CN103769175A - Preparation method and application of composite photocatalyst - Google Patents
Preparation method and application of composite photocatalyst Download PDFInfo
- Publication number
- CN103769175A CN103769175A CN201410075595.7A CN201410075595A CN103769175A CN 103769175 A CN103769175 A CN 103769175A CN 201410075595 A CN201410075595 A CN 201410075595A CN 103769175 A CN103769175 A CN 103769175A
- Authority
- CN
- China
- Prior art keywords
- composite photo
- preparation
- catalyst
- autoclave
- chlorine
- 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
Images
Landscapes
- Catalysts (AREA)
Abstract
The invention provides a preparation method and an application of a composite photocatalyst and relates to the field of catalysts. The preparation method comprises the following steps: dissolving bismuth salt and a chlorine-containing compound into a solvent; putting a mixture into a high-pressure reaction kettle; sealing the high-pressure reaction kettle and keeping the temperature of 160-180 DEG C for 6-12 hours; cooling to a room temperature; centrifuging a solution in the high-pressure reaction kettle to obtain sediment; washing and drying to obtain bismuth oxychloride; adding the bismuth oxychloride into a water solution containing an iron compound and putting a mixture into the high-pressure reaction kettle; sealing the high-pressure reaction kettle and keeping the temperature of 160-180 DEG C for 12-24 hours; cooling to the room temperature; centrifuging the solution in the high-pressure reaction kettle to obtain sediment I; and washing and drying to obtain the composite photocatalyst. The preparation method of the composite photocatalyst is simple and feasible; the obtained composite photocatalyst is stable in structure and has the high photocatalytic activity; the photocatalytic activity of the bismuth oxychloride is effectively improved and a mixed solution containing rhodamine B and methyl orange can be effectively degraded.
Description
Technical field
The present invention relates to catalyst field, be specifically related to a kind of preparation and application thereof of composite photo-catalyst.
Background technology
Semiconductor light-catalyst, under the irradiation of ultraviolet light or visible ray, not only can obtain Hydrogen Energy by splitting water, and also can be applied to solar cell solar energy is converted to chemical energy, can also be inorganic molecules H by organic pollutant degradation
2o and CO
2deng, demonstrate huge application prospect.In order to obtain the semiconductor light-catalyst of high activity, high stability, people have carried out a large amount of research and development, and wherein most representative semiconductor light-catalyst is nano titanium dioxide photocatalyst.In order to improve quantum yield and solar energy utilization ratio, researcher has carried out a large amount of study on the modification to titanium dioxide optical catalyst, as: adopt metal cation and nonmetalloid anion doped, titanium dioxide and other oxides compound etc.Research work has obtained some gratifying progress, but can not meet the needs of practical application.
Summary of the invention
The preparation method who the object of this invention is to provide a kind of composite photo-catalyst, the method is simple, and the composite photo-catalyst of acquisition has higher photocatalytic activity.
Another object of the present invention is to provide the application of above-mentioned composite photo-catalyst aspect degradable organic pollutant.
The preparation method of composite photo-catalyst of the present invention, simple, the composite photo-catalyst Stability Analysis of Structures that obtains, there is higher photocatalytic activity, effectively improved the photocatalytic activity of chlorine oxygen bismuth, the mixed solution that can efficient degradation contains rhodamine B and methyl orange.
Composite photo-catalyst of the present invention can be applied to degradable organic pollutant aspect, for example rhodamine B and methyl orange.
Object of the present invention adopts following technical scheme to realize.
A preparation method for composite photo-catalyst, comprises the steps:
(1) bismuth salt and chlorine-containing compound are dissolved in solvent, put into autoclave; By autoclave sealing, keep 6～12 hours at 160 ℃～180 ℃, be cooled to room temperature; Solution centrifugal in autoclave is got to precipitation, washing and the dry chlorine oxygen bismuth that obtains;
(2) chlorine oxygen bismuth is added in the aqueous solution of iron containing compounds, put into autoclave; By autoclave sealing, 160 ℃～180 ℃ keep 12～24 hours, are cooled to room temperature; Solution centrifugal in autoclave is got to precipitation, after washing and being dried, obtain composite photo-catalyst.
