CN108043390A - Nanometer sheet Bi2WO6/SnO2The method of catalytic degradation liguid phase pollutant - Google Patents

Nanometer sheet Bi2WO6/SnO2The method of catalytic degradation liguid phase pollutant Download PDF

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CN108043390A
CN108043390A CN201711358232.4A CN201711358232A CN108043390A CN 108043390 A CN108043390 A CN 108043390A CN 201711358232 A CN201711358232 A CN 201711358232A CN 108043390 A CN108043390 A CN 108043390A
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sno
nanometer sheet
suspension
added
small
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邹学军
于鸣
于一鸣
李思佳
苑承禹
董玉瑛
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Dalian Minzu University
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Dalian Nationalities University
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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
    • B01J23/00Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002Mixed oxides other than spinels, e.g. perovskite
    • B01J35/39
    • B01J35/40
    • B01J35/61
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08Heat treatment
    • B01J37/10Heat treatment in the presence of water, e.g. steam
    • 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
    • C02F1/00Treatment of water, waste water, or sewage
    • C02F1/72Treatment of water, waste water, or sewage by oxidation
    • C02F1/725Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
    • BPERFORMING OPERATIONS; TRANSPORTING
    • B01PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01JCHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00Constitutive chemical elements of heterogeneous catalysts
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • CCHEMISTRY; METALLURGY
    • C02TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02FTREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
    • C02F2101/00Nature of the contaminant
    • C02F2101/30Organic compounds
    • C02F2101/34Organic compounds containing oxygen
    • C02F2101/345Phenols

Abstract

This divisional application is related to nanometer sheet Bi2WO6/SnO2The method of catalytic degradation liguid phase pollutant, will be using the Bi of hydro-thermal method synthesis2WO6It adds in ethylene glycol, stirring to obtain Bi2WO6Suspension.To Bi2WO6SnCl is added in suspension4·5H2O obtains mixing suspension.Urea is added in into deionized water simultaneously, the solution obtained is rapidly added mixing suspension, and is stirred at room temperature.Then, mixed solution, which is transferred in reaction kettle, heats reaction, the Bi finally obtained2WO6/SnO2Nanometer sheet.Bi prepared by the present invention2WO6/SnO2Nanometer sheet large specific surface area, adsorption capacity are strong;With better visible absorption performance, improve a lot to photocatalytic oxidation degradation organic pollution;And Bi of the present invention2WO6/SnO2The preparation method of nanometer sheet is fairly simple, easily operated.

