WO1999033564A1 - Photocatalyseurs tres poreux pour la mise en oeuvre de lumiere visible - Google Patents
Photocatalyseurs tres poreux pour la mise en oeuvre de lumiere visible Download PDFInfo
- Publication number
- WO1999033564A1 WO1999033564A1 PCT/EP1998/008055 EP9808055W WO9933564A1 WO 1999033564 A1 WO1999033564 A1 WO 1999033564A1 EP 9808055 W EP9808055 W EP 9808055W WO 9933564 A1 WO9933564 A1 WO 9933564A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- photocatalysts
- light
- visible light
- tio
- ions
- Prior art date
Links
- 239000011941 photocatalyst Substances 0.000 title claims description 27
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 11
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 11
- 239000003054 catalyst Substances 0.000 claims description 18
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 13
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 11
- 239000000203 mixture Substances 0.000 claims description 11
- 229910052697 platinum Inorganic materials 0.000 claims description 11
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 11
- 150000002500 ions Chemical class 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 8
- 229910052742 iron Inorganic materials 0.000 claims description 7
- 150000003839 salts Chemical class 0.000 claims description 6
- 239000011521 glass Substances 0.000 claims description 5
- 239000011572 manganese Substances 0.000 claims description 5
- 229910052750 molybdenum Inorganic materials 0.000 claims description 5
- 238000002360 preparation method Methods 0.000 claims description 5
- 229910052703 rhodium Inorganic materials 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 229910052748 manganese Inorganic materials 0.000 claims description 4
- 229910052759 nickel Inorganic materials 0.000 claims description 4
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 claims description 3
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 claims description 3
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
- 229910052799 carbon Inorganic materials 0.000 claims description 3
- 229910052804 chromium Inorganic materials 0.000 claims description 3
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 3
- 239000011733 molybdenum Substances 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 claims description 3
- 239000011148 porous material Substances 0.000 claims description 3
- 229910052707 ruthenium Inorganic materials 0.000 claims description 3
- 238000003980 solgel method Methods 0.000 claims description 3
- 229910052719 titanium Inorganic materials 0.000 claims description 3
- 239000010936 titanium Substances 0.000 claims description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052721 tungsten Inorganic materials 0.000 claims description 3
- 239000010937 tungsten Substances 0.000 claims description 3
- 239000007864 aqueous solution Substances 0.000 claims description 2
- 239000003344 environmental pollutant Substances 0.000 claims description 2
- 239000012634 fragment Substances 0.000 claims description 2
- 229910052741 iridium Inorganic materials 0.000 claims description 2
- 239000004570 mortar (masonry) Substances 0.000 claims description 2
- 231100000719 pollutant Toxicity 0.000 claims description 2
- 229910052702 rhenium Inorganic materials 0.000 claims description 2
- 238000001665 trituration Methods 0.000 claims description 2
- 229910052726 zirconium Inorganic materials 0.000 claims description 2
- 238000001354 calcination Methods 0.000 claims 3
- 238000001035 drying Methods 0.000 claims 3
- 238000010521 absorption reaction Methods 0.000 claims 2
- 125000003545 alkoxy group Chemical group 0.000 claims 2
- POILWHVDKZOXJZ-ARJAWSKDSA-M (z)-4-oxopent-2-en-2-olate Chemical class C\C([O-])=C\C(C)=O POILWHVDKZOXJZ-ARJAWSKDSA-M 0.000 claims 1
- 150000007942 carboxylates Chemical class 0.000 claims 1
- 239000004568 cement Substances 0.000 claims 1
- 239000000919 ceramic Substances 0.000 claims 1
- 150000003841 chloride salts Chemical class 0.000 claims 1
- 150000001860 citric acid derivatives Chemical class 0.000 claims 1
- 150000001875 compounds Chemical class 0.000 claims 1
- 150000004820 halides Chemical class 0.000 claims 1
- 239000005445 natural material Substances 0.000 claims 1
- 150000002823 nitrates Chemical class 0.000 claims 1
- 239000000123 paper Substances 0.000 claims 1
- 239000004033 plastic Substances 0.000 claims 1
- 238000006068 polycondensation reaction Methods 0.000 claims 1
- 238000006116 polymerization reaction Methods 0.000 claims 1
- 239000002023 wood Substances 0.000 claims 1
- 239000000463 material Substances 0.000 abstract description 27
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 238000004519 manufacturing process Methods 0.000 abstract description 9
- 238000000746 purification Methods 0.000 abstract description 4
- 229910010413 TiO 2 Inorganic materials 0.000 description 36
- 229910052751 metal Inorganic materials 0.000 description 13
- 239000002184 metal Substances 0.000 description 13
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 238000003756 stirring Methods 0.000 description 7
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 description 6
- 230000015556 catabolic process Effects 0.000 description 6
