789090A (en) * 2021-09-16 2021-12-14 广州特种承压设备检测研究院 Graphene modified photocatalytic water-based paint and preparation method and application thereof

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