Description

Nanometer sheet Bi2WO6/SnO2The method of catalytic degradation liguid phase pollutant
The application is Application No. 2017110589158, the applying date is November 1, entitled " Simple water in 2017 Hot method synthesis has visible light-responded photochemical catalyst Bi2WO6/SnO2The divisional application of the preparation method of nanometer sheet ".
Technical field
The present invention relates to a kind of semiconductor light-catalysts and preparation method for curbing environmental pollution.
Background technology
Energy crisis and environmental problem have been that the mankind have to face two Tough questions, how effectively to control and control It is the emphasis in comprehensive environmental improvement to the pollution of environment to manage various chemical pollutants.In recent years, as high-level oxidation technology it One Photocatalytic Oxidation With Semiconductors technology, is just being subject to that domestic and foreign scholars' is widely studied, this technology can using solar energy as The energy effectively utilizes solar energy, reduces the energy consumption of people come the pollutant in environment of degrading.
Photocatalytic Oxidation With Semiconductors technology starts from the TiO that Japanese Scientists Fujishima and Honda have found light irradiation2 Single Crystalline Electrodes can be by H2O is decomposed, and utilizes TiO2Semiconductor light-catalyst convert light energy into electric energy and chemical energy just become partly lead The research hotspot of body photocatalysis field.However, Detitanium-ore-type TiO2Energy gap for 3.2eV, excitation wavelength is 387.5nm belongs to the ultraviolet light range in sunlight.And for solar energy, what main energetic concentrated on 400~600nm can See optical range, this considerably reduce TiO2Therefore the efficiency of semiconductor light-catalyst, is developed to visible light-responded new Semi-conducting material is one of key content of Study on photocatalyst.
At present, in numerous semiconductor light-catalysts newly developed, researcher develops tungstate compound, and finding should Class catalyst has smaller energy gap, can sufficiently utilize sunlight, is a kind of promising photochemical catalyst.But with The defects of research is goed deep into, and it is poor that researcher has found that stability occurs in most tungstate compound, easy photoetch, limits it Development.
The content of the invention
To make up the deficiencies in the prior art, the present invention provide it is a kind of not only have it is visible light-responded, to organic pollution With degradation capability and stability is good, uncorruptible photochemical catalyst Bi2WO6/SnO2Nanometer sheet and preparation method.
The present invention is achieved in that hydro-thermal method synthesis has visible light-responded photochemical catalyst Bi2WO6/SnO2Nanometer sheet Preparation method, include the following steps:
S1. pure Bi2WO6With mixing Bi2WO6Sample is synthesized using hydro-thermal method.
By 1mmol Na2WO4·2H2O, 1.98mmol Bi (NO3)3·5H2O is dissolved in 100mL distilled water, stirs 30min, Obtained flaxen suspension.By suspension be transferred in 100mL autoclaves 90 DEG C of -220 DEG C of reaction 12-36 it is small when, After reaction, natural cooling, filtering, washing when 60 DEG C of dryings 24 are small, obtain the pure Bi of product2WO6
S2.Bi2WO6/SnO2The synthesis of nanometer sheet:
Bi is added in into ethylene glycol2WO6, stirring to obtain Bi2WO6Suspension;By Bi2WO6Suspension is added to SnCl4· 5H2Mixing suspension is prepared in O, aqueous solution of urea is prepared, aqueous solution of urea is rapidly added in mixing suspension, and in room temperature When lower stirring 1 is small, be then transferred into reaction kettle heat 150-210 DEG C of 12-24 it is small when, it is washed, when 80 DEG C of dryings 24 are small;Most Bi is made afterwards2WO6/SnO2Nanometer sheet, wherein Bi2WO6Account for SnO2The 24.47%-88.13% of quality.
The present invention has visible light-responded photochemical catalyst Bi by one pot process2WO6/SnO2Nanometer sheet passes through simultaneously Reaction time and reaction temperature are controlled, forms the spherical morphology of bigger serface so that the material of preparation has larger ratio Surface area is conducive to the absorption degradation of pollutant.
Another object of the present invention is that the Bi prepared using the method for the present invention is claimed2WO6/SnO2Nanometer sheet catalysis drop The method for solving liguid phase pollutant, is as follows:Weigh 100mgBi2WO6/SnO2Nanometer sheet adds in 5mg/L 100mL phenol In solution, the magnetic agitation 30min under dark situation is then placed under xenon lamp and irradiates while stirring, carries out catalytic reaction.
The present invention by reasonably regulating and controlling Bi2WO6And SnO2Proportioning adjusts technological parameter, and nanometer sheet is anti-through solvent heat Microstructure should be obtained as flake nano grade compound Bi2WO6/SnO2.Compared with prior art, the present invention has the following advantages:
1st, Bi prepared by the present invention2WO6/SnO2The large specific surface area of nanometer sheet, adsorption capacity are strong;
2nd, Bi prepared by the present invention2WO6/SnO2Nanometer sheet has and preferably may be used compared with traditional photochemical catalyst titanium dioxide See absorbing properties, improve a lot to photocatalytic oxidation degradation organic pollution;
3rd, Bi provided by the invention2WO6/SnO2The preparation method of nanometer sheet is fairly simple, easily operated, raw suitable for industry Production.
Description of the drawings
Fig. 1 is the Bi in embodiment 12WO6/SnO2The scanning electron microscope (SEM) photograph that 8000 times of nanometer sheet amplification factor.
Fig. 2 is the Bi in embodiment 1 and embodiment 22WO6/SnO2Nanometer sheet XRD diffracting spectrums.
Fig. 3 is the Bi in embodiment 12WO6/SnO2Nanometer sheet UR-Vis DRS spectrum analysis figures.
Fig. 4 is the Bi of the different content in embodiment 12WO6/SnO2Heterojunction structure light degradation datagram.
Specific embodiment
The present invention is described in detail below by the drawings and specific embodiments, but is not limited the scope of the invention.Such as without special Illustrate, experimental method of the present invention is conventional method, and experiment equipment used, material, reagent etc. can be chemically public Department's purchase.Photocatalysis TiO is arrived involved in application examples2, model P25, buy in win create industrial group.