- VXUYXOFXAQZZMF-UHFFFAOYSA-N titanium(IV) isopropoxide Chemical compound CC(C)O[Ti](OC(C)C)(OC(C)C)OC(C)C VXUYXOFXAQZZMF-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000004140 cleaning Methods 0.000 description 4
- 238000006731 degradation reaction Methods 0.000 description 4
- 239000004408 titanium dioxide Substances 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 description 3
- 238000011835 investigation Methods 0.000 description 3
- 239000002245 particle Substances 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 239000012266 salt solution Substances 0.000 description 3
- 239000000725 suspension Substances 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 2
- 239000011149 active material Substances 0.000 description 2
- 238000004887 air purification Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 208000017983 photosensitivity disease Diseases 0.000 description 2
- 231100000434 photosensitization Toxicity 0.000 description 2
- 238000006862 quantum yield reaction Methods 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910052709 silver Inorganic materials 0.000 description 2
- 238000001179 sorption measurement Methods 0.000 description 2
- BHKKSKOHRFHHIN-MRVPVSSYSA-N 1-[[2-[(1R)-1-aminoethyl]-4-chlorophenyl]methyl]-2-sulfanylidene-5H-pyrrolo[3,2-d]pyrimidin-4-one Chemical compound N[C@H](C)C1=C(CN2C(NC(C3=C2C=CN3)=O)=S)C=CC(=C1)Cl BHKKSKOHRFHHIN-MRVPVSSYSA-N 0.000 description 1
- 101710134784 Agnoprotein Proteins 0.000 description 1
- 206010020751 Hypersensitivity Diseases 0.000 description 1
- 229910004298 SiO 2 Inorganic materials 0.000 description 1
- 229910002367 SrTiO Inorganic materials 0.000 description 1
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 1
- 238000001720 action spectrum Methods 0.000 description 1
- 230000000274 adsorptive effect Effects 0.000 description 1
- 239000013566 allergen Substances 0.000 description 1
- 208000026935 allergic disease Diseases 0.000 description 1
- 230000007815 allergy Effects 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 239000008346 aqueous phase Substances 0.000 description 1
- 238000000149 argon plasma sintering Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- MJSNUBOCVAKFIJ-LNTINUHCSA-N chromium;(z)-4-oxoniumylidenepent-2-en-2-olate Chemical compound [Cr].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O MJSNUBOCVAKFIJ-LNTINUHCSA-N 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- ZKXWKVVCCTZOLD-FDGPNNRMSA-N copper;(z)-4-hydroxypent-3-en-2-one Chemical compound [Cu].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O ZKXWKVVCCTZOLD-FDGPNNRMSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 229940120124 dichloroacetate Drugs 0.000 description 1
- JXTHNDFMNIQAHM-UHFFFAOYSA-N dichloroacetic acid Chemical compound OC(=O)C(Cl)Cl JXTHNDFMNIQAHM-UHFFFAOYSA-N 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000192 extended X-ray absorption fine structure spectroscopy Methods 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 229910052500 inorganic mineral Inorganic materials 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- KEHCHOCBAJSEKS-UHFFFAOYSA-N iron(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Fe+2] KEHCHOCBAJSEKS-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000011707 mineral Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000013110 organic ligand Substances 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 239000000075 oxide glass Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 239000006069 physical mixture Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 238000010248 power generation Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- -1 roof tiles Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 239000010703 silicon Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000352 supercritical drying Methods 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910000314 transition metal oxide Inorganic materials 0.000 description 1
- 229910052720 vanadium Inorganic materials 0.000 description 1
- 239000002351 wastewater Substances 0.000 description 1
- 239000003643 water by type Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01G—CAPACITORS; CAPACITORS, RECTIFIERS, DETECTORS, SWITCHING DEVICES, LIGHT-SENSITIVE OR TEMPERATURE-SENSITIVE DEVICES OF THE ELECTROLYTIC TYPE
- H01G9/00—Electrolytic capacitors, rectifiers, detectors, switching devices, light-sensitive or temperature-sensitive devices; Processes of their manufacture
- H01G9/20—Light-sensitive devices
- H01G9/2027—Light-sensitive devices comprising an oxide semiconductor electrode
- H01G9/2031—Light-sensitive devices comprising an oxide semiconductor electrode comprising titanium oxide, e.g. TiO2
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
-
- 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
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
- Y02E10/542—Dye sensitized solar cells
-
- 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
Definitions
- the invention relates to photocatalysts, essentially consisting of metal oxides doped with metal ions with special photocatalytic activity, their production and their use with light in the wavelength range of visible light.
