Method for forming an oxide coated substrate

0001(Cross-reference of related applications) This application claims the benefit of U.S. Patent Provisional Application No. 61 / 749,815 filed on January 7, 2013, which is hereby incorporated by reference in its entirety. ..

0002Photocatalytic materials are useful for fluid purification. However, the use of nanophotocatalytic powder raises issues such as the need to separate the powder from the fluid being treated. Some solutions to this problem include supporting the photocatalytic material on a carrier and thus facilitating the separation of the photocatalytic material from the fluid to be treated. This support may require methods such as dip coating, slip casting and the like. Another method is the synthesis of magnetically separable photocatalysts. This synthesis may require the preparation of a core-shell magnetic photocatalytic composite and the separation of the composite after the ferrofluid is required for water purification. Both methods require the synthesis of the photocatalyst in the first step, followed by application to the required substrate. In addition, such methods may require expensive equipment and chemicals.

0003Several methods have been proposed for the production of photocatalytically active coatings. In general, these methods first form a powder and then bond the powder to the desired surface. These methods may have the problem of inadequate adhesion of the powder to the desired substrate. In general, methods and equipment for coating a substrate with a photocatalytic material include flow-based manipulation, batch processing, polymerization and the like.

<p num="0004"> The present disclosure relates to a method for adhering an inorganic material to a substrate. Some embodiments include a method of forming an oxide-coated substrate. The method comprises heating a reaction mixture containing a material capable of forming an oxide material, such as a pre-coating mixture. Any oxide material, such as an oxide coating for a substrate, or a powder oxide material can be formed. This oxide formation reaction mixture, such as a precoating mixture, contains a solubilized reducing additive and a solubilized oxidation additive. Additional additives may be present in the oxide formation reaction mixture. An oxide-forming reaction mixture such as a pre-coating mixture can be heated in the presence of a substrate to synthesize an oxide coating on the substrate. Typically, the oxide formation reaction mixture is heated at a temperature high enough to allow the additive to undergo an exothermic reaction and at a temperature low enough to control the phase and composition of the oxide.</p>

<p num="0005"> Some embodiments include a method of forming an oxide-coated substrate, which method comprises heating the pre-coating mixture in the presence of the substrate to synthesize an oxide coating on the substrate. The pre-coating mixture comprises a solubilized reduction additive, a solubilized oxidation additive and the substrate; and an exothermic reaction of the solubilized reduction additive and the solubilized oxidation additive. Heating is carried out at a temperature high enough to allow the oxide to be controlled and low enough to control the phase and composition of the oxide.</p><p num="0006"> In some embodiments, it is possible to attach the photocatalytic material to a substrate, thereby facilitating the separation of the photocatalytic material from the fluid to which the photocatalytic material is exposed.</p><p num="0007"> Some embodiments can allow the photocatalytic material to be supported on a three-dimensional substrate.</p><p num="0008"> Some embodiments can allow the attachment of doped or undoped temperature sensitive metal oxides, thereby substantially reducing the production of unwanted by-products of the substrate material. Adhesion is possible while preserving the material properties and / or the doping properties of the material. In some embodiments, the oxide material is a non-metallic oxide such as silicon dioxide or Bi.₂O₃Is. In some embodiments, the oxide material is a metal oxide, eg, TiO.₂Is. In some embodiments, the oxide is non-stoichiometric.</p><p num="0009"> One embodiment includes an in situ attachment method of the catalyst material on a substrate.</p><p num="0010"> One embodiment comprises a method of forming an oxide-coated substrate, the method of contacting a solubilized reducing additive with a solubilized oxidation additive and the surface of the substrate; said additives and groups. It is possible to control the phase and composition of the metal oxide at a temperature sufficiently high enough to allow the additive to undergo an exothermic reaction, including the step of heating the material to synthesize an oxide coating on the substrate. The heating is performed at a temperature as low as possible.</p><p num="0011"> Some embodiments include oxide-attached substrates produced by any of the methods described herein.</p><p num="0012"> Some embodiments include a method of forming a photocatalyst powder, which method comprises heating a mixture containing a solubilized reduction additive and a solubilized oxidation additive to form an oxide. The heating here is sufficiently high enough to allow the solubilized reduction additive and the solubilized oxidation additive to undergo an exothermic reaction, and the phase and composition of the oxide can be controlled. Do it at a low temperature.</p><p num="0013"> These and other embodiments will be described in more detail below.</p>

