CN100342965C - Microorganism reduced noble metal (S) modified TiO2 catalyst and its prepn. method - Google Patents
Microorganism reduced noble metal (S) modified TiO2 catalyst and its prepn. method Download PDFInfo
- Publication number
- CN100342965C CN100342965C CNB2005101255757A CN200510125575A CN100342965C CN 100342965 C CN100342965 C CN 100342965C CN B2005101255757 A CNB2005101255757 A CN B2005101255757A CN 200510125575 A CN200510125575 A CN 200510125575A CN 100342965 C CN100342965 C CN 100342965C
- Authority
- CN
- China
- Prior art keywords
- tio2
- noble metal
- microorganism
- titanium dioxide
- catalyst
- 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.)
- Expired - Fee Related
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Landscapes
- Catalysts (AREA)
Abstract
The present invention relates to a modified TiO2 catalyst for microorganism reduced noble metals and a preparation method thereof, particularly to a modified TiO2 catalyst which adopts the microorganism reducing method to reduce the noble metals and is used for the photocatalytic degradation of phenol under visible light and a preparation method thereof. A formula is No-La/TiO2, wherein the No is at least one of noble metal (Ag) and noble metal (Pd). When the TiO2 catalyst is prepared, TiO2 is baked, after the TiO2 is dispersed through ultra audible sound, the TiO2 is added in a culture bottle for bacteria containing microorganisms (RO8) and microorganisms (SH10) to carry out dark culture, the TiO2 is dipped by nitrate or chloride solution of the noble metal, after the TiO2 is stopped, the TiO2 is washed, and the TiO2 is placed in flowing nitrogen gas. The TiO2 catalyst is prepared through noble metal particles with nanometer dimensions which are evenly loaded on the surface of the TiO2 by the 'anchor' and reducing action of microorganism thalli. The present invention has the advantages of high photocatalytic activity and simple method, the phenol degradation rate reaches more than 88 percent, and the present invention can be widely used for the photocatalytic degradation of organic waste water such as phenol, etc.
Description
Technical field
The present invention relates to a kind of TiO
2Catalyst especially relates to a kind of photocatalysis phenols wastewater degraded that is used for, and adopts microorganism reduced noble metal (S) modified TiO
2Catalysts and its preparation method.
Background technology
Phenols wastewater results from the processes such as PETROLEUM PROCESSING, coal tarization, textile printing and dyeing, papermaking in a large number, belongs to the waste water of difficult degradation.Phenols can cause protein denaturation and solidify, to all toxic effect of many living individuals.Contain phenols wastewater at present and handle and to adopt complicated life assemblage process degraded usually, as anaerobic-anoxic-aerobic method (A/A/O method) etc.These technological operation controls are difficulty comparatively, simple life assemblage technique processing method can not make phenols degrade fully simultaneously, situations such as the low and treatment effect instability of the degradation capability of existence such as high concentration phenols are difficult to realize containing the qualified discharge of phenols wastewater usually.Handle the shortcoming of phenols wastewater technology in order to overcome mentioned microorganism, the phenols wastewater treatment process technology that the associating of many biological methods and other physical method and chemical method occurred is as bioanalysis and absorption method process integration and bioanalysis and ion-exchange process integration technology etc.But these methods also have many deficiencies, mainly show as adsorbent or ion exchange resin regeneration technique complexity, and the regeneration difficulty, and the chemical reagent consumption amount is big etc.Since photocatalysis oxidation technique having occurred and be applied to the degraded of organic pollution the seventies in 20th century, particularly phenols, benzene class degradation capability are strong to the bio-refractory organic matter with it for photocatalytic oxidation, non-secondary pollution and getting more and more people's extensive concerning.Application number is to have introduced a kind of titanium dioxide that utilizes in the patent application of CN90108252.X to contain the phenolic wastewater method for the photochemical catalyst photocatalytic oxidation degradation, and this method can make the phenolic wastewater that contains of high concentration effectively be degraded.But because the relative broad of energy gap of titanium dioxide semiconductor can only absorb the ultraviolet light that accounts for sunshine 4%, and photocatalysis efficiency is lower, and its application is restricted.Titania modified is one of effective ways of improving the optically catalytic TiO 2 performance.
The method of optically catalytic TiO 2 modification at present mainly contains two classes: a class is to ooze assorted by conductor oxidate or rare earth oxide, Wu Shu newly waits and has reported the research (Wu Shuxin etc. that improve the optically catalytic TiO 2 performance by serial containing transition metal oxide, the research of dopen Nano TiO2 photocatalysis performance, Acta PhySico-Chimica Sinica, 2004,20 (2): 138-143), show the photocatalysis performance that can improve titanium dioxide by suitable containing transition metal oxide.Another kind of is by carried noble metal (as Ag, Pd, Au etc.), Liu keeps new grade and has introduced the Effect on Performance (Liu Shouxin etc. of noble metal silver modification to the photocatalytic degradation phenol of titanium dioxide, Ag supports the influence to the TiO2 photocatalytic activity, catalysis journal 2004,25 (2): 133～137), show by the modification of noble metal silver and can obviously improve the degradation of phenol photocatalytic activity.
