CN105170189B - A kind of preparation method of the spherical composite photo-catalysts of BiOBr/NiO@ACSs - Google Patents
A kind of preparation method of the spherical composite photo-catalysts of BiOBr/NiO@ACSs Download PDFInfo
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Abstract
The invention provides a kind of preparation method of the spherical composite photo-catalysts of BiOBr/NiO@ACSs, low raw-material cost, preparation manipulation mild condition, specifically based on phenolic compound and aldehyde compound, using cyano group phenol and nickel nitrate as object, sequentially add triethanolamine or potassium hydroxide catalyst, polyvinyl alcohol or dodecyl sodium sulfate dispersant and melamine or polyphenyl amine hardener, formation is activated, obtains the NiO@ACSs with high efficiency of additive capability；Finally it is combined the BiOBr/NiO ACSs composite photo-catalysts that BiOBr formation high absorption properties and high photocatalysis efficiency have both.
Description
Technical field
The present invention relates to a kind of preparation method of the spherical composite photo-catalysts of BiOBr/NiO@ACSs, belong to photocatalysis technology
Field.
Background technology
In recent years, energy shortage and environmental pollution, which are increasingly becoming, threatens human survival and the significant problem of health.Photocatalysis
Technology is a kind of green environment improvement new technology for Environmental pollutant of being degraded by catalyst of semiconductor using solar energy.It
Directly using solar energy, be not required to artificial energy source, can thoroughly mineralising is various is difficult to biodegradable organic pollution, without secondary dirt
Dye, has a good application prospect.The photochemical catalyst of current business is mainly TiO2, but TiO2Wider (the Eg=of photochemical catalyst forbidden band
3.2eV), it is only capable of by the ultraviolet excitation (account for solar energy 3.8%) in sunshine, it is impossible to utilize the visible ray in sunshine
(account for solar energy 45%) so that its solar energy utilization ratio is low, the large-scale commercial for seriously hindering photocatalysis technology is promoted.
Develop the photochemical catalyst of high-performance visible light response has turned into one of current most popular research direction, is also that photocatalysis technology enters
One step moves towards the inexorable trend and developing direction of industrialization.
(X=Cl, Br, l) are the class novel photocatalysis material that was found in recent years to BiOX BiOX, and its is distinctive to open
Put formula lamellar structure, internal electric field and indirect transition pattern and be conducive to efficiently separating and electric charge transfer for hole-electron pair so that
BiOX has than TiO2Higher photocatalytic activity.Therefore, BiOX solid solution is the potential novel visible catalysis of a class
Material.But from the point of view of existing result of study, the photocatalysis performance for the associated catalysts reported at present also reaches far away preferable journey
Degree, their photocatalysis efficiency still needs to further raising, and because existing photochemical catalyst specific surface area is all smaller, shape is not solid
Fixed, photochemical catalyst is poor to the adsorption capacity of organic pollution, in addition in most cases, organic pollution concentration it is very low, it is necessary to
Long period can be only achieved light-catalysed purpose.Therefore on existing Research foundation, exploitation catalytic efficiency is higher and has simultaneously
The photochemical catalyst for having high efficiency of additive capability is necessary.
The content of the invention
It is an object of the invention to provide one kind is with low cost, operating condition is gentle, efficient absorption-light-catalysed method system
The spherical composite photo-catalysts of standby BiOBr/NiO@ACSs, have solved problems of the prior art.
Therefore, the invention provides a kind of preparation method of the spherical composite photo-catalysts of BiOBr/NiO@ACSs, including such as
Lower step,
(1) phenolic compound and aldehyde compound are added to the water according to mol ratio 1: 3~9；Will be relative to the phenols
Compound quality fraction is respectively 5%~20% cyano group phenol and 1.5%~7.5% nickel nitrate to be added in above-mentioned solution,
Then add relative to the catalyst that the phenolic compound mass fraction is 1%~1.5%, stir and heat to 90 DEG C
~96 DEG C, it is respectively 5%~15% to continue to add relative to the phenolic compound mass fraction after stirring 30min~50min
Dispersant and 2%~10% curing agent, continue stir 3h~6h, be cooled to after room temperature, be filtrated to get resin balls；
(2) by above-mentioned resin balls and potassium hydroxide according to mol ratio 1: 4~8, under nitrogen protection by room temperature to 750
DEG C~950 DEG C activated, soak time be 2~5h, be naturally cooling to room temperature, wash, be filtrated to get NiO@ACSs；
(3) after mass ratio is mixed for 2~5 CTAB and KBr, mixture and step (2) products therefrom of gained are pressed
It is added to according to mass ratio for 1~6 in alcohol solvent, then adds five water bismuth nitrates, stirring obtains turbid solution；
(4) turbid solution is transferred in Teflon autoclaves, at a temperature of 110 DEG C~200 DEG C thermal response 10~
16h, is precipitated, scrubbed, and the spherical composite photo-catalysts of BiOBr/NiO@ACSs are obtained after drying.