- this catalyst is decomposed during the reaction, a process that can only be partially suppressed by adding hydrogen peroxide (Bruemann, DW; Bockelmann, D .; Goslich, R .; Hilgendorff, M. In Aquatic and Surface Photochemistry; Schut GR ; Zepp, RG; Crosby, DG, Eds .; Lewis Publishers: Boca Raton, 1994, pp349-367.).
- the photosensitization by a dye is one with a ruthenium (II) bipyridyl complex loaded nanocrstalline TiO 2 electrode (DE 4207659 A1). It is questionable whether the organic ligands are photostable with longer exposure times.
- Examples of the photocatalytically active Pt-TiO 2 catalyst produced from Na 2 PtCI 6 x 6 H 2 O and titanium isopropoxide show the presence of atomically isolated PtCI 4 units in titanium dioxide.
- ESCA investigations electron spectroscopy for chemical analysis
- High-resolution transmission electron microscopic examinations show that the titanium oxide is present as an amorphous material with nanometer-sized crystalline domains enclosed therein, and Pt can be found homogeneously distributed throughout the material.
- Suitable catalyst materials with a large surface are materials which essentially contain more than 60% a metal oxide or mixtures of metal oxides of titanium, zinc, iron, manganese, molybdenum or tungsten and less than 40% ions from the group Pt, Rh, Contain Mn, Cr, Ru, Ni, Pd, Fe, Co, Ir, Cu, Mo, Zr, Re, Ag, Au and absorb the light in the visible wavelength range.
- TiO 2 is preferably used as the metal oxide, preferably doped with Pt or Rh.
- Another embodiment consists of bringing the components together in the aqueous phase, e.g. B. by bringing together Na 2 PtCI 6 as an aqueous solution with a microporous TiO 2 powder.
- porous titanium oxide can show photocatalytic activity with visible light if, due to the production process of the titanium oxide, 0.01-10% organic fragments or carbon deposits remain in the titanium dioxide.
- Such a material that is photocatalytically active in visible light is characterized by a yellowish-brownish to black color.
- the photocatalysts presented therefore work with visible light and are not subject to decomposition.
- the production is preferably carried out wet-chemically according to a one-step sol-gel process.
- the process has the advantage that it immediately provides materials with large surfaces and that both the pore size and the concentration of the active centers can be varied within wide limits by the process.
- Fig. 1 shows the decrease in the 4-chlorophenol concentration when exposed to visible light (455 nm) in the presence of a conventional (Degussa P25) and a new hybrid catalyst.
- Air purification indoors and outdoors by photocatalytic degradation of pollutants can also be carried out by coating such thin photocatalytically active layer on the interior walls of rooms, exterior walls of buildings including window and roof areas, walkway slabs and road surfaces.
- the simplicity of manufacturing these photocatalysts and their adhesion to all mineral surfaces should have an advantageous effect.
- Even when using the materials to purify water, the use of visible light allows much more effective applications: Since water itself is not for UV but for visible light is practically completely permeable, the coverage of the catalysts with water is much less critical than when using UV light according to the conventional technique.
- the use of the materials as a solar cell to generate electricity from visible light opens up completely new uses for solar cells, because in contrast to silicon, the sol-gel materials presented here as a thin film at low cost on many materials, such as roof tiles, glass panes, building claddings etc. can be applied.
