• 专利附录
  • 专利说明
  • 权利要求
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    • 专利摘要:
    The present invention relates to a process for the synthesis of titanium functionalized from a titanium precursor and to the use thereof in photocatalysis processes and for the degradation of organic compounds. (Machine-translation by Google Translate, not legally binding)
    公开号:ES2539624A1
    申请号:ES201300536
    申请日:2013-06-05
    公开日:2015-07-02
    发明作者:Javier GARCÍA MARTÍNEZ；Marisa RICO SANTACRUZ；Elena SERRANO TORREGROSA；Jesús Rubén BERENGUER MARÍN；Elena LALINDE PEÑA；Ángel Eduardo SEPÚLVEDA SAN PEDRO
    申请人:Universidad de Alicante；Universidad de La Rioja；
    IPC主号:
    专利说明:

    DESCRIPTION

    Procedure for the synthesis of functionalized titanias in situ and their use.

    Field of the invention 5

    The present invention is generally framed in the field of materials chemistry and refers in particular to Titania-based hybrid materials with different chemical functionalities incorporated in its structure.
     10
    State of the art

    Functionalized titanias constitute one of the most important hybrid materials within the fields of materials science and nanoscience and nanotechnology, since they have an impact on structural and functional applications. fifteen

    Said hybrid materials are formed by an inorganic network, in which different units (either organic, or inorganic) are incorporated. These inorganic networks can be, for example, siliceous based, which in the presence of surfactants gives rise to PMOs (periodic mesoporous organosilices). The incorporation into these 20 networks of different organic or inorganic functionalities can increase their applications in fields such as adsorption, catalysis, photonics and microelectronics.

    Alternatively to silica based networks, inorganic titanium networks can be used. Several studies have focused on making such incorporation by modifying the 25 precursors of titanium (Schubert U., J. Mater. Chem., 15, 2005, 3701), but they are far from achieving the good results obtained with PMO's. Therefore, another possibility is to directly incorporate organic compounds on the surface of previously synthesized titanias. It is possible to modify the commercial titania P25 Degussa by covalently bonding an organic compound on its surface to obtain materials 30 with an improved photocatalytic activity by 43%, compared to the P25 Degussa (Eibanowski M., Mkowska B., Journal of Photochemistry and PhotobiologT A: Chemistry, 99, 1996, 85). Through chemical adsorption, tilanias were modified superficially with saturated solutions of 5-sulfosalicylic acid, improving the efficiency in degradation reactions of p-nitrophenol (Li S., Zheng F., Liu X, Wu F., Oeng N. , Yang 35 J., Chemosphere, 61, 2005, 589).

    Given the application of titanias in energy conversion processes (solar cells), metal complexes, in particular ruthenium, have been incorporated by post-synthetic modification of TiO2 or direct incorporation of metallic ruthenium through isomorphic substitution.

    In all cases, the photocatalytic properties of hybrid materials are superior to those of unmodified titania. In view of the aforementioned, it is observed how the modification of titanias through the incorporation of chemical functionality presents improvements in the properties of these materials, especially as regards their photocatalytic activity.

    So far, as described in the literature, functionalized titanias have been synthesized by methods based on the incorporation of different functionalities 50 (organic or coordination compounds) superficially in titania,
    traditionally by post-synthetic methods. This has associated numerous disadvantages in the final materials, such as low dispersion and adsorption of functionality, partial blockage of the pores of the material and under control of the active phase, among others.