0014<figref num="1">FIG. 1 is a schematic flowchart of an embodiment of the method described herein.</figref>

0015<figref num="2">FIG. 2 is a schematic diagram of the experiments described herein.</figref>

0016<figref num="3">FIG. 3 shows the dye decomposition by the embodiment of the adherent base material described in the present specification over time as compared with the dye decomposition by the base material alone.</figref>

0017<figref num="4">FIG. 4 shows an X-ray diffraction pattern of the substrate sample alone compared with the embodiment of the substrate-attached sample described.</figref>

0018<figref num="5">FIG. 5 shows a diffuse reflection spectrogram comparing embodiments of oxide-attached substrates with carrier-only, commercially available powders and metal oxide powders.</figref>

0019<figref num="6">FIG. 6 shows an embodiment of an oxide-attached substrate and a dispersed X-ray spectroscopic analysis of the substrate alone.</figref>

0020Typically, the method comprises heating the oxide-forming reaction mixture to synthesize an oxide, such as an oxide coating, on a substrate. The components of the oxide formation reaction mixture, such as the precoat mixture, are heated at any suitable temperature that can result in oxide formation, eg, any suitable temperature that can result in a coating of oxide on the substrate. can do. For example, in some embodiments, the oxide-forming reaction mixture or pre-coating mixture is applied at about 100 ° C to about 1500 ° C, about 100 ° C to about 800 ° C, about 200 ° C to about 400 ° C, At least about 100 ° C, at least about 200 ° C, at least about 300 ° C, about 800 ° C or less, about 600 ° C or less, about 500 ° C or less, about 450 ° C or less, about 400 ° C or less, or about It could be heated at temperatures below 375 ° C, or at any temperature within the range limited by any of these values, or between any of these values.

0021The heat released during an exothermic reaction can allow it to continue to self-propagate once the reaction has begun. For example, the reaction can be initiated by applying heat at a temperature higher than at least one flash point of the additive, and in some cases, the heat from the reaction causes the temperature of the reaction mixture to rise above the flash point. Can continue to be. Therefore, as long as the temperature of the oxide-forming reaction mixture, such as the pre-coating mixture, remains above the flash point due to the heat from the reaction, the reaction can continue without external heating. Thus, the exothermic reaction may continue until substantial completion. Such a reaction can be described as a self-propagating low temperature synthesis process. Self-propagating cold synthesis may be advantageous over flame synthesis in that it can occur in the liquid phase but not in the gas phase. In addition, since self-propagation synthesis can occur at low temperatures, it may be easier to maintain the desired phase and / or nominally desired element of the metal oxide. For example, the anatase phase is photocatalytically active, and in this respect the rutile phase is much less pronounced, so anatase TiO₂Is preferable to the rutile phase. Applying temperatures above 700 ° C increases the amount of rutile phase present in the composite. In some embodiments, the reaction occurs substantially entirely in the liquid phase.

0022The heating can be carried out for any suitable time that may allow the formation of oxides such as oxide coatings on the surface of the substrate. In some embodiments, the oxide-forming reaction mixture, such as a pre-coating mixture, is applied for about 1 to about 400 minutes, about 1 to about 40 minutes, about 20 minutes, or within a range limited by any of these values. , Or any amount of time between any of these values.

0023In some embodiments, the oxide-forming reaction mixture, such as a pre-coating mixture, is placed at about 100 ° C to about 1500 ° C, about 100 ° C to about 800 ° C, about 200 ° C to about 400 ° C, about 800 ° C. Less than ° C, less than about 600 ° C, less than about 500 ° C, less than about 450 ° C, less than about 400 ° C, or less than about 375 ° C, about 1 minute to about 400 minutes, about 1 minute to about 40 Can be heated for minutes, or about 20 minutes. In some embodiments, the substrate release reaction can be carried out under the same heating conditions to produce a photocatalytic powder.