- the loosely covered sol was now without stirring for a further 6 days and gelled during this time.
- the gel was left in the hood without a cover for a further 10 days, during which time it hardened and became brittle.
- the resulting glass was then heated to 65 ° C. at a heating rate of 0.1 ° C./min, held at this temperature for 100 minutes and then heated to 250 ° C. at the same heating speed.
- the material was kept at this temperature for 5 h and then cooled to room temperature at a cooling rate of 0.5 ° C./min.
- the loosely covered sol was now without stirring for a further 8 days and gelled during this time.
- the gelled pieces were placed in a 250 ml autoclave filled and mixed with 5 bar N 2 .
- the autoclave was heated slowly (1 ° C / min) to 270 ° C, the pressure rising to about 22 bar. After the end temperature had been reached, the autoclave was slowly let down at 0.1 bar / min. The heating was then switched off and, after reaching room temperature, the autoclave was opened and the finished catalyst was removed.
- the catalyst was prepared as in Example 1, but instead of the metal salt (1 au), any organic compound soluble in EtOH was added to the sol.
- the gel obtained was then dried in air, preferably under an inert gas, and fired.
- a black to yellow colored TiO 2 resulted, which can be used analogously to Example 2-7 as a photocatalytically active material in visible light.
- the catalyst (0.5 g / l) was suspended in an ultrasonic bath for 15 min in 14 ml of a solution of 4-chlorophenol (2.5x10 '4 M). The mixture was then magnetically stirred for 20 min and then exposed to an Osram XBO 150 W xenon lamp for 3 h with further stirring; an edge filter with wavelengths ⁇ > 400 nm and ⁇ > 455 nm ensured the elimination of UV radiation. The degradation of 4-chlorophenol was followed by high pressure liquid chromatography. Tab. 1
- the glass plate was placed in the cell provided with rubber seals, covered with the redox electrolyte and with the second
- Indium tin oxide plate tightly sealed. Exposure to visible light leads to the occurrence of photo tension.
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- Materials Engineering (AREA)
- Power Engineering (AREA)
- Health & Medical Sciences (AREA)
- Water Supply & Treatment (AREA)
- Biomedical Technology (AREA)
- Analytical Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Hydrology & Water Resources (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Life Sciences & Earth Sciences (AREA)
- Catalysts (AREA)
Abstract
L'invention concerne des oxydes métalliques dopés présentant une activité photocatalytique particulière, leur procédé de production et leur utilisation. Ces nouveaux matériaux permettent la mise en oeuvre de lumière visible dans des applications photocatalytiques, et notamment la purification de l'air et de l'eau, ainsi que la production de courant photoélectrique (cellule photovoltaïque) avec de la lumière dans la plage de longueurs d'onde de la lumière visible.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19757496.3 | 1997-12-23 | ||
DE1997157496 DE19757496A1 (de) | 1997-12-23 | 1997-12-23 | Hochporöse Photokatalysatoren zur Verwertung von sichtbarem Licht |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1999033564A1 true WO1999033564A1 (fr) | 1999-07-08 |
Family
ID=7853154
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/EP1998/008055 WO1999033564A1 (fr) | 1997-12-23 | 1998-12-10 | Photocatalyseurs tres poreux pour la mise en oeuvre de lumiere visible |