    There is therefore a need to provide a method of synthesis of titania-based hybrid materials with the functionality incorporated directly into the wall of the titania, thus avoiding all the inconveniences discussed above and maintaining the textural, structural and morphological properties of the titania without modify, but with improved photocatalytic properties.
     10
    The versatility of the methodology presented for the in situ synthesis of these titanias allows the incorporation of various functionalities directly in its structure, making it possible to obtain hybrid materials based on Titania that have more effective properties than those prepared by traditional methods.
     fifteen
    Description of the invention

    The present invention relates to functionalized or doped titanias and the method of obtaining them.
     twenty
    Thus, in a first aspect, the present invention relates to functionalized titanias comprising an inorganic titanium oxide network characterized in that the chemical functionality is incorporated in said inorganic network. In a more particular embodiment, the chemical functionality of titania is an organic compound, a ligand or a coordination compound. In another more particular embodiment, the functionality of the titania is an organic compound, more particularly, the organic compound is selected from oxalic acid, 4,6-dihydroxypyrimidine, hydroquinone, terephthalic acid or p-phenylenediamine. In another more particular embodiment, the functionality of the titania is a coordination compound, more particularly, the coordination compound is a ruthenium coordination compound. 30

    "Functionalized titanias" in the present invention designates titanias that incorporate functional groups on the surface (grafting) or in the structure of the titania (in situ). The latter materials include doped titanias with different functional compounds in their structure. In the present invention functionalized and doped titania will be used interchangeably.

    "Functional compound" in the present invention designates a compound comprising a functional group in its structure being responsible for the functionality incorporated in the titania, in the present invention functional compound and functionality will be used interchangeably.

    In another aspect, the present invention relates to a process for the in situ synthesis of functionalized titanias (hereinafter, the process of the present invention) comprising the following steps:

    a) Mix a titania precursor with a functional compound in a solvent or solvent mixture,

    b) add water to the mixture obtained in a) to obtain a gel, 50

    c) dry the gel obtained in step b) to obtain the functionalized titania.

    By "in situ synthesis" in the present invention we refer to the incorporation of functionality in the structure of the titania by ce-hydrolysis of the titanium precursor with the functional compound. 5

    By "synthesis by grafting" we mean the incorporation of the functional group on the surface of the titania by hydrolysis of it with the surface groups of a previously synthesized titania.
     10
    In a particular embodiment, in step a) a surfactant is added.

    In a particular embodiment, the titania precursor is a titanium alkoxide, more particularly, the titanium alkoxide is selected from titanium (IV) butoxide or titanium (IV) isopropoxide. However, any titanium alkoxide can serve as a precursor to titania.

    In a particular embodiment, the solvent of step a) is ethanol.

    In a more particular embodiment, the functional compound or functionality incorporated is an organic compound, a ligand or a coordination compound. In a more particular embodiment, the functional compound or functionality incorporated is an organic compound, more particularly, the organic compound is selected from oxalic acid, 4,6-dihydroxypyrimidine, hydroquinone, terephthalic acid or p-phenylenediamine. In another more particular embodiment, the functional compound or functionality incorporated 25 is a coordination compound, more particularly, the coordination compound is a ruthenium coordination compound.

    In another aspect, the present invention relates to a functionalized or doped titania (hereinafter titanias of the present invention) obtained by the process of the present invention.

    Another aspect of the present invention relates to the use of the titanias of the present invention in photocatalysis processes.
     35
    Another aspect of the present invention relates to the use of the titanias of the present invention for the degradation of organic components.

    Another aspect of the present invention relates to the use of the titanias of the present invention for the manufacture of photovoltaic cells. 40

    Brief description of the figures

    Figure 1 shows the diffraction patterns of mesoporous titanias synthesized in situ with different incorporated organic compounds (Table 1), compared with the TiO2 mesoporous titania.

    Figure 2 shows the diffraction patterns of mesoporous titanias with the organic compounds 2 (4,6-Dihydroxypyrimidine) and 5 (p-Phenylenediamine) incorporated and of the optimized materials (indicated by an asterisk) compared with the 50 mesoporous titania TiO2 .
    Figure 3 shows the infrared spectra of synthesized mesoporous titanias, compared to the TiO2 target (A) and the organic compounds 2 (4,6-Dihydroxypyrimidine) (B) and 5 (p-Phenylenediamine) (C). The characteristic bands are shown in parentheses.
     5
    Figure 4 shows the infrared spectra of the titanias synthesized with compounds 2 (4,6-Dihydroxypyrimidine) (A) and 5 (p-Phenylenediamine) (B), compared with their corresponding organic compounds and with TiO2. The characteristic bands of the incorporation of organic compounds are shown in parentheses.
     10
    Figure 5 shows the final appearance of mesoporous titanias: TiO2-2 * (A), TiO2-5 * (B) and TiO2 (C).