Yet transition metal oxide doping process is wayward, and the composite semiconductor oxide of formation is active unstable.The method of modifying of carried noble metal is owing to producing inhomogeneous agglomeration at semiconductor surface in dipping, the reduction process, cause the metallic that loads on titanium dioxide surface can not form complete nanoscale and assemble, influence the performance of titanium dioxide optical catalyst photocatalysis performance.
Summary of the invention
The object of the present invention is to provide a kind of phenols photocatalytic degradation under the visible light condition that is used for, utilize the reduced noble metal (S) modified TiO of micro-reduction method
2Catalysts and its preparation method.This catalyst has under the visible light condition characteristics such as the high and preparation method of photocatalytic activity is simple.
The said microorganism reduced noble metal (S) modified TiO of the present invention
2The general formula of catalyst is:
No-La/TiO
2，
Wherein, No is a precious metals ag, at least a among the Pd, and the content of No is titanium dioxide (TiO by mass percentage
2) 2%～3%, the content of La is 0%～1% of titanium dioxide.
Said titanium dioxide is anatase titanium dioxide, and the noble metal of institute's load is to utilize the nitrate or the chloride of at least a reduction noble metal among microorganism bacillus (being called R08) and the pseudomonad Aeromonas (being called SH10) to obtain.
The said microorganism reduced noble metal (S) modified TiO of the present invention
2The Preparation of catalysts method the steps include:
1) titanium dioxide is at 150～200 ℃ of roasting 1～2h;
2) adding contains microorganism R08 after frequency is the ultrasonic dispersion of 20～40KHz, and lucifuge is cultivated 4～6h at least a culture of bacteria bottle among the SH10;
3) noble metal nitrate or the oxide solution with 0.05～0.15mol/L floods, and leaves standstill the back and washs with deionized water and absolute ethyl alcohol, places flowing nitrogen to preserve at last.
The present invention is by utilizing microbial cells " grappling " and the reduction noble metal at titanium dioxide surface uniform load nanoscale on titanium dioxide, thereby make high dispersive modified with noble metals titanium dioxide optical catalyst, have photocatalysis at visible-range, and photocatalytic activity improves greatly.Its preparation process of the present invention is simple, can be widely used in the photocatalytic degradation of organic wastewaters such as phenols.
The specific embodiment
The invention will be further described below by embodiment.
Embodiment 1
Microbial method prepares load type titania photocatalyst Ag/TiO
2: take by weighing anatase titanium dioxide 0.4g, 200 ℃ of roasting 1h in muffle furnace, after the ultrasonic dispersion of 40KHz, add lucifuge effect 5h in the blake bottle that contains SH10 then, bacterium is anchored on the titanium dioxide surface, centrifugation goes out nutrient solution, and the titanium dioxide that will contain bacterium divides dipping 0.15mol/L AgNO 3 times
3, making the Ag load capacity is 3%, room temperature leaves standstill 24h under the flowing nitrogen protection, washs respectively 4 times with deionized water and absolute ethyl alcohol then, places flowing nitrogen to preserve at last.
The photocatalytic activity evaluation of catalyst is carried out in homemade telescopic suspension bed photocatalytic reaction device, and visible light source is＞the 250W high-pressure sodium lamp of 410nm, reaction condition: normal pressure, room temperature, air mass flow is: 200ml/min.Light-catalyzed reaction time 4h.Phenol or catechol concentration are 100mg/L in the simulation phenol wastewater, and treating capacity is 200mL.The activity rating result shows that its phenol degrading rate is more than 88%.
Embodiment 2
Microbial method prepares load type titania photocatalyst Pd/TiO
2: take by weighing tax titanium ore type titanium dioxide 0.4g, 200 ℃ of roasting 1h in muffle furnace, after the ultrasonic dispersion of 20KHz, add then and contain that lucifuge effect 4h makes bacterium be anchored on titanium dioxide surface in the R08 blake bottle, centrifugation goes out nutrient solution, will contain bacterium R08 titanium dioxide and divide dipping 0.05mol/L PdCl 3 times
2Solution makes load capacity finally reach 2wt%, and room temperature leaves standstill 24h under the flowing nitrogen protection, uses deionization and absolute ethanol washing 4 times, places flowing nitrogen to preserve at last.The photocatalytic activity evaluation of catalyst is with embodiment 1.The activity rating result shows that its phenol degrading rate is more than 83%.
