JP2019508225A - 大気汚染物質を分解するための光触媒複合材料 - Google Patents
大気汚染物質を分解するための光触媒複合材料 Download PDFInfo
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- JP2019508225A JP2019508225A JP2018533682A JP2018533682A JP2019508225A JP 2019508225 A JP2019508225 A JP 2019508225A JP 2018533682 A JP2018533682 A JP 2018533682A JP 2018533682 A JP2018533682 A JP 2018533682A JP 2019508225 A JP2019508225 A JP 2019508225A
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- JP
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- Prior art keywords
- composite material
- photocatalytic
- titanium dioxide
- photocatalytic composite
- visible light
- 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.)
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- 230000001699 photocatalysis Effects 0.000 title claims abstract description 79
- 239000002131 composite material Substances 0.000 title claims description 101
- 239000000809 air pollutant Substances 0.000 title description 4
- 231100001243 air pollutant Toxicity 0.000 title description 4
- 239000000356 contaminant Substances 0.000 claims abstract description 32
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 124
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 41
- 229910021389 graphene Inorganic materials 0.000 claims description 41
- 239000004408 titanium dioxide Substances 0.000 claims description 40
- 238000000034 method Methods 0.000 claims description 36
- 239000011941 photocatalyst Substances 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 23
- 239000000203 mixture Substances 0.000 claims description 17
- 229910052797 bismuth Inorganic materials 0.000 claims description 15
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 13
- 239000011248 coating agent Substances 0.000 claims description 12
- 239000000463 material Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 239000012855 volatile organic compound Substances 0.000 claims description 10
- 238000010521 absorption reaction Methods 0.000 claims description 8
- OZKCXDPUSFUPRJ-UHFFFAOYSA-N oxobismuth;hydrobromide Chemical group Br.[Bi]=O OZKCXDPUSFUPRJ-UHFFFAOYSA-N 0.000 claims description 7
- 125000001246 bromo group Chemical group Br* 0.000 claims description 6
- 125000001309 chloro group Chemical group Cl* 0.000 claims description 6
- 125000002346 iodo group Chemical group I* 0.000 claims description 6
- 239000004567 concrete Substances 0.000 claims description 2
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical class [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract 2
- 229910010413 TiO 2 Inorganic materials 0.000 description 53
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 36
- 239000000243 solution Substances 0.000 description 31
- MWUXSHHQAYIFBG-UHFFFAOYSA-N Nitric oxide Chemical compound O=[N] MWUXSHHQAYIFBG-UHFFFAOYSA-N 0.000 description 28
- 239000000725 suspension Substances 0.000 description 24
- 238000001179 sorption measurement Methods 0.000 description 19
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 230000008569 process Effects 0.000 description 17
- 238000006243 chemical reaction Methods 0.000 description 16
- 239000000843 powder Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 15
- 238000005259 measurement Methods 0.000 description 11
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- 238000000354 decomposition reaction Methods 0.000 description 10
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000003054 catalyst Substances 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- 230000000694 effects Effects 0.000 description 6
- 238000003760 magnetic stirring Methods 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
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- -1 bismuth oxide halide Chemical class 0.000 description 5
- 239000006227 byproduct Substances 0.000 description 5
- 239000008367 deionised water Substances 0.000 description 5
- 229910021641 deionized water Inorganic materials 0.000 description 5
- 238000002156 mixing Methods 0.000 description 5