Embodiment 1
(1) by 1mmol Na2WO4·2H2O, 1.98mmol Bi (NO3)3·5H2O is dissolved in 100mL distilled water, stirring Suspension is transferred in 100mL stainless steel autoclaves and is maintained at 180 DEG C 24 by 30min, obtained flaxen suspension Hour.After natural cooling, product filtering is washed repeatedly with deionized water and ethyl alcohol, is then made pure when 60 DEG C of dryings 24 are small Bi2WO6
(2) 0.7g Bi are added in 50mL ethylene glycol2WO6, stirring 3 it is small when obtain Bi2WO6Suspension.To Bi2WO6Suspension Middle addition 0.7g SnCl4·5H2O obtains mixing suspension.0.4g urea is added in into 30mL deionized waters, it is water-soluble to obtain urea Liquid.Aqueous solution of urea is rapidly added in mixing suspension, be stirred at room temperature 1 it is small when, be then transferred into polytetrafluoroethylene (PTFE) Lined steel reaction kettle when 180 DEG C of heating 16 are small, collected, repeatedly washed with deionized water, when 80 DEG C of dryings 24 are small, finally To 72.12wt%-Bi2WO6/SnO2Nanometer sheet.
Embodiment 2
(1) by 1mmol Na2WO4·2H2O, 1.98mmol Bi (NO3)3·5H2O is dissolved in 100mL distilled water, stirring Suspension is transferred in 100mL stainless steel autoclaves and is maintained at 90 DEG C 36 by 30min, obtained flaxen suspension Hour.After natural cooling, product filtering is washed repeatedly with deionized water and ethyl alcohol, is then made pure when 60 DEG C of dryings 24 are small Bi2WO6
(2) 0.7g Bi are added in 50mL ethylene glycol2WO6, stirring 3 it is small when obtain Bi2WO6Suspension.To Bi2WO6Suspension Middle addition 0.86g SnCl4·5H2O obtains mixing suspension.Meanwhile 0.4g urea is added in 30mL deionized waters, obtain urea Aqueous solution.Aqueous solution of urea is rapidly added in mixing suspension, be stirred at room temperature 1 it is small when, be then transferred into polytetrafluoroethyl-ne Alkene inner lining steel reaction kettle when 150 DEG C of heating 24 are small, collected and deionized water is repeatedly washed, when 80 DEG C of dryings 24 are small, finally Obtain 88.13wt%-Bi2WO6/SnO2Nanometer sheet.
Embodiment 3
(1) by 1mmol Na2WO4·2H2O, 1.98mmol Bi (NO3)3·5H2O is dissolved in 100mL distilled water, stirring Suspension is transferred in 100mL stainless steel autoclaves and is maintained at 220 DEG C 12 by 30min, obtained flaxen suspension Hour.After natural cooling, product filtering is washed repeatedly with deionized water and ethyl alcohol, is then made pure when 60 DEG C of dryings 24 are small Bi2WO6
(2) 0.7g Bi are added in 50mL ethylene glycol2WO6, stirring 3 it is small when obtain Bi2WO6Suspension.To Bi2WO6Suspension Middle addition 0.86g SnCl4·5H2O obtains mixing suspension.Meanwhile 0.4g urea is added in 30mL deionized waters, obtain urea Aqueous solution.Aqueous solution of urea is rapidly added in mixing suspension, be stirred at room temperature 1 it is small when, be then transferred into polytetrafluoroethyl-ne Alkene inner lining steel reaction kettle when 150 DEG C of heating 24 are small, collected and deionized water is repeatedly washed, when 80 DEG C of dryings 24 are small, finally Obtain 88.13wt%-Bi2WO6/SnO2Nanometer sheet.
Embodiment 4
(1) by 1mmol Na2WO4·2H2O, 1.98mmol Bi (NO3)3·5H2O is dissolved in 100mL distilled water, stirring Suspension is transferred in 100mL stainless steel autoclaves and is maintained at 90 DEG C 36 by 30min, obtained flaxen suspension Hour.After natural cooling, product filtering is washed repeatedly with deionized water and ethyl alcohol, is then made pure when 60 DEG C of dryings 24 are small Bi2WO6
(2) 0.7g Bi are added in 50mL ethylene glycol2WO6, stirring 3 it is small when obtain Bi2WO6Suspension.To Bi2WO6Suspension Middle addition 0.23g SnCl4·5H2O obtains mixing suspension.Meanwhile 0.4g urea is added in 30mL deionized waters, obtain urea Aqueous solution.Aqueous solution of urea is rapidly added in mixing suspension, be stirred at room temperature 1 it is small when, be then transferred into polytetrafluoroethyl-ne Alkene inner lining steel reaction kettle when 150 DEG C of heating 24 are small, collected and deionized water is repeatedly washed, when 80 DEG C of dryings 24 are small, finally Obtain 24.47wt%-Bi2WO6/SnO2Nanometer sheet.
Application examples 1
Buy business photocatalysis TiO2, without any processing, it is directly used in light-catalyzed reaction as a comparison.
Bi is prepared by the method in embodiment 12WO6/SnO2Nanometer sheet takes the pure Bi of 100mg2WO6, add in 5mg/L 100mL In phenol solution, the magnetic agitation 30min under dark situation is put under xenon lamp and irradiates while stirring afterwards, is taken once per 15min Sample, the sample of taking-up centrifuges 20min under 2000r/min, then takes out supernatant with liquid-transfering gun, then goes out to survey it in 510nm Absorbance, and record data.
Experimental result is as shown in figure 4, under visible light conditions, pure Bi2WO6Pyrogentisinic Acid has when nanometer sheet is as catalyst General catalytic oxidation activity.
Application examples 2
Buy business photocatalysis TiO2, without any processing, it is directly used in light-catalyzed reaction as a comparison.
72.12%Bi is prepared by the method in embodiment 12WO6/SnO2Nanometer sheet takes 100mg72.12%Bi2WO6/SnO2 Nanometer sheet is added in 5mg/L 100mL phenol solutions, and the magnetic agitation 30min under dark situation is put into xenon lamp and stirs below afterwards Side irradiation is mixed, takes a sample per 15min, the sample of taking-up centrifuges 20min under 2000r/min, then is taken out with liquid-transfering gun Then clear liquid goes out to survey its absorbance, and records data in 510nm.
Experimental result is as shown in figure 4, under visible light conditions, 72.12%Bi2WO6/SnO2When nanometer sheet is as catalyst, Under visible light conditions, there is stronger catalytic oxidation activity to liguid phase pollutant.
The above is only the preferable specific embodiment of the invention, but the protection domain of the invention is not This is confined to, in the technical scope that any one skilled in the art discloses in the invention, according to the present invention The technical solution of creation and its inventive concept are subject to equivalent substitution or change, should all cover the invention protection domain it It is interior.

