CN105170189A - Preparation method of spherical BiOBr/NiO@ACSs composite photocatalyst - Google Patents
Preparation method of spherical BiOBr/NiO@ACSs composite photocatalyst Download PDFInfo
- Publication number
- CN105170189A CN105170189A CN201510638283.7A CN201510638283A CN105170189A CN 105170189 A CN105170189 A CN 105170189A CN 201510638283 A CN201510638283 A CN 201510638283A CN 105170189 A CN105170189 A CN 105170189A
- Authority
- CN
- China
- Prior art keywords
- acss
- nio
- biobr
- catalyst
- preparation
- 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.)
- Granted
Links
Abstract
The invention provides a preparation method of a spherical BiOBr/NiO@ACSs composite photocatalyst. The preparation method has the advantages of low cost of raw materials and mild preparation operation conditions, specifically, phenolic compounds and aldehyde compounds are taken as the hosts, cyanophenol and nickel nitrate are taken as the guests, a triethanolamine or a potassium hydroxide catalyst, a polyvinyl alcohol or sodium dodecyl sulfate dispersing agent or a melamine or polyaniline curing agent are added sequentially, a product is activated, and NiO@ACSs with efficient adsorption property is obtained; finally, NiO@ACSs is composited with BiOBr, and the BiOBr/NiO@ACSs composite photocatalyst with high adsorption property and high photocatalytic efficiency is obtained.
Description
Technical field
The present invention relates to the preparation method of the spherical composite photo-catalyst of a kind of BiOBr/NiO@ACSs, belong to photocatalysis technology field.
Background technology
In recent years, energy shortage and environmental pollution become the significant problem threatening human survival and health day by day.Photocatalysis technology is a kind of is that catalyst utilizes the green environment of solar energy degraded Environmental pollutant to administer new technology with semiconductor.It directly utilizes solar energy, does not need artificial energy source, can thoroughly mineralising is various is difficult to biodegradable organic pollution, non-secondary pollution, has a good application prospect.The photochemical catalyst mainly TiO of current business
2, but TiO
2photochemical catalyst forbidden band wider (Eg=3.2eV), only can by the ultraviolet excitation (accounting for 3.8% of solar energy) in sunshine, the visible ray in sunshine (accounting for 45% of solar energy) can not be utilized, make its solar energy utilization ratio low, the large-scale commercial seriously hindering photocatalysis technology is promoted.The photochemical catalyst of exploitation high-performance visible light response has become one of the most popular current research direction, is also inexorable trend and developing direction that photocatalysis technology moves towards industrialization further.
BiOX BiOX (X=Cl, Br, l) be the class novel photocatalysis material be found in recent years, its distinctive open lamellar structure, internal electric field and indirect transition pattern are conducive to right effective of hole-electron and are separated and Charger transfer, BiOX is had and compares TiO
2higher photocatalytic activity.Therefore, BiOX solid solution is the potential novel visible catalysis material of a class.But from existing result of study, the photocatalysis performance of the associated catalysts of current report also reaches far away desirable degree, their photocatalysis efficiency still needs further raising, and due to existing photochemical catalyst specific area all less, shape is not fixed, and the adsorption capacity of photochemical catalyst to organic pollution is poor, in addition in most cases, organic contamination substrate concentration is very low, needs the long period just can reach light-catalysed object.Therefore, on existing Research foundation, the higher and photochemical catalyst simultaneously with high efficiency of additive capability of exploitation catalytic efficiency is necessary.
Summary of the invention
The object of the present invention is to provide a kind of with low cost, operating condition is gentle, efficient adsorption-light-catalysed method prepares the spherical composite photo-catalyst of BiOBr/NiO@ACSs, solves problems of the prior art.