Embodiment 3
Microbial method prepares load type titania photocatalyst Ag-La/TiO
2: with the La (NO of 0.01mol
3)
3Solution impregnation TiO
2, make the content of La account for 0.5% of gross mass, dry back drops to room temperature in 450 ℃ of roasting 3h, takes by weighing the titanium dioxide that 0.4g is soaked with La, and all the other steps are with embodiment 1, and the phenol degrading rate is more than 87%.
Embodiment 4
The microbial method legal system is equipped with load type titania photocatalyst Pd-La/TiO
2: with the La (NO of 0.01mol/L
3)
3Solution impregnation TiO
2Make the content of La account for 0.5% of gross mass, dry back drops to room temperature in 450 ℃ of roasting 3h, takes by weighing the titanium dioxide that 0.4g is soaked with La, and all the other steps are with embodiment 2, and catechol is degraded more than 86%.
Embodiment 5
Microbial method prepares load type titania photocatalyst Ag-Pd/TiO
2: carry out the preliminary treatment (seeing embodiment 1 or 2) of titanium dioxide earlier, bacterium SH10 is anchored on the titanium dioxide (sees embodiment 1) then, centrifugation goes out nutrient solution, will contain bacterium SH10 titanium dioxide and flood the AgNO that contains 0.05mol/L earlier
3Solution, and then dipping contains the PdCl of 0.01mol/L
2Solution makes load capacity finally reach Ag:2wt%, Pd:0.4wt%.The static 24h of room temperature under the flowing nitrogen protection washs respectively 4 times with deionization and absolute ethyl alcohol, places flowing nitrogen to preserve at last.The activity rating result shows that its phenol degrading rate is more than 88%.
Claims (2)
1, microorganism reduced noble metal (S) modified TiO
2Catalyst is characterized in that its general formula is:
No-La/TiO
2，
Wherein, No is a precious metals ag, at least a among the Pd, and the content of No is 2%～3% of titanium dioxide by mass percentage, the content of La is 0%～1% of titanium dioxide; Described titanium dioxide is anatase titanium dioxide; Described noble metal is to utilize the microorganism bacillus, is called R08 and pseudomonad Aeromonas, is called the nitrate of at least a reduction noble metal among the SH10 or the metal that chloride obtains.
2, microorganism reduced noble metal (S) modified TiO as claimed in claim 1
2Method for preparing catalyst is characterized in that the steps include:
1) titanium dioxide is at 150～200 ℃ of roasting 1～2h;
2) adding contains microorganism R08 after frequency is the ultrasonic dispersion of 20～40KHz, and lucifuge is cultivated 4～6h at least a culture of bacteria bottle among the SH10;
3) noble metal nitrate or the chloride solution with 0.05～0.15mol/L floods, and leaves standstill the back and washs with deionized water and absolute ethyl alcohol, places flowing nitrogen to preserve at last.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101255757A CN100342965C (en) | 2005-11-21 | 2005-11-21 | Microorganism reduced noble metal (S) modified TiO2 catalyst and its prepn. method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2005101255757A CN100342965C (en) | 2005-11-21 | 2005-11-21 | Microorganism reduced noble metal (S) modified TiO2 catalyst and its prepn. method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN1792433A CN1792433A (en) | 2006-06-28 |
| CN100342965C true CN100342965C (en) | 2007-10-17 |
Family
ID=36804202
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2005101255757A Expired - Fee Related CN100342965C (en) | 2005-11-21 | 2005-11-21 | Microorganism reduced noble metal (S) modified TiO2 catalyst and its prepn. method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100342965C (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100441300C (en) * | 2006-12-31 | 2008-12-10 | 厦门大学 | Method of preparing loading type silver catalyst by micro-reduction |
| CN100500335C (en) * | 2007-02-15 | 2009-06-17 | 厦门大学 | Preparing process of water-soluble nano silver powder containing biomass |
| CN101875011A (en) * | 2009-04-30 | 2010-11-03 | 中国科学院福建物质结构研究所 | TiO2 carrier-supported precious metal palladium as well as preparation method and application thereof |
| CN104229989B (en) * | 2014-10-11 | 2016-02-10 | 北京师范大学 | A kind of method of anaerobic grain sludge self-retaining load biological nano palladium and the application in Degradation of Azo Dyes |
| CN107376993B (en) * | 2017-06-15 | 2019-11-08 | 昆明理工大学 | The preparation method and application of the immobilized palladium chtalyst composite material of the corn stalk stalks of rice, wheat, etc. |
| CN108147494B (en) * | 2018-02-09 | 2023-07-21 | 北方工业大学 | Adsorption type floating island |