0024It may be useful to heat at the smoked temperature. The smoky temperature may be high enough to cause the additive to undergo an exothermic reaction and low enough to substantially control the phase and composition of the metal oxide. The smoky temperature can ignite the material to be burned, which, once ignited, continues to self-propagate. Smoked temperature is from 100 ° C to about 800 ° C, from about 200 ° C to about 400 ° C, less than about 800 ° C, less than about 600 ° C, less than about 500 ° C, less than about 450 ° C, about 400 It can be less than ° C, or less than about 375 ° C. Smoking temperature can be affected by factors such as the flash point of the additive material and / or the decomposition temperature of the additive. In some embodiments, the smoky temperature and the resulting reaction temperature are not high enough to change the phase of the resulting material.

0025In some embodiments, the oxidative and / or reducing additives need not be solubilized.

0026In some embodiments, the mixture containing the solubilized oxidation additive and the solubilized reducing additive can be heated prior to the addition of the substrate. In some embodiments, this preheating can be performed at about 90 ° C to about 250 ° C, about 120 ° C to about 180 ° C, or about 150 ° C. In some embodiments, this preheating can be performed for about 5 to about 40 minutes, or about 20 minutes. In some embodiments, this preheating can be done with agitation.

0027Optionally, some methods can include annealing of oxide-attached substrates. In some embodiments, the oxide-attached substrate is annealed between about 300 ° C and about 450 ° C, or between about 350 ° C and about 450 ° C, or about 400 ° C. In some embodiments, the annealing is applied for a period between 10 seconds and 1 hour, or 5 minutes to about 45 minutes, or about 10 minutes to about 30 minutes, and / or about 30 minutes.

0028In some embodiments, a sufficient batch amount of additive and substrate for which coating is desired is placed in the reaction vessel. In some embodiments, the additive reacts in situ and adheres directly to the substrate surface.

0029In another embodiment, the method may be performed under standard atmospheric conditions.

0030The reducing additive comprises any additive capable of reducing the oxidizing additive, such as a compound or salt, and is also within the meaning of the term "reducing additive" commonly understood by those skilled in the art. Contains any additives that go into. The reduction additive may or may not be solubilized in the oxide formation reaction mixture or may not be solubilized in the oxide formation reaction mixture. In some embodiments, the reducing additive may include metal and / or non-metal precursors.

0031The reduction additive may contain an organic component. The organic component can be part or all of the reducing additive. Examples of suitable organic components include amino acids such as alanine, glycine, leucine and / or valine; hydrazines such as hydrazine, carbohydrazide, diformylhydrazine, tetraformyltrisazine and / or hexamethlylenetetramine. be able to. In some embodiments, the organic component is glycine.

0032The reduction additive may include a metal, eg, a metal salt (including a metal salt of an organic acid) or an organometallic compound. In some embodiments, the reducing additive may include the following metals or non-metals: titanium, tungsten, cerium, tin, zinc, zirconium, bismuth, copper, indium, iron, silver, strontium, lithium, calcium. , Carbon, nitrogen and / or combinations thereof. In some embodiments, the reducing metal precursor comprises an organic titanate.

0033The reduction additive may include a metal precursor. Precursors include any material that gives the oxide product an elemental or chemical characteristic. For example, metal precursors donate metals to oxide products. A reducing additive containing a metal precursor may also be referred to as a reducing metal precursor. The reducing metal precursor may be an organometallic compound or a metal salt of an organic acid. In some embodiments, the reducing metal precursor may comprise a metal octanate.<chemistry num="1"><img id="000002" he="50" wi="170" file="JP2016507366A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>