For this reason, the invention provides the preparation method of the spherical composite photo-catalyst of a kind of BiOBr/NiO@ACSs, comprise the steps,
(1) phenolic compound and aldehyde compound are added to the water according to mol ratio 1: 3 ~ 9; By be respectively relative to described phenolic compound mass fraction 5% ~ 20% add in above-mentioned solution to the nickel nitrate of cyano group phenol and 1.5% ~ 7.5%, then adding relative to described phenolic compound mass fraction is the catalyst of 1% ~ 1.5%, stir and heat to 90 DEG C ~ 96 DEG C, add after continuing to stir 30min ~ 50min and be respectively the dispersant of 5% ~ 15% and the curing agent of 2% ~ 10% relative to described phenolic compound mass fraction, continue to stir 3h ~ 6h, after cool to room temperature, filter and obtain resin balls;
(2) by above-mentioned resin balls and potassium hydroxide according to mol ratio 1: 4 ~ 8, activated by room temperature to 750 DEG C ~ 950 DEG C under nitrogen protection, soak time is 2 ~ 5h, and Temperature fall, to room temperature, washing, filters and obtains NiO@ACSs;
(3) by mass ratio be 2 ~ 5 CTAB and KBr mixing after, the mixture of gained and step (2) products therefrom are 1 ~ 6 join in alcohol solvent according to mass ratio, and then add five water bismuth nitrates, stirring obtains turbid solution;
(4) proceed in Teflon autoclave by described turbid solution, thermal response 10 ~ 16h at 110 DEG C ~ 200 DEG C temperature, is precipitated, and through washing, obtains the spherical composite photo-catalyst of BiOBr/NiO@ACSs after oven dry.
Preferably, described phenols is p-cresol, p-t-butyl phenol or ethyl naphthol.
Preferably, described aldehydes is formaldehyde or furfural.
Preferably, described catalyst is triethanolamine or potassium hydroxide.
Preferably, described dispersant is polyvinyl alcohol or dodecyl sodium sulfate.
Preferably, described curing agent is melamine or polyaniline.
Preferably, described phenolic compound and described aldehyde compound mol ratio are 1: 6.
In step (4), described sediment washs successively through water and ethanol, 3 times at least repeatedly; Bake out temperature is 80 DEG C ~ 90 DEG C.
The preparation method of the spherical composite photo-catalyst of BiOBr/NiO@ACSs provided by the invention, low raw-material cost, preparation manipulation mild condition, specifically based on phenolic compound and aldehyde compound, with cyano group phenol and nickel nitrate for object, add triethanolamine or potassium hydroxide catalyst, polyvinyl alcohol or dodecyl sodium sulfate dispersant and melamine or polyaniline curing agent successively, formation is activated, obtains the NiO@ACSs with high efficiency of additive capability; The BiOBr/NiO@ACSs composite photo-catalyst that last compound BiOBr formation high absorption property and high photocatalysis efficiency have both.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the spherical composite photo-catalyst of BiOBr/NiO@ACSs of embodiment 1 provided by the invention preparation;
Fig. 2 be embodiment 4 provided by the invention preparation the spherical composite photo-catalyst of BiOBr/NiO@ACSs and comparative example 1-2 to the degraded figure of 10mol/L phenol solution.
Detailed description of the invention
Understand technical scheme of the present invention better to make those skilled in the art can be implemented, below in conjunction with the drawings and specific embodiments, the invention will be further described, but illustrated embodiment is not as a limitation of the invention.
Embodiment 1
Be to be added to the water p-cresol and formaldehyde at 1: 3 according to mol ratio; By be respectively relative to p-cresol mass fraction 5% add in above-mentioned solution to the nickel nitrate of cyano group phenol and 1.5%, then adding relative to p-cresol mass fraction is the triethanolamine of 1%, stir and heat to 90 DEG C, continue stirring to add after 30 minutes and be respectively the polyvinyl alcohol of 5% and the polyaniline of 2% relative to p-cresol mass fraction, continue stirring 3 hours, after cool to room temperature, filter and obtain resin balls;
By above-mentioned resin balls and potassium hydroxide according to mol ratio 1: 4, under nitrogen protection, activated in high temperature process furnances by room temperature to 750 DEG C, soak time 2 hours, Temperature fall, to room temperature, washing, filters and obtains NiO@ACSs;
By mass ratio be 2 CTAB and KBr mixing after, the mixture of CTAB and KBr and above-mentioned products therefrom NiO@ACSs are 1 join in alcohol solvent according to mass ratio, and then add five water bismuth nitrates, continuation stirring obtains milky turbidity liquid; Then proceed in Teflon autoclave by above-mentioned turbid solution, thermal response 10h at 110 DEG C of temperature, is precipitated, with water and ethanol washing, and 3 times at least repeatedly, then 80 DEG C of oven dry, obtain the spherical composite photo-catalyst of BiOBr/NiO@ACSs.