Claims (1)

1. nanometer sheet Bi2WO6/SnO2The method of catalytic degradation liguid phase pollutant, which is characterized in that by Bi2WO6/SnO2Add in liquid In phase pollutant, the magnetic agitation under dark situation is then placed under xenon lamp and irradiates while stirring, carries out catalytic reaction;
The Bi2WO6/SnO2The preparation method of nanometer sheet is:
(1) by 1mmol Na2WO4·2H2O, 1.98mmol Bi (NO3)3·5H2O is dissolved in distilled water, obtains suspension, will suspend Liquid be transferred in autoclave 90 DEG C of -220 DEG C of reaction 12-36 it is small when, it is after reaction, natural cooling, filtering, washing, dry It is dry, obtain Bi2WO6
(2) Bi is added in into ethylene glycol2WO6, stirring to obtain Bi2WO6Suspension;By Bi2WO6Suspension is added to SnCl4·5H2O In prepare mixing suspension;Aqueous solution of urea is prepared, aqueous solution of urea is added in mixing suspension, and is stirred at room temperature 1 Hour, it is washed, dry when 150-210 DEG C of 12-24 of heating is small in reaction kettle;Bi is made2WO6/SnO2Nanometer sheet, wherein Bi2WO6Account for SnO2The 24.47%-88.13% of quality.
CN201711358232.4A 2017-11-01 2017-11-01 Nanometer sheet Bi2WO6/SnO2The method of catalytic degradation liguid phase pollutant Pending CN108043390A (en)

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