    Figure 6 shows the adsorption / desorption isotherms at 77 K (A) and their corresponding pore size distribution (8) of the materials prepared with different organic compounds (table 1), compared with the TiO2 mesoporous titania.

    Figure 7 shows the adsorption / desorption isotherms at 77 K (A) and their corresponding pore size distribution (8) of mesoporous titanias synthesized with organic compounds 2 (4,6-Dihydroxypyrimidine) and 5 (p-Phenylenediamine ), compared with 20 mesoporous titania (TiO2).

    Figure 8 shows the TEM images of TiO2 (A), TiO2-2 * (B) and TiO2-5 * (C), scale bar = 5 nm.
     25
    Figure 9 shows the absorbance spectrum for the degradation reaction of an aqueous 6G rhodamine solution (5 * 10-5M) in the presence of different samples of synthesized titania: A) TiO2 (white), B) TiO2-2 * and C) TiO2-5 *.

    Figure 10 shows the representation and calculation of the photocatalytic activity constant 30 (K) of different samples of synthesized titania.

    Figure 11 shows the structure of the ruthenium complex [cis-Ru (NCS) 2L2] (L = 2,2'-bipyridyl-4,4'-dicarboxylate), commonly known as N3.
     35
    Figure 12 shows the X-ray diffraction patterns of the different titanias synthesized with the ruthenium complex incorporated into its structure during in situ synthesis thereof (TiO2_IS) and incorporated by grafting after synthesis (TiO2_G), in comparison with the titania not functionalized (TiO2).
     40
    Figure 13 shows infrared spectra of the different titanias synthesized with the ruthenium complex incorporated into its structure during its synthesis (TiO2_IS, curve c) and incorporated by grafting after synthesis (TiO2_G, curve d), compared to the non-functionalized titania (TiO2, curve b) and the ruthenium complex (curve a). Four. Five

    Figure 14 shows the adsorption / desorption isotherms at 77 K (A) and their corresponding pore size distribution (8) of the different synthesized titanias with a ruthenium complex incorporated into its structure during the in situ synthesis of the same (TiO2_IS) and incorporated by grafting after synthesis (TiO2_G), in comparison with the non-functionalized titania (TiO2).
    Figure 15 shows the TEM images of TiO2 (A), TiO2_IS (B) and TiO2_G (C), scale bar = 5 nm.

    Figure 16 shows the absorbance spectrum for the degradation reaction of an aqueous solution of rhodamine 6G (5 * 10-5 M) in the presence of the materials: a) TiO2, b) 5 TiO2_IS and e) TiO2_G.

    Figure 17 shows the representation and calculation of the photocatalytic activity constant (K) of the TiO2, TiO2_IS and TiO2_G materials.
     10
    Detailed description of the invention

    The present invention relates to obtaining new titanias formed by an inorganic network of titanium oxide (TiO2), in which different chemical functionalities, in particular organic compounds and / or metal compounds, have been incorporated during synthesis via in situ of said network, for applications in very diverse fields such as photocatalysis and degradation of organic pollutants.

    This strategy allows obtaining titania-based hybrid materials by incorporating these functionalities into the network structure itself, thereby preventing blockage in the typical mesoporosity of this type of materials, which are usually prepared by superficial incorporation into the titania by post-synthetic techniques. Therefore, the new titanias of the present invention overcome the disadvantages of traditional titanias, such as low dispersion and adsorption of functionality, partial blockage of the pores of the material and low control of the active phase, among others, and keeping the textural, structural and morphological properties of the titania unmodified, but with better properties, for example, photocatalytic.