The SEM figure of the spherical composite photo-catalyst of BiOBr/NiO@ACSs prepared by the present embodiment is specifically shown in accompanying drawing 1, and as seen from Figure 1, the obtained spherical composite photo-catalyst of BiOBr/NiO@ACSs is the equally distributed round that diameter is more than or equal to 1mm.
Embodiment 2
Be to be added to the water ethyl naphthol and furfural at 1: 9 according to mol ratio; By be respectively relative to ethyl naphthol mass fraction 20% add in above-mentioned solution to the nickel nitrate of cyano group phenol and 7.5%, then adding relative to ethyl naphthol mass fraction is the potassium hydroxide of 1.5%, stir and heat to 96 DEG C, continue stirring to add after 40 minutes and be respectively the dodecyl sodium sulfate of 15% and the melamine of 10% relative to ethyl naphthol mass fraction, continue stirring 4 hours, after cool to room temperature, filter and obtain resin balls;
Be 1: 8 by above-mentioned resin balls and potassium hydroxide according to mol ratio, under nitrogen protection, activated in high temperature process furnances by room temperature to 800 DEG C, soak time 3 hours, Temperature fall, to room temperature, washing, filters and obtains NiO@ACSs; By mass ratio be 5 CTAB and KBr mixing after, be 3 join in alcohol solvent with above-mentioned products therefrom NiO@ACSs according to mass ratio, then add five water bismuth nitrates, stir and obtain turbid solution; Then proceed in Teflon autoclave by described turbid solution, thermal response 12h at 150 DEG C of temperature, is precipitated, with water and ethanol washing, and 3 times at least repeatedly, then 85 DEG C of oven dry, after oven dry, obtain the spherical composite photo-catalyst of BiOBr/NiO@ACSs.
Embodiment 3
Be to be added to the water p-t-butyl phenol and furfural at 1: 6 according to mol ratio; By be respectively relative to p-t-butyl phenol mass fraction 10% add in above-mentioned solution to the nickel nitrate of cyano group phenol and 5%, then adding relative to p-t-butyl phenol mass fraction is the potassium hydroxide of 1.3%, stir and heat to 92 DEG C, continue stirring to add after 50 minutes and be respectively the polyvinyl alcohol of 12% and the polyaniline of 10% relative to p-t-butyl phenol mass fraction, continue stirring 6 hours, after cool to room temperature, filter and obtain resin balls;
Be 1: 6 by above-mentioned resin balls and potassium hydroxide according to mol ratio, under nitrogen protection, activated in high temperature process furnances by room temperature to 950 DEG C, soak time 5 hours, Temperature fall, to room temperature, washing, filters and obtains NiO@ACSs; By mass ratio be 3 CTAB and KBr mixing after, be 6 join in alcohol solvent with above-mentioned products therefrom NiO@ACSs according to mass ratio, stir and obtain turbid solution; Then proceed in Teflon autoclave by described turbid solution, thermal response 16h at 200 DEG C of temperature, is precipitated, with water and ethanol washing, and 3 times at least repeatedly, then 90 DEG C of oven dry, after oven dry, obtain the spherical composite photo-catalyst of BiOBr/NiO@ACSs.
Embodiment 4
The spherical composite photo-catalyst of BiOBr/NiO@ACSs prepared by embodiment of the present invention 1-3 respectively Pyrogentisinic Acid's solution is degraded, concrete experimental procedure is: preparation concentration is the phenol solution of 10mg/L, getting load has the sample 1-3 of above-mentioned photochemical catalyst to be placed in culture dish, add the phenol solution that 30mL initial concentration is 10mg/L, the light source adopted is 500W xenon lamp, optical source wavelength scope is 200nm ~ 800nm, illumination 1.5 hours, stop reaction taking out photochemical catalyst sample, reacted phenol solution is for subsequent use.
Comparative example 1
The light source adopted the phenol solution of 10mg/L is 500W xenon lamp, and optical source wavelength scope is 200nm ~ 800nm, directly carries out photodissociation illumination 1.5 hours, and stop reaction taking out photochemical catalyst sample, reacted phenol solution is for subsequent use.
Comparative example 2
P25 (titanium dioxide) is adopted directly to carry out photocatalysis to the phenol solution of 10mg/L, concrete experimental procedure is: preparation concentration is the phenol solution of 10mg/L, a certain amount of P25 (titanium dioxide) is placed in culture dish, add the phenol solution that 30mL initial concentration is 10mg/L, the light source adopted is 500W xenon lamp, and optical source wavelength scope is 200nm ~ 800nm, illumination 1.5 hours, stop reaction taking out photochemical catalyst sample, reacted phenol solution is for subsequent use.