The mol ratio of bismuth salt and chlorine-containing compound is 1:(0.5～1.5).
In step (2), the mol ratio of chlorine oxygen bismuth and iron containing compounds is 1:(0.1～0.2).
Described bismuth salt is five nitric hydrate bismuths; Does is described solvent what ethylene glycol (can also be?).
Described chlorine-containing compound is sodium chloride.
Described iron containing compounds is ferric trichloride.
Described washing methods is: wash with distilled water.
Described drying means is: baking temperature is 55～65 ℃, and be 5～7 hours drying time.
The present invention also provides composite photo-catalyst prepared by described method and the application aspect photocatalyst for degrading organic matter thereof.
The preparation method of composite photo-catalyst of the present invention, simple, the composite photo-catalyst Stability Analysis of Structures that obtains, there is higher photocatalytic activity, effectively improved the photocatalytic activity of chlorine oxygen bismuth, the mixed solution that can efficient degradation contains rhodamine B and methyl orange.
Composite photo-catalyst of the present invention can be applied to degradable organic pollutant aspect, for example rhodamine B and methyl orange.
Accompanying drawing explanation
Fig. 1 is SEM (SEM) figure of the spherical chlorine oxygen bismuth prepared of embodiment 1, and the multiplication factor of wherein scheming A is 3500 times, and the multiplication factor of figure B is 7500 times.
Fig. 2 is X-ray diffraction (XRD) figure of the spherical chlorine oxygen bismuth prepared of embodiment 1.
Fig. 3 is transmission electron microscope (TEM) figure of embodiment 1 composite photo-catalyst.
Fig. 4 is X-ray diffraction (XRD) figure of embodiment 1 composite photo-catalyst.
Fig. 5 is the curve map of embodiment 1 composite photo-catalyst catalysis rhodamine B (RhB) degraded, abscissa: UV-irradiation time; C represents through UV-irradiation (l<420 nm) RhB concentration value after a period of time, C
0represent the initial concentration of RhB.
Fig. 6 is the curve map of embodiment 1 composite photo-catalyst catalysis methyl orange (MO) degraded, abscissa: UV-irradiation time; C represents MO concentration after ultraviolet light (l<420 nm) irradiates a period of time, C
0represent the initial concentration of MO.
The specific embodiment
Room temperature in the present invention is 10-30 ℃.
The compactedness of mesohigh reactor of the present invention is 70-85%.
embodiment 1
(1) get 0.73g(0.0015mol) five nitric hydrate bismuths and 0.044g (0.00075mol) sodium chloride is dissolved in 30mL ethylene glycol, and stirring and dissolving, moves in autoclave.By autoclave sealing, the baking oven of putting into 170 ℃ keeps 6 hours, is cooled to room temperature.Solution centrifugal in autoclave is got to precipitation, with distilled water washing, under 55 ℃ of conditions, be dried 5 hours, obtain 0.34g intermediate product.The X-ray diffraction (XRD) of intermediate product is schemed as shown in Figure 2, with the XRD standard card comparison of chlorine oxygen bismuth, and the chlorine oxygen bismuth that the intermediate product of preparation is pure phase.Can find out from scanning electron microscope diagram (Fig. 1), it is the spherical of 8mm left and right that chlorine oxygen bismuth is diameter, is evenly distributed.
(2) get 0.027g(0.0001mol) Iron(III) chloride hexahydrate is dissolved in 50mL water and obtains the aqueous solution of iron containing compounds.0.26g (0.001mol) chlorine oxygen bismuth is added in the aqueous solution of iron containing compounds, stir 30min, move into autoclave.By autoclave sealing, the baking oven of putting into 160 ℃ keeps 12 hours, is cooled to room temperature.Solution centrifugal in autoclave is got to precipitation, with distilled water washing, under 60 ℃ of conditions, be dried 6 hours, obtain composite photo-catalyst.Di-iron trioxide is successfully compounded on chlorine oxygen bismuth as seen from Figure 4, occurs (110) face of di-iron trioxide, has formed composite photo-catalyst.As seen from Figure 3, the ferric oxide particle in composite photo-catalyst covers on chlorine oxygen bismuth surface uniformly, and ferric oxide particle particle diameter is in 50nm left and right.