0034M in this equation can be Sn, Ni, Sr, Ba, Fe, Bi, V, Mo, W, Zn, Cu and / or a combination thereof. In another embodiment, the metal octanate may be tin (II) octanate.<chemistry num="2"><img id="000003" he="50" wi="170" file="JP2016507366A_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>Tin octanate (II)

0035In another embodiment, the reducing metal precursor comprises an organic titanate. In another embodiment, the organic titanate is titanium (IV) bisammonium lactate dihydroxyde, oxo-oxalattitanium (IV) ammonium, hydroxycarboxylate-peroxotitanium, hydrocarboxylate-peroxotitanium, titanium lactate. , Titanium maleate and / or titanium citrate. In another embodiment, the organic titanate is titanium (IV) bisammonium lactate dihydroxyde, oxo-oxalatitanium (IV) ammonium, hydroxycarboxylate-peroxotitanium, hydrocarboxylate-peroxotitanium, titanium lactate , Titanium maleate and / or titanium citrate can be selected. In some embodiments, the organic titanate is titanium lactate.

0036In some embodiments, the metal-containing precursor comprises titanium (IV) bis (ammonium lactoto) dihydroxydo.

0037Oxidizing additives include any additive capable of oxidizing the reducing additive, such as a compound or salt, and also within the meaning of the term "oxidizing additive" commonly understood by those of ordinary skill in the art. Contains any additives that go into. In some embodiments, the solubilized oxidative additive can be an independent compound and a separate compound from the solubilized reducing additive. In another embodiment, the oxidation additive and the reduction additive do not share a common chemical element. In another embodiment, the oxidation additive and the reducing additive share a common chemical element. In another embodiment, the independent oxidative additive can include a metallic or non-metallic oxidative precursor. In another embodiment, the independent oxidative additive can include a dopant. In another embodiment, the oxidizing precursor is optionally ammonium perchlorate (NH).₄ClO₄), Ammonium nitrate (NH₄NO₃), Ammonium chlorate (NH₄ClO₃), Hydrogen peroxide (H₂O₂) And / or any one or more of organic peroxides. In some embodiments, the organic peroxide can be a ketone peroxide, diacyl peroxide, dialkyl peroxide, peroxyester, peroxyketal, hydroperoxide, peroxydicarbonate, peroxymonocarbonate and / or a combination thereof. .. In one embodiment, the oxidizing precursor is ammonium nitrate.

0038In another embodiment, the oxidative additive may comprise an oxidative compound, in which case the reduction additive comprises a compound having a calculated valence that is at least 4 valence units different from the compound of the oxidative additive. To do. This valence should be calculated as described in Combustion Synthesis, Patil, Kashinath C; Aruna, Singanahally T, and Sambandan, Ekambaram, Current Opinion in Solid State &amp; Materials Science, 2: 158-165 (1997). Can be done.

0039In some embodiments, a single substance or compound, such as a salt formed from an oxidizing agent and a reducing agent, can be both a reducing additive and an oxidizing additive. Thus, both oxidation and reduction may occur in the substance or compound, or the substance or compound acts as either a reduction additive or an oxidation additive in the oxide formation reaction mixture. There will also be. Ammonium perchlorate (NH) is an example of a salt formed from an oxidizing agent and a reducing agent.₄ClO₄), Ammonium nitrate, ammonium chlorate, ammonium peroxide. In some embodiments, another oxidizing precursor is selected from hydrogen peroxide. In some embodiments, another oxidative precursor is selected from organic peroxides.

0040In some embodiments, the oxide attached to the substrate may be a catalyst. In some embodiments, the oxide may be a metal oxide, such as a semiconductor or photocatalyst. In some embodiments, the metal oxide may be doped or undoped. In some embodiments, the metal oxide is titanium oxide, tungsten oxide, cerium oxide, tin oxide, zinc oxide, zirconium oxide, bismuth oxide, copper oxide, indium oxide, iron oxide, silver oxide, strontium oxide, oxidation. It may be lithium, calcium oxide or a combination thereof. In some embodiments, the metal oxide is TiO₂, WO₃, CeO₂, SnO₂, ZnO, SrTiO₃, BaTiO₃, Fe₂O₃, LiVWO₆, AgVWO₆, In₂O₃, CaCuTi₃O₁₂, ZnFe₂O₄, ZrTiO₄, ZrTi_0.75Fe₀.₂₅O₄, ZrTi_0.90Sn_0.10O₄, AgCa₂Zn₂V₃O₁₂, Zr_0.95Pr_0.05TiO₄, Bi₂O₃, Cu₂O, CuO, BiVO₄, Or a combination thereof.