    In addition, since the functionality is incorporated within the structure of the titania, 30 remains protected by it, increasing thermal and hydrothermal stability.

    In particular, for the present invention, work will be carried out at room temperature to achieve and maintain the anatase type structure of the titania. This type of structure is much more active than that of rutile and brookite, all possible modifications of the titania. Thanks to the ambient temperature condition it is possible to inhibit the passage of anatase to rutile, which helps to improve the photocatalytic properties.

    In particular, in order to obtain the titania of the present invention it is preferred not to use surfactants as structure directing agents, nor to perform calcination of any kind. In this way, savings in materials and reagents are achieved, thus achieving a versatile and simple synthesis procedure.

    The synthesis of functionalized titanias in situ is carried out by the sol-gel method from a titanium precursor, titanium butoxide (IV) ([Ti (OnBu) 4], TBOT 98% 45 Aldrich), absolute ethanol and water as a solvent, as well as the functionality to be incorporated (organic compound or metal complex). To this end, the synthesis proposed by Y. Wang et al. [Wang Y., Jiang Z., Yang F., Material Science and Engineering B, 128, 2006, 229] was adapted. Among the chemical functionalities to incorporate we have several possibilities: 50

    a) Organic compounds

    The incorporation of the organic compounds, described in Table 1, which shows the name of the organic compounds used in the synthesis of the new functionalized titanias and the nomenclature used of the final materials was carried out. Of all the synthesized hybrid materials, the data related to titanias with organic compounds 2 and 5 incorporated in its structure are presented in more detail, by way of example and including results of photocatalytic activity.

    Table 1. Organic compounds used in the synthesis of new functional 10 raised titanias and nomenclature used in the final materials.



    b) Metal complexes 15

    The metal complex that was incorporated into the titanias was [cis-Ru (NCS) 2L2] (L = 2,2'-bipyridyl-4,4'-dicarboxylate), commonly known as N3 (Figure 11). This complex allowed the design of an alternative solar cell to the Gratzël cells, where the functionalization of the titania is carried out superficially, unlike those presented here, where the functionalization is carried out directly in the structure of the material during the synthesis of it.

    Example 1: Titanias with organic compounds incorporated in its structure
     25
    The synthesis of titanias with incorporated organic compounds was carried out by dissolving the corresponding organic compound (Table 1) in 5 g (14.7 mmol) of the titanium precursor for two hours at 40 ° C under magnetic stirring. Subsequently, 36 ml of absolute ethanol are added. Then, 123.5 g (6.86 mol) of water was added dropwise, immediately causing precipitation of the solid. The synthesis gel, with a molar ratio of 1TBOT: 0.1Org: 41.3 EtOH: 467H2O, where Org refers to the organic compound, was allowed to react at room temperature for 24 hours under magnetic stirring, followed by an oven treatment (or under magnetic stirring) at 80 ° C
    for 24 hours The solid obtained was filtered, washed with water and acetone, successively, and allowed to dry in an oven at 100 ° C for 8 hours. Optimized materials (marked with an asterisk) were obtained by mixing 5 g (14.7 mmol) of the titanium precursor with a solution of the corresponding organic compound (Table 2) in 36 ml of absolute ethanol for two hours at 40 ° C under previous magnetic stirring. 5 water addition.