Preferably, the phenols is p-cresol, p-t-butyl phenol or ethyl naphthol.
Preferably, the aldehydes is formaldehyde or furfural.
Preferably, the catalyst is triethanolamine or potassium hydroxide.
Preferably, the dispersant is polyvinyl alcohol or dodecyl sodium sulfate.
Preferably, the curing agent is melamine or polyaniline.
Preferably, the phenolic compound and the aldehyde compound mol ratio are 1: 6.
In step (4), the sediment is washed successively through water and ethanol, at least repeatedly 3 times；Drying temperature is 80 DEG C~90
℃。
The preparation method for the spherical composite photo-catalysts of BiOBr/NiO@ACSs that the present invention is provided, low raw-material cost, system
Standby operating condition is gentle, specifically based on phenolic compound and aldehyde compound, using cyano group phenol and nickel nitrate as object, successively
Add triethanolamine or potassium hydroxide catalyst, polyvinyl alcohol or dodecyl sodium sulfate dispersant and melamine or polyaniline
Curing agent, formation is activated, obtains the NiO@ACSs with high efficiency of additive capability；Finally it is combined BiOBr formation high adsorptions
The BiOBr/NiO ACSs composite photo-catalysts that can have both with high photocatalysis efficiency.
Brief description of the drawings
Fig. 1 is the SEM figures of the spherical composite photo-catalysts of BiOBr/NiO@ACSs prepared by the embodiment 1 that the present invention is provided；
Fig. 2 is the spherical composite photo-catalyst of BiOBr/NiO@ACSs and comparative example prepared by the embodiment 4 that the present invention is provided
Degraded figures of the 1-2 to 10mol/L phenol solutions.
Embodiment
In order that those skilled in the art more fully understand that technical scheme can be practiced, below in conjunction with the accompanying drawings
The invention will be further described with specific embodiment, but illustrated embodiment is not as a limitation of the invention.
Embodiment 1
P-cresol and formaldehyde are added to the water according to mol ratio for 1: 3；It will distinguish relative to p-cresol mass fraction
It is relative to p-cresol mass fraction in cyano group phenol and the above-mentioned solution of 1.5% nickel nitrate addition, then adding for 5%
1% triethanolamine, stirs and heats to 90 DEG C, continues to add relative to p-cresol mass fraction after stirring 30 minutes
Respectively 5% polyvinyl alcohol and 2% polyaniline, continue to stir 3 hours, are cooled to after room temperature, are filtrated to get resin balls；
By above-mentioned resin balls and potassium hydroxide according to mol ratio 1: 4, under nitrogen protection, by room temperature in high temperature process furnances
It is warming up to 750 DEG C to be activated, soak time 2 hours is naturally cooling to room temperature, washs, is filtrated to get NiO@ACSs；
After mass ratio is mixed for 2 CTAB and KBr, the mixture of CTAB and KBr and above-mentioned products therefrom
NiO@ACSs are added in alcohol solvent according to mass ratio for 1, then add five water bismuth nitrates, it is muddy that continuation stirring obtains milky
Turbid liquid；Then above-mentioned turbid solution is transferred in Teflon autoclaves, thermal response 10h, is precipitated at a temperature of 110 DEG C,
Washed with water and ethanol, at least repeatedly 3 times, then in 80 DEG C of drying, obtain the spherical composite photo-catalysts of BiOBr/NiO@ACSs.
The SEM figures of the spherical composite photo-catalysts of BiOBr/NiO@ACSs manufactured in the present embodiment are specifically shown in accompanying drawing 1, by Fig. 1
As can be seen that the spherical composite photo-catalysts of obtained BiOBr/NiO@ACSs are the equally distributed ball that diameter is more than or equal to 1mm
Shape thing.