0041In some embodiments, the titanium in the metal oxide is an alternative to tungsten, cerium, tin, zinc, zirconium, bismuth, copper, indium, iron, silver, strontium, lithium, calcium, carbon and / or Consists of nitrogen. In some embodiments, the metal dopant independently comprises tungsten, cerium, tin, zinc, zirconium, bismuth, copper, indium, iron, silver, strontium, lithium, calcium, carbon and / or nitrogen. Can be done.

0042In some embodiments, the oxide is a mixed metal oxide. In some embodiments, the oxide is a non-metal oxide. In some embodiments, the oxide is a mixed metal / non-metal oxide. In some embodiments, the metal oxide is optionally titanium oxide, tungsten oxide, cerium oxide, tin oxide, zinc oxide, zirconium oxide, bismuth oxide, copper oxide, indium oxide, iron oxide, silver oxide, oxidation. It can be strontium, lithium oxide, calcium oxide and / or a combination thereof. In some embodiments, the non-metal oxide can optionally be silicon oxide.

0043The metal oxide attached to the base material is Ti (C, N, O).₂May include. In some embodiments, the doped metal oxide attached to the substrate is TiSn (C, N, O).₂May include. In other embodiments, the doped metal oxide attached to the substrate is TiM (C, N, O).₂May include, where M can be tungsten, cerium, tin, zinc, zirconium, bismuth, copper, indium, iron, silver, strontium, lithium, calcium, carbon or nitrogen, or a combination thereof. .. In other embodiments, the doped metal oxide attached to the substrate is M.¹M²(C, N, O)₂May include, M here¹And M²Can be independently tungsten, cerium, tin, zinc, zirconium, bismuth, copper, indium, iron, silver, strontium, lithium, calcium, carbon or nitrogen.

0044Metal oxide is TiO₂In some embodiments, TiO₂The phase is substantially anatase. In some embodiments, the amount of anatase phase relative to the rutile phase is greater than at least 10% anatase, 20% anatase, 50% anatase, 80% anatase, 90% anatase, 95% anatase and / or 99% anatase. Metal oxide is TiSn (CNO)₂In some embodiments, the dopant concentration, eg Sn, C and / or N, is substantially as nominally desired, eg Ti._0.85Sn_0.15(O_1.90C_0.05N_0.05) Remains.

0045The metal oxides are the United States patent provisional application No. 61 / 587,889 filed January 18, 2012, and the United States filed January 14, 2013 and published August 1, 2013. It may be as described in Patent Application Publication No. 2013/0192976, the patent document of which is incorporated by reference with respect to those descriptions of suitable metal oxide materials.

0046For some oxides, such as catalysts, dopants may also improve the properties of the coating, such as catalytic properties. The dopant precursor can be added to the solution containing the oxidation additive and the reduction additive. The resulting oxide coating when the oxide formation reaction mixture is heated can contain dopant atoms from the dopant precursor.

0047The dopant can be any atom or combination of atoms that replaces the atom of the oxide and improves some related properties of the oxide. Examples of useful dopant atoms include Sn, C, N and the like. In some embodiments, the dopant is Sn. In another embodiment, the dopant is C. In another embodiment, the dopant is N. In some embodiments, the dopant can be titanium, tungsten, cerium, tin, zinc, zirconium, bismuth, copper, indium, iron, silver, strontium, lithium, calcium, carbon, nitrogen, or a combination thereof. it can.