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 4
- 238000005119 centrifugation Methods 0.000 description 4
- 238000002485 combustion reaction Methods 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 0.000 description 4
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 description 3
- 125000004432 carbon atom Chemical group C* 0.000 description 3
- 230000003197 catalytic effect Effects 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 241000894007 species Species 0.000 description 3
- 238000001228 spectrum Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 239000010936 titanium Substances 0.000 description 3
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 2
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 2
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 238000003916 acid precipitation Methods 0.000 description 2
- 238000013459 approach Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
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- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910000416 bismuth oxide Inorganic materials 0.000 description 2
- 229940073609 bismuth oxychloride Drugs 0.000 description 2
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000003421 catalytic decomposition reaction Methods 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 230000003247 decreasing effect Effects 0.000 description 2
- 238000009792 diffusion process Methods 0.000 description 2
- PPNKDDZCLDMRHS-UHFFFAOYSA-N dinitrooxybismuthanyl nitrate Chemical compound [Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O PPNKDDZCLDMRHS-UHFFFAOYSA-N 0.000 description 2
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- BWOROQSFKKODDR-UHFFFAOYSA-N oxobismuth;hydrochloride Chemical group Cl.[Bi]=O BWOROQSFKKODDR-UHFFFAOYSA-N 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 description 2
- 229910052719 titanium Inorganic materials 0.000 description 2
- 241000196324 Embryophyta Species 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- 229910004616 Na2MoO4.2H2 O Inorganic materials 0.000 description 1
- 230000032900 absorption of visible light Effects 0.000 description 1
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 239000010426 asphalt Substances 0.000 description 1
- QCUOBSQYDGUHHT-UHFFFAOYSA-L cadmium sulfate Chemical compound [Cd+2].[O-]S([O-])(=O)=O QCUOBSQYDGUHHT-UHFFFAOYSA-L 0.000 description 1
- 229910000331 cadmium sulfate Inorganic materials 0.000 description 1
- 239000004202 carbamide Substances 0.000 description 1
- 150000001768 cations Chemical class 0.000 description 1
- 230000008859 change Effects 0.000 description 1
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- 238000004299 exfoliation Methods 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
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- 230000036541 health Effects 0.000 description 1
- 239000012456 homogeneous solution Substances 0.000 description 1
- 238000009396 hybridization Methods 0.000 description 1
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 239000005457 ice water Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000000543 intermediate Substances 0.000 description 1
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Substances [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 1
- 239000004922 lacquer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000012046 mixed solvent Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 229910000476 molybdenum oxide Inorganic materials 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000006303 photolysis reaction Methods 0.000 description 1
- 230000015843 photosynthesis, light reaction Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002002 slurry Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
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- 239000002966 varnish Substances 0.000 description 1
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Classifications
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/802—Visible light