Country Status (2)
Country | Link |
---|---|
DE (1) | DE19757496A1 (fr) |
WO (1) | WO1999033564A1 (fr) |
Cited By (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1359237A1 (fr) * | 2002-05-01 | 2003-11-05 | Ube Industries, Ltd. | Fibre photocatalytique contenant de la silice ayant une activité dans une zone de lumière visible et procédé pour sa production |
DE102009012461A1 (de) | 2009-03-12 | 2010-09-16 | Kme Germany Ag & Co. Kg | Schadstoffabbauendes Metallband für das Bauwesen |
US8172951B2 (en) | 2000-12-21 | 2012-05-08 | Massholder Karl F | Method of cleaning with an aqueous composition containing a semiconductor |
CN107597145A (zh) * | 2017-09-21 | 2018-01-19 | 柳州若思纳米材料科技有限公司 | 一种碳复合硫代钨酸锰催化剂的制备方法 |
Families Citing this family (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19920753A1 (de) | 1999-04-23 | 2000-10-26 | Bayer Ag | Verfahren zur Herstellung von amorphen, edelmetallhaltigen Titan-Silizium-Mischoxiden |
WO2001021262A1 (fr) * | 1999-09-22 | 2001-03-29 | Carrier Corporation | Catalyseurs pour la destruction de composes d'organophosphonate |
US6596915B1 (en) | 1999-09-22 | 2003-07-22 | Carrier Corporation | Catalysts for destruction of organophosphonate compounds |
DE10013934A1 (de) * | 2000-03-21 | 2001-09-27 | Studiengesellschaft Kohle Mbh | Poröse dotierte Titanoxide als selektive Oxiations- und Dehydrierkatalysatoren |
NL1015634C2 (nl) * | 2000-07-06 | 2002-01-08 | Korea Clean Air System Co | Werkwijze voor de bereiding van een ferroelektrische fotohalfgeleidende bekleding en inrichting voor het verwijderen van milieuluchtverontreinigingen onder toepassen van deze bekleding en elektrische energie. |
FR2813393B1 (fr) | 2000-08-22 | 2002-10-18 | Commissariat Energie Atomique | Fabrication d'un capteur chimique a fibre optique comprenant un indicateur colore, utilisable notamment pour la mesure de l'acidite nitrique |
DE10150014B4 (de) * | 2001-10-11 | 2006-05-24 | BÖHME, Mario | Schwimmbeckenauskleidung zur Entkeimung von Wasser |
DE102007019166A1 (de) * | 2007-04-20 | 2008-10-30 | Fachhochschule Kiel | Verfahren zur Herstellung von Substraten für die Oberflächen-verstärkte Raman-Spektroskopie |
DE102008020977A1 (de) | 2007-04-30 | 2008-11-06 | Henkel Ag & Co. Kgaa | Deodorans |
EP2722370B1 (fr) | 2012-10-17 | 2014-05-28 | STO SE & Co. KGaA | Revêtements photocatalytiques avec matières de remplissage |
CN104230067B (zh) * | 2013-06-08 | 2017-02-15 | 中国科学院理化技术研究所 | 含有机污染物废水的处理装置及方法 |
Citations (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS635301A (ja) * | 1986-06-25 | 1988-01-11 | Matsushita Electric Works Ltd | 反射鏡 |
DE4240558A1 (de) * | 1992-12-02 | 1994-06-09 | Franz Dietrich Oeste | Verfahren und Vorrichtungen zur Reinigung von Gasen, Abgasen, Dämpfen und Solen von unerwünschten chemischen Stoffen |
JPH07462A (ja) * | 1993-06-17 | 1995-01-06 | Takenaka Komuten Co Ltd | 院内感染防止方法 |
JPH08198601A (ja) * | 1994-03-29 | 1996-08-06 | Natl Inst For Res In Inorg Mater | 層状構造を有するチタン酸化物及びその誘導体を光触媒とする水の分解方法 |
JPH093481A (ja) * | 1995-06-16 | 1997-01-07 | Kao Corp | 半導体光触媒を用いる水素添加方法 |
WO1997026991A1 (fr) * | 1996-01-22 | 1997-07-31 | Petroleum Energy Center | Photocatalyseur, procede de production de ce photocatalyseur, et procede de reaction photocatalytique |
EP0826531A2 (fr) * | 1996-08-30 | 1998-03-04 | Kabushiki Kaisha Equos Research | Filtre pour la purification de l'air et dispositif de purification de l'air pour automobile |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5399541A (en) * | 1991-05-14 | 1995-03-21 | Nippon Shokubai Co., Ltd. | Catalyst for treating wastewater |