Catalyst described in embodiment 1-3 is measured respectively by spectrophotometer, and comparative example 1-2 carries out the phenol solution after catalytic reaction, specifically as shown in Figure 2, through above-mentioned photochemical catalyst photodissociation after 1.5 hours, through direct illumination degrading and the phenol solution degradation rate through P25 process very low, and the degradation rate of phenol solution reaches more than 97%.The above embodiment is only that its protection domain is not limited thereto in order to absolutely prove the preferred embodiment that the present invention lifts.The equivalent alternative or conversion that those skilled in the art do on basis of the present invention, all within protection scope of the present invention, protection scope of the present invention is as the criterion with claims.
Claims (9)
1. a preparation method for the spherical composite photo-catalyst of BiOBr/NiO ACSs, comprises the steps,
(1) phenolic compound and aldehyde compound are added to the water according to mol ratio 1: 3 ~ 9; By be respectively relative to described phenolic compound mass fraction 5% ~ 20% add in above-mentioned solution to the nickel nitrate of cyano group phenol and 1.5% ~ 7.5%, then adding relative to described phenolic compound mass fraction is the catalyst of 1% ~ 1.5%, stir and heat to 90 DEG C ~ 96 DEG C, add after continuing to stir 30min ~ 50min and be respectively the dispersant of 5% ~ 15% and the curing agent of 2% ~ 10% relative to described phenolic compound mass fraction, continue to stir 3h ~ 6h, after cool to room temperature, filter and obtain resin balls;
(2) by above-mentioned resin balls and potassium hydroxide according to mol ratio 1: 4 ~ 8, activated by room temperature to 750 DEG C ~ 950 DEG C under nitrogen protection, soak time is 2h ~ 5h, and Temperature fall, to room temperature, washing, filters and obtains NiO@ACSs;
(3) by mass ratio be 2 ~ 5 CTAB and the mixing of Australia potassium after, the mixture of gained and step (2) products therefrom are 1 ~ 6 join in alcohol solvent according to mass ratio, and then add five water bismuth nitrates, stirring obtains turbid solution;
(4) described turbid solution is proceeded in Teflon autoclave, at 110 DEG C ~ 200 DEG C temperature, react 10 ~ 16h, be precipitated, through washing, after oven dry, obtain the spherical composite photo-catalyst of BiOBr/NiO@ACSs.
2. the preparation method of the spherical composite photo-catalyst of BiOBr/NiO@ACSs according to claim 1, is characterized in that, described phenols is p-cresol, p-t-butyl phenol or ethyl naphthol.
3. the preparation method of the spherical composite photo-catalyst of BiOBr/NiO@ACSs according to claim 1, is characterized in that, described aldehydes is formaldehyde or furfural.
4. the preparation method of the spherical composite photo-catalyst of BiOBr/NiO@ACSs according to claim 1, is characterized in that, described catalyst is triethanolamine or potassium hydroxide.
5. the preparation method of the spherical composite photo-catalyst of BiOBr/NiO@ACSs according to claim 1, is characterized in that, described dispersant is polyvinyl alcohol or dodecyl sodium sulfate.
6. the preparation method of the spherical composite photo-catalyst of BiOBr/NiO@ACSs according to claim 1, is characterized in that, described curing agent is melamine or polyaniline.
7. the preparation method of the spherical composite photo-catalyst of BiOBr/NiO@ACSs according to claim 1, is characterized in that, phenolic compound described in step (1) and described aldehyde compound mol ratio are 1: 6.
8. the preparation method of the spherical composite photo-catalyst of BiOBr/NiO@ACSs according to claim 1, is characterized in that, in step (4), described sediment washs successively through water and ethanol, 3 times at least repeatedly.