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2259/00—Type of treatment
- B01D2259/80—Employing electric, magnetic, electromagnetic or wave energy, or particle radiation
- B01D2259/804—UV light
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- 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
- Y02C—CAPTURE, STORAGE, SEQUESTRATION OR DISPOSAL OF GREENHOUSE GASES [GHG]
- Y02C20/00—Capture or disposal of greenhouse gases
- Y02C20/10—Capture or disposal of greenhouse gases of nitrous oxide (N2O)
Abstract
Description
本出願は、2015年12月22日に出願された、カナダ特許出願第2,916,078号の利益を主張し、その内容全体が、双方とも参照として本明細書に組み込まれる。
序説
N2+O2→2NO
NO+1/2O2−NO2
光触媒+hν→eCB −+hνB +
hνB ++H2O吸着→HO吸着・+H+
eCB −+O2吸着→O2吸着・−
NO+3HO吸着・→HNO3+H2O
NO2+HO吸着・→HNO3
NO+O2吸着・−→NO3 −
光触媒+hν→eCB −+hνB +
O2−(表面)+hνB +→O−(表面)
NO(吸着)+eCB −→NO−(吸着)
NO−(吸着)+O−(表面)→N(吸着)+O(吸着)+O2−(吸着)
2N(吸着)→N2(吸着)→N2(気体)
2O(吸着)→O2(吸着)→O2(気体)
a)結晶性二酸化チタン、
b)酸化グラフェン及び
c)Xが、クロロ、ブロモ又はヨードである、次式Bi−O−Xのビスマスオキシハライドを含むUV及び可視光光触媒複合材料が提供される。
a)二酸化チタン、
b)第一の複合材料であって、
i)酸化グラフェン及び
ii)Xが、クロロ、ブロモ又はヨードである、次式Bi−O−Xのビスマスオキシハライドを含む第一の複合材料を含むUV及び可視光光触媒複合材料を含む。
ここで図面を参照して本出願を更に詳細に記述する。
本明細書で使用するとき、用語「可視光」は、約400nmと約750nmの間の波長(複数可)を有する光を指す。光触媒複合材料によって空中浮遊汚染物質を分解するために、本範囲のすべての波長が、「可視光」内に存在することが必要とは限らない。
(II)UV及び可視光光触媒複合材料
i)二酸化チタン並びに
ii)第一の複合材料であって、
a)酸化グラフェン及び
b)Xが、クロロ、ブロモ又はヨードである、次式Bi−O−Xのビスマスオキシハライドを含む第一の複合材料を含むUV及び/又は可視光光触媒複合材料に関する。
a)結晶性二酸化チタン、
b)酸化グラフェン及び
c)Xが、クロロ、ブロモ又はヨードである、次式Bi−O−Xのビスマスオキシハライドを含むUV及び/又は可視光光触媒複合材料を含む。
(III)空中浮遊汚染物質を分解するための使用及び方法
a)本明細書で開示されるUV及び/又は可視光光触媒複合材料を適切な表面に施すこと、
b)空中浮遊汚染物質を分解するために適切な表面をUV光、可視光又は太陽光にさらすことを含み、
空中浮遊汚染物質は、NOx又は揮発性有機化合物である、空中浮遊汚染物質の分解方法を含む。
(IV)複合材料の調製方法
i)ビスマス含有化合物を適切な溶媒に混合して溶液を形成する工程
ii)ハロゲン化物含有化合物を溶液に添加して懸濁液を形成する工程
iii)酸化グラフェンを懸濁液に添加する工程
iv)懸濁液を熱水処理して第一の複合材料を形成する工程
v)二酸化チタンを熱処理する工程
vi)第一の複合材料と二酸化チタンを水溶液中で混合する工程
vii)水溶液を熱水処理して光触媒複合材料を得る工程
実施例
実施例1:光触媒材料の合成
手順(a)
手順(b)
実施例2:NOx測定
式中、nmeasureは、測定したカウント数、nbgは、バックグラウンドからのカウント数、ncalは、較正気体からのカウント数、及びCcalは、較正気体濃度であり、この実験において4.75ppbだった。nmeasure、nbg及びncalのカウント数は、測定が、安定状態に到達したときの平均値からとった。一般的に、NO及びNOxカウントについて、30ポイントが平均され、NOyに対して、120ポイントが平均される。以下の本報告の一部では、NO、NO2及びNOyの抽出した平均カウントのみが使用され、変換された濃度比率c/c0が、グラフにされ、示される。
実施例3−従来技術の触媒
(i)TiO2 P25光触媒
(ii)BiOBr/GO光触媒
(iii)FeでドーピングされたTiO2
(iv)NでドーピングされたTiO2
(v)CuでドーピングされたTiO2
(vi)Cu/NでともにドーピングされたTiO2
(vii)ZnCdS/MoS2
実施例5−BiOBr/GO/TiO2
明細書内で参照される全引用文献
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Claims (24)
- UV及び/又は可視光光触媒複合材料であって、
i)結晶性二酸化チタン並びに
ii)第一の複合材料であって、
a)酸化グラフェン及び
b)Xが、クロロ、ブロモ又はヨードである、次式Bi−O−Xのビスマスオキシハライドを含む第一の複合材料を含む光触媒複合材料。 - 前記材料が、約470nmのUV−vis吸収端を有する、請求項1に記載の光触媒複合材料。
- 前記二酸化チタンが、アナターゼ、ルチル及び/又はブルッカイトを含む、請求項1又は2に記載の光触媒複合材料。
- 前記二酸化チタンが、アナターゼ及びルチルを含む、請求項3に記載の光触媒複合材料。
- 前記二酸化チタンが、約3:1の比率のアナターゼ及びルチルを含む、請求項4に記載の光触媒複合材料。
- 前記ビスマスオキシハライドが、ビスマスオキシブロミドである、請求項1〜5のいずれか1項に記載の光触媒複合材料。
- 前記二酸化チタン及び前記第一の複合材料が、約0.5:1〜約3:1の間の重量比で存在する、請求項1〜6のいずれか1項に記載の光触媒複合材料。
- 前記二酸化チタン及び前記第一の複合材料が、約1:1の重量比で存在する、請求項7に記載の光触媒複合材料。
- 前記酸化グラフェンが、グラフェンを更に含む、請求項1〜8のいずれか1項に記載の光触媒複合材料。
- 前記二酸化チタンが、前記第一の複合材料に堆積する、請求項1〜9のいずれか1項に記載の光触媒複合材料。
- UV及び/又は可視光光触媒複合材料であって、
a)結晶性二酸化チタン、
b)酸化グラフェン及び
c)Xが、クロロ、ブロモ又はヨードである、次式Bi−O−Xのビスマスオキシハライドを含む材料。 - 前記材料が、約470nmのUV−vis吸収端を有する、請求項11に記載の光触媒複合材料。
- 前記二酸化チタンが、アナターゼ、ルチル及び/又はブルッカイトを含む、請求項12に記載の光触媒複合材料。
- 前記二酸化チタンが、アナターゼ及びルチルを含む、請求項13に記載の光触媒複合材料。
- 前記二酸化チタンが、約3:1の比率のアナターゼ及びルチルを含む、請求項14に記載の光触媒複合材料。
- 前記ビスマスオキシハライドが、ビスマスオキシブロミドである、請求項11〜15のいずれか1項に記載の光触媒複合材料。
- 前記酸化グラフェンが、グラフェンを更に含む、請求項11〜16のいずれか1項に記載の光触媒複合材料。
- 請求項1〜17のいずれか1項に記載のUV及び/又は可視光光触媒複合材料及び前記光触媒複合材料を分散させるために適切な溶媒を含む組成物。
- 前記溶媒が、C1〜C6アルコール、水又はそれらの組合せである、請求項18に記載の組成物。
- 請求項1〜17のいずれか1項に記載の前記UV及び/又は可視光光触媒複合材料又はNOx及び/又は揮発性有機化合物(VOC)を分解するための請求項18又は19に記載の組成物の使用。
- 前記NOxが、NO又はNO2である、請求項20に記載の使用。
- 空中浮遊汚染物質の分解方法であって、前記方法が、
a)表面を請求項1〜17のいずれか1項に記載の光触媒複合材料又は請求項18若しくは19に記載の前記組成物でコーティングすること、及び
b)前記表面を前記空中浮遊汚染物質を分解するために可視光及び/又はUV光にさらすことを含み、
前記空中浮遊汚染物質が、NOx又は揮発性有機キャリヤーである、方法。 - 前記表面が、空中浮遊汚染物質と接触する任意の表面である、請求項22に記載の方法。
- 前記表面が、車道、トンネル、壁、コンクリート、舗装道路、自動車又は汚染防止装置である、請求項22に記載の方法。
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