    By X-ray diffraction (Figures 1 and 2) it was confirmed that the synthesized materials have anatase structure. The incorporation of the organic compounds in the titanias was corroborated by infrared spectroscopy (Figures 3 and 4), elementary analysis 10 (Table 2). Likewise, the final appearance of the materials clearly denotes the incorporation of said compounds since the titanias synthesized with organic compounds incorporated in their structure are colored while the titania without functional raising is a white powder (Figure 5).
     fifteen
    In addition, the size of the crystalline domain was calculated by X-ray diffraction and its decrease was observed by incorporating organic compounds. By means of nitrogen adsorption isotherms (Figures 6 and 7 and Tables 2 and 3) the textural parameters of the materials were obtained, observing that no mesoporosity blockage occurs due to the incorporation of the organic compounds. twenty

    Table 2. Textural and structural parameters of the different synthesized mesoporous titanias, compared with mesoporous titania (TiO2) and incorporation performance of organic compounds 1 to 5 in mesoporous titanias with incorporated organic compounds. 25


    a Average pore diameter estimated from nitrogen isotherms using the BJH method.

    b Mesopore volume from the isotherms measured at a relative pressure of 0.95. 30

    c BET area estimated from the multipoint BET method, using adsorption data in the relative pressure range (P / P0) 0.05-0.30.

    d Particle domain size calculated from X-ray diffraction, using the Scherrer equation.

    e Mass percentage of nitrogen, carbon and hydrogen, determined by elementary analysis.

    f Incorporation performance of organic compounds calculated from carbon 40 results obtained by elemental analysis.
    Table 3. Textural and structural parameters of the mesoporous titanias prepared with different amounts of the organic compounds 2 (4,6-Dihydroxypyrimidine) and 5 (p-Phenylenediamine), compared with the mesoporous TiO2 titania and their incorporation performance.
     5


    a Organic content (% mass) determined by elementary analysis (from% C) and thermogravimetric analysis (TGA).
     10
    b Incorporation performance calculated from elementary analysis data. The values in brackets indicate the incorporation performance calculated from the thermogravimetric analysis (TGA) data.

    c Average pore diameter (dp) estimated from nitrogen isotherms using the BJH method. fifteen

    d Mesopore volume from the isotherms measured at a relative pressure of 0.95.

    e BET area estimated from the BET multipoint method, using adsorption data in the relative pressure range (P / P0) 0.05-0.30. twenty

    f Particle domain size calculated from X-ray diffraction, using the Scherrer equation.

    g Particle size calculated by TEM. 25

    h Distance between the crystalline planes of the titania, calculated using the Bragg equation.

    i Distance between the crystalline planes of the titania calculated by TEM.
     30
    Additionally, the images obtained by electron transmission microscopy are presented (Figure 8), which showed that the materials with the incorporated organic compounds have the same morphology as the titanias used as targets. The photocatalytic activity of these materials was evaluated from the degradation reaction of rhodamine 6G by visible ultraviolet spectroscopy (Figures 9 and 10 and Table 4). In a typical test, in a 250 ml beaker, the photocatalyst (0.4 g / l) is suspended in 200 ml of an aqueous rhodamine suspension (5 · 10-5 M) and stirred for 30 m in protected from light. After that time the vessel is placed inside a black box for the protection of ambient light and a double-jacketed reactor equipped with a high pressure mercury lamp (125 W) is introduced, which is the light source UV-Vis, and a cooling circuit. The degradation reaction is followed by performing UV-Vis spectra at intervals of 2 min. The equipment used is equipped with a fiber optic sensor that, introduced into the beaker, allows the monitoring of the reaction
    on-site. The spectra are made in a wavelength range of 300 to 700 nm, with a resolution of 0.5 nm. In view of the results, an increase in the photocatalytic activity of titanias synthesized in situ with organic compounds incorporated against the titanias used as a target is observed. This improvement in the photocatalytic properties, more noticeable in the case of the organic compound 5, can be associated with the decrease of the 0.4 eV bandgap with respect to the titania used as a target, consequence of the increase of the maximum valence band after the incorporation of the organic compounds, as determined by XPS.