Embodiment 2
(1) get 0.73g (0.0015mol) five nitric hydrate bismuths and 0.087g (0.001mol) sodium chloride is dissolved in 30mL ethylene glycol, stirring and dissolving, moves in autoclave.By autoclave sealing, the baking oven of putting into 160 ℃ keeps 12 hours, is cooled to room temperature.Solution centrifugal in autoclave is got to precipitation, with distilled water washing, under 60 ℃ of conditions, be dried 6 hours, obtain 0.28g chlorine oxygen bismuth.
(2) get 0.0405g (0.00015mol) Iron(III) chloride hexahydrate and be dissolved in 50mL water and obtain the aqueous solution of iron containing compounds.0.26g (0.001mol) chlorine oxygen bismuth is added in the aqueous solution of iron containing compounds, stir 40min, move into autoclave.By autoclave sealing, the baking oven of putting into 170 ℃ keeps 18 hours, is cooled to room temperature.Solution centrifugal in autoclave is got to precipitation, with distilled water washing, under 55 ℃ of conditions, be dried 5 hours, obtain composite photo-catalyst.Can find out that by X-ray diffraction (XRD) figure di-iron trioxide is successfully compounded on chlorine oxygen bismuth, occur (110) face of di-iron trioxide, form composite photo-catalyst.By transmission electron microscope (TEM), figure can find out, the ferric oxide particle in composite photo-catalyst covers on chlorine oxygen bismuth surface uniformly, and ferric oxide particle particle diameter is in 50nm left and right.
Embodiment 3
(1) get 0.73g (0.0015mol) five nitric hydrate bismuths and 0.1305g (0.00225mol) sodium chloride is dissolved in 30mL ethylene glycol, stirring and dissolving, moves in autoclave.By autoclave sealing, the baking oven of putting into 180 ℃ keeps 9 hours, is cooled to room temperature.Solution centrifugal in autoclave is got to precipitation, with distilled water washing, under 65 ℃ of conditions, be dried 5 hours, obtain 0.35g chlorine oxygen bismuth.
(2) get 0.054g (0.0002mol) Iron(III) chloride hexahydrate and be dissolved in 50mL water and obtain the aqueous solution of iron containing compounds.0.26g (0.001mol) chlorine oxygen bismuth is added in the aqueous solution of iron containing compounds, stir 20min, move into autoclave.By autoclave sealing, the baking oven of putting into 180 ℃ keeps 24 hours, is cooled to room temperature.Solution centrifugal in autoclave is got to precipitation, with distilled water washing, under 65 ℃ of conditions, be dried 7 hours, obtain composite photo-catalyst.Can find out that by X-ray diffraction (XRD) figure di-iron trioxide is successfully compounded on chlorine oxygen bismuth, occur (110) face of di-iron trioxide, form composite photo-catalyst of the present invention.By transmission electron microscope (TEM), figure can find out, the ferric oxide particle in composite photo-catalyst covers on chlorine oxygen bismuth surface uniformly, and ferric oxide particle particle diameter is in 50nm left and right.
Embodiment 4
The spherical chlorine oxygen bismuth that embodiment 1 is made and composite photo-catalyst are respectively as photocatalyst for degrading rhodamine B (RhB) and methyl orange (MO).