Embodiment 2
Ethyl naphthol and furfural are added to the water according to mol ratio for 1: 9；To be respectively relative to ethyl naphthol mass fraction
20% adds in above-mentioned solution to cyano group phenol and 7.5% nickel nitrate, then adds and is relative to ethyl naphthol mass fraction
1.5% potassium hydroxide, stirs and heats to 96 DEG C, continues to add relative to ethyl naphthol mass fraction after stirring 40 minutes
Respectively 15% dodecyl sodium sulfate and 10% melamine, continue to stir 4 hours, are cooled to after room temperature, filter
To resin balls；
According to mol ratio it is 1: 8 by above-mentioned resin balls and potassium hydroxide, under nitrogen protection, by room in high temperature process furnances
Temperature is warming up to 800 DEG C and activated, soak time 3 hours, is naturally cooling to room temperature, washs, is filtrated to get NiO ACSs；By matter
After amount is than the CTAB for 5 and KBr mixing, alcohol solvent is added to according to mass ratio for 3 with above-mentioned products therefrom NiO@ACSs
In, five water bismuth nitrates are then added, stirring obtains turbid solution；Then the turbid solution is transferred in Teflon autoclaves,
Thermal response 12h, is precipitated at a temperature of 150 DEG C, is washed with water and ethanol, at least repeatedly 3 times, then in 85 DEG C of drying, drying
After obtain the spherical composite photo-catalysts of BiOBr/NiO@ACSs.
Embodiment 3
P-t-butyl phenol and furfural are added to the water according to mol ratio for 1: 6；Will be relative to p-t-butyl phenol quality
Fraction is respectively 10% in cyano group phenol and the above-mentioned solution of 5% nickel nitrate addition, then adding relative to tert-butyl benzene
Phenol mass fraction is 1.3% potassium hydroxide, stirs and heats to 92 DEG C, continues to add relative to right after stirring 50 minutes
Tert-butyl phenol mass fraction is respectively 12% polyvinyl alcohol and 10% polyaniline, continues to stir 6 hours, is cooled to room temperature
Afterwards, resin balls are filtrated to get；
According to mol ratio it is 1: 6 by above-mentioned resin balls and potassium hydroxide, under nitrogen protection, by room in high temperature process furnances
Temperature is warming up to 950 DEG C and activated, soak time 5 hours, is naturally cooling to room temperature, washs, is filtrated to get NiO ACSs；By matter
After amount is than the CTAB for 3 and KBr mixing, alcohol solvent is added to according to mass ratio for 6 with above-mentioned products therefrom NiO@ACSs
In, stirring obtains turbid solution；Then the turbid solution is transferred in Teflon autoclaves, the thermal response at a temperature of 200 DEG C
16h, is precipitated, and is washed with water and ethanol, at least repeatedly 3 times, then in 90 DEG C of drying, BiOBr/NiO@ACSs are obtained after drying
Spherical composite photo-catalyst.
Embodiment 4
The spherical composite photo-catalysts of BiOBr/NiO@ACSs prepared by 1-3 of the embodiment of the present invention distinguish Pyrogentisinic Acid's solution
Degraded, specific experimental procedure is：The phenol solution that concentration is 10mg/L is prepared, the examination for being loaded with above-mentioned photochemical catalyst is taken
Sample 1-3 is placed in culture dish, adds the phenol solution that 30mL initial concentrations are 10mg/L, the light source used is 500W xenon lamp, light
Source wavelength scope is 200nm~800nm, and illumination 1.5 hours stops reaction and takes out photochemical catalyst sample, reacted phenol is molten
Liquid is standby.
Comparative example 1
The light source that phenol solution to 10mg/L is used is 500W xenon lamp, and optical source wavelength scope is 200nm~800nm, directly
Row photodissociation illumination 1.5 hours is tapped into, stops reaction and takes out photochemical catalyst sample, reacted phenol solution is standby.
Comparative example 2
Photocatalysis is directly carried out to 10mg/L phenol solution using P25 (titanium dioxide), specific experimental procedure is：System
The phenol solution that standby concentration is 10mg/L, a certain amount of P25 (titanium dioxide) is placed in culture dish, adds 30mL initial concentrations
For 10mg/L phenol solution, the light source used is 500W xenon lamp, and optical source wavelength scope is 200nm~800nm, and illumination 1.5 is small
When, stop reaction and take out photochemical catalyst sample, reacted phenol solution is standby.
Measure catalyst described in embodiment 1-3 respectively by spectrophotometer, and comparative example 1-2 is carried out after catalytic reaction
Phenol solution, it is specific as shown in Fig. 2 after above-mentioned photochemical catalyst photodissociation 1.5 hours, through direct illumination degrading and through P25
The phenol solution degradation rate of processing is very low, and the degradation rate of phenol solution is up to more than 97%.Embodiment described above be only for
The preferred embodiment for absolutely proving the present invention and being lifted, its protection domain not limited to this.Those skilled in the art exist
The equivalent substitute made on the basis of the present invention or conversion, within protection scope of the present invention, protection scope of the present invention with
Claims are defined.
