Method for obtaining a photocatalytic polymer

Abstract

A method for obtaining a photocatalytic polymer is provided. The method is carried out by mixing aluminium trihydroxide (ATH) and a photocatalytic particle in a polar solvent at a pH between 5 and 7 under stirring, adding silane or siloxane, stirring for a period of time of 100 min at a temperature between 30 and 50° C., extracting the solid phase being formed and drying for obtaining a photocatalytic additive, adding the photocatalytic additive to an acrylic or polyester resin and polymerizing. The method may be applied onto any type of polymer base, such as vinyl, fluoropolymers, polyamide, polycarbonates, polyethylene or epoxides. Another aspect of the invention is the photocatalytic additive being obtained. The resulting polymer shows catalytic homogeneity, operating the photocatalytic particles in all the surfaces of the material with the same activity.

Claims

1. A method for obtaining a photocatalytic polymer, the method comprising: a) mixing aluminium trihydroxide and at least a photocatalytic particle in water at a pH between 5 and 7 under stirring; b) adding a silane or a siloxane, c) stirring for a minimum of time of 100 min at a temperature between 30 and 50° C., d) extracting the solid phase being formed and drying for obtaining a photocatalytic additive, and e) adding said photocatalytic additive to an acrylic or polyester resin and polymerizing for obtaining the photocatalytic polymer.

2. A The method according to claim 1, wherein said aluminium trihydroxide is added at a concentration between 10 and 65% by weight with respect to the final weight of the photocatalytic additive.

3. The method according to claim 1, wherein said photocatalytic particle is selected from the group consisting of TiO.sub.2 rutile, ZnS, SnO.sub.2, ZnO, ZnS, SnO.sub.2, ZnO CdS, Fe.sub.2O.sub.3, Cu.sub.2O, WO.sub.3, SnO.sub.2 and TiO.sub.2 anatase, and mixtures thereof.

4. The method according to claim 3, wherein said photocatalyst particle is selected from the group consisting of TiO.sub.2 rutile, ZnS, SnO.sub.2, ZnO and TiO.sub.2 anatase.

5. The method according to claim 4, wherein said photocatalytic particle is TiO.sub.2 rutile and/or TiO.sub.2 anatase.

6. The method according to claim 1, comprising the removal of particles lower than 0.5 μm before adding silane or siloxane.

7. The method according to claim 1, wherein said siloxane is bis[3-(trietkoxysylyl)propyl] tetrasulphide.

8. The method according to claim 1, wherein said silane is an alkyl silane, unsaturated silane, aromatic silane or aminosilane.

9. The method according to claim 8, wherein said alkyl silane is methyltrimethoxysilane.

10. The method according to claim 8, wherein said unsaturated silane is gamma-methacryloxypropyl-trimethoxysilane.

11. The method according to claim 8, wherein said aromatic silane is vinyl-tris-(ethoxy)silane.

12. The method according to claim 8, wherein said aminosilane is gamma-aminopropyltriethoxysilane or N-beta-(aminoethyl)-gamma aminopropyltrimethoxysilane.

13. The method according to claim 1, wherein said extraction of the solid phase from step d) is by decantation.

14. The method according to claim 1, comprising an additional step of milling said photocatalytic additive before the addition to the resin of step e).

15. A photocatalytic additive, comprising at least a photocatalytic particle, aluminium trihydroxide and a silane or siloxane, wherein said photocatalytic additive is obtained according to the method of claim 1.

16. A polymer acrylic material, comprising the photocatalytic additive of claim 15, wherein said photocatalytic particle is selected from the group consisting of TiO.sub.2 rutile, ZnS, SnO.sub.2, ZnO, ZnS, SnO.sub.2, ZnO CdS, Fe.sub.2O.sub.3, Cu.sub.2O, WO.sub.3, SnO.sub.2, TiO.sub.2 anatase, and mixtures thereof.

17. A polyester polymer material, comprising the photocatalytic additive of claim 15, wherein said photocatalytic particle is selected from the group consisting of TiO.sub.2 rutile, ZnS, SnO.sub.2, ZnO, ZnS, SnO.sub.2, ZnO CdS, Fe.sub.2O.sub.3, Cu.sub.2O, WO.sub.3, SnO.sub.2, TiO.sub.2 anatase, and mixtures thereof.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows a SEM image of the acrylic material surface with photocatalytic properties.

(2) FIG. 2 shows the image of an acrylic material with TiO.sub.2 acting as a photocatalyst, interacting with the ATH.

(3) FIG. 3 shows an image of the same acrylic of FIG. 2 after sand-blasting, showing the photocatalyst, which are small particles of a whiter colour, interacting with ATH whitish particles of a bigger size.

(4) FIG. 4 shows an enlargement of the image of the same acrylic material of FIG. 3 after a second sand-blasting, showing the same interaction of the photocatalyst with the ATH.

EXAMPLES

(5) With the purpose of showing the present invention in an illustrative manner, although being non-limiting anyhow, the following examples are provided. The material for assessment as a material susceptible of being photocatalytic, was quantified following the corresponding ISO standard for each assay. Should not exist a specific standard for the assay, an adaptation has been done of another ISO of similar characteristics according to the assay to be performed.

Example 1: Preparation of the Photocatalytic Mixture 1: ATH—Photocatalysts TiO.SUB.2 .Rutile/TiO.SUB.2 .Anatase with Gamma-Methacryloxypropyl-Trimethoxysilane

(6) 55 litres of buffered water at a pH 6.5 were added 30% by weight of TiO.sub.2 rutile and 5% TiO.sub.2 anatase. This mixture was stirred until completing homogenization. Then aluminium trihydroxide (ATH) was added at a 19.4% percentage under stirring until completing homogenization. Then 10% of gamma-methacryloxypropyl-trimethoxysilane was added and it was stirred for 100 minutes at a temperature of 40° C. All percentages are by weight over the final dissolution weight. The resulting mixture was sieved in the range from 0.5 μm to 1.5 μm and it was left to stand until completing the material deposition. The solid part was separated by decantation and was left to dry until completing total evaporation of the remains of the aqueous phase, and then a milling step took place where the material aggregates were homogenized and broken. The resulting solid was subjected to mechanical stirring for breaking the main agglomerates for obtaining dispersed particles. Then, a second sieving of the material was performed for discarding particles lower than 1.0 μm to 1.5 μm, which may affect health by inhalation thereof, and those bigger than 100 μm for optimizing the final product features.

Example 2: Preparation of the Photocatalytic Mixture 2: ATH—Photocatalysts TiO.SUB.2 .Rutile/ZnO with Gamma-Methacryloxypropyl-Trimethoxysilane

(7) 55 litres of buffered water at a pH 6.5 were added 20% by weight of TiO.sub.2 rutile and 15% ZnO. This mixture was stirred until completing homogenization. Then ATH was added at a 19.4% percentage under stirring until completing homogenization. Then 10% of gamma-methacryloxypropyl-trimethoxysilane was added and it was stirred for 100 minutes at a temperature of 40° C. All percentages are by weight over the final dissolution weight. The sieving, decanting and stirring methods until obtaining the final product were the same as in Example 1.0

Example 3: Preparation of the Photocatalytic Mixture 3: ATH—Photocatalysts TiO.SUB.2 .Rutile/ZnS with Gamma-Methacryloxypropyl-Trimethoxysilane

(8) 55 litres of buffered water at a pH 6.5 were added 20% by weight of TiO.sub.2 rutile and 15% ZnS. This mixture was stirred until completing homogenization. Then ATH was added at a 19.4% percentage under stirring until completing homogenization. Then 10% of gamma-methacryloxypropyl-trimethoxysilane was added and it was stirred for 100 minutes at a temperature of 40° C. All percentages are by weight over the final dissolution weight. The sieving, decanting and stirring methods until obtaining the final product were the same as in Example 1.

Example 4: Preparation of the Photocatalytic Mixture 4: ATH—Photocatalyst TiO.SUB.2 .Rutile/TiO.SUB.2 .Anatase with bis[3-(trietkoxysylyl)propyl] tetrasulphide

(9) 55 litres of buffered water at a pH 6.5 were added 30% by weight of TiO.sub.2 rutile and 5% anatase. This mixture was stirred until completing homogenization. Then ATH was added at a 19.4% percentage under stirring. Then 10% of bis[3-(trietkoxysylyl)propyl] tetrasulphide was added and it was stirred for 100 minutes at a temperature of 40° C. All percentages are by weight over the final dissolution weight. The sieving, decanting and stirring methods until obtaining the final product were the same as in Example 1.

Example 5: Preparation of the Photocatalytic Mixture 5: ATH—Photocatalyst TiO.SUB.2 .Rutile/TiO.SUB.2 .Anatase with Gamma-Aminopropyltriethoxysilane

(10) 55 litres of buffered water at a pH 6.5 were added 30% by weight of TiO.sub.2 rutile and 5% TiO.sub.2 anatase. This mixture was stirred until completing homogenization. Then ATH was added at a 19.4% percentage. Then 10% of gamma-aminopropyltriethoxysilane was added and it was stirred for 100 minutes at a temperature of 40° C. All percentages are by weight over the final dissolution weight. The sieving, decanting and stirring methods until obtaining the final product were the same as in Example 1.

Example 6: Preparation of the Photocatalytic Mixture 6: ATH—Photocatalyst TiO.SUB.2 .Rutile/TiO.SUB.2 .Anatase with vinyl-tris-(ethoxy)silane

(11) 55 litres of buffered water at a pH 6.5 were added 30% by weight of TiO.sub.2 rutile and 5% TiO.sub.2 anatase. This mixture was stirred until completing homogenization. Then ATH was added at a 19.4% percentage. Then 10% vinyl-tris-(ethoxy)silane was added and it was stirred for 100 minutes at a temperature of 40° C. All percentages are by weight over the final dissolution weight. The sieving, decanting and stirring methods until obtaining the final product were the same as in Example 1.

Example 7: Preparation of Acrylic Piece with TiO.SUB.2 .Rutile/TiO.SUB.2 .Anatase as Photocatalysts, without Interaction Process

(12) 10 kg of methyl methacrylate resin (MMA), at a 35% percentage, were added 0.09% of distilled water, 30% TiO.sub.2 rutile and 5% TiO.sub.2 anatase. All percentages are by weight with respect to the total weight. The mixture obtained was stirred for 30 minutes and ATH was added at a 29.7% percentage. After stirring for 60 minutes, benzoyl peroxide was added as initiator at a 0.2% percentage with respect to the total, and it was stirred for 2 minutes. After this time, it was vacuumed for eliminated the air retained therein and after that the mixture was introduced in a mould for obtaining the final piece.

Example 8: Preparation of Acrylic Piece with Photocatalytic Mixture 1

(13) 10 kg of methyl methacrylate resin (MMA), at 35% weight percentage, were added 0.09% of distilled water and 0.3% of dimethylaniline. All percentages are by weight with respect to the total weight. Then, the photocatalytic mixture 1 from Example 1 was added at a 64.4% percentage and it was stirred for obtaining a complete dispersion and homogenization. It was subjected to a first vacuum for eliminating the air generated during stirring and matter introduction. Benzoyl peroxide was added on the homogenised mixture as polymerization initiator at a 0.2% percentage. It was vacuum stirred and degasified, and it was introduced into a mould for obtaining the final piece.

Example 9: Preparation of Polyester Piece with Photocatalytic Mixture 1

(14) 10 kg of polyester and styrene resin, at 33.3% percentage, were added 0.03% of cobalt octoate as accelerator. Then, the photocatalytic mixture 1 from Example 1 was added at a 64.4% percentage and it was stirred together with the polyester resin for a complete dispersion and homogenization. A first vacuum was performed for eliminating the air generated during stirring and matter introduction. Methyl ethyl ketone was added on the homogenised mixture as polymerization initiator at a 2.2% percentage. The resulting mixture was introduced into a mould or into a metallic aluminium band for obtaining the final piece.

Example 10: Preparation of Acrylic Piece with Photocatalytic Mixture 2

(15) 10 kg of a MMA resin base, at 35% percentage, were added 0.09% of distilled water and 0.3% of dimethylaniline. Then, the photocatalytic mixture 2 from Example 2 was added at a 64.4% percentage and it was stirred together with the MMA resin for a complete dispersion and homogenization. A first vacuum was then performed for eliminating the air generated during stirring and matter introduction. Benzoyl peroxide was added on the homogenised mixture as polymerization initiator at a 0.2% percentage. The resulting mixture was vacuum degasified and subsequently was introduced into a mould or metallic aluminium band for obtaining the desired final shape of the acrylic material.

Example 11: Preparation of Acrylic Piece with Photocatalytic Mixture 3

(16) The example 10 is repeated under the same conditions with the photocatalytic mixture 3 prepared in Example 3 with the same percentages, for obtaining a final piece from the acrylic material.

Example 12: Preparation of Acrylic Piece with Photocatalytic Mixture 4

(17) The example 10 is repeated under the same conditions with the photocatalytic mixture 4 prepared in Example 4 with the same percentages, for obtaining a final piece from the acrylic material.

Example 13: Preparation of Acrylic Piece with Photocatalytic Mixture 5

(18) The example 10 is repeated under the same conditions with the photocatalytic mixture 5 prepared in Example 5 with the same percentages, for obtaining a final piece from the acrylic material.

Example 14: Preparation of Acrylic Piece with Photocatalytic Mixture 6

(19) The example 10 is repeated under the same conditions with the photocatalytic mixture 6 prepared in Example 6 with the same percentages, for obtaining a final piece from the acrylic material.

Example 15: Characterization of the Piece Obtained in Example 8

(20) The surface distribution was characterized by scanning electron microscope (SEM; Leica-Zeiss LEO 440, with 1-30 kV electron beam gun), differentiating between dark-coloured organic matter and clear-coloured inorganic matter. The images taken from the material obtained in Example 8 show the perfect distribution of the inorganic particles with mineral fillers and the photocatalyst inside the polymer organic matrix of polymethylmethacrylate (PMMA) (FIG. 1).

Microanalysis of the Material on Image

(21) 57.2% CO.sub.2 (organic matter) 42.8% Al.sub.2O.sub.3 (inorganic matter)

(22) The presence of surface TiO.sub.2 is also characterized in the samples, with homogeneity being observed all along the surface, as it can be observed in FIG. 2.

(23) The pieces were strongly sand-blasted over the surface with the purpose of eliminating the upper layer of the material and analysing the inner area of the piece. The object thereof is to analyse homogeneity of the material in its whole mass and see the photocatalyst distribution layer by layer in its entire mass. The SEM image of FIG. 3 shows again the distribution of white inorganic particles inside the PMMA polymer matrix.

(24) Sand-blasting and image enlargement are performed again so as to check again a new layer of material with the presence of the photocatalyst on the surface, as it can be observed in FIG. 4.

Example 16: Physical Characterization of the Obtained Pieces

(25) The physical characterization of the pieces obtained in the previous examples following ISO standards, is shown in the following Tables 1 and 2.

(26) TABLE-US-00001 TABLE 1 Photocatalytic acrylic material characterization Assay Example Example Example Example Example Example Properties standard 8 10 11 12 13 14 Density (g/cm.sup.3) ISO 1183 1.71-1.77 1.72-1.77 1.71-1.76 1.74-1.79 1.71-1.75 1.72-1.78 Flexural modulus ISO 178  8500-11950  8450-10550  8600-12000  8550-11500  8600-11950  8400-10900 (MPa) Flexural strength ISO 178 60-69 61-70 60-75 66-75 60-71 58-66 (MPa) Tensile strength ISO 178 40-60 35-57 42-61 40-60 39-58 43-61 (MPa) Compression ISO 178  95-115  95-115  90-111  93-113  96-115  94-114 strength (MPa) Barcol Hardness ISO 62-63 63-64 62-63 63-64 63-65 62-63 19712-2 Shore Hardness ISO 90-95 90-95 90-95 90-95 90-95 90-95 19712-2 Rockwell ISO 86-93 86-93 86-93 86-93 86-93 86-93 Hardness 19712-2

(27) TABLE-US-00002 TABLE 2 Characterization photocatalytic polyester material Properties Assay standard Example 9 Density (g/cm.sup.3) ISO 1183 1.75-1.81 Flexural modulus (MPa) ISO 178  8900-12500 Flexural strength (MPa) ISO 178 58-68 Tensile strength (MPa) ISO 178 51-69 Compression strength (MPa) ISO 178  99-119 Barcol Hardness ISO 19712-2 64-67 Shore Hardness ISO 19712-2 90-95 Rockwell Hardness ISO 19712-2  95-100

Example 17: Degradation of Methylene Blue in an Aqueous Solution on the Piece from Example 8

(28) The piece obtained in example 8 was assayed according to ISO 10678:2010. The results are summarized in the following Table 3:

(29) TABLE-US-00003 TABLE 3 Results of methylene blue degradation by photocatalysis in piece from example 8 E.sub.P, E.sub.P, av R.sub.irr R.sub.dark PMB t.sub.m E, E.sub.av (mol m.sup.−2 (mol m.sup.−2 (mol m.sup.−2 (mol m.sup.−2 ζ.sub.MB (min) A.sub.λ, irr A.sub.λ, dark (W m.sup.−2) h.sup.−1) h.sup.−1) h.sup.−1) h.sup.−1) (%) 0 0.739 0.739 10 0.11 — — — — 180 0.736 0.720 10 0.11 2.40E−06 −4.71E−08 2.45E−06 0.0022

(30) It is observed that the methylene blue concentration resulting from the photocatalytic activity has been reduced in 0.49%.

Example 18: Degradation of Methylene Blue in an Aqueous Solution on the Piece from Example 9

(31) The piece being assayed was that described in example 9 according to ISO 10678:2010. The results are summarized in the following Table 4:

(32) TABLE-US-00004 TABLE 4 Results of methylene blue degradation by photocatalysis E.sub.P, E.sub.P, av R.sub.irr R.sub.dark PMB t.sub.m E, E.sub.av (mol m.sup.−2 (mol m.sup.−2 (mol m.sup.−2 (mol m.sup.−2 ζ.sub.MB (min) A.sub.λ, irr A.sub.λ, dark (W m.sup.−2) h.sup.−1) h.sup.−1) h.sup.−1) h.sup.−1) (%) 0 0.739 0.739 10 0.11 — — — — 180 0.748 0.720 10 0.11 6.72E−06 −4.71E−08 6.77E−06 0.0062

(33) It is observed that the methylene blue concentration resulting from the photocatalytic activity has been reduced in 2.40%.

Example 19: Degradation of Methylene Blue in an Aqueous Solution on the Piece from Example 12

(34) The piece being assayed was described in example 12, in an assay being the same as in the previous example according ISO 10678:2010. The results are summarized in the following Table 5:

(35) TABLE-US-00005 TABLE 5 Results of methylene blue degradation by photocatalysis in the piece from example 12 E.sub.P, E.sub.P, av R.sub.irr R.sub.dark PMB t.sub.m E, E.sub.av (mol m.sup.−2 (mol m.sup.−2 (mol m.sup.−2 (mol m.sup.−2 ζ.sub.MB (min) A.sub.λ, irr A.sub.λ, dark (W m.sup.−2) h.sup.−1) h.sup.−1) h.sup.−1) h.sup.−1) (%) 0 0.747 0.723 10 0.11 — — — — 180 0.745 0.720 10 0.11 1.61E−06 −4.71E−08 1.62E−05 0.-0147

(36) It is observed that the methylene blue concentration resulting from the photocatalytic activity has been reduced in 0.22%.

Example 20: Degradation of Methylene Blue in an Aqueous Solution on the Piece from Example 7

(37) The piece being assayed was that described in example 7 according to ISO 10678:2010. The results are summarized in the following Table 6:

(38) TABLE-US-00006 TABLE 6 Results of methylene blue degradation by photocatalysis in the piece from example 7 E.sub.P, E.sub.P, av R.sub.irr R.sub.dark PMB t.sub.m E, E.sub.av (mol m.sup.−2 (mol m.sup.−2 (mol m.sup.−2 (mol m.sup.−2 ζ.sub.MB (min) A.sub.λ, irr A.sub.λ, dark (W m.sup.−2) h.sup.−1) h.sup.−1) h.sup.−1) h.sup.−1) (%) 0 0.725 0.723 10 0.11 — — — — 180 0.743 0.720 10 0.11 −5.52E−06 −4.71E−08 −5.47E−06 −0.0050

(39) It can be observed that the methylene blue concentration resulting from the photocatalytic activity is ≤0%, thus showing no activity.

Example 21: Degradation of Methylene Blue in an Aqueous Solution on the Piece from Example 8

(40) The assay was performed on the sample from example 8. The assay conditions have been adapted according to ISO 27447: 2009. The UV irradiation source is between 315 to 400 nm of 22 W. The pieces were pre-treated by leaving them under the irradiation source for 12 hours. After this time, a known and controlled amount of each pesticide to be assessed was deposited on the surface. These were left under photocatalysis conditions for 8 hours of irradiation. After that time the samples were each introduced in a 50 mL Falcon tube and were extracted with 10 mL with PAR-grade (Pesticide Analysis Residue) acetonitrile as solvent under stirring for 5 minutes. The samples were centrifuged for 5 minutes at 4000 r.p.m. After settling, 0.400 μL of the extract were transferred into a vial which was added 0.600 μL of ethyl acetate.

(41) All the vials, as well as the calibration line prepared under the same conditions, are analysed in a gas chromatography equipment (GC Agilent 7890B) fitted with an automatic injector (Agilent 7693A) coupled to a mass spectrometer with triple quadrupole analyser (QqQ) MS/MS-Q EI 7000 operating in EI (electronic ionization) mode. It is observed that the amount of pesticide is reduced in each case, with the results shown in Table 7:

(42) TABLE-US-00007 TABLE 7 Results of pesticides elimination in example 8 Initial Final Concentration concentration Pesticide (ppb) (ppb) % Reduction 1,2,3,6- 137.3 90.3 34.2 tetrahydrofthalamide 2-Phenylphenol 122.8 9.2 92.5 4,4′- 89.1 8.6 90.3 Dichlorobenzophenone Acephate 68.4 43.2 36.8 Aclonifen 76.6 27.7 63.8 Acrinathrin 71.3 0.0 100.0 Alachlor 94.5 16.0 83.1 Anthraquinone 88.0 0.4 99.5 Atrazine 91.0 27.7 69.6 Azinphos-ethyl 80.0 15.7 80.3 Benalaxyl 84.8 41.5 51.1 Benfluralin 86.7 2.4 97.3 Bifenthrin 102.2 16.8 83.6 Boscalid 96.5 19.0 80.3 Bromopropylate 102.8 41.8 59.3 Bupirimate 88.2 3.1 96.5 Buprofezin (Z) 97.7 12.6 87.1 Captan 55.0 5.4 90.2 Chinomethionate 115.3 0.0 100.0 Chlorfenvinphos 86.4 0.0 100.0 Chlorothalonil 66.1 1.6 97.6 Chlorpyrifos 95.2 1.5 98.5 Chlorpyrifos-methyl 79.7 2.1 97.4 Chlorthal-dimethyl 89.7 23.2 74.2 Cyflufenamid 101.9 47.1 53.8 Coumaphos 71.9 1.0 98.6 Cyfluthrin 85.1 4.1 95.2 Cypermethrin 91.3 0.0 100.0 Cyproconazole 101.2 48.5 52.1 o.p′-DDT 77.7 15.2 80.4 Deltamethrin 66.7 0.0 100.0 Diazinon 100.7 27.7 72.5 Dichlobenil 93.4 12.7 86.4 Dichlofluanid 82.7 11.7 85.9 Dichlorvos 57.1 12.6 77.9 Dicloran 85.1 0.0 100.0 Dicofol 89.3 7.7 91.4 Dieldrin 90.8 4.4 95.2 Diethyltoluamide 92.3 43.7 52.6 Diflufenican 73.0 16.5 77.4 Diphenylamine 117.8 0.0 100.0 Endosulfan I 94.8 69.4 26.9 Endosulfan II 96.3 32.6 66.1 Endrin 86.0 15.9 81.5 Ethion 99.6 34.4 65.4 Ethoprophos 93.1 41.4 55.6 Ethoxyquin 335.3 0.0 100.0 Etofenprox 97.9 12.6 87.2 Etoxazole 97.3 8.5 91.3 Etridiazole 79.8 8.4 89.5 Famoxadone 89.6 12.4 86.2 Fenazaquin 98.9 0.0 100.0 Fenitrothion 87.7 9.9 88.7 Fenpropathrin 99.3 2.3 97.7 Fenthion 1114.7 0.0 100.0 Fenvalerate + 90.0 0.0 100.0 Esfenvalerate Fluazifop-butyl 89.0 2.6 97.1 Flucythrinate 97.0 0.0 100.0 Fludioxonil 86.8 0.0 100.0 Fluquinconazole 83.5 36.3 56.5 Flusilazole 92.7 63.8 31.2 Folpet 49.7 18.7 62.4 Fonofos 151.1 18.1 88.1 Heptachlor 82.9 32.3 61.0 Heptenophos 74.4 11.9 84.0 Indoxacarb 75.1 15.0 80.1 Iprodione 64.7 9.5 85.3 Isofenphos-methyl 161.4 27.4 83.0 Kresoxim-methyl 102.5 0.0 100.0 Lambda-cyhalothrin 87.1 0.9 99.0 Lindane 94.0 85.1 9.5 Malaoxon 38.8 25.4 34.5 Malathion 80.4 36.6 54.5 Metalaxyl 89.8 27.7 69.2 Metazachlor 90.3 14.6 83.8 Methidathion 67.1 4.2 93.7 Metrafenone 90.9 0.0 100.0 Myclobutanil 94.2 52.5 44.3 Nuarimol 96.2 0.0 100.0 Ofurace 81.6 12.0 85.3 Oxadiazon 97.8 2.5 97.4 Oxadixyl 92.3 25.2 72.7 Oxyfluorfen 81.9 0.0 100.0 Parathion 80.3 8.8 89.0 Parathion-methyl 67.2 5.3 92.1 Penconazole 95.2 13.4 85.9 Permethrin 98.8 29.2 70.5 Phenthoate 84.4 50.2 40.5 Phosalone 79.0 2.5 96.9 Phosmet 61.6 6.0 90.2 Piperonyl butoxide 99.8 0.0 100.0 Pirimiphos-ethyl 110.4 0.0 100.0 Pirimiphos-methyl 108.0 5.2 95.2 Procymidone 88.9 19.8 77.7 Profenofos 75.6 20.2 73.3 Prometryn 100.7 3.5 96.6 Propargite 90.2 16.5 81.7 Propiconazole 93.4 22.6 75.8 Propyzamide 94.8 39.1 58.7 Pyrazophos 84.2 0.0 100.0 Pyridaben 98.1 0.0 100.0 Pyridaphenthion 82.1 3.6 95.6 Pyrifenox 89.2 12.3 86.2 Pyriproxyfen 95.1 8.2 91.4 Quinalphos 92.1 0.0 100.0 Quinoxyfen 87.6 0.0 100.0 Quizalofop-ethyl 92.8 0.0 100.0 Simazine 93.3 16.3 82.5 Spirodiclofen 83.9 5.7 93.2 Spiromesifen 79.5 13.4 83.1 Sulfotep 92.7 52.3 43.6 Tau-fluvalinate 74.1 0.0 100.0 Tebufenpyrad 91.9 17.0 81.5 Tefluthrin 100.9 44.9 55.5 Terbuthylazine 101.3 25.8 74.5 Tetradifon 99.4 0.0 100.0 Triadimefon 99.3 5.8 94.2 Triadimenol 97.5 31.4 67.8 Triazophos 82.0 39.7 51.6 Trifluralin 91.6 1.8 98.0 Vinclozolin 100.5 24.9 75.2 Zoxamide 57.0 3.7 93.6

Example 22. Degradation NO.SUB.x .in Gas Phase on Piece from Example 8

(43) The assay was performed with the piece obtained in the example 8, following the ISO 22197-1 standard. The results are reflected in Table 8, where an effective NO.sub.x removal.

(44) TABLE-US-00008 TABLE 8 NO.sub.x removal in example 8 Units: μmol NOT NOT Unreacted Generated Removed Sample provided provided NO.sub.2 NO.sub.2 NO.sub.x Example 8 36.24 0.22 36.02 0.04 0.17

Example 23: Degradation of Methylene Blue in an Aqueous Solution on the Piece from Example 13

(45) The piece being assayed was described in example 13, in an assay being the same as that of the previous example according to ISO 10678:2010. The results are summarized in the following Table 9:

(46) TABLE-US-00009 TABLE 9 Results of methylene blue degradation by photocatalysis in the piece from example 13 E.sub.P, E.sub.P, av R.sub.irr R.sub.dark PMB t.sub.m E, E.sub.av (mol m.sup.−2 (mol m.sup.−2 (mol m.sup.−2 (mol m.sup.−2 ζ.sub.MB (min) A.sub.λ, irr A.sub.λ, dark (W m.sup.−2) h.sup.−1) h.sup.−1) h.sup.−1) h.sup.−1) (%) 0 0.747 0.723 10 0.11 — — — — 180 0.746 0.720 10 0.11 2.83E−06 −4.71E−08 2.87E−06 0.0026

(47) It is observed that the methylene blue concentration resulting from the photocatalytic activity has been reduced in 0.11%.

Example 24. NO.SUB.x .Degradation in Gas Phase on the Piece from Example 14

(48) The assay was performed with the piece obtained in example 14, following the ISO 22197-1 standard. The results are reflected in Table 10, where an effective elimination of NO.sub.x.

(49) TABLE-US-00010 TABLE 10 Elimination of NO.sub.x in example 14 Units: μmol NOT Removed Unreacted Generated Removed Sample provided NO NO.sub.2 NO.sub.2 NO.sub.x Example 6 37.3 0.22 37.08 0.10 0.12

Example 25. Determination of Antibacterial Activity in the Piece from Example 8

(50) The assay was performed with the piece obtained in example 8, following the ISO 22197-1 standard. The results being reflected in Table 11 show an effective removal of the S. Aureus bacterium of 72.11% more.

(51) TABLE-US-00011 TABLE 11 Antibacterial effect in example 8 Slope Increase S. Aureus Cells/ml reduction (%) Innoculated 1.41E+05 0 — Bacteria Assay untreated piece 17.8 — Assay piece example 8 30.64 72.11%