Preparation dye solution, the RhB that contains 10mg/L and the aqueous solution of MO.Take respectively 0.05g spherical chlorine oxygen bismuth and composite photo-catalyst, add respectively in 200ml dye solution, first lucifuge stirs 30min, makes dyestuff reach absorption/desorption balance at catalyst surface.Then open xenon source, under UV-irradiation, carry out light-catalyzed reaction, get 4ml reactant liquor every 10min, after centrifugation, the concentration of rhodamine B (RhB) and methyl orange (MO) in spectrophotometer detection reaction liquid for supernatant.Determine RhB concentration in degradation process according to 550nm place light absorption value, 463nm place light absorption value is determined MO concentration in degradation process.
In dye solution, RhB degrades situation as shown in Figure 5, (abscissa: UV-irradiation time; C represents the RhB concentration value and the C that after a period of time, measure through UV-irradiation (l<420 nm)
0represent the initial concentration of RhB.) as can be seen from Figure 5,95% RhB in 35 minutes degradable reaction systems of composite photo-catalyst in embodiment 1,30% the RhB and chlorine oxygen bismuth has only been degraded in reaction system for 35 minutes, hence one can see that, and in embodiment 1, composite photo-catalyst has more efficient photocatalytic activity than chlorine oxygen bismuth.
In dye solution, MO degrades situation as shown in Figure 6, (abscissa: UV-irradiation time from scheming; C represents the MO concentration of measuring after ultraviolet light (l<420 nm) irradiates a period of time, C
0represent the initial concentration of MO.) as can be seen from this figure, 93% MO in 35 minutes degradable reaction systems of composite photo-catalyst in embodiment 1, only degraded for 35 minutes in reaction system 42% MO of chlorine oxygen bismuth, hence one can see that, and in embodiment 1, composite photo-catalyst has more efficient photocatalytic activity than chlorine oxygen bismuth.
Embodiment 2 also has similar catalytic performance with the composite photo-catalyst of preparation in 3.
Claims (10)
1. a preparation method for composite photo-catalyst, is characterized in that comprising the steps:
(1) bismuth salt and chlorine-containing compound are dissolved in solvent, put into autoclave; By autoclave sealing, keep 6～12 hours at 160 ℃～180 ℃, be cooled to room temperature; Solution centrifugal in autoclave is got to precipitation, washing and the dry chlorine oxygen bismuth that obtains;
(2) chlorine oxygen bismuth is added in the aqueous solution of iron containing compounds, put into autoclave; By autoclave sealing, 160 ℃～180 ℃ keep 12～24 hours, are cooled to room temperature; Solution centrifugal in autoclave is got to precipitation, after washing and being dried, obtain composite photo-catalyst.
2. the preparation method of composite photo-catalyst according to claim 1, the mol ratio that it is characterized in that bismuth salt and chlorine-containing compound is 1:(0.5～1.5).
3. the preparation method of composite photo-catalyst according to claim 2, is characterized in that in step (2), the mol ratio of chlorine oxygen bismuth and iron containing compounds is 1:(0.1～0.2).
4. the preparation method of composite photo-catalyst according to claim 3, is characterized in that described bismuth salt is five nitric hydrate bismuths; Described solvent is ethylene glycol.
5. the preparation method of composite photo-catalyst according to claim 4, is characterized in that described chlorine-containing compound is sodium chloride.
6. the preparation method of composite photo-catalyst according to claim 5, is characterized in that described iron containing compounds is ferric trichloride.
7. the preparation method of composite photo-catalyst according to claim 6, is characterized in that described washing methods is: wash with distilled water.
8. the preparation method of composite photo-catalyst according to claim 7, is characterized in that described drying means is: baking temperature is 55～65 ℃, and be 5～7 hours drying time.
9. the composite photo-catalyst that prepared by the described method of one of claim 1-8.