    Table 4. Values of the photocatalytic activity constant, regression coefficients and 10 conversions for 1, 2 and 3 hours of different titania samples.



    a Kinetic constant (mean and standard deviation of at least 3 tests) of the 1st order of degradation of an aqueous solution of rhodamine 6G (5 * 10-5 M). The values in parentheses represent the constant used to calculate the conversions and the

    b regression coefficient corresponding to said test.
     twenty
    c Degree of conversion (in%) achieved by the samples after 1, 2 and 3 hours of reaction.

    d Relationship between the average of the kinetic constants obtained for each sample with respect to the non-functionalized titania (TiO2 sample).
     25
    e Bandgap energy estimated from the XPS analysis.

    Example 2: Titanias with metal complexes incorporated in its structure

    The synthesis of titanias works with the ruthenium compound (Figure 11) 30 incorporated into its structure was performed by initially dissolving the compound in 35.37 ml of absolute ethanol for one hour under magnetic stirring. Next, 5 g (14.7 mmol) of the titanium precursor was added and allowed to stir overnight. Then 123.5 g (6.86 mol) of water was added dropwise, causing the immediate precipitation of the solid. The synthesis gel, with a molar ratio of 1TBOT: 0.0038CM: 41.3 EtOH: 467H2O, where CM refers to the metal complex, was allowed to react at room temperature for 24 hours under magnetic stirring, followed by an oven treatment (or by magnetic stirring) at 80 ° C for 24 hours. The solid obtained was filtered, washed with water and acetone, successively, and allowed to dry in an oven at 1 ° C for 8 hours. 40

    The anatase structure was confirmed by X-ray diffraction (Figure 12) and the incorporation of the metal complex by infrared spectroscopy (Figure 13). Additionally, the crystalline domain was calculated by X-ray diffraction and it was observed how the incorporation of the complex affects its size. The textural parameters of the nitrogen adsorption (Figure 14 and Table 5) were obtained.
    the materials and it was observed that there was no mesoporosity blockage due to the incorporation of the metal complex.

    Additionally, by means of ICP, the amount of complex that has been incorporated into the synthesized materials can be known, observing a yield of incorporation 5 of 92.5% in the case of titania with the incorporated ruthenium compound at the same time as the synthesis of the material (on-site) and 60% for the titania synthesized via grafting. The high performance of incorporation into the material synthesized via in-situ demonstrates the effectiveness of the method of synthesis of these new titanias (Table 5).
     10
    Table 5. Textural and structural parameters of the different titanias synthesized with a ruthenium complex incorporated into its structure during its synthesis (TiO2_IS) and incorporated by grafting after synthesis (TiO2_G), compared to the titanium without functionalizing (TiO2 ).
     fifteen


    a Average pore diameter estimated from nitrogen isotherms using the BJH method.

    b Mesopore volume from the isotherms measured at a relative pressure of 0.95. twenty

    c BET area estimated from the multipoint BET method, using adsorption data in the relative pressure range (P / P0) 0.05-0.30.

    d Calculated from ICP-OES analysis. The values in parentheses represent the theoretical values. 25

    e Particle domain size calculated from X-ray diffraction, using the Scherrer equation.

    f Particle size calculated by TEM. 30

    g Distance between the crystalline planes of the titania, calculated using the Bragg equation.

    h Distance between the crystalline planes of the titania, calculated by TEM.
     35
    The images obtained by electron transmission microscopy (Figure 15) corroborate, as in the previous cases, that the materials with the incorporated metal complex have the same morphology as the mesoporous titanias used as targets. The photocatalytic activity of these materials is evaluated from the degradation reaction of rhodamine 6G by visible ultraviolet spectroscopy 40, with a procedure similar to that described in example 1 (Figures 16 and 17). As with titanias with organic compounds, by incorporating metal complexes, in particular N3, significant improvements in the photocatalytic properties of these materials are observed. The material synthesized via in-situ has a photocatalytic activity three times higher than that of the titania used as white and twice higher than the titania synthesized by grafting (Table 6), both of which are superior to the titania used as white.