0048When including a dopant precursor in an oxide formation reaction mixture, it is useful if the resulting dopant concentration (Sn, C and / or N concentration) is at least 75% of the nominally desired dopant concentration after the synthesis process. Can be. In another embodiment, the resulting dopant concentration is at least 75% of the dopant concentration of similar particulate material produced by other conventional processes. In some embodiments, the dopant concentration remains at least 25%, 35%, 40%, 50%, 66% of the desired nominal complexity. Diffuse spectrum analysis can be one method for determining the retention of dopants in the oxide to be attached.

0049In some embodiments, the metal precursor may result in the metal element of the oxide formed on the substrate.

0050If the desired product is a doped metal oxide, the precursor may be a metal precursor, a dopant precursor, or a precursor for a non-metal element. In some embodiments where the desired final product is doped titanium oxide, the precursor may comprise Ti, O or one or more desired dopant elements. In some other embodiments, the desired dopant element may include Sn, C and / or N.

0051In general, the additive does not have to contain any of the atoms that are incorporated into the desired product, but can. Additives can be involved in the entire reaction; for example, they can be reducing elements / reducing agents or oxidizing elements / oxidizing agents.

0052In some embodiments, the substrate is substantially non-porous. In some embodiments, the substrate can be a polymer, glass, or sheet metal. In another embodiment, the substrate is porous. In some embodiments, the substrate is mullite, pumice, concrete, and / or a ceramic metal oxide (eg, alumina [Al].₂O₃], Silica, zirconia, ceria, hafnia).

0053After the oxide coating is formed on the surface of the substrate by heating the substrate in the presence of the precoat mixture, the substrate having the oxide coating can be annealed. Annealing can remove residual or residual carbon and increase the crystallinity of the oxide coating. The substrate can be annealed at any suitable temperature that can remove residual or residual carbon and increase the crystallinity of the oxide coating. In some embodiments, the oxide-attached substrate is annealed at about 300 ° C to about 450 ° C, or about 350 ° C to about 450 ° C, or about 400 ° C. In some embodiments, annealing is applied for about 10 seconds to about 100 hours, about 10 seconds to about 1 hour, about 1 minute to about 100 hours, about 5 minutes to about 45 minutes, or about 10 minutes to about 30 minutes. In another embodiment, annealing is applied for a period within the range limited by any of these values or between any of these values.

0054Some embodiments include a method of attaching an inorganic material to a substrate. This includes a method of forming an oxide-coated substrate, which is a step of bringing the solubilized reducing additive and the solubilized oxidation additive into contact with the substrate surface; the additive and substrate. The heating comprises a step of synthesizing an oxide coating film on the substrate, the heating being sufficiently high enough to allow the additive to undergo an exothermic reaction, and controlling the phase and composition of the metal oxide. Perform at a temperature as low as possible.

0055In one embodiment, a method (S10) for forming an oxide-attached substrate is described, as shown in FIG. 1, which method comprises a solubilized reducing additive and a solubilized oxidation additive. The step of contacting the additive with the surface of the base material and the step of heating the additive and the base material to synthesize an oxide coating film on the base material (S20) may be included, and the heating causes the additive to undergo an exothermic reaction. The temperature is high enough to allow the metal oxide to be controlled, and low enough to control the phase and composition of the metal oxide (S30). In other embodiments, the method may optionally supply an aqueous solution of reducing additives; and / or an oxide on a substrate surface. May be supplied to form.

0056Some embodiments include batch manufacturing methods. The reaction of the material may occur in a spatial relationship that is relatively static with respect to the heat source. The material to be reacted can be a batch additive. The reaction of the material can occur in the reaction vessel. In some embodiments, the reaction of the additive with the substrate in situ forms a metal oxide on the surface of the substrate.

0057In some embodiments, the reducing and oxidizing additives are solubilized. The solvent may be an aqueous solvent or a non-aqueous solvent. Non-aqueous solvent is C_1-10Alcohol, C_3-10It can be a ketone and / or a combination thereof. C_1-10Alcohols can optionally be methanol, ethanol, propanol and / or butanol. The aqueous solvent can optionally be water. In some embodiments, the additive is aqueous.

0058The following documents are incorporated herein by reference in their entirety. U.S. Pat. Nos. 3,586,423, 4,300,819, 4,998,817, 5,363,152, 5,408,278, 5,774,202, 5,917,573, 6,135,595, 6,149,270, 6,811,258 , 7,931,369, 8,314,049, US Patent Application Publication No. 2006/0087062, 2007/0113881, International Publication No. 2003/070640, US Patent Application Publication No. 2010/0062928 and 2012/0077668, and Patil, Kashinath C; Aruna, Singanahally T, and Sambandan, Ekambaram, Current Opinion in Solid State &amp; Materials Science, 2: 158-165 (1997).

<p num="0059"> A few embodiments will be further clarified by the following examples. These examples are intended to illustrate embodiments of the present disclosure, but are not intended to limit the scope or basic principles of the present disclosure in any way. [Example 1] Ti (C, N, O) on porous ceramic₂: Sn and Ti (C, N, O)₂Combustion synthesis approach for supporting in situ</p><p num="0060"> (a) TiSn (CNO)₂Coated Ceramic (Ex-1): 3.78 g tin 2-ethylhexanoate (II) [also known as tin (II) octanoate and / or stannous octanoate] (Spectrum Chemicals, Gardena, CA, USA), 30 mL 50 wt% titanium (IV) bis (ammonium lactato) dihydroxydo solution (titanium lactate, [Tyzor LA]) (Sigma Aldrich, St. Louis, CA, USA) and 15.0 g ammonium nitrate (NH)₄NO₃) (Sigma Aldrich, St. Louis, Missouri, USA) was dissolved in about 25 mL of reverse osmosis (RO) purified water, then heated to about 150 ° C. and stirred for about 20 minutes.</p><p num="0061"> Mullite ceramic substrate (60% Al) in the obtained precursor mixture₂O₃+ 38% SiO₂) (MTI, Richmond, Calif., USA) was immersed in approximately 2 x 2 mm pieces and then heated at approximately 350 ° C. for approximately 40 minutes under ambient and pressure conditions in a preheated muffle furnace. The coated fragment is then removed from the reaction vessel and the surface or top surface of the precursor-covered substrate is placed in a preheated muffle furnace and then under ambient conditions for about 20 minutes, about 400. Annealed at ° C. The ceramic was then rotated 180 ° along its longest axis to expose the back surface, and then annealed at about 400 ° C for an additional 20 minutes. [Example 2] (Ex-2)</p><p num="0062"> Samples of photocatalytically active powders were prepared in a manner similar to that described in Example 1, except that no support medium (mullite) was inserted into the precursor mixture prior to heating and annealing. (Comparative Example 1) (CE-1)</p><p num="0063"> An untreated mullite sheet of the same size and shape as described in Example 1 was obtained as Comparative Example-1 (CE-1). (Comparative example 2)</p><p num="0064"> Comparative Example 2 (CE-2) was 90 mg of P25 powder (P25 titania) obtained from Evonik (Evonik Degussa Corp., Parsippany, NJ, USA). Experimental configuration of photocatalytic action using supported Ti (O, C, N) 2: Sn</p><p num="0065"> As shown in FIG. 2, approximately 70 mL of Basic Blue 41 fiber dye (BB41) (Sigma Aldrich, Missouri, USA) containing Ex-1 and CE-1 produced as described in Examples (a) and (c) above. St. Louis, Missouri). Each sample was exposed to ambient sunlight on a sunny day with continuous stirring. 1 mL samples of each sample were taken at 1 hour intervals and the dye concentration was determined by visual inspection at about 620 nm (Cary-50, spectrophotometer [Agilent Technologies, Santa Clara, Calif., USA). The results are shown in Figure 3. As can be seen from FIG. 3, the Ex-1 carrier element showed photocatalytic activity, but CE-1 did not. Characterization of supported P-cat Powder XRD characterization:</p><p num="0066"> Ex-1 and CE-1 powder samples analyzed using powder X-ray diffraction (Rigaku Miniflex II [Rigaku Americas, Woodland, Texas, USA]) using Cu K-alpha radiation at a scan rate of 1 ° / min. I did. The results of X-ray diffraction are highlighted by blue lines and shown in Figure 4, confirming the presence of the anatase phase. One spectrum was identified as mullite as the main phase with silica and alumina as the subphase. This spectrum shows that the mullite carrier has a silica main phase. In addition, anatase TiO according to the consideration in FIG.