10. the application of composite photo-catalyst aspect photocatalyst for degrading organic matter described in a claim 9.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410075595.7A CN103769175B (en) | 2014-03-04 | 2014-03-04 | A kind of preparation method of composite photo-catalyst and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410075595.7A CN103769175B (en) | 2014-03-04 | 2014-03-04 | A kind of preparation method of composite photo-catalyst and application thereof |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103769175A true CN103769175A (en) | 2014-05-07 |
| CN103769175B CN103769175B (en) | 2015-09-23 |
Family
ID=50562209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201410075595.7A Active CN103769175B (en) | 2014-03-04 | 2014-03-04 | A kind of preparation method of composite photo-catalyst and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103769175B (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105251517A (en) * | 2015-10-30 | 2016-01-20 | 武汉工程大学 | Preparation method of Fe-doped oxyhalogen bismuth nanometer material |
| CN106145185A (en) * | 2015-03-24 | 2016-11-23 | 滕怡然 | A kind of novel processing step of lamellar fluorine oxygen bismuth photocatalyst |
| CN106145186A (en) * | 2015-03-24 | 2016-11-23 | 滕怡然 | A kind of lamellar fluorine oxygen bismuth and application thereof |
| CN110773206A (en) * | 2019-11-27 | 2020-02-11 | 中国科学院青岛生物能源与过程研究所 | Fe with high catalytic degradation activity 2O 3BiOCl composite photocatalyst and preparation method and application thereof |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2003097750A1 (en) * | 2002-05-14 | 2003-11-27 | Engelhard Corporation | IMPROVED BiOC1 PIGMENT |
| US6743285B1 (en) * | 1999-09-01 | 2004-06-01 | Merck Patent Gmbh | Pigment mixture comprising BiOCI pigments |
| CN102553620A (en) * | 2011-12-23 | 2012-07-11 | 华中师范大学 | Visible light photocatalyst Bi12O17Cl2 and preparation method thereof |
| CN103241775A (en) * | 2013-05-15 | 2013-08-14 | 哈尔滨理工大学 | Preparation method of Fe2O3/BiOCl nano-composite powder |
| CN103265076A (en) * | 2013-06-07 | 2013-08-28 | 南京信息工程大学 | Preparation method of sheet-like bismuth oxychloride photocatalyst |
-
2014
- 2014-03-04 CN CN201410075595.7A patent/CN103769175B/en active Active
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6743285B1 (en) * | 1999-09-01 | 2004-06-01 | Merck Patent Gmbh | Pigment mixture comprising BiOCI pigments |
| WO2003097750A1 (en) * | 2002-05-14 | 2003-11-27 | Engelhard Corporation | IMPROVED BiOC1 PIGMENT |
| CN102553620A (en) * | 2011-12-23 | 2012-07-11 | 华中师范大学 | Visible light photocatalyst Bi12O17Cl2 and preparation method thereof |
| CN103241775A (en) * | 2013-05-15 | 2013-08-14 | 哈尔滨理工大学 | Preparation method of Fe2O3/BiOCl nano-composite powder |
| CN103265076A (en) * | 2013-06-07 | 2013-08-28 | 南京信息工程大学 | Preparation method of sheet-like bismuth oxychloride photocatalyst |
Non-Patent Citations (1)
| Title |
|---|
| YING ZHANG ET AL.: "Novel magnetically separable AgCl/iron oxide composites with enhanced photocatalytic activity driven by visible light", 《JOURNAL OF ALLOYS AND COMPOUNDS》, vol. 574, 4 June 2013 (2013-06-04) * |
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106145185A (en) * | 2015-03-24 | 2016-11-23 | 滕怡然 | A kind of novel processing step of lamellar fluorine oxygen bismuth photocatalyst |
| CN106145186A (en) * | 2015-03-24 | 2016-11-23 | 滕怡然 | A kind of lamellar fluorine oxygen bismuth and application thereof |
| CN106145186B (en) * | 2015-03-24 | 2017-09-15 | 滕怡然 | A kind of sheet fluorine oxygen bismuth and its application |
| CN106145185B (en) * | 2015-03-24 | 2017-09-15 | 滕怡然 | A kind of preparation method of sheet fluorine oxygen bismuth photochemical catalyst |
| CN105251517A (en) * | 2015-10-30 | 2016-01-20 | 武汉工程大学 | Preparation method of Fe-doped oxyhalogen bismuth nanometer material |