9. the preparation method of the spherical composite photo-catalyst of BiOBr/NiO@ACSs according to claim 1, is characterized in that, in step (4), bake out temperature is 80 DEG C ~ 90 DEG C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510638283.7A CN105170189B (en) | 2015-09-23 | 2015-09-23 | A kind of preparation method of the spherical composite photo-catalysts of BiOBr/NiO@ACSs |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510638283.7A CN105170189B (en) | 2015-09-23 | 2015-09-23 | A kind of preparation method of the spherical composite photo-catalysts of BiOBr/NiO@ACSs |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105170189A true CN105170189A (en) | 2015-12-23 |
| CN105170189B CN105170189B (en) | 2017-10-24 |
Family
ID=54892897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510638283.7A Active CN105170189B (en) | 2015-09-23 | 2015-09-23 | A kind of preparation method of the spherical composite photo-catalysts of BiOBr/NiO@ACSs |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN105170189B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20150174567A1 (en) * | 2013-12-20 | 2015-06-25 | Massachusetts Institute Of Technology | Hybrid photocatalyst for wastewater remediation |
-
2015
- 2015-09-23 CN CN201510638283.7A patent/CN105170189B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| US20150174567A1 (en) * | 2013-12-20 | 2015-06-25 | Massachusetts Institute Of Technology | Hybrid photocatalyst for wastewater remediation |
| CN103920508A (en) * | 2014-03-28 | 2014-07-16 | 山东大学 | Nitrated carbon fiber loaded bismuth oxyhalide nanoflower and preparation method of nanoflower |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN105170189B (en) | 2017-10-24 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104128184B (en) | A kind of float type CoFe2O4/TiO2/ float bead composite photochemical catalyst and preparation method thereof | |
| CN105170189A (en) | Preparation method of spherical BiOBr/NiO@ACSs composite photocatalyst | |
| CN100551831C (en) | Visible light-responded Bi 2WO 6The photocatalyst fused salt preparation method | |
| CN105749893A (en) | Preparation method of modified active carbon fiber with surface-loaded nanometer titanium dioxide (TiO2) | |
| CN106865685B (en) | Treatment method for photocatalytic degradation of rhodamine B dye wastewater | |
| CN108940332B (en) | High-activity MoS2/g-C3N4/Bi24O31Cl10Preparation method of composite photocatalyst | |
| CN109046425A (en) | Composite photo-catalyst TiO derived from a kind of MOF base2/g-C3N4Preparation method | |
| CN105170130A (en) | Preparation method and application of high-dispersion CeO2 modified TiO2 meso-porous photocatalyst | |
| CN101745402A (en) | Bi2WO6 photocatalysis membrane loaded by base with high specific surface, method and application thereof | |
| CN102302955A (en) | Floating polypyrrole-TiO2/floating bead photocatalyst, and preparation method and application thereof | |
| CN101816931B (en) | Method for preparing visible light response catalyst Bi3.84W0.16O6.24 by hydrothermal method | |
| CN102218335B (en) | Preparation method of hydrophobic immobilized photocatalyst with solar photocatalysis activity | |
| CN108855138A (en) | A kind of Z-type structure Mn0.5Cd0.5S/Ag/Bi2WO6Composite photocatalyst and preparation method thereof | |
| CN101491769A (en) | Strontium carbonate with visible photoresponse and preparation method thereof | |
| CN103721699A (en) | NaInO2 photocatalyst and preparation method thereof | |
| CN102069006A (en) | Photocatalytic metal-molecular sieve composite catalyst and preparation method thereof | |
| CN105195183A (en) | Preparation method of Co3O4@ACSs/BiOCl spherical adsorption and photocatalysis compound catalyst | |
| CN110280287A (en) | It is a kind of effectively to construct Z-type ternary heterojunction CdS/NiS/g-C3N4The preparation method of photochemical catalyst | |
| CN108855233B (en) | Method for preparing copper-loaded nano titanium dioxide chitosan composite microspheres by using microfluidic technology through photodegradable dye | |
| CN102294256B (en) | Preparation method of vanadium-nitrogen co-doped TiO2 photocatalyst | |
| CN103881122B (en) | The preparation method of the polyvinyl chloride/nano tin ash composite membrane of high visible light catalytic activity | |
| CN106732587B (en) | A kind of preparation method of the ZnO polycrystal nanobelt package assembly of high H2-producing capacity atomic state Ag modification | |
| CN104689818A (en) | ZnO/Ag@AgInO2 heterogeneous Z type photocatalytic material and preparation method thereof | |
| CN101491770A (en) | Strontium carbonate- titanium dioxide composite photocatalyst with visible phtoresponse and preparation method thereof | |
| CN115181265B (en) | Methylene modified covalent triazine framework material and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |