Abstract:
Visible-light-active and photostable, multilayered materials and their preparation method based on surface-modified titanium(IV) oxide have been invented.

Description:
DISCIPLINE OF TECHNOLOGY 
       [0001]    The subjects of this invention are active in visible light, photostable multilayered materials and the method of their preparation. 
       STATE OF THE ART 
       [0002]    Scientific literature describes many pieces of information about photocatalytically active materials based on TiO 2 . They may be used in a variety of science or engineering disciplines, e.g. as electrochrome material components (D. Di Yao et al., Nanoscale 2013, 5, 10353-10359), dielectrics and optic layers (V-S. Dang et al., Phys. Status Solidi A 2013, 1-9), solar cells sensitized to visible light (F. Chu et al., ACS Appl. Mater. Interfaces 2013, 5, 7170-7175), or lithium batteries (J. S. Chen, X. W. Lou, Materials Today 2012, 15, 246-254). TiO 2  layers can be the components of self-cleaning surfaces, anti-frost panes and antibacterial, self-sterilizing plates (Q. F. Xu et al., ACS Appl. Mater. Interfaces 2013, 5, 8915-8924). Materials based on TiO 2  might also be used in the processes of water and air cleaning (R. Daghrir et al., Ind. Eng. Chem. Res. 2013, 52 (10), 3581-3599). 
         [0003]    The photocatalytic activity of titanium(IV) oxide occurs in the range of UV radiation. In order to increase its activity, e.g. in the range of visible light, it is necessary to photosensitize the material by appropriate organic and inorganic compounds or to introduce a mixture of transitional metal elements (Mn, Nb, V) or non-metal elements (N, S, P). It is known that as a result of titanium(IV) oxide modification with organic compounds containing hydroxyl or carboxylic group in the molecule, surface complex of Ti(IV)-modifier absorbing visible light can be obtained (W. Macyk et al., Coord. Chem. Rev. 2010, 254, 2687-2701). It is also known that such materials in the powder form (M. Buchalska et al., Dalton Trans. 2013, 42, 9468-9475) or coatings (patent claim P 400098, PCT/EP2013/065400) can present photocatalytic activity during irradiation by UV, UV-vis or visible light. A well-known method of applying thin layers of material on different type surfaces is ALD (Atomic Layer Deposition). 
         [0004]    The layer thickness depends reproducibly on the deposition parameters (inter alia on the number of cycles used) (Steven M. George, Chem. Rev. 2010, 110, 111-131). The “spin-coating” technique is a well-known method of applying thin layers of materials on flat surfaces, described in M. Pichumani et al., SoftMatter 2013, 9, 3220-3229. The observed drawback of this technique is difficulty in obtaining durable and stable photocatalytic coatings of titanium(IV) oxide active in visible light. 
         [0005]    For example, these defects are observed in materials described in patent application P 397593. Therefore, there is still a need for a preparation method that allows to obtain stable coatings based on modified TiO 2  photosensitized to visible light. 
         [0006]    This problem was unexpectedly solved by providing a layered photocatalysts according to the described invention. 
       DETAILED DESCRIPTION OF THE INVENTION 
       [0007]    The subjects of this invention are photocatalytic materials based on titanium(IV) oxide activated with visible light, characterized in that:
       a) the base consists of a surface-modified by aromatic organic compound which contains at least two —OH or —COOH groups or hexachloroplatinate(IV) ion, microcrystalline or nanocrystalline titanium(IV) oxide in the form of powder, suspension, colloid or coating;   b) additionally covered with a thin protective layer of titanium(IV) oxide deposited by ALD technique (for materials in the form of powders or coatings) or “spin-coating” technique (for materials in the form of coatings).       
 
         [0010]    Preferably, nanocrystalline titanium(IV) oxide is surface-modified by the organic compound selected from the group, which contains:
   a) compound of formula 1   
 
         [0000]    
       
                 
         
             
             
         
       
     
         [0012]    where: R 1 -R 4  denotes —H or saturated or unsaturated substituents, NH 2 , —NH 3   +  or —SO 3 M in which M denotes H + , K + , Na + , Li + , NH 4   + , and R 5  and R 6  denote —OH or —COOH,
   b) ascorbic acid,   c) 2,5-dihydroxyterephthalic acid,   d) hexachloroplatinic acid,   e) hematoxylin of formula:   
 
         [0000]    
       
                 
         
             
             
         
       
       
         f) bromopyrogallol red of formula: 
       
     
         [0000]    
       
                 
         
             
             
         
       
     
         [0018]    Particularly preferably, the organic compound is a compound selected from the group consisting of phthalic acid, 4-sulphophthalic acid, 4-amino-2-hydroxybenzoic acid, 3-hydroxy-2-naphthylic acid, salicylic acid, 6-hydroxysalicylic acid, 5-hydroxysalicylic acid, 5-sulphosalicylic acid, 3,5-dinitrosalicylic acid, disodium salt of 1,4-dihydroxy-1,3-benzenedisulphonic acid, gallic acid, pyrogallol, 2,3-naphthalenediol, 4-methylcatecho1,3,5-di-tert-butylcatechol,p-nitrocatechol, 3,4-dihydroxy-L-phenyloalanine(DOPA), catechol, 2,5-dihydroxyterephthalic acid, rutin, ascorbic acid. Also preferably a surface modifier is hexachloroplatinic acid or a salt of this acid. The invention also relates to the preparation method of multilayered photocatalytic materials made of titanium(IV) oxide activated with visible light, characterized in that it comprises two steps:
   a)surface modification of titanium(IV) oxide (powder or coating) by covering it with a modifier in the form of solution,   b)depositing the protective layer of titanium(IV) oxide on the modified material by the ALD technique (on the material in a powder or coating form) or the “spin-coating” technique (on the material in a form of coating),   
 
         [0021]    Preferably, for the synthesis crystalline titanium(IV) oxide is used, characterized by anatase structure or being a mixture of anatase and rutile. 
         [0022]    Preferably, surface modification of the material is carried out in water or alcohol solution of the modifier of minimal concentration 10 −4  mol/dm 3  and then followed by drying. 
         [0023]    Preferably, the organic compound is one of the following: phthalic acid, 4-sulphophthalic acid, 4-amino-2-hydroxybenzoic acid, 3-hydroxy-2-naphthoic acid, salicylic acid, 6-hydroxysalicylic acid, 5-hydroxysalicylic acid, 5-sulphosalicylic acid, 3,5-dinitrosalicylic acid, 2,5-dihydroxyterephthalic acid, aurintricarboxilic acid (Table 1), disodium salt of 1,4-dihydroxy-1,3-benzenedisulphonic acid, gallic acid, pyrogallol, 2,3-naphtalenediol, 4-methylcatechol, 3,5-di-tert-butylcatechol, p-nitrocatechol, 3,4-dihydroxy-L-phenylalanine (DOPA), catechol (table 2), rutin, ascorbic acid. Also preferably, the surface modifier is hexachloroplatinic acid or the salt of this acid. Also preferably, deposition of the protective layer is carried out by the ALD technique. 
         [0024]    Preferably, titanium(IV) alcoholates e.g. (isopropylate) are used as the precursors for the synthesis of the protective layer. 
         [0025]    Preferably the temperature of deposition of the material with the protective layer is not higher than 150° C. 
         [0026]    Preferably, when mean thickness d of the external TiO 2  layer is in the range of 1-20 nm. 
         [0000]    
       
         
               
             
               
               
               
             
           
               
                 TABLE 1 
               
             
             
               
                   
               
               
                 Phthalic acid and derivatives of salicyic acid. 
               
             
          
           
               
                 Compound symbol 
                 Compound name 
                 Structural formula 
               
               
                   
               
               
                 A-1 
                 phthalic acid 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 A-2 
                 4-sulphophtalic acid 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 S-1 
                 4-amino-2-hydroxybenzoic acid 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 S-2 
                 3-hydroxy-2-naphthoic acid 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 S-3 
                 salicylic acid 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 S-4 
                 6-hydroxysalicylic acid 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 S-5 
                 5-hydroxysalicylic acid 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 S-6 
                 5-sulphosalicylic acid 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 S-7 
                 3,5-dinitrosalicylic acid 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 S-8 
                 2,5-dihydroxyterephthalic acid 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 S-9 
                 aurintricarboxilic acid 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
             
          
         
       
     
         [0000]    
       
         
               
             
               
               
               
             
           
               
                 TABLE 2 
               
             
             
               
                   
               
               
                 Catechol derivatives. 
               
             
          
           
               
                 Compound 
                   
                   
               
               
                 symbol 
                 Compound name 
                 Structural formula 
               
               
                   
               
               
                 K-1 
                 Disodium salt of 1,4- dihydroxy-1,3- benzenedisulphonic acid 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 K-2 
                 gallic acid 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 K-3 
                 pyrogallol 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 K-4 
                 2,3-naphthalenediol 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 K-5 
                 4-methylcatechol 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 K-6 
                 3,5-di-tert-butylcatechol 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 K-7 
                 p-nitrocatechol 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 K-8 
                 3,4-dihydroxy-l-phenylalanine (DOPA) 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
               
                 K-9 
                 1,2-dihydroxy benzene (catechol) 
                 
                   
                             
                     
                         
                         
                     
                   
                 
               
               
                   
               
             
          
         
       
     
         [0027]    The material according to the invention exhibits photocatalytic activity upon irradiation with visible light (λ&gt;400 nm; photocatalysis is the result of the absorption of visible light by the resulting titanium surface complex of the charge-transfer type) as well as ultraviolet light (λ&lt;400 nm; photocatalysis is the result of the absorption of ultraviolet light by the resulting surface complex of the charge-transfer type or directly by titanium dioxide). 
         [0028]    The irradiation generates so-called reactive oxygen species (OH*, O 2   − , H 2 O 2 ,  1 O 2 ) responsible for the oxidation of organic compounds. The additional layer of TiO 2  applied on the surface of the material protects the titanium surface complex against negative influence of reactive oxygen species. The application of the protective layer should not cause significantly reduced photocatalytic activity of the material, but significantly enhance its durability. 
     
    
     
         [0029]    In order to aid understanding the essence of the invention as defined above, below examples are given and figures are attached. 
           [0030]      FIG. 1  presents the structure of photocatalytic materials of TiO 2  modified with surface protective layer. 
           [0031]      FIG. 2  presents decrease in absorbance at λ=400 nm (absorption band of TiO 2  surface complex with organic modifier) during irradiation (XBO-150, λ&gt;435 nm) of materials in the powder form with or without TiO 2  protective layer. A) K-9@P25, B) K-4@P25. Test details are described in example 4. 
           [0032]      FIG. 3  presents increase in hydroxyterephthalic acid concentration during irradiation of terephthalic acid solution in the presence of materials in the powder form with or without the external protective layer A) K-9@N100, B) K-4@N100, C) K-9@P25, D) K-4@P25. Test details are described in example 5. 
           [0033]      FIG. 4  presents changes in 4-chlorophenol concentration during irradiation in the presence of material in the powder form with or without the external protective layer. Test details are described in example 5. 
       
    
    
     EXAMPLE 1 
     Preparation of a Powder Form Visible-Light-Activated Photocatalyst With Protective Layer Deposited Using the ALD Technique 
       [0034]    The starting substrates for the synthesis of materials are:
       not modified titanium(IV) oxide commercially available   organic surface modifiers   titanium isopropylate, deionized water       
 
         [0038]    0.2 g of commercially available TiO 2  material was weighted (Evonik P25 or Hombikat N100). Than 1 ml of organic modifier solution from the group S (S-2, S-3, Table 1) or the group K (K-4, K-9, Table 2) prepared in 1 mmol/dm 3  concentration of methanol was added into titanium(IV) oxide. 
         [0039]    The substances were thoroughly stirred and then left to sediment for 24 h. After this time the supernatant liquid was collected from sediment and the sediment was flushed with water three times. Materials collected in the form of powders were air-dried. After drying, the powders were grinded using a mortar. 
         [0040]    Every such prepared material was put into a crystallizer, which then was put into the reaction chamber of the ALD reactor (Picosun R-150). 
         [0041]    The synthesis of the protective layer was performed using titanium(IV) isopropylate and deionized water as precursors. The precursors were administered in impulses every 0.2 second, sparging the system with nitrogen after each impulse for 3 seconds. The synthesis was finished after 300 cycles. The synthesis was carried out in the temperature of 150° C. The ready materials were air-dried. 
       EXAMPLE 2 
     Preparation of a Coating Form Visible-Light-Activated Photocatalyst on Glass Plate With Protective Layer Deposited Using the ALD Technique 
       [0042]    The starting substrates for the synthesis of materials are:
       glass plates (basic microscope slides)   not-modified nanocrystalline titanium(IV) oxide (anatase structure) in the form of colloidal water solution of particles smaller than 100 nm and surface modifiers.       
 
         [0045]    The synthesis of coating on glass plates was carried out using the spin-coating technique from 5% w/w colloidal solution of titanium(IV) oxide. Application on a plate was performed at the speed of rotation of the plate of 8000 cycles/min. The plate was rotated for 30 seconds and, meanwhile, three times 200 ml of the colloidal solution were put into the reactor. 
         [0046]    The plate was left to dry and then it was immersed in the solution of organic modifier of the S group (S-2,S-3, Table 1) or the K group (K-4,K-9, Table 2) prepared in the 1 mmol/dm 3  concentration of methanol for 10 seconds. The plates were air-dried. Such prepared plates were put into the reaction chamber of the ALD (Picosun R-150) reactor. The synthesis of the protective layer was performed using titanium(IV) isopropylate and deionized water as precursors. The precursors were administered in impulses of 0.2 seconds, sparging the system with nitrogen after each impulse. The synthesis was finished after 300 such cycles. The synthesis was carried out in the temperature of 150° C. The ready materials were air-dried. 
       EXAMPLE 3 
     Preparation of a Coating Form of Visible-Light-Activated Photocatalyst on Glass Plate With the Protective Layer Deposited Using the “Spin-Coating” Technique 
       [0047]    The starting substrates for the synthesis of materials are:
       glass plates (basic microscope slides)   not-modified nanocrystalline titanium(IV) oxide (anatase structure), in the form of colloidal water solution of particles smaller than 100 nm and surface modifiers.       
 
         [0050]    The synthesis of coating on glass plates was carried out using the spin-coating technique from 5% w/w colloidal solution of titanium(IV) oxide. Application on a plate was performed at the plate rotation speed of 8000 cycles/min. The plate was rotated for 30 seconds and, meanwhile, three times 200 ml of the colloidal solution were put into the reactor. The plate was left to dry and then it was immersed in the solution of organic modifier of the S group (S-2,S-3, Table 1) or the K group (K-4,K-9, Table 2) or the solution of hexachloroplatinic acid prepared in the 1 mmol/dm3 concentration of methanol for approx. 10 seconds. After drying, another layer of TiO 2  was applied in an analogous manner, resulting in a modified TiO 2  layer with a protective coating. 
       EXAMPLE 4 
     Photostability Tests of Powder Form of Materials With Protective Layer 
       [0051]    Measurements of the photostability of powder materials modified by organic compounds from the K group (K-4, K-9, Table 2) with an additional protective layer deposited using the ALD technique were performed. An analogous test was performed for the same materials without the protective layer. 
         [0052]    20 mg of the tested material was added into 2 g of analytically pure BaSO 4 . The substances were thoroughly mixed and the resulting mixture was formed into a tablet. 
         [0053]    Such a prepared tablet was put into a special holder designed for the analysis of diffuse-reflectance spectra and then irradiated for 30 min, recording diffuse-reflectance spectra of the sample every 5 min. Irradiation system consisted of a xenon illuminator XBO-150, a water filter with solution of copper(II) sulfate (cutting off radiation from the near infrared, λ&gt;700 nm) and an upper flow filter tolerant for the irradiation in the range of λ&gt;435 nm. 
         [0054]    The sample was placed in the distance of 40 cm from the light source. 
         [0055]      FIG. 2  presents changes in absorbance at λ=400 nm (absorption band of TiO 2  surface complex with organic modifier) for samples of modified TiO 2  with the protective layer and an analogous sample without it. 
         [0056]    Samples protected with an additional TiO 2  coating are characterized by a better photostability (lower degradation of the sensibilizer) than the analogous samples without it. 
         [0057]    Results obtained are summarized in  FIG. 2 . 
       EXAMPLE 5 
     Photocatalytic Activity Tests of Powder Materials With Protective Coating 
     Variant 1. Photooxidation of Terephthalic Acid 
       [0058]    Measurements of the photocatalytic activity of powder materials modified by organic compounds from the K group (K-4, K-9, Table 2) with an additional protective layer deposited using the ALD technique were performed. An analogous test was performed for the same materials without the protective layer. 
         [0059]    Suspension of the material was prepared (1 g/dm 3 ) in water solution of terephthalic acid (C=3×10 −3  mol dm −3  TA, 0.02 mol dm −3  NaOH).The suspension was put into a cylindrical cuvette of 5 cm diameter, capacity of 18 ml and with 1 cm optical path length. Such a prepared suspension was irradiated for 30 min (irradiation conditions as in example 4) collecting 1.5 ml of the sample every 5 minutes. The samples were filtered using a CME syringe filter with pores of 0.22 m in diameter. Hydroxyterephthalic acid results in the reaction of terephthalic acid with photogenerated hydroxyl radicals. The hydroxyterephthalic exhibits good emission properties. 
         [0060]    The progress of reaction (increase in the product concentration) was monitored by recording the emission spectra of the collected solutions in the range of 320-600 nm (λ exc 315 nm). Results were summarized in  FIG. 3 . Materials with the protective layer consisting TiO 2  are characterized by a higher activity than materials without it. 
       Variant 2 
     Photodegradation of 4-Chlorophenol 
       [0061]    Measurements were taken to assess the photoactivity of powder material modified by an organic compound from the S group (S-3, Table 1) and containing an additional protective layer deposited by the ALD technique. 
         [0062]    An analogous test was performed for the same material without a protective layer. 
         [0063]    Suspension of the material (1 g/dm 3 ) in water solution of 4-chlorophenol (C=2.5×10 −4  mol/dm 3 ) was prepared. The suspension was put into a cylindrical cuvette, 5 cm in diameter, capacity of 18 ml and with 1 cm optical path length. 
         [0064]    Such a prepared suspension was irradiated for 30 minutes (irradiation conditions as in example 4), collecting 1.5 ml of the sample every 5 minutes. The samples were filtered using a CME syringe filter with pores of 0.22 m in diameter. The reaction progress was monitored with the use of a spectrophotometer by registering the disappearance of absorbance at a wavelength of λ=280 nm. 
         [0065]    Results are summarized in  FIG. 4 . Materials with the protective layer consisting TiO 2  are characterized by a higher activity than materials without it.