₂The existence of is confirmed. DRS characterization:</p><p num="0067"> Powdered samples of Ex-1, Ex-2, CE-1 and CE-2 were analyzed using dispersion reflection spectroscopy (DRS). These results are shown in Fig. 5. These results indicate that tin doping enhances absorption in the visible spectrum (400 nm to 800 nm), but CE-1 does not. Ex-1 (Ti (O, C, N)₂: Sn-supported mullite carrier) is Ex-2 (Ti (O, C, N))₂: Sn powder) shows visible absorption very similar. Anatase TiO observed in XRD pattern and visible absorption due to the doped anatase phase₂Is the anatase phase Ti (O, C, N) on the carrier₂Confirm the support of: Sn. SEM and EDS characterization:</p><p num="0068"> Ex-1 and Ce-1 powder samples were also analyzed using energy dispersive X-ray spectroscopy (EDS). The results are shown in Fig. 6. This CE-1 analysis revealed the presence of aluminum and silicon. This Ex-1 analysis confirmed the presence of titanium in addition to aluminum and silicon (Fig. 6).</p><p num="0069"> Thus, XRD, DRS and EDS characterization confirmed that the oxide material was supported or immobilized on the carrier while maintaining the nominally desired doping property of the oxide material.</p><p num="0070"> Unless otherwise indicated, all numbers representing quantities of components, properties, such as molecular weights, reaction conditions, etc., as used herein and in the claims are all understood to be modified by the term "about". It shall be. Therefore, unless otherwise indicated, the numerical parameters shown herein and in the accompanying claims are approximations that may vary depending on the desired properties sought to be obtained. At a minimum, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter is interpreted, at least in light of the number of significant digits reported and by applying conventional rounding techniques. Should.</p><p num="0071"> The terms "a", "an", "the" and similar instructions used herein (especially in the context of subsequent claims) are used herein unless otherwise indicated or explicitly denied by the context. , It shall be interpreted as including both the singular and the plural. All methods described herein may be performed in any suitable order, unless otherwise indicated here or without explicit denial by context. The use of any and all examples or exemplary words (eg, "such as") provided herein is merely to better elucidate the claims and to the scope of any claim. No restrictions are imposed. There is no term herein to be construed as indicating any claim non-statement element essential to the implementation of the claim.</p><p num="0072"> The grouping of alternative elements or embodiments disclosed herein should not be construed as limiting. Each group member may be referred to and claimed individually, or in any combination with other members of the group or other elements found herein. It may also be described in the section. It is expected that one or more members of a group may be included in or removed from a group for convenience and / or patentability reasons. In the presence of any such inclusion or deletion, the specification is considered to include a group modified to satisfy the written specification of all Markush groups used in the appended claims.</p><p num="0073"> Certain embodiments are described herein, including the best methods known to us. Of course, variants of these described embodiments will be apparent to those skilled in the art by reading the above description. The inventors anticipate that those skilled in the art will make use of such variants as appropriate, and the inventors carry out the claims separately from those specifically described herein. Intended to be. Accordingly, this claim includes all modifications and equivalents of the subject matter described in the claims, as permitted by applicable law. Moreover, unless otherwise indicated herein or expressly denied by context, any combination of the above elements in all possible variants thereof is intended.</p><p num="0074"> Finally, it should be understood that the embodiments disclosed herein illustrate the principles of this claim. Other modifications that may be utilized are within the scope of this claim. Therefore, alternative embodiments may be utilized according to the teachings herein, by way of example, but not by limitation. Therefore, this claim is not limited to the exact embodiments shown and described.</p>