    Table 6. Values of the photocatalytic activity constant, regression coefficients and conversions for different times of the different synthesized titanias with a ruthenium complex incorporated into its structure during its synthesis (TiO2_IS) and incorporated by grafting after synthesis ( TiO2_G), in comparison with the non-functionalized titania (TiO2). 5



    a Kinetic constant (mean and standard deviation of at least 3 tests) of the 1st order degradation reaction of an aqueous 6G rhodamine solution (5 * 10-5 M). The values in brackets represent the constant used for the calculation of conversions and the

    b regression coefficient corresponding to said test.

    c Degree of conversion (in%) achieved by the samples after 1, 2 and 3 hours of reaction. fifteen

    d Relationship between the average of the kinetic constants obtained for each sample with respect to the non-functionalized titania (TiO2 sample).

    twenty
    权利要求:
    Claims (16)
    [1]

    1. Functionalized titania comprising an inorganic titanium oxide network characterized in that the chemical functionality is incorporated in the inorganic network.
     5
    [2]
    2. Functionalized titania according to claim 1 characterized in that the chemical functionality is an organic compound, a ligand or a coordination compound.

    [3]
    3. Functionalized titania according to claim 2, characterized in that the organic compound is selected from oxalic acid, 4,6-dihydroxypyrimidine, hydroquinone, terephthalic acid or p-phenylenediamine.

    [4]
    4. Functionalized titania according to claim 2, characterized in that the coordination compound is a ruthenium coordination compound.
     fifteen
    [5]
    5. Procedure for the synthesis of functionalized titanias comprising the following stages:
    a) Mix a titania precursor with a functional compound in a solvent or solvent mixture,
    b) add water to the mixture obtained in a) to obtain a gel,
    c) dry the gel obtained in step b) to obtain the functional titania hoisted.
     25
    [6]
    6. Method according to claim 5, characterized in that in step a) a surfactant is added.

    [7]
    7. Method according to any of claims 5-6, characterized in that the titania precursor is a titanium alkoxide. 30

    [8]
    Method according to claim 7, characterized in that the titanium alkoxide is selected from among titanium (IV) butoxide or titanium (IV) isopropoxide.

    [9]
    9. Process according to any of claims 5-8, characterized in that the solvent is ethanol.

    [10]
    10. Method according to any of claims 5-9, characterized in that the functional compound is an organic compound, a ligand or a coordination compound. 40

    [11]
    11. Method according to claim 10 characterized in that the organic compound is selected from oxalic acid, 4,6-dihydroxypyrimidine, hydroquinone, terephthalic acid or p-phenylenediamine.
     Four. Five
    [12]
    12. Method according to claim 10 characterized in that the coordination compound is a ruthenium coordination compound.

    [13]
    13. Functionalized or doped titania obtained by the process according to any of claims 1-12. fifty

    [14]
    14. Use of titania according to claim 13 in photocatalysis processes.

    [15]
    15. Use of the titania according to claim 13 for the degradation of organic components.
     5
    [16]
    16. Use of the titania according to claim 13, for the manufacture of photovoltaic cells.
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    同族专利:
    公开号 | 公开日
    WO2014195547A1|2014-12-11|
    ES2539624B2|2016-01-04|
    引用文献:
    公开号 | 申请日 | 公开日 | 申请人 | 专利标题
    US5451252A|1992-07-11|1995-09-19|Kronos Inc.|Subpigmentary titanium dioxide with improved photostability|
    CN111036295B|2019-12-30|2021-10-08|湖南大学|Photocatalyst and preparation method and application thereof|
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    申请号 | 申请日 | 专利标题
    ES201300536A|ES2539624B2|2013-06-05|2013-06-05|Procedure for the synthesis of functionalized titanias in situ and their use|ES201300536A| ES2539624B2|2013-06-05|2013-06-05|Procedure for the synthesis of functionalized titanias in situ and their use|
    PCT/ES2014/070449| WO2014195547A1|2013-06-05|2014-06-02|Method for the in situ synthesis of functionalized titanias, and use thereof|
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