| CN105251517B (en) * | 2015-10-30 | 2018-06-29 | 武汉工程大学 | A kind of preparation method of Fe doping oxyhalogen bismuth nano material |
| CN110773206A (en) * | 2019-11-27 | 2020-02-11 | 中国科学院青岛生物能源与过程研究所 | Fe with high catalytic degradation activity 2O 3BiOCl composite photocatalyst and preparation method and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103769175B (en) | 2015-09-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN107866234B (en) | High-activity ZnIn2S4/TiO2Preparation method of Z-system catalyst material | |
| CN103301867B (en) | Carbon nitride photocatalyst of a kind of inorganic ions doping and preparation method thereof | |
| CN102974373B (en) | Preparation method of visible-light photocatalytic material | |
| CN103623849B (en) | A kind of Graphene/BiOCl xbr 1-xmicro-nano composite photo-catalyst and preparation method thereof | |
| CN105664979B (en) | A kind of mesoporous nano microspheroidal Ln-Bi5O7I photochemical catalysts and preparation method thereof | |
| CN105032468A (en) | Cu2O-TiO2/g-C3N4 ternary complex and preparation and application method thereof | |
| CN103480353A (en) | Method for synthesis of carbon quantum dot solution by hydrothermal process to prepare composite nano-photocatalyst | |
| CN108525677B (en) | Cerium dioxide/indium zinc sulfide nanosheet composite catalyst and application thereof in visible light catalysis of CO2Use in transformation | |
| CN101993043A (en) | Visible light photocatalyst of BiOBr micro sphere and preparation method thereof | |
| CN104525266A (en) | Preparation method of metal-organic framework material photocatalyst and application | |
| CN105664995B (en) | A kind of multielement codoped nanaotitania catalysis material | |
| CN106552651B (en) | Bi12O17Br2Synthesis and application method of photocatalyst | |
| CN103111335B (en) | Ionic crystal type visible-light-induced photocatalyst based on Dawson type poly-tungstate and preparation method thereof | |
| CN103769175B (en) | A kind of preparation method of composite photo-catalyst and application thereof | |
| CN105056973B (en) | Efficient Bi2S3-BiFeO3 composite visible-light-driven photocatalyst prepared through in-situ growth with chemical corrosion method and application of Bi2S3-BiFeO3 composite visible-light-driven photocatalyst | |
| CN109985618A (en) | A kind of H occupies BiVO4The catalysis material of-OVs, preparation method and applications | |
| CN103831093A (en) | Zinc oxide based composite photocatalytic nano-material and preparation method thereof | |
| CN104289252A (en) | Preparation method of copper metal organic framework material with photo-catalytic performance | |
| CN104475131A (en) | Visible light response type nanosheet bismuth oxychloride catalyst and preparation method thereof | |
| CN104826628A (en) | Preparation method of graphene-iron doped TiO2 nanowire with high catalytic degradation activity under visible light | |
| CN104707641A (en) | Metal-nitrogen co-doped titanium dioxide hollow sphere catalyst and preparation method thereof | |
| CN103480395A (en) | Preparation and application of core-shell-structure bismuth sulfide@bismuth oxide composite microspheres | |
| CN103801283A (en) | Preparation method for lanthanum and gadolinium-codoped titanium dioxide mesoporous microsphere | |
| CN103657625A (en) | Preparation method of rutile type boron-doped titania (B-TiO2) microsphere with exposed high energy crystal face {001} | |
| CN102806078B (en) | Method for preparing one-dimensional hollow superstructure photocatalytic material of Bi system composite oxide |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20181205 Address after: 224000 Area B of Fucheng Industrial Park, Funing County, Yancheng City, Jiangsu Province Patentee after: Jiangsu Fusheng Environmental Protection Group Co., Ltd. Address before: 210044 Ning six road, Pukou District, Nanjing, Jiangsu Province, No. 219 Patentee before: Nanjing University of Information Science and Technology |