Claims (9)
1. a kind of preparation method of the spherical composite photo-catalysts of BiOBr/NiO@ACSs, comprises the following steps,
(1) phenolic compound and aldehyde compound are added to the water according to mol ratio 1: 3~9；Will be relative to the phenols chemical combination
Amount of substance fraction is respectively 5%~20% cyano group phenol and 1.5%~7.5% nickel nitrate to be added in above-mentioned solution, then
Add relative to the catalyst that the phenolic compound mass fraction is 1%~1.5%, stir and heat to 90 DEG C~96
DEG C, continue stir 30min~50min after add relative to the phenolic compound mass fraction be respectively 5%~15% point
Powder and 2%~10% curing agent, continue to stir 3h~6h, are cooled to after room temperature, are filtrated to get resin balls；
(2) by above-mentioned resin balls and potassium hydroxide according to mol ratio 1: 4~8, under nitrogen protection by room temperature to 750 DEG C~
950 DEG C are activated, and soak time is 2h~5h, is naturally cooling to room temperature, washs, is filtrated to get NiO@ACSs；
(3) after mass ratio is mixed for 2~5 CTAB and KBr, the mixture and step (2) products therefrom of gained are according to matter
Then amount adds five water bismuth nitrates than being added to for 1~6 in alcohol solvent, and stirring obtains turbid solution；
(4) turbid solution is transferred in Teflon autoclaves, 10~16h is reacted at a temperature of 110 DEG C~200 DEG C, is obtained
It is scrubbed to precipitation, the spherical composite photo-catalysts of BiOBr/NiO@ACSs are obtained after drying.
2. the preparation method of the spherical composite photo-catalysts of BiOBr/NiO@ACSs according to claim 1, it is characterised in that
The phenols is p-cresol, p-t-butyl phenol or ethyl naphthol.
3. the preparation method of the spherical composite photo-catalysts of BiOBr/NiO@ACSs according to claim 1, it is characterised in that
The aldehydes is formaldehyde or furfural.
4. the preparation method of the spherical composite photo-catalysts of BiOBr/NiO@ACSs according to claim 1, it is characterised in that
The catalyst is triethanolamine or potassium hydroxide.
5. the preparation method of the spherical composite photo-catalysts of BiOBr/NiO@ACSs according to claim 1, it is characterised in that
The dispersant is polyvinyl alcohol or dodecyl sodium sulfate.
6. the preparation method of the spherical composite photo-catalysts of BiOBr/NiO@ACSs according to claim 1, it is characterised in that
The curing agent is melamine or polyaniline.
7. the preparation method of the spherical composite photo-catalysts of BiOBr/NiO@ACSs according to claim 1, it is characterised in that
Phenolic compound described in step (1) is 1: 6 with the aldehyde compound mol ratio.
8. the preparation method of the spherical composite photo-catalysts of BiOBr/NiO@ACSs according to claim 1, it is characterised in that
In step (4), the sediment is washed successively through water and ethanol, at least repeatedly 3 times.
9. the preparation method of the spherical composite photo-catalysts of BiOBr/NiO@ACSs according to claim 1, it is characterised in that
In step (4), drying temperature is 80 DEG C~90 DEG C.
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| CN107537521A (en) * | 2017-09-29 | 2018-01-05 | 大连理工大学 | A kind of preparation method and application of the BiOBr micro-flowers photochemical catalysts of the high exposure ratio of { 001 } active crystal face |
| CN109589999A (en) * | 2019-01-14 | 2019-04-09 | 合肥学院 | A kind of dyestuff waste liquid processing preparation method of NiO/BiOBr composite photo-catalyst |
| CN110152646A (en) * | 2019-06-14 | 2019-08-23 | 太原理工大学 | A kind of solid-carrying type CeO2The preparation method and applications of@ACSs photochemical catalyst |
| CN110180543A (en) * | 2019-06-14 | 2019-08-30 | 太原理工大学 | A kind of solid-carrying type Cu2The preparation method and applications of O/Cu@ACSs photochemical catalyst |
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| CN103623803A (en) * | 2012-08-30 | 2014-03-12 | 上海纳晶科技有限公司 | Visible light photocatalyst and preparation method therefor |
| CN103920508A (en) * | 2014-03-28 | 2014-07-16 | 山东大学 | Nitrated carbon fiber loaded bismuth oxyhalide nanoflower and preparation method of nanoflower |
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| CN103623803A (en) * | 2012-08-30 | 2014-03-12 | 上海纳晶科技有限公司 | Visible light photocatalyst and preparation method therefor |
| CN103920508A (en) * | 2014-03-28 | 2014-07-16 | 山东大学 | Nitrated carbon fiber loaded bismuth oxyhalide nanoflower and preparation method of nanoflower |
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