CH686206A5 (it) * | 1992-03-26 | 1996-01-31 | Asulab Sa | Cellule photoelectrochimique regeneratrice transparente. |
DE4237390C1 (de) * | 1992-11-06 | 1994-04-21 | Dirk Dipl Chem Bockelmann | Verfahren zur Fixierung von Metalloxidkatalysatorteilchen auf einem Träger |
EP0690825B1 (fr) * | 1993-03-05 | 1999-06-02 | Solvay Deutschland GmbH | Procede de traitement catalytique des effluents contenant des composes organiques et inorganiques, de preference resultant de la production d'epichlorhydrine |
DE4491188D2 (de) * | 1993-03-05 | 1995-04-27 | Solvay Umweltchemie Gmbh | Verfahren zur Entfernung des Sauerstoff-, Nitrit- und/oder Nitratgehaltes in Wasser |
SG43801A1 (en) * | 1993-07-12 | 1997-11-14 | Ishihara Sangyo Kaisha | Photocatalyst and process for purifying water with same |
DE4327101A1 (de) * | 1993-08-12 | 1995-02-16 | Werner Quinten | Halbleitende Metalloxidbeschichtungen mit einstellbaren Halbleiter- und Schichteigenschaften sowie Verfahren zum Herstellen derartigen Beschichtungen und Verwendungszwecke |
DE4327122A1 (de) * | 1993-08-12 | 1995-02-16 | Werner Quinten | Funktionsoptimierte Belegung von Photosensibilisatoren auf Maßgeschneiderten Halbleiteroxidbeschichtungen |
DE9312084U1 (de) * | 1993-08-12 | 1994-08-11 | Quinten, Werner, 66839 Schmelz | Photovoltaische Zellen |
-
1997
- 1997-12-23 DE DE1997157496 patent/DE19757496A1/de not_active Withdrawn
-
1998
- 1998-12-10 WO PCT/EP1998/008055 patent/WO1999033564A1/fr active Application Filing
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS635301A (ja) * | 1986-06-25 | 1988-01-11 | Matsushita Electric Works Ltd | 反射鏡 |
DE4240558A1 (de) * | 1992-12-02 | 1994-06-09 | Franz Dietrich Oeste | Verfahren und Vorrichtungen zur Reinigung von Gasen, Abgasen, Dämpfen und Solen von unerwünschten chemischen Stoffen |
JPH07462A (ja) * | 1993-06-17 | 1995-01-06 | Takenaka Komuten Co Ltd | 院内感染防止方法 |
JPH08198601A (ja) * | 1994-03-29 | 1996-08-06 | Natl Inst For Res In Inorg Mater | 層状構造を有するチタン酸化物及びその誘導体を光触媒とする水の分解方法 |
JPH093481A (ja) * | 1995-06-16 | 1997-01-07 | Kao Corp | 半導体光触媒を用いる水素添加方法 |
WO1997026991A1 (fr) * | 1996-01-22 | 1997-07-31 | Petroleum Energy Center | Photocatalyseur, procede de production de ce photocatalyseur, et procede de reaction photocatalytique |
EP0818239A1 (fr) * | 1996-01-22 | 1998-01-14 | Petroleum Energy Center | Photocatalyseur, procede de production de ce photocatalyseur, et procede de reaction photocatalytique |
EP0826531A2 (fr) * | 1996-08-30 | 1998-03-04 | Kabushiki Kaisha Equos Research | Filtre pour la purification de l'air et dispositif de purification de l'air pour automobile |
Non-Patent Citations (4)
Title |
---|
DATABASE WPI Section Ch Week 8807, Derwent World Patents Index; Class L02, AN 88-046924, XP002099815 * |
DATABASE WPI Section Ch Week 9511, Derwent World Patents Index; Class D22, AN 95-077176, XP002099814 * |
DATABASE WPI Section Ch Week 9641, Derwent World Patents Index; Class D15, AN 96-408181, XP002099816 * |
DATABASE WPI Section Ch Week 9711, Derwent World Patents Index; Class D23, AN 97-115591, XP002099813 * |
Cited By (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8172951B2 (en) | 2000-12-21 | 2012-05-08 | Massholder Karl F | Method of cleaning with an aqueous composition containing a semiconductor |
EP1359237A1 (fr) * | 2002-05-01 | 2003-11-05 | Ube Industries, Ltd. | Fibre photocatalytique contenant de la silice ayant une activité dans une zone de lumière visible et procédé pour sa production |