| CN109331819B (en) * | 2018-11-16 | 2020-07-28 | 浙江工业大学 | Titanium dioxide supported Pt-Pd bimetallic photocatalyst and preparation method and application thereof |
| CN113262793B (en) * | 2021-05-28 | 2023-06-09 | 中南大学 | Titanium dioxide composite photocatalyst and preparation and application methods thereof |
-
2005
- 2005-11-21 CN CNB2005101255757A patent/CN100342965C/en not_active Expired - Fee Related
Non-Patent Citations (2)
| Title |
|---|
| Ag担载对TiO2光催化活性的影响 刘守新，曲振平，韩秀文，孙承林，包信和，催化学报，第25卷第2期 2004 * |
| 第九届全国化学工艺学术年会论文集 618-619，中国石化出版社 2005 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN1792433A (en) | 2006-06-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN100342965C (en) | Microorganism reduced noble metal (S) modified TiO2 catalyst and its prepn. method | |
| Ali | Water photo splitting for green hydrogen energy by green nanoparticles | |
| Xia et al. | Design and synthesis of robust Z-scheme ZnS-SnS2 nn heterojunctions for highly efficient degradation of pharmaceutical pollutants: Performance, valence/conduction band offset photocatalytic mechanisms and toxicity evaluation | |
| Srinivasan et al. | Bactericidal and detoxification effects of irradiated semiconductor catalyst, TiO 2 | |
| Foster et al. | Photocatalytic disinfection using titanium dioxide: spectrum and mechanism of antimicrobial activity | |
| Coleman et al. | Bactericidal effects of titanium dioxide-based photocatalysts | |
| Ayati et al. | A review on catalytic applications of Au/TiO2 nanoparticles in the removal of water pollutant | |
| Khalil et al. | The removal of the toxic Hg (II) salts from water by photocatalysis | |
| CN107617447B (en) | Ag @ MOFs/TiO2Preparation method and application of photocatalyst | |
| Li et al. | Advanced oxidation of orange II using TiO2 supported on porous adsorbents: The role of pH, H2O2 and O3 | |
| Tahir et al. | A review on remediation of harmful dyes through visible light-driven WO 3 photocatalytic nanomaterials | |
| Wen et al. | Attachment of Ag/AgCl nanoparticles on CdMoO4 microspheres for effective degradation of doxycycline under visible light irradiation: Degradation pathways and mineralization activity | |
| CN105709687A (en) | Nano titanium dioxide composite material applicable to wastewater treatment | |
| Shet et al. | Photocatalytic degradation of phenol using Ag core-TiO 2 shell (Ag@ TiO 2) nanoparticles under UV light irradiation | |
| Zheng et al. | Effect of different type of scavengers on the photocatalytic removal of copper and cyanide in the presence of TiO 2@ yeast hybrids | |
| Uzunova-Bujnova et al. | Crystal structure, morphology and photocatalytic activity of modified TiO2 and of spray-deposited TiO2 films | |
| Sheydaei et al. | Continuous flow photoelectrocatalysis/reverse osmosis hybrid reactor for degradation of a pesticide using nano N-TiO2/Ag/Ti electrode under visible light | |
| CN101066795A (en) | Process of catalytically reducing nitrate nitrogen in water with Fe0/TiO2 | |
| CN102380379B (en) | Ag/ZnO-AC photochemical catalyst and preparation method thereof | |
| Shifu et al. | Photocatalytic oxidation of nitrite by sunlight using TiO2 supported on hollow glass microbeads | |
| CN104422019A (en) | Complex multi-functional indoor air pollution control unit | |
| Chen et al. | Efficient degradation of ciprofloxacin by Cu2O/g-C3N4 heterostructures with different morphologies driven under the visible light | |
| Khan et al. | Synthesis of titanium doped hydroxyapatite using waste marble powder for the degradation of Congo Red dye in wastewater | |
| CN103771638A (en) | Photo-catalysis method adopting ultrasonic atomizing process to enhance water pollution treatment effect | |
| Liu et al. | NaBiS2 decorated polysaccharide sponges for adsorption–photocatalytic degradation of dye under visible light illumination |
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 | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Assignee: Fujian Yutong Industry & Trade Co., Ltd. Assignor: Xiamen University Contract fulfillment period: 2008.5.15 to 2013.5.14 contract change Contract record no.: 2009351000003 Denomination of invention: Microorganism reduced noble metal (S) modified TiO2 catalyst and its prepn. method Granted publication date: 20071017 License type: General permission Record date: 2009.1.14 |
|
| LIC | Patent licence contract for exploitation submitted for record |
Free format text: COMMON LICENSE; TIME LIMIT OF IMPLEMENTING CONTACT: 2008.5.15 TO 2013.5.14; CHANGE OF CONTRACT Name of requester: FUJIAN YUTONG INDUSTRY + TRADE CO., LTD. Effective date: 20090114 |
|
| C17 | Cessation of patent right | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20071017 Termination date: 20121121 |