KR100936447B1 (ko) * | 2002-05-01 | 2010-01-13 | 우베 고산 가부시키가이샤 | 가시광 활성을 갖는 실리카-기초 광촉매 섬유 및 그제조방법 |
DE102009012461A1 (de) | 2009-03-12 | 2010-09-16 | Kme Germany Ag & Co. Kg | Schadstoffabbauendes Metallband für das Bauwesen |
CN107597145A (zh) * | 2017-09-21 | 2018-01-19 | 柳州若思纳米材料科技有限公司 | 一种碳复合硫代钨酸锰催化剂的制备方法 |
Also Published As
Publication number | Publication date |
---|---|
DE19757496A1 (de) | 1999-06-24 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE69735209T2 (de) | Photokatalysator mit ultrafeinen metallpartikeln, hochfunktionelles material beladen mit dem photokatalysator und methode zu ihrer herstellung | |
Messih et al. | Facile approach for homogeneous dispersion of metallic silver nanoparticles on the surface of mesoporous titania for photocatalytic degradation of methylene blue and indigo carmine dyes | |
EP2100927B1 (fr) | Photocatalyseur à base de dioxyde de titane contenant du carbone et son procédé de fabrication | |
Li et al. | Palladium oxide nanoparticles on nitrogen‐doped titanium oxide: accelerated photocatalytic disinfection and post‐illumination catalytic “memory” | |
WO1999033564A1 (fr) | Photocatalyseurs tres poreux pour la mise en oeuvre de lumiere visible | |
Zhang et al. | Photocatalytic and photoelectrochemical studies on N-doped TiO2 photocatalyst | |
DE112005001602T5 (de) | Katalytisches Material sowie Verfahren zu seiner Herstellung | |
CN1321743C (zh) | 含铋复合氧化物BiMO4和Bi2NO6型半导体光催化剂及制备和应用 | |
Monfort et al. | Photooxidative properties of various BiVO4/TiO2 layered composite films and study of their photocatalytic mechanism in pollutant degradation | |
US20110147317A1 (en) | Catalytic Compositions, Composition Production Methods, and Aqueous Solution Treatment Methods | |
Li et al. | Carbon black-doped anatase TiO2 nanorods for solar light-induced photocatalytic degradation of methylene blue | |
DE19911738A1 (de) | Mit Fe·3··+·-Ionen dotierter Titandioxid-Photokatalysator | |
DE112004002861B4 (de) | Apatit und Verwendung dafür | |
Bai et al. | One-pot synthesis of Ag nanoparticles/ZnO nanorods heterostructures for organic dyes decoloring | |
DE102005057770A1 (de) | Beschichtungszusammensetzung (I) | |
JP5627006B2 (ja) | 光触媒およびその製造方法 | |
Parvathiraja et al. | Plasmonic core–shell nanoparticles of Ag@ TiO2 for photocatalytic degradation of Rhodamine B | |
KR101903991B1 (ko) | 높은 가시광 활성을 갖는 복합체 및 이의 제조방법 | |
DE102005057747A1 (de) | Beschichtungszusammensetzung (II) | |
CN104941651A (zh) | 一种含铜的氧化锌/石墨烯量子点催化剂及制备方法 | |
KR20140104471A (ko) | 광촉매 및 광촉매의 제조 방법 | |
EP2614037B1 (fr) | Photocatalyseur à base de tungstate d'étain ainsi que sa fabrication | |
Ama et al. | TiO2/Ag2O-Exfoliated Graphite as Visible Light-Responsive Nanostructure for Improved Photoelectrochemical Degradation of BPA | |
CN1544144A (zh) | 可见光响应的光催化剂及其应用 | |
EP2680968B1 (fr) | Photocatalyseur à base de molybdate d'étain et son mode de production |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
AK | Designated states |
Kind code of ref document: A1 Designated state(s): CA JP US |
|
AL | Designated countries for regional patents |
Kind code of ref document: A1 Designated state(s): AT BE CH CY DE DK ES FI FR GB GR IE IT LU MC NL PT SE |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application | ||
DFPE | Request for preliminary examination filed prior to expiration of 19th month from priority date (pct application filed before 20040101) | ||
122 | Ep: pct application non-entry in european phase | ||
NENP | Non-entry into the national phase